Photosensitive composition

Abstract

A photosensitive composition containing a radical polymerizable compound, a photo-radical polymerization initiator, and at least one selected from the group consisting of a chain transfer agent and a radical scavenger.

Description

[0001] This application is a divisional application of the application No. 201980018463.1 filed by the applicant and the invention name is “Photosensitive Composition”. The application date of the parent case is March 20, 2019, and the priority date is March 26, 2018. Technical Field

[0002] The present invention relates to a photosensitive composition for pulse exposure, and more particularly to a photosensitive composition for use in a solid imaging element or a color filter. Background Art

[0003] There is a technique for producing a color filter or the like using a photosensitive composition containing a radical polymerizable compound and a photoradical polymerization initiator (see Patent Documents 1 and 2).

[0004] Previous technical literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application No. 2012-532334

[0007] Patent Document 2: KR101573937B Summary of the invention

[0008] Technical issues to be solved by the invention

[0009] The present inventors have conducted in-depth research on photosensitive compositions containing free radical polymerizable compounds and photo-free radical polymerization initiators, and found that by subjecting these photosensitive compositions to pulse exposure, the curability becomes good, and it is easy to form a pattern with a good opening shape along the mask. In addition, the present inventors have further conducted research results and found that in the case of pulse exposure, it is difficult to make the line width of the pattern obtained by changing the exposure amount thicker or thinner than the opening size of the mask, and it is easy to form a good pattern along the opening shape of the mask. Therefore, by changing the opening size of the mask, it is easy to form a pattern with a desired line width.

[0010] On the other hand, the case where the line width of a pattern obtained by adjusting the formulation of a composition or the like is made coarser or finer than the opening size of the mask without changing the opening size of the mask has also been studied.

[0011] Means for solving technical problems

[0012] Therefore, an object of the present invention is to provide a photosensitive composition for pulse exposure that can adjust the line width of an obtained pattern without changing the aperture size of a mask.

[0013] According to the research of the present inventors, it was found that a photosensitive composition comprising a radical polymerizable compound and a photoradical polymerization initiator further contains at least one selected from a chain transfer agent and a radical scavenger, thereby being able to produce a pulse exposure photosensitive composition capable of adjusting the line width of the obtained pattern without changing the opening size of the mask, thereby completing the present invention. Therefore, the present invention provides the following.

[0014] <1> A photosensitive composition for pulse exposure, the photosensitive composition comprising:

[0015] Free radical polymerizable compounds;

[0016] Photo radical polymerization initiator; and

[0017] At least one selected from chain transfer agents and free radical scavengers.

[0018] <2> The photosensitive composition according to <1>, further comprising a color material.

[0019] <3> The photosensitive composition according to <1> or <2>, wherein

[0020] The chain transfer agent is at least one selected from the group consisting of a thiol compound, a thiocarbonylsulfide compound, and a dimer of an aromatic α-methylalkenyl.

[0021] <4> The photosensitive composition according to <1> or <2>, wherein

[0022] The free radical scavenger is at least one selected from the group consisting of hindered phenol compounds, hindered amine compounds, N-oxyl compounds, hydrazyl compounds and verdazyl compounds.

[0023] <5> The photosensitive composition according to any one of <1> to <4>, wherein

[0024] The content of the chain transfer agent in the total solid content of the photosensitive composition is 0.01 to 10% by mass.

[0025] <6> The photosensitive composition according to any one of <1> to <5>, wherein

[0026] The chain transfer agent is contained in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the radical polymerizable compound.

[0027] <7> The photosensitive composition according to any one of <1> to <6>, wherein

[0028] The chain transfer agent is contained in an amount of 0.2 to 200 parts by mass based on 100 parts by mass of the photoradical polymerization initiator.

[0029] <8> The photosensitive composition according to any one of <1> to <7>, wherein

[0030] The content of the radical scavenger in the total solid content of the photosensitive composition is 0.01 to 10% by mass.

[0031] <9> The photosensitive composition according to any one of <1> to <8>, wherein

[0032] The radical scavenger is contained in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the radical polymerizable compound.

[0033] <10> The photosensitive composition according to any one of <1> to <9>, wherein

[0034] The radical scavenger is contained in an amount of 0.2 to 200 parts by mass based on 100 parts by mass of the photoradical polymerization initiator.

[0035] <11> The photosensitive composition according to any one of <1> to <10>, comprising a resin having an acid group.

[0036] <12> The photosensitive composition according to any one of <1> to <11>, which is a photosensitive composition for pulse exposure using light having a wavelength of 300 nm or less.

[0037] <13> The photosensitive composition according to any one of <1> to <12>, which is used for a photosensitive film having a maximum instantaneous illuminance of 50,000,000 W / m 2 The photosensitive composition was subjected to pulse exposure under the above conditions.

[0038] <14> The photosensitive composition according to any one of <1> to <13>, which is a photosensitive composition for a solid imaging element.

[0039] <15> The photosensitive composition according to any one of <1> to <13>, which is a photosensitive composition for color filters.

[0040] Effects of the Invention

[0041] According to the present invention, it is possible to provide a photosensitive composition for pulse exposure that can adjust the line width of an obtained pattern without changing the opening size of a mask. DETAILED DESCRIPTION

[0042] Hereinafter, the contents of the present invention will be described in detail.

[0043] In this specification, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0044] In the marking of groups (atomic groups) in this specification, the marking not indicating substituted or unsubstituted includes groups (atomic groups) without substitution and also includes groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0045] In the present specification, “(meth)acrylate” means both or either acrylate and methacrylate, “(meth)acrylic acid” means both or either acrylic acid and methacrylic acid, and “(meth)acryloyl” means both or either acryloyl and methacryloyl.

[0046] In this specification, the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values ​​measured by GPC (gel permeation chromatography).

[0047] In this specification, infrared light refers to light with a wavelength of 700 to 2500 nm.

[0048] In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition.

[0049] In the present specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process can be achieved.

[0050] <Photosensitive Composition>

[0051] The photosensitive composition of the present invention is characterized in that it is used for pulse exposure, and contains a radical polymerizable compound, a photoradical polymerization initiator, and at least one selected from a chain transfer agent and a radical scavenger.

[0052] The photosensitive composition of the present invention is a photosensitive composition for pulse exposure. By subjecting the photosensitive composition of the present invention to pulse exposure, a large amount of free radicals can be instantly generated in the exposure portion by components such as a photoradical polymerization initiator. By instantly generating a large amount of free radicals in the exposure portion, the effects of deactivation caused by oxygen and the like are suppressed, thereby effectively curing the free radical polymerizable monomer. Therefore, the photosensitive composition of the present invention has excellent curability and pattern forming properties. In addition, pulse exposure refers to an exposure method in which exposure is performed by repeatedly irradiating and pausing light in a short period of time (e.g., milliseconds or less). Moreover, by using the photosensitive composition of the present invention, the line width of the obtained pattern can be adjusted even without changing the opening size of the mask. That is, by containing a free radical scavenger in the photosensitive composition of the present invention, the line width of the obtained pattern can be narrowed, and by increasing the amount of the free radical scavenger added, the line width of the obtained pattern can be made narrower. Furthermore, by including a chain transfer agent in the photosensitive composition of the present invention, the line width of the obtained pattern can be widened, and by increasing the amount of the chain transfer agent blended, the line width of the obtained pattern can be further widened.

[0053] In addition, conventionally, when a photosensitive composition containing a radical polymerizable compound and a photoradical polymerization initiator is exposed to continuous light such as i-rays to form a pattern, the amount of the photoradical polymerization initiator blended is adjusted to adjust the line width of the pattern, but when the photosensitive composition is subjected to pulse exposure, even if the amount of the photoradical polymerization initiator blended is reduced or increased as shown in the examples described below, the line width of the obtained pattern is hardly affected. However, the effect of adjusting the line width by blending a chain transfer agent or a radical scavenger is surprising.

[0054] The photosensitive composition of the present invention is a photosensitive composition for pulse exposure. The light used for exposure may be light having a wavelength exceeding 300nm or light having a wavelength below 300nm, but from the perspective of easily obtaining excellent curability, light having a wavelength below 300nm is preferred, light having a wavelength below 270nm is more preferred, and light having a wavelength below 250nm is further preferred. Furthermore, the aforementioned light is preferably light having a wavelength of 180nm or more. Specifically, KrF rays (wavelength 248nm), ArF rays (wavelength 193nm), etc. may be cited, and KrF rays (wavelength 248nm) are preferred from the perspective of easily obtaining more excellent curability.

[0055] The exposure conditions of pulse exposure are preferably as follows. Considering that it is easy to generate a large number of free radicals instantly, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and further preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but can be set to 1 femtosecond (fs) or more, and can also be set to 10 femtoseconds or more. From the viewpoint of curability, the frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and further preferably 4 kHz or more. Considering that it is easy to suppress the deformation of the substrate, etc. caused by the exposure heat, the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and further preferably 10 kHz or less. From the viewpoint of curability, the maximum instantaneous illuminance is preferably 50000000 W / m 2 More preferably 100000000 W / m 2 More preferably, 200000000 W / m 2 Furthermore, from the perspective of suppressing high-intensity failure, the upper limit of the maximum instantaneous illuminance is preferably 1000000000 W / m 2 Below, more preferably 800000000 W / m 2 Below, more preferably 500000000 W / m 2 Below. In addition, pulse width refers to the length of time that light is irradiated in a pulse cycle. And, frequency refers to the number of pulse cycles per 1 second. And, maximum instantaneous illuminance refers to the average illuminance during the time that light is irradiated in a pulse cycle. And, pulse cycle refers to the cycle in which the irradiation and pause of light in pulse exposure are set to 1 cycle.

[0056] The photosensitive composition of the present invention is preferably used as a composition for forming a color filter, a light-shielding film, an infrared transmission filter, etc. As a color filter, a filter having a colored pixel that transmits light of a specific wavelength can be cited, preferably a filter having at least one colored pixel selected from red pixels, blue pixels, green pixels, yellow pixels, cyan pixels and magenta pixels. An infrared transmission filter is a filter that transmits at least a portion of infrared light. As an infrared transmission filter, a filter that satisfies the spectral characteristics that the maximum value of the transmittance within the range of wavelengths of 400 to 640 nm is less than 20% (preferably less than 15%, more preferably less than 10%), and the minimum value of the transmittance within the range of wavelengths of 1100 to 1300 nm is more than 70% (preferably more than 75%, more preferably more than 80%), etc. can be cited. Preferably, the infrared transmission filter is a filter that satisfies any of the following spectral characteristics (1) to (4).

[0057] (1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1300 nm.

[0058] (2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1300 nm.

[0059] (3): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1300 nm.

[0060] (4): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm.

[0061] When the photosensitive composition of the present invention is used as a composition for an infrared transmission filter, the photosensitive composition of the present invention preferably satisfies a spectral characteristic in which the ratio Amin / Bmax of the minimum absorbance value Amin in the wavelength range of 400 to 640 nm to the maximum absorbance value Bmax in the wavelength range of 1100 to 1300 nm is 5 or more. Amin / Bmax is more preferably 7.5 or more, further preferably 15 or more, and particularly preferably 30 or more.

[0062] The absorbance Aλ at an arbitrary wavelength λ is defined by the following formula (1).

[0063] A λ=-log(Tλ / 100)……(1)

[0064] Aλ is the absorbance at wavelength λ, and Tλ is the transmittance (%) at wavelength λ.

[0065] In the present invention, the absorbance value may be a value measured in a solution state or a value measured in a film state prepared using the photosensitive composition. When measuring the absorbance in a film state, it is preferred to apply the photosensitive composition on a glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and then use a film prepared by drying at 100° C. for 120 seconds using a hot plate for measurement.

[0066] When the photosensitive composition of the present invention is used as a composition for an infrared transmission filter, the photosensitive composition of the present invention more preferably satisfies any one of the following spectral characteristics (11) to (14).

[0067] (11): The ratio Aminl / Bmaxl of the minimum absorbance value Aminl in the wavelength range of 400 to 640 nm to the maximum absorbance value Bmax1 in the wavelength range of 800 to 1300 nm is 5 or more, preferably 7.5 or more, more preferably 15 or more, and further preferably 30 or more. According to this embodiment, a film that blocks light in the wavelength range of 400 to 640 nm and transmits light with a wavelength of 720 nm or more can be formed.

[0068] (12): The ratio Amin2 / Bmax2 of the minimum absorbance value Amin2 in the wavelength range of 400 to 750 nm to the maximum absorbance value Bmax2 in the wavelength range of 900 to 1300 nm is 5 or more, preferably 7.5 or more, more preferably 15 or more, and further preferably 30 or more. According to this embodiment, a film that blocks light in the wavelength range of 400 to 750 nm and transmits light with a wavelength of 850 nm or more can be formed.

[0069] (13): The ratio Amin3 / Bmax3 of the minimum absorbance value Amin3 in the wavelength range of 400 to 850 nm to the maximum absorbance value Bmax3 in the wavelength range of 1000 to 1300 nm is 5 or more, preferably 7.5 or more, more preferably 15 or more, and further preferably 30 or more. According to this embodiment, a film that blocks light in the wavelength range of 400 to 850 nm and transmits light with a wavelength of 940 nm or more can be formed.

[0070] (14): The ratio Amin4 / Bmax4 of the minimum absorbance value Amin4 in the wavelength range of 400 to 950 nm to the maximum absorbance value Bmax4 in the wavelength range of 1100 to 1300 nm is 5 or more, preferably 7.5 or more, more preferably 15 or more, and further preferably 30 or more. According to this embodiment, a film that blocks light in the wavelength range of 400 to 950 nm and transmits light with a wavelength of 1040 nm or more can be formed.

[0071] The photosensitive composition of the present invention can be preferably used as a photosensitive composition for solid imaging elements. In addition, the photosensitive composition of the present invention can be preferably used as a photosensitive composition for color filters. Specifically, it can be preferably used as a photosensitive composition for forming pixels of a color filter, and can be more preferably used as a photosensitive composition for forming pixels of a color filter used in a solid imaging element.

[0072] Hereinafter, each component used in the photosensitive composition of the present invention will be described.

[0073] 《Free Radical Polymerizable Compounds》

[0074] The photosensitive composition of the present invention contains a radical polymerizable compound. Examples of the radical polymerizable compound include compounds having an ethylenically unsaturated bond group such as a vinyl group, an allyl group, a methallyl group, a styrene group, a styryl group, and a (meth)acryloyl group.

[0075] The radical polymerizable compound may be a monomer (hereinafter also referred to as a radical polymerizable monomer) or a polymer (hereinafter also referred to as a radical polymerizable polymer). The molecular weight of the radical polymerizable monomer is preferably less than 2000, more preferably less than 1500, and further preferably less than 1000. The lower limit is preferably greater than 100, and further preferably greater than 150. The weight average molecular weight (Mw) of the radical polymerizable polymer is preferably 2000 to 2000000. The upper limit is preferably less than 1000000, and more preferably less than 500000. The lower limit is preferably greater than 3000, and more preferably greater than 5000. In addition, the radical polymerizable polymer can also be used as the resin described later.

[0076] In the present invention, as a radical polymerizable compound, a radical polymerizable monomer and a radical polymerizable polymer may also be used in combination. By using both in combination, it is easy to take into account both coating properties and curing properties. When both are used in combination, the content of the radical polymerizable monomer is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, and further preferably 50 to 200 parts by mass relative to 100 parts by mass of the radical polymerizable polymer.

[0077] [Free radical polymerizable monomer]

[0078] As the radical polymerizable monomer, a compound having two or more radical polymerizable groups (preferably an ethylenically unsaturated bond group) (a compound having two or more functional groups), more preferably a compound having 2 to 15 radical polymerizable groups (a compound having two to 15 functional groups), further preferably a compound having 2 to 10 radical polymerizable groups (a compound having two to 10 functional groups), and particularly preferably a compound having 2 to 6 radical polymerizable groups (a compound having two to six functional groups). Specifically, the radical polymerizable monomer is preferably a (meth)acrylate compound having two or more functional groups, more preferably a (meth)acrylate compound having two to 15 functional groups, further preferably a (meth)acrylate compound having two to 10 functional groups, and particularly preferably a (meth)acrylate compound having two to six functional groups. Specific examples include compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, and paragraphs 0254 to 0257 of JP-A-2008-292970, and the contents of these compounds are incorporated into the present specification.

[0079] The radical polymerizable group value of the radical polymerizable monomer is preferably 1 mmol / g or more, more preferably 6 mmol / g or more, and further preferably 10 mmol / g or more. The upper limit is preferably 30 mmol / g or less. In addition, the radical polymerizable group value of the radical polymerizable monomer is calculated by dividing the number of radical polymerizable groups contained in one molecule of the radical polymerizable monomer by the molecular weight of the polymerizable monomer. In addition, the ethylenically unsaturated bond value (hereinafter referred to as C=C value) of the radical polymerizable monomer is preferably 1 mmol / g or more, more preferably 6 mmol / g or more, and from the viewpoint of curability, it is further preferably 10 mol / g or more. The upper limit is preferably 30 mmol / g or less. The C=C value of the radical polymerizable monomer is calculated by dividing the number of ethylenically unsaturated bond groups contained in one molecule of the radical polymerizable monomer by the molecular weight of the radical polymerizable monomer.

[0080] The free radical polymerizable monomer is preferably a free radical polymerizable monomer having a fluorene skeleton. Regarding the free radical polymerizable monomer having a fluorene skeleton, it is believed that even if a large amount of free radicals are instantly generated by a photo-free radical polymerization initiator by pulse exposure, it is difficult to generate self-reactions such as free radical polymerizable groups reacting with each other in the same molecule, so that the free radical polymerizable monomer can be efficiently cured by pulse exposure to form a film with a high crosslinking density.

[0081] As the free radical polymerizable monomer having a fluorene skeleton, a compound having a partial structure represented by formula (Fr) is preferred. Furthermore, the free radical polymerizable monomer having a fluorene skeleton is preferably a compound having two or more ethylenically unsaturated bond groups, more preferably a compound having 2 to 15 ethylenically unsaturated bond groups, further preferably a compound having 2 to 10 ethylenically unsaturated bond groups, and particularly preferably a compound having 2 to 6 ethylenically unsaturated bond groups.

[0082] (Fr)

[0083] [Chemical formula 1]

[0084]

[0085] The wavy lines represent bonding bonds, R f1 and R f2 Each independently represents a substituent, and m and n each independently represent an integer of 0 to 5. When m is 2 or more, m R f1 Can be the same or different, m R f1 The two R's f1 They may also be bonded to each other to form a ring. When n is 2 or more, n R f2 Can be the same or different, n R f2 The two R's f2 They may also be bonded to each other to form a ring. f1 and R f2 The substituent represented by includes a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR f11 、-COR f12 、-COOR f13 、-OCOR f14 、-NR f15 R f16 、-NHCOR f17 、-CONR f18 R f19 、-NHCONR f20 R f21 、-NHCOOR f22 、-SR f23 、-SO2R f24 、-SO2OR f25 、-NHSO2R f26 or -SO2NR f27 R f28 . R f11 ~R f28 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.

[0086] Specific examples of the radical polymerizable monomer having a fluorene skeleton include compounds having the following structures: Commercially available products of the radical polymerizable monomer having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0087] [Chemical formula 2]

[0088]

[0089] As the radical polymerizable monomer, compounds represented by the following formulae (M0-1) to (M0-6) can also be preferably used. In the formulae, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

[0090] [Chemical formula 3]

[0091]

[0092] In the above formula, n is 0 to 14, and m is 1 to 8. A plurality of R and T groups present in one molecule may be the same or different.

[0093] In each of the compounds represented by the above formulae (MO-1) to (MO-6), at least one of the multiple Rs represents -OC(=O)CH=CH2, -OC(=O)C(CH3)=CH2, -NHC(=O)CH=CH2 or -NHC(=O)C(CH3)=CH2.

[0094] Specific examples of the compounds represented by the above formulae (MO-1) to (MO-6) include compounds described in paragraphs 0248 to 0251 of JP-A-2007-269779.

[0095] It is also preferable to use a compound having a caprolactone structure as the radical polymerizable monomer. The compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).

[0096] [Chemical formula 4]

[0097]

[0098] In formula (Z-1), all six Rs are groups represented by formula (Z-2) or 1 to 5 of the six Rs are groups represented by formula (Z-2) and the remainder are groups represented by formula (Z-3), acid groups or hydroxyl groups.

[0099] [Chemical formula 5]

[0100]

[0101] In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.

[0102] [Chemical formula 6]

[0103]

[0104] In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

[0105] As the radical polymerizable monomer, a compound represented by the formula (Z-4) or (Z-5) can also be used.

[0106] [Chemical formula 7]

[0107]

[0108] In formula (Z-4) and (Z-5), E each independently represents -((CH2) y CH2O)-or-((CH2) y CH(CH3)O)-, y each independently represents an integer from 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom or a carboxyl group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m each independently represents an integer from 0 to 10, and the total number of m is an integer from 0 to 40. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n each independently represents an integer from 0 to 10, and the total number of n is an integer from 0 to 60.

[0109] In formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Furthermore, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

[0110] In formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Furthermore, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

[0111] Furthermore, -((CH2) in formula (Z-4) or formula (Z-5) y CH2O)-or-((CH2) y CH(CH3)O)- is preferably in a form in which the terminal on the oxygen atom side is bonded to X.

[0112] The radical polymerizable monomer also preferably uses compounds described in Japanese Patent Publication No. 2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, compounds described in Japanese Patent Publication No. 2017-194662, 8UH-1006, 8UH-1012 (all manufactured by TAISEI FINE CHEMICAL CO,. LTD.), LIGHTACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL CO., LTD.), etc.

[0113] (Free radical polymerizable polymer)

[0114] Examples of the radical polymerizable polymer include resins containing a repeating unit having a radical polymerizable group.

[0115] Examples of the repeating unit having a radical polymerizable group include the following (A2-1) to (A2-4).

[0116] [Chemical formula 8]

[0117]

[0118] R 1 represents a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. 1 A hydrogen atom or a methyl group is preferred.

[0119] L 51 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, -O-, -S-, -CO-, -COO-, -OCO-, -SO2-, -NR 10 -(R 10 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom) or a group consisting of a combination thereof. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 15, and further preferably 1 to 10. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be any of a straight chain, a branched chain, and a cyclic group. Furthermore, the cyclic alkylene group may be any of a monocyclic ring and a polycyclic ring. The number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 14, and further preferably 6 to 10.

[0120] P 1 represents a radical polymerizable group. Examples of the radical polymerizable group include ethylenically unsaturated bond groups such as a vinyl group, an allyl group, a methallyl group, a styrene group, a styryl group, and a (meth)acryloyl group.

[0121] The free radical polymerizable base value of the polymerizable polymer is preferably 0.5 to 3 mmol / g. The upper limit is preferably 2.5 mmol / g or less, more preferably 2 mmol / g or less. The lower limit is preferably 0.9 mmol / g or more, more preferably 1.2 mmol / g or more. In addition, the free radical polymerizable base value of the free radical polymerizable polymer is a numerical value representing the molar amount of the free radical polymerizable base value per 1 g of solid content of the free radical polymerizable polymer. In addition, the C=C value of the free radical polymerizable polymer is preferably 0.6 to 2.8 mmol / g. The upper limit is preferably 2.3 mmol] / g or less, more preferably 1.8 mmol / g or less. The lower limit is preferably 1.0 mmol / g or more, more preferably 1.3 mmol / g or more. In addition, the C=C value of the free radical polymerizable polymer is a numerical value representing the molar amount of the ethylenically unsaturated bond group per 1 g of solid content of the free radical polymerizable polymer.

[0122] The radical polymerizable polymer also preferably contains a repeating unit having an acid group. These polymers can be used as alkali-soluble resins. As the acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, etc. can be cited, preferably a carboxyl group. In the case where the radical polymerizable polymer contains a repeating unit having an acid group, the acid value of the radical polymerizable polymer is preferably 30 to 200 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more, and further preferably 100 mgKOH / g or more. The upper limit is preferably 180 mgKOH / g or less, more preferably 150 mgKOH / g or less.

[0123] Specific examples of the radical polymerizable polymer include resins having the following structures. In the following structural formula, Me represents a methyl group.

[0124] [Chemical formula 9]

[0125]

[0126] The content of the radical polymerizable compound in the total solid content of the photosensitive composition is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less. From the viewpoint of curability, the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more.

[0127] From the perspective of easy suppression of pattern thickness, the content of the radical polymerizable monomer in the total solid content of the photosensitive composition is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. From the perspective of curability, the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.

[0128] 《Photoradical polymerization initiator》

[0129] The photosensitive composition of the present invention contains a photoradical polymerization initiator. The photoradical polymerization initiator is preferably a compound that reacts with light having a wavelength of 300 nm or less to generate radicals.

[0130] The photoradical polymerization initiator is also preferably a compound that easily performs two-photon absorption. In addition, two-photon absorption refers to an excitation process that absorbs two photons simultaneously.

[0131] The photoradical polymerization initiator is preferably at least one compound selected from the group consisting of an alkylphenone compound, an acylphosphine compound, a benzophenone compound, a thioxanthone compound, a triazine compound, and an oxime compound, and is more preferably an oxime compound.

[0132] Examples of the alkylphenone compound include benzyl dimethyl ketal compounds, α-hydroxyalkylphenone compounds, and α-aminoalkylphenone compounds.

[0133] Examples of the benzyl dimethyl ketal compound include 2,2-dimethoxy-2-phenylacetophenone, and examples of commercially available products include IRGACURE-651 (manufactured by BASF Corporation).

[0134] Examples of the α-hydroxyalkylphenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl)-2-methyl-propane-1-one. Examples of commercially available products of the α-hydroxyalkylphenone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF).

[0135] Examples of the α-aminoalkylphenone compound include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone. Examples of commercially available α-aminoalkylphenone compounds include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF).

[0136] Examples of the acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Examples of commercially available acylphosphine compounds include IRGACURE-819 and IRGACURE-TPO (both manufactured by BASF).

[0137] Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′,4,4′-tetrakis(tert-butylperoxyhydroxy)benzophenone, and 2,4,6-trimethylbenzophenone.

[0138] Examples of the thioxanthone compound include 2-isopropyl-thioxanthone, 4-isopropyl-thioxanthone, 2,4-diethyl-thioxanthone, 2,4-dichloro-thioxanthone, and 1-chloro-4-propoxy-thioxanthone.

[0139] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2- [5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0140] Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. The compounds described in Techno1ogy (1995, pp. 202-232), the compounds described in Japanese Patent Publication No. 2000-066385, the compounds described in Japanese Patent Publication No. 2000-080068, the compounds described in Japanese Patent Publication No. 2004-534797, the compounds described in Japanese Patent Publication No. 2006-342166, the compounds described in Japanese Patent Publication No. 2017-019766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. WO2015 / 152153, the compounds described in International Publication No. WO2017 / 051680, etc. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. As commercially available products of oxime compounds, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by CHANGZHOU TRONLYNEW ELECTRONIC MATERIALS CO., LTD), ADECAOPTOMER N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). In addition, oxime compounds are preferably non-coloring compounds, compounds with high transparency and not easy to discolor other components. As commercially available products, ADEKA ARKLS NCI-730, NCI-831, NCI-930 (all manufactured by ADEKA CORPORATION) and the like can be cited.

[0141] Furthermore, as the oxime compound, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated into this specification.

[0142] Furthermore, as oxime compounds, oxime compounds having fluorine atoms can also be used. Specific examples of oxime compounds having fluorine atoms include compounds described in Japanese Unexamined Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in Japanese Unexamined Patent Publication No. 2014-500852, and compounds (C-3) described in Japanese Unexamined Patent Publication No. 2013-164471. This content is incorporated into this description.

[0143] In addition, as an oxime compound, an oxime compound having a nitro group can also be used. The oxime compound having a nitro group is also preferably set as a dimer. As a specific example of an oxime compound having a nitro group, there can be cited the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and paragraphs 0070 to 0079 of Japanese Patent Publication No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent Publication No. 4223071, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

[0144] Furthermore, as the oxime compound, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. WO2015 / 036910.

[0145] Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited to these.

[0146] [Chemical formula 10]

[0147]

[0148] [Chemical formula 11]

[0149]

[0150] In the present invention, as the photo-radical polymerization initiator, a photo-radical polymerization initiator having two or more functions or three functions can be used. By using these photo-radical polymerization initiators, two or more free radicals are generated from one molecule of the photo-radical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is reduced and the solubility in solvents etc. is improved, and it is difficult to precipitate over time, thereby being able to improve the stability over time of the photosensitive composition. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include dimers of oxime compounds described in JP-T 2010-527339, JP-T 2011-524436, International Publication WO2015 / 004565, paragraphs 0407 to 0412 of JP-T 2016-532675, paragraphs 0039 to 0055 of International Publication WO2017 / 033680, JP-T 2013-522445, and JP-T 2014-032676. Compounds (E) and (G) described in the gazette, Cmpd1 to 7 described in International Publication No. WO2016 / 034963, oxime ester photoinitiators described in paragraph 0007 of JP-A-2017-523465, photoradical polymerization initiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, and photopolymerization initiators (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, etc.

[0151] In the present invention, a pinacol compound can also be used as a photoradical polymerization initiator. Examples of the pinacol compound include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, 1,2-bis(trimethylsilyloxy)-1, 1,2,2-tetraphenylethane, 1,2-bis(triethylsilyloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsilyloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsilyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsilyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsilyloxy-1,1,2,2-tetraphenylethane, etc. In addition, regarding the pinacol compound, reference can be made to the records of JP-T 2014-521772, JP-T 2014-523939, and JP-T 2014-521772, and these contents are incorporated into this specification.

[0152] In the present invention, as the photoradical polymerization initiator, it is preferred to use a photoradical polymerization initiator including a photoradical polymerization initiator b1 satisfying the following condition 1.

[0153] Condition 1: Maximum instantaneous illumination 375000000W / m 2 Under the conditions of a pulse width of 8 nanoseconds and a frequency of 10 Hz, for a propylene glycol monomethyl ether acetate solution containing 0.035 mmol / L of the photoradical polymerization initiator b1, the quantum yield q355 after pulse exposure to light with a wavelength of 355 nm is greater than 0.05.

[0154] The quantum yield q355 of the photoradical polymerization initiator b1 is preferably 0.10 or more, more preferably 0.15 or more, further preferably 0.25 or more, further preferably 0.35 or more, and particularly preferably 0.45 or more.

[0155] In this specification, the quantum yield q of the photoradical polymerization initiator b1 is 355 The value is obtained by dividing the number of decomposed molecules of the photoradical polymerization initiator b1 after pulse exposure under the above condition 1 by the number of absorbed photons of the photoradical polymerization initiator b1. Regarding the number of absorbed photons, the number of irradiated photons is obtained from the exposure time using pulse exposure under the above condition 1, the absorbance at 355 nm before and after exposure is converted into transmittance, and the number of irradiated photons is multiplied by (1-transmittance), thereby obtaining the number of absorbed photons. Regarding the number of decomposed molecules, the decomposition rate of the photoradical polymerization initiator b1 is obtained from the absorbance of the photoradical polymerization initiator b1 after exposure, and the number of decomposed molecules is obtained by multiplying the decomposition rate by the number of molecules of the photoradical polymerization initiator b1. In addition, a propylene glycol monomethyl ether acetate solution containing 0.035 mmol / L of the photoradical polymerization initiator b1 is added to an optical cell of 1 cm × 1 cm × 4 cm, and the absorbance of the photoradical polymerization initiator b1 can be measured using a spectrophotometer. As a spectrophotometer, for example, HP8453 manufactured by Agilent can be used. As the photoradical polymerization initiator b1 that satisfies the above-mentioned condition 1, IRGACURE-OXE01, OXE02, OXE03 (all manufactured by BASF) and the like can be cited. In addition, the compound of the following structure can also be preferably used as the photoradical polymerization initiator b1 that satisfies the above-mentioned condition 1. Among them, from the viewpoint of adhesion, IRGACURE-OXE01 and OXE02 can be preferably used. In addition, from the viewpoint of curability, it is preferred to use a compound represented by the following formula (I3).

[0156] [Chemical formula 12]

[0157]

[0158] Furthermore, the photoradical polymerization initiator b1 preferably further satisfies the following condition 2.

[0159] Condition 2: Maximum instantaneous illumination 375000000W / m 2 Under the conditions of pulse width of 8 nanoseconds and frequency of 10 Hz, for a film with a thickness of 1.0 μm containing 5 mass % of photoradical polymerization initiator b1 and 95 mass % of resin, the quantum yield q265 after pulse exposure to light with a wavelength of 265 nm is greater than 0.05.

[0160] The quantum yield q265 of the photoradical polymerization initiator b1 is preferably 0.10 or more, more preferably 0.15 or more, and further preferably 0.20 or more.

[0161] In this specification, the quantum yield q of the photoradical polymerization initiator b1 is 265 After the pulse exposure under the above condition 2, every 1cm 2 The value obtained by dividing the number of decomposed molecules of the photoradical polymerization initiator b1 of the film by the number of absorbed photons of the photoradical polymerization initiator b1. The number of absorbed photons was obtained from the exposure time of the pulse exposure under the above condition 2, and the number of absorbed photons per 1 cm 2 The number of photons absorbed was obtained by multiplying the number of photons irradiated by the film by (1-transmittance). The decomposition rate of the photoradical polymerization initiator b1 was obtained from the change in the absorbance of the film before and after exposure. The decomposition rate of the photoradical polymerization initiator b1 was multiplied by the number of photons per 1 cm 2 The number of molecules of the photo-radical polymerization initiator b1 in the film was calculated based on the number of molecules per cm after exposure. 2 The number of decomposed molecules of the photo-radical polymerization initiator b1 of the film. The film density is 1.2 g / cm 3 Calculate the area of ​​each membrane 1cm 2 The weight of the film is expressed as "((per 1cm 2 The molecular mass per 1 cm was calculated as follows: film weight × 5 mass % (content of photoradical polymerization initiator b1) / molecular mass of photoradical polymerization initiator b1) × 6.02 × 1023 (Avogadro constant) 2 The number of molecules of the photoradical polymerization initiator b1 present in the film.

[0162] Furthermore, the photoradical polymerization initiator b1 used in the present invention preferably satisfies the following condition 3.

[0163] Condition 3: Maximum instantaneous illumination 625000000W / m 2, pulse width 8 nanoseconds, frequency 10Hz, a film containing 5% by mass of photo radical polymerization initiator b1 and resin, after being exposed to light of any wavelength in the range of 248 to 365nm with one pulse, the radical concentration in the film reached 100% per 1cm 2 Membrane 0.000000001mmol or more.

[0164] The free radical concentration in the film in the above condition 3 is preferably 1 cm 2 The molecular weight of the membrane is 0.000000005 mmol or more, more preferably 0.00000001 mmol or more, further preferably 0.00000003 mmol or more, and particularly preferably 0.0000001 mmol or more.

[0165] In this specification, the decomposition rate per incident photon number is calculated by multiplying the quantum yield of the initiator b1 in the light of the measured wavelength by (1-transmittance of the film), and the decomposition rate per 1 cm is calculated from "number of mol of photons per pulse" × "decomposition rate of the initiator b1 per incident photon number". 2 The radical concentration in the film was calculated by assuming that the photoradical polymerization initiator b1 decomposed by light irradiation would all become radicals (not disappear after reaction in the middle).

[0166] The resin used in the measurement in the above conditions 2 and 3 is not particularly limited as long as it is compatible with the photoradical polymerization initiator b1. For example, a resin (A) having the following structure can be preferably used. The numerical value attached to the repeating unit is a molar ratio, the weight average molecular weight is 40,000, and the dispersion degree (Mn / Mw) is 5.0.

[0167] Resin (A)

[0168] [Chemical formula 13]

[0169]

[0170] Since it is easy to generate a large number of free radicals instantly by pulse exposure, the photoradical polymerization initiator b1 is preferably an alkylphenone compound and an oxime compound, and more preferably an oxime compound. In addition, the photoradical polymerization initiator b1 is preferably a compound that easily undergoes two-photon absorption. In addition, two-photon absorption refers to the excitation process of absorbing two photons at the same time.

[0171] The photoradical polymerization initiator used in the present invention may include only one type or may include two or more types of photoradical polymerization initiators. When the photoradical polymerization initiator includes two or more types of photoradical polymerization initiators, each photoradical polymerization initiator may also be a photoradical polymerization initiator b1 that satisfies the above-mentioned condition 1. In addition, one or more types of photoradical polymerization initiators b1 that satisfy the above-mentioned condition 1 and photoradical polymerization initiators b2 that do not satisfy the above-mentioned condition 1 may be included, respectively. When the two or more types of photoradical polymerization initiators included in the photoradical polymerization initiator are only the photoradical polymerization initiator b1 that satisfies the above-mentioned condition 1, it is easy to instantly generate the amount of free radicals required for curing the radical polymerizable compound by pulse exposure. When the two or more types of photoradical polymerization initiators included in the photoradical polymerization initiator include one or more types of photoradical polymerization initiators b1 that satisfy the above-mentioned condition 1 and photoradical polymerization initiators b2 that do not satisfy the above-mentioned condition 1, it is easy to suppress desensitization over time due to pulse exposure.

[0172] From the perspective of easy sensitivity adjustment, the photoradical polymerization initiator used in the present invention preferably includes two or more photoradical polymerization initiators. In addition, when the photoradical polymerization initiator used in the present invention includes two or more photoradical polymerization initiators, from the perspective of curability, the photoradical polymerization initiator preferably satisfies the following condition 1a.

[0173] Condition 1a: Maximum instantaneous illumination 375000000W / m 2 Under the conditions of a pulse width of 8 nanoseconds and a frequency of 10 Hz, for a propylene glycol monomethyl ether acetate solution containing 0.035 mmol / L of a mixture of two or more photo radical polymerization initiators in the proportion contained in the photosensitive composition, the quantum yield q355 after pulse exposure to light of a wavelength of 355 nm is preferably 0.05 or more, more preferably 0.10 or more, further preferably 0.15 or more, further preferably 0.25 or more, further preferably 0.35 or more, and especially preferably 0.45 or more.

[0174] Furthermore, from the viewpoint of curability, when the photoradical polymerization initiator used in the present invention contains two or more photoradical polymerization initiators, the photoradical polymerization initiator preferably satisfies the following condition 2a.

[0175] Condition 2a: Maximum instantaneous illumination 375000000W / m 2The quantum yield q of a film having a thickness of 1.0 μm containing 5% by mass of a mixture of two or more photo-radical initiators in the ratio contained in the photosensitive composition and 95% by mass of a resin after pulse exposure to light with a wavelength of 265 nm under the conditions of a pulse width of 8 nanoseconds and a frequency of 10 Hz is 265 It is preferably 0.05 or more, more preferably 0.10 or more, further preferably 0.15 or more, and particularly preferably 0.20 or more.

[0176] Furthermore, from the viewpoint of curability, when the photoradical polymerization initiator used in the present invention contains two or more photoradical polymerization initiators, the photoradical polymerization initiator preferably satisfies the following condition 3a.

[0177] Condition 3a: Maximum instantaneous illuminance 625000000 W / m 2 , pulse width 8 nanoseconds, frequency 10 Hz, for a film containing 5 mass % of a mixture of two or more photo radical initiators in the ratio contained in the photosensitive composition and a resin, after pulse exposure to light of any wavelength in the range of 248 to 365 nm for 0.1 second, the radical concentration in the film preferably reaches 1 cm 2 The molecular weight of the membrane is 0.000000001 mmol or more, more preferably 0.000000005 mmol or more, further preferably 0.00000001 mmol or more, particularly preferably 0.00000003 mmol or more, and most preferably 0.0000001 mmol or more.

[0178] The content of the photoradical polymerization initiator in the total solid content of the photosensitive composition is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more. In addition, from the viewpoint of curability, the content of the photoradical polymerization initiator is preferably 10 to 200 parts by mass relative to 100 parts by mass of the radical polymerizable compound. The upper limit is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. When the photosensitive composition of the present invention contains two or more photoradical polymerization initiators, it is preferred that the total amount of these is within the above range.

[0179] Furthermore, the content of the above-mentioned photoradical polymerization initiator b1 in the total solid content of the photosensitive composition is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more. Furthermore, from the viewpoint of curability, the content of the above-mentioned photoradical polymerization initiator b1 is preferably 10 to 200 parts by mass relative to 100 parts by mass of the radical polymerizable compound. The upper limit is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less. The lower limit is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. When the photosensitive composition of the present invention contains two or more photoradical polymerization initiators b1, it is preferred that the total amount thereof is within the above range.

[0180] 《Chain transfer agent, free radical scavenger》

[0181] The photosensitive composition of the present invention contains at least one selected from a chain transfer agent and a radical scavenger.

[0182] As described above, by including a radical scavenger in the photosensitive composition of the present invention, the line width of the obtained pattern can be narrowed. Furthermore, by increasing the amount of the radical scavenger blended, the line width of the obtained pattern can be further narrowed. Furthermore, by including a chain transfer agent in the photosensitive composition of the present invention, the line width of the obtained pattern can be widened, and by increasing the amount of the chain transfer agent blended, the line width of the obtained pattern can be further widened.

[0183] (Chain transfer agent)

[0184] First, the chain transfer agent used in the photosensitive composition of the present invention is described. Examples of the chain transfer agent include thiol compounds, thiocarbonylthio compounds, and dimers of aromatic α-methylalkenyl groups. Thiool compounds are preferred because they can easily adjust the line width of a pattern even with a small amount of the compounding amount. In addition, the chain transfer agent is preferably a compound with little coloration.

[0185] [Thiol compounds]

[0186] The thiol compound is a compound having one or more thiol groups, preferably a compound having two or more thiol groups. The upper limit of the number of thiol groups contained in the thiol compound is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, further preferably 8 or less, and particularly preferably 6 or less. The lower limit of the number of thiol groups contained in the thiol compound is preferably 3 or more. From the reason that the effect of the present invention is easy to obtain more significantly, the thiol compound is particularly preferably a compound having 4 thiol groups.

[0187] Furthermore, the thiol compound is preferably a compound derived from a polyfunctional alcohol.

[0188] The thiol compound is preferably a compound represented by the following formula (SH-1).

[0189] L 1 -(SH) n ……Formula (SH-1)

[0190] (where SH represents a thiol group, L 1 represents an n-valent group, where n represents an integer greater than 1. )

[0191] In formula (SH-1), L 1 The n-valent groups represented by may include hydrocarbon groups, heterocyclic groups, -O-, -S-, -NR-, -CO-, -COO-, -OCO-, -SO2- or groups containing combinations thereof. R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Furthermore, the aliphatic hydrocarbon group may be cyclic or non-cyclic. Furthermore, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may not have a substituent. Furthermore, the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic ring or a condensed ring. The heterocyclic group may be a monocyclic ring or a condensed ring. As the heterocyclic group, a 5-membered ring or a 6-membered ring is preferred. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Furthermore, as heteroatoms constituting the heterocyclic group, nitrogen atoms, oxygen atoms, sulfur atoms, etc. may be mentioned. 1 The number of carbon atoms in is preferably 3-100, more preferably 6-50.

[0192] In formula (SH-1), n ​​represents an integer greater than or equal to 1. The upper limit of n is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, further preferably 8 or less, and particularly preferably 6 or less. The lower limit of n is preferably 2 or more, more preferably 3 or more. It is particularly preferred that n is 4.

[0193] Specific examples of thiol compounds include compounds of the following structures. Commercially available thiol compounds include PEMP (manufactured by SC Organic Chemical Co., Ltd., thiol compound), SANCELER M (manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD., thiol compound), and Karenz MT BD1 (manufactured by SHOWA DENKOKK, thiol compound).

[0194] [Chemical formula 14]

[0195]

[0196] [Chemical formula 15]

[0197]

[0198] [Chemical formula 16]

[0199]

[0200] [Chemical formula 17]

[0201]

[0202] [Thiocarbonylsulfide compounds]

[0203] Examples of the thiocarbonylsulfide compound include bis(thiocarbonyl)disulfide compounds (compounds represented by the following formula (SC-1)), dithioester compounds (compounds represented by the following formula (SC-2)), trithiocarbonate compounds (compounds represented by the following formula (SC-3)), dithiocarbamate compounds (compounds represented by the following formula (SC-4)), and xanthate compounds (compounds represented by the following formula (SC-5)) having a thiocarbonylsulfide group (-SC(=S)-) in the molecule.

[0204] [Chemical formula 18]

[0205]

[0206] In formula (SC-1) to formula (SC-5), Z 1 ~Z 11 Each independently represents a substituent.

[0207] As Z 1 ~Z 11 The substituent represented by may be alkyl, aryl, heteroaryl, -SR Z1 、-NR Z1 R Z2 、-NR Z1 -NR Z2 R Z3 、-COOR Z1 、-OCOR Z1 、-CONR Z1 R Z2 、-P(=O)(OR Z1 )2 or -OP(=O)R Z1 R Z2 (Among them, R Z1 , R Z2 and R Z3 Each of the above groups is independently an alkyl group, an aryl group or a heteroaryl group. ) etc. Furthermore, in the above groups, one or more hydrogen atoms bonded to a carbon atom may be substituted by a cyano group, a carboxyl group or the like.

[0208] The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0209] The aryl group has preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 12 carbon atoms.

[0210] The heteroaryl group is preferably a monocyclic heteroaryl group or a fused heteroaryl group having 2 to 8 fused rings, and more preferably a monocyclic heteroaryl group or a fused heteroaryl group having 2 to 4 fused rings. The number of heteroatoms constituting the heteroaryl ring is preferably 1 to 3. The heteroatoms constituting the heteroaryl ring are preferably nitrogen atoms, oxygen atoms or sulfur atoms. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the heteroaryl ring is preferably 3 to 30, more preferably 3 to 18, and more preferably 3 to 12.

[0211] Specific examples of the bis(thiocarbonyl)disulfide compound include tetraethylthiuram disulfide, tetramethylthiuram disulfide, bis(n-octylmercapto-thiocarbonyl)disulfide, bis(n-dodecylmercapto-thiocarbonyl)disulfide, bis(benzylmercapto-thiocarbonyl)disulfide, bis(n-butylmercapto-thiocarbonyl)disulfide, bis(tert-butylmercapto-thiocarbonyl)disulfide, bis(n-heptylmercapto-thiocarbonyl)disulfide, Bis(n-hexylmercapto-thiocarbonyl) disulfide, bis(n-pentylmercapto-thiocarbonyl) disulfide, bis(n-nonylmercapto-thiocarbonyl) disulfide, bis(n-decylmercapto-thiocarbonyl) disulfide, bis(tert-dodecylmercapto-thiocarbonyl) disulfide, bis(n-tetradecylmercapto-thiocarbonyl) disulfide, bis(n-hexadecylmercapto-thiocarbonyl) disulfide, bis(n-octadecylmercapto-thiocarbonyl) disulfide, and the like.

[0212] Specific examples of the dithioester compound include 2-phenyl-2-propylbenzoic acid thioester, 4-cyano-4-(phenylthiocarbonylthio)pentanoic acid, and 2-cyano-2-propylbenzene disulfate.

[0213] Specific examples of the trithiocarbonate compound include S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonate, 4-cyano-4-[(dodecylsulfanyl thiocarbonyl)sulfanyl]pentanoic acid, cyanomethyldodecyl trithiocarbonate, and 2-(dodecylthiocarbonylthiothio)-2-methyl propionic acid.

[0214] Specific examples of the dithiocarbamate compound include cyanomethylmethyl(phenyl)dithiocarbamate and cyanomethyldiphenyldithiocarbamate.

[0215] Specific examples of the xanthate compound include xanthate ester and the like.

[0216] [Dimer of aromatic α-methylalkenyl]

[0217] Examples of the dimer of aromatic α-methylalkenyl include 2,4-diphenyl-4-methyl-1-pentene and the like.

[0218] The molecular weight of the chain transfer agent is preferably 200 or more because it can suppress contamination of the device due to sublimation, etc. The upper limit is preferably 1000 or less, more preferably 800 or less, and further preferably 600 or less because it can increase the SH value per weight.

[0219] (Free Radical Scavenger)

[0220] Next, the free radical scavenger used in the photosensitive composition of the present invention is described. As the free radical scavenger, naphthalene derivatives, thioether compounds, hindered phenol compounds, hindered amine compounds, N-oxyl compounds, hydrazine compounds and verdazyl compounds can be cited, preferably hindered phenol compounds, hindered amine compounds, N-oxyl compounds, hydrazine compounds and verdazyl compounds (Japanese original: フェルダジル compounds). In addition, for the purpose of adjusting the sensitivity of the photosensitive composition by controlling the amount of free radicals generated by the photoradical polymerization initiator contained in the photosensitive composition during exposure, the free radical scavenger is preferably a compound that reacts quantitatively with free radicals. From this point of view, the free radical scavenger is preferably an N-oxyl compound and a hydrazine compound. In addition, from the perspective of free radical scavenging ability, N-oxyl compounds can be preferably used. In addition, from the perspective of easy control of sensitivity adjustment, hydrazine compounds can be preferably used. In addition, the free radical scavenger is preferably a compound with less coloring.

[0221] [Naphthalene derivatives]

[0222] Examples of the naphthalene derivatives include naphthohydroquinone compounds such as naphthohydroquinone sulfonate onium salts. Specific examples thereof include 1,4-dihydroxynaphthalene, 6-amino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-methylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-ethylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-propylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-butylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 2-(α,α-dimethyl)naphthalene, 2-(α,α-dimethylbenzyl)naphthalene, 2-tert-amylnaphthalene, and 2-trimethylsilyl-1,4,5,8,-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene. Among these, 1,4-dihydroxynaphthalene is particularly preferred.

[0223] [Thioether compounds]

[0224] The sulfide compound is not particularly limited as long as it is a compound having at least one sulfide group in the molecule. For example, 3,3'-dimethyl thiodipropionate, di-L-thiodipropionate, dinonyl thiodipropionate, didecyl thiodipropionate, undecyl thiodipropionate, dodecyl thiodipropionate, ditridecyl thiodipropionate, ditetradecyl thiodipropionate, dipentadecyl thiodipropionate, hexadecyl thiodipropionate, diheptadecyl thiodipropionate, dioctadecyl thiodipropionate, di-L-thiodibutyrate, dinonyl thiodibutyrate, didecyl thiodibutyrate, diundecyl thiodibutyrate, didodecyl thiodibutyrate, ditridecyl thiodibutyrate, ditetradecyl thiodibutyrate, dipentadecyl thiodibutyrate, hexadecyl thiodibutyrate, methyl 3-methoxy-2-[2-[cyclopropyl(3-fluorophenylimino)methylthiomethyl]phenyl]acrylate, and diheptadecyl thiodibutyrate can be mentioned. Among these, dimethyl 3,3'-thiodipropionate is particularly preferred.

[0225] [Hindered amine compounds]

[0226] Examples of the hindered amine compound include compounds having a partial structure represented by the following formula (HA1).

[0227] Formula (HA1)

[0228] [Chemical formula 19]

[0229]

[0230] In the formula, the wavy line represents the bonding bond, R T1 ~R T4 Each independently represents a hydrogen atom or an alkyl group, R T5 represents an alkyl group, an alkoxy group, an aryloxy group or an oxygen radical.

[0231] The alkyl group is preferably a linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. The alkoxy group is preferably a linear alkoxy group having 1 to 4 carbon atoms.

[0232] The molecular weight of the hindered amine compound is preferably 2000 or less, more preferably 1000 or less. Commercially available products of the hindered amine compound include ADK STAB LA-52, LA-57, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402AF, LA-502XP (manufactured by ADEKA Corporation), TINUVIN765, TINUVIN770 DF, TINUVIN XT55FB, TINUVIN111 FDL, TINUVIN783 FDL, TINUVIN791 FB, TINUVIN123, TINUVIN144, TINUVIN152 (manufactured by BASF Corporation), and the like.

[0233] [Hindered phenol compounds]

[0234] Examples of the hindered phenol compound include compounds having a structure represented by the following formula (HP1).

[0235] Formula (HP1)

[0236] [Chemical formula 20]

[0237]

[0238] In the formula, the wavy line represents a bonding bond, Rp1 represents an alkyl group having 3 or more carbon atoms, Rp2 represents a substituent, m represents an integer greater than 1, n represents an integer greater than 0, and m+n is 4 or less.

[0239] Specific examples of hindered phenol compounds include 4-tert-butylcatechol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc. Commercially available products of hindered phenol compounds include ADK STAB A0-20, ADK STAB A0-30, ADK STAB AO-40, ADK STAB A0-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all from ADEKA Corporation).

[0240] [N-oxyl compounds]

[0241] As N-oxyl compounds, there are no particular limitations as long as they are compounds having an N-oxyl group, and known compounds can be used. For example, piperidine 1-oxyl compounds and pyrrolidine 1-oxyl compounds can be mentioned. As piperidine 1-oxyl compounds, for example, piperidine 1-oxy, 2,2,6,6-tetramethylpiperidine 1-oxy, 4-oxy-2,2,6,6-tetramethylpiperidine 1-oxy, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy, 4-acetylamino-2,2,6,6-tetramethylpiperidine 1-oxy, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxy and 4-phosphonooxy-2,2,6,6-tetramethylpiperidine 1-oxy can be mentioned. As pyrrolidine 1-oxyl compounds, for example, 3-carboxyl-PROXYL, 3-carboxyl-2,2,5,5-tetramethylpyrrolidine 1-oxy can be mentioned.

[0242] [Hydrazine compounds]

[0243] The hydrazine compound is not particularly limited as long as it is a compound having a hydrazine group, and a known compound can be used, for example, 2,2-diphenyl-1-picrylhydrazine, 2,2-di(4-tert-octylphenyl)-1-picrylhydrazine, etc. can be mentioned.

[0244] [Quadruplex nitrogen compounds]

[0245] The quatrazolium compound is not particularly limited as long as it is a compound having a quatrazolium group, and a known compound can be used, for example, triphenylquatrazolium and the like.

[0246] When the photosensitive composition of the present invention contains a chain transfer agent, the content of the chain transfer agent in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass. The upper limit is preferably 9% by mass or less, more preferably 8% by mass or less, and further preferably 7% by mass or less. The lower limit is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more.

[0247] Furthermore, the chain transfer agent is preferably contained in an amount of 0.1 to 100 parts by mass relative to 100 parts by mass of the radical polymerizable compound. The upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and the lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more.

[0248] Furthermore, the amount of the chain transfer agent is preferably 0.2 to 200 parts by mass relative to 100 parts by mass of the photoradical polymerization initiator. The upper limit is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 20 parts by mass or less. The lower limit is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2 parts by mass or more.

[0249] When the photosensitive composition of the present invention contains a radical scavenger, the content of the radical scavenger in the total solid content of the photosensitive composition is preferably 0.01 to 10.0% by mass. The upper limit is preferably 9% by mass or less, more preferably 8% by mass or less, and further preferably 7% by mass or less. The lower limit is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more.

[0250] Furthermore, the radical scavenger is preferably contained in an amount of 0.1 to 100 parts by mass relative to 100 parts by mass of the radical polymerizable compound. The upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less. The lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more.

[0251] Furthermore, it is preferred that 0.2 to 200 parts by mass of a radical scavenger be contained relative to 100 parts by mass of the photoradical polymerization initiator. The upper limit is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 20 parts by mass or less. The lower limit is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2 parts by mass or more.

[0252] When the photosensitive composition of the present invention contains a chain transfer agent and a radical scavenger, it is preferred that 300 to 10 parts by mass of the radical scavenger be contained relative to 100 parts by mass of the chain transfer agent. The upper limit is preferably 250 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more.

[0253] Furthermore, the total content of the chain transfer agent and the radical scavenger in the total solid content of the photosensitive composition is preferably 0.01 to 10.0% by mass. The upper limit is preferably 9% by mass or less, more preferably 8% by mass or less, and further preferably 7% by mass or less. The lower limit is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more.

[0254] Furthermore, the chain transfer agent and the radical scavenger are preferably contained in a total amount of 0.1 to 100 parts by mass relative to 100 parts by mass of the radical polymerizable compound. The upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less. The lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more.

[0255] Furthermore, it is preferred that the total amount of the chain transfer agent and the radical scavenger is 0.2 to 200 parts by mass relative to 100 parts by mass of the photoradical polymerization initiator. The upper limit is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 20 parts by mass or less. The lower limit is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2 parts by mass or more.

[0256] "Color Material"

[0257] The photosensitive composition of the present invention preferably contains a colorant. Examples of the colorant include chromatic colorants, black colorants, infrared absorbing pigments, etc. The colorant used in the photosensitive composition of the present invention preferably contains at least a chromatic colorant.

[0258] (Color colorant)

[0259] As color colorants, red colorants, green colorants, blue colorants, yellow colorants, purple colorants, orange colorants and the like can be cited. Color colorants can be pigments or dyes. Pigments are preferred. The average particle size (r) of the pigment is preferably 20nm≤r≤300nm, more preferably 25nm≤r≤250nm, and further preferably 30nm≤r≤200nm. The so-called "average particle size" herein refers to the average particle size of the secondary particles of the primary particles polymerized with the pigment. In addition, the particle size distribution of the secondary particles of the pigment that can be used (hereinafter referred to as "particle size distribution") is preferably more than 70% by mass of the total secondary particles contained in the range of the average particle size ±100nm, and more preferably more than 80% by mass.

[0260] The pigment is preferably an organic pigment. Examples of the organic pigment include the following pigments.

[0261] Colorimetric 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, 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),

[0262] 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),

[0263] 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, 145 6, 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 pigments),

[0264] CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (the above are green pigments),

[0265] CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (the above are purple pigments),

[0266] 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).

[0267] These organic pigments can be used alone or in combination of two or more.

[0268] Furthermore, as the yellow pigment, a metal azo pigment containing: at least one anion selected from the group consisting of an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof; two or more metal ions; and a melamine compound can also be used.

[0269] [Chemical formula 21]

[0270]

[0271] In the formula, R 1 and R 2 are independently -OH or -NR 5 R 6 , R 3 and R 4 are independently =O or =NR 7 , R 5 ~R 7 are independently a hydrogen atom or an alkyl group. 5 ~R 7 The number of carbon atoms of the alkyl group represented is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain, preferably a straight chain or a branched chain, and more preferably a straight chain. The alkyl group may further have a substituent. The substituent is preferably a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, and an amino group.

[0272] In formula (I), R 1 and R 2 Preferably, it is -OH. 3 and R 4 Preferably =O.

[0273] The melamine compound in the metal azo pigment is preferably a compound represented by the following formula (II).

[0274] [Chemical formula 22]

[0275]

[0276] Where R 11 ~R 13 are independently a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. The alkyl group may be any of a straight chain, a branched chain, and a cyclic group, preferably a straight chain or a branched chain, and more preferably a straight chain. The alkyl group may further have a substituent. The substituent is preferably a hydroxyl group. Preferably R 11 ~R 13 At least one of them is a hydrogen atom, and more preferably R 11 ~R 13 All are hydrogen atoms.

[0277] The metal azo pigment is preferably a metal azo pigment comprising: at least one anion selected from the azo compound represented by the above formula (I) and an azo compound of a tautomeric structure thereof; at least Zn 2+ Cu 2+ In this embodiment, based on 1 mol of the total metal ions of the metal azo pigment, preferably 95 to 100 mol% of Zn 2+ Cu2+ , more preferably 98 to 100 mol%, further preferably 99.9 to 100 mol%, and particularly preferably 100 mol%. 2+ With Cu 2+ The molar ratio of Zn is preferably 2+ :Cu 2+ =199:1 to 1:15, more preferably 19:1 to 1:1, and even more preferably 9:1 to 2:1. In this embodiment, the metal azo pigment may further contain Zn 2+ Cu 2+ Other divalent or trivalent metal ions (hereinafter also referred to as metal ion Mel). Examples of metal ions Mel 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+ , preferably selected from Al 3+ , Fe 2+ , Fe3+ 、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 2+ , Ca 2+ , Sr 2+ , Mn 2+ and Y 3+ At least one of, more preferably selected from Al 3+ , Fe 2+ , Fe 3+ 、Co 2+ 、Co 3+ ,La 3+ 、Ce 3+ , Pr 3+ 、Nd 3+ 、Sm 3+ , Tb 3+ 、Ho 3+ and Sr 2+ At least one of, particularly preferably selected from Al 3+ , Fe 2+ , Fe 3+ 、Co 2 + and Co 3+ The content of the metal ion Me1 is preferably 5 mol% or less, more preferably 2 mol% or less, and further preferably 0.1 mol% or less, based on 1 mol of the total metal ions of the metal azo pigment.

[0278] Regarding the above-mentioned metal azo pigments, reference can be made to the descriptions in paragraphs 0011 to 0062 and 0137 to 0276 of JP-A-2017-171912, paragraphs 0010 to 0062 and 0138 to 0295 of JP-A-2017-171913, paragraphs 0011 to 0062 and 0139 to 0190 of JP-A-2017-171914, and paragraphs 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915, and these contents are incorporated into the present specification.

[0279] Furthermore, as a red pigment, a compound having a structure in which an aromatic ring group having a group bonded to an oxygen atom, a sulfur atom or a nitrogen atom is introduced into the aromatic ring and bonded to a diketopyrrolopyrrole skeleton can be used. Such a compound is preferably a compound represented by formula (DPP1), and more preferably a compound represented by formula (DPP2).

[0280] [Chemical formula 23]

[0281]

[0282] In the above formula, R 11 and R 13 Each independently represents a substituent, R 12 and R14 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, n11 and n13 each independently represent an integer of 0 to 4, and X 12 and X 14 Each independently represents an oxygen atom, a sulfur atom or a nitrogen atom, and X 12 When it is an oxygen atom or a sulfur atom, m12 represents 1, X 12 In the case of a nitrogen atom, m12 represents 2, and X 14 When it is an oxygen atom or a sulfur atom, m14 represents 1, X 14 When it is a nitrogen atom, m14 represents 2. 11 and R 13 Preferred specific examples of the substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an amide group, a cyano group, a nitro group, a trifluoromethyl group, a sulfoxide group, and a sulfone group.

[0283] Furthermore, as a green pigment, a zinc phthalocyanine halogenide pigment can be used, wherein the number of halogen atoms in one molecule is 10 to 14 on average, the number of bromine atoms is 8 to 12 on average, and the number of chlorine atoms is 2 to 5 on average. Specific examples include compounds described in International Publication No. WO2015 / 118720.

[0284] Furthermore, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue pigment, and specific examples thereof include compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

[0285] There is no particular restriction on dyes, and known dyes can be used. For example, dyes such as pyrazole azo, phenylamino azo, triarylmethane, anthraquinone, anthrapyridine quinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole methine azo, xanthene, phthalocyanine, benzopyran, indigo, pyrrolemethine can be cited. In addition, polymers of these dyes can also be used. In addition, dyes described in Japanese Patent Publication No. 2015-028144 and Japanese Patent Publication No. 2015-034966 can also be used.

[0286] (Black colorant)

[0287] As black coloring agent, inorganic black coloring agents such as carbon black, metal nitrogen oxide (titanium black etc.), metal nitride (titanium nitride etc.), dibenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds etc. can be enumerated. Preferred dibenzofuranone compounds and perylene compounds of organic black coloring agents. As dibenzofuranone compounds, compounds described in Japanese Patent Table 2010-534726 Gazette, Japanese Patent Table 2012-515233 Gazette, Japanese Patent Table 2012-515234 Gazette etc. can be enumerated, for example, " Irgaphor Black " manufactured by BASF can be obtained. As perylene compounds, CI Pigment Black (Pigment Black) 31, 32 etc. can be enumerated. Examples of the methine azo compound include those described in Japanese Patent Application Laid-Open No. 1-170601 and Japanese Patent Application Laid-Open No. 2-34664, and are available as "CHROMO FINE BLACK A1103" manufactured by Daini Chi Seika Co]or & Chemi ca]s Mfg. Co., Ltd. The dibenzofuranone compound is preferably a compound represented by any of the following formulae or a mixture thereof.

[0288] [Chemical formula 24]

[0289]

[0290] In the formula, R 1 and R 2 Each independently represents a hydrogen atom or a substituent, R 3 and R 4 Each independently represents a substituent, a and b each independently represent an integer of 0 to 4, and when a is 2 or more, a plurality of R 3 Can be the same or different, multiple R 3 can be bonded to form a ring. When b is 2 or more, multiple R 4 Can be the same or different, multiple R4 They may be bonded to form a ring.

[0291] R 1 ~R 4 The substituent represented by the present invention is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, -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 、-SO2R 314 、-SO2OR 315 、-NHSO2R 316 or -SO2NR 317 R 318 , R 301 ~R 318 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.

[0292] For details of the dibenzofuranone compound, reference can be made to paragraphs 0014 to 0037 of JP-A-2010-534726, the contents of which are incorporated herein.

[0293] (Infrared absorbing pigment)

[0294] As the infrared absorbing pigment, a compound having a maximum absorption wavelength in the range of 700 to 1300 nm, more preferably in the range of 700 to 1000 nm is preferred. The infrared absorbing pigment may be a pigment or a dye.

[0295] In the present invention, as an infrared absorbing pigment, a compound having a π conjugated plane containing a monocyclic or condensed aromatic ring can be preferably used. The number of atoms other than hydrogen constituting the π conjugated plane possessed by the infrared absorbing pigment is preferably 14 or more, more preferably 20 or more, further preferably 25 or more, and particularly preferably 30 or more. The upper limit is, for example, preferably 80 or less, more preferably 50 or less. The π conjugated plane possessed by the infrared absorbing pigment preferably contains two or more monocyclic or condensed aromatic rings, more preferably contains 3 or more of the aromatic rings, further preferably contains 4 or more of the aromatic rings, and particularly preferably contains 5 or more of the aromatic rings. The upper limit is preferably 100 or less, more preferably 50 or less, and further preferably 30 or less. Examples of the aromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an indene ring, a heptalene ring, an indecene ring, a perylene ring, a condensed pentadiene ring, a quaterrylene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed tetraphenyl ring,

[0043] The invention further comprises a chrysene ring, a triphenylene ring, a fluorene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a triazole ring, a benzotriazole ring, an oxazole ring, a benzoxazole ring, an imidazoline ring, a pyrazine ring, a quinoxaline ring, a pyrimidine ring, a quinazoline ring, a pyridazine ring, a triazine ring, a pyrrole ring, an indole ring, an isoindole ring, a carbazole ring, and a condensed ring having these rings.

[0296] The infrared absorbing pigment is preferably selected from at least one of pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaternaryl triphenyl compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimonium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds and dibenzofuranone compounds, more preferably selected from at least one of pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds and diimonium compounds, further preferably selected from at least one of pyrrolopyrrole compounds, cyanine compounds and squarylium compounds, and particularly preferably pyrrolopyrrole compounds.

[0297] Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of JP-A-2009-263614, compounds described in paragraphs 0037 to 0052 of JP-A-2011-68731, and compounds described in paragraphs 0010 to 0033 of International Publication No. WO2015 / 166873, and the contents thereof are incorporated into the present specification.

[0298] Examples of the squarylium compound include compounds described in paragraphs 0044 to 0049 of Japanese Patent Publication No. 2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese Patent Publication No. 6065169, compounds described in paragraph 0040 of International Publication No. WO2016 / 181987, compounds described in International Publication No. WO2013 / 133099, compounds described in International Publication No. WO2014 / 088063, compounds described in Japanese Patent Publication No. 2014-126642, compounds described in Japanese Patent Publication No. 201 The compounds described in Japanese Patent Publication No. 6-146619, the compounds described in Japanese Patent Publication No. 2015-176046, the compounds described in Japanese Patent Publication No. 2017-25311, the compounds described in International Publication No. WO2016 / 154782, the compounds described in Japanese Patent No. 5884953, the compounds described in Japanese Patent No. 6036689, the compounds described in Japanese Patent No. 5810604, the compounds described in Japanese Patent Publication No. 2017-068120, etc., are incorporated into this specification.

[0299] Examples of cyanine compounds include compounds described in paragraphs 0044 to 0045 of Japanese Patent Application Publication No. 2009-108267, compounds described in paragraphs 0026 to 0030 of Japanese Patent Application Publication No. 2002-194040, compounds described in Japanese Patent Application Publication No. 2015-172004, compounds described in Japanese Patent Application Publication No. 2015-172102, compounds described in Japanese Patent Application Publication No. 2008-088426, compounds described in Japanese Patent Application Publication No. 2017-031394, and the like, and the contents of these compounds are incorporated into this specification.

[0300] As diimide compounds, for example, compounds described in Japanese Unexamined Patent Publication No. 2008-528706 can be cited, and the contents are incorporated into this specification. As phthalocyanine compounds, for example, compounds described in paragraph 0093 of Japanese Unexamined Patent Publication No. 2012-077153, phthalocyanine titanyl described in Japanese Unexamined Patent Publication No. 2006-343631, and compounds described in paragraphs 0013 to 0029 of Japanese Unexamined Patent Publication No. 2013-195480 can be cited, and the contents are incorporated into this specification. As naphthalocyanine compounds, for example, compounds described in paragraph 0093 of Japanese Unexamined Patent Publication No. 2012-077153 can be cited, and the contents are incorporated into this specification.

[0301] In the present invention, a commercially available infrared absorbing dye can be used. For example, SDO-C33 (manufactured by Arimoto Chemical Co., Ltd.), EX Color IR-14, EX Color IR-10A, EX Color TX-EX-801B, EX Color TX-EX-805K (manufactured by Nippon Shokubai Co., Ltd.), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, Shigenox NIA-839 (manufactured by HAKKO Chemical Co., Ltd.), Epolite V-63, Epolight 3801, Epolight 3036 (manufactured by EPOLIN), PRO-JET 825 LDI (manufactured by FUJIFIL M Co., Ltd.), NK-3027, NK-5060 (manufactured by Hayashibara Co., Ltd.), YKR-3070 (manufactured by Mitsui Chemical Co., Ltd.), Chemicals, Inc.) and the like.

[0302] From the viewpoint of the filmization of the obtained film, the content of the color material in the total solid content of the photosensitive composition is preferably more than 40 mass %, more preferably more than 50 mass %, further preferably more than 55 mass %, especially preferably more than 60 mass %. If the content of the color material is more than 40 mass %, it is easy to form a film with good spectral characteristics. From the viewpoint of film forming, the upper limit is preferably less than 80 mass %, more preferably less than 75 mass %, further preferably less than 70 mass %.

[0303] The color material used in the photosensitive composition of the present invention preferably includes at least one selected from a chromatic colorant and a black colorant. In addition, the content of the chromatic colorant and 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 further preferably 70% by mass or more. The upper limit can be set to 100% by mass, and can also be set to 90% by mass or less.

[0304] Furthermore, the color material used in the photosensitive composition of the present invention preferably contains at least a green colorant. Furthermore, the content of the green colorant in the total mass of the color material is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit can be set to 100% by mass, and can also be set to 75% by mass or less.

[0305] The content of the pigment in the total mass of the color material used in the photosensitive composition of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. If the content of the pigment in the total mass of the color material is within the above range, it is easy to obtain a film that suppresses the spectral variation caused by heat.

[0306] When the photosensitive composition of the present invention is used as a composition for color filter (more specifically, a composition for forming colored pixels of a color filter), the content of the chromatic colorant in the total solid content of the photosensitive composition is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more. In addition, the content of the chromatic colorant in the total mass of the color material is preferably 25% by mass or more, more preferably 45% by mass or more, and further preferably 65% ​​by mass or more. The upper limit can be set to 100% by mass, and can also be set to 75% by mass or less. In addition, the above-mentioned color material preferably contains at least a green colorant. In addition, the content of the green colorant in the total mass of the above-mentioned color material is preferably 35% by mass or more, more preferably 45% by mass or more, and further preferably 55% by mass or more. The upper limit can be set to 100% by mass, and can also be set to 80% by mass or less.

[0307] When the photosensitive composition of the present invention is used as a composition for forming a light-shielding film, the content of the black colorant (preferably an inorganic black colorant) in the total solid content of the photosensitive composition is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more. In addition, 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 further preferably 70% by mass or more. The upper limit can be set to 100% by mass, and can also be set to 90% by mass or less.

[0308] When the photosensitive composition of the present invention is used as a composition for an infrared transmission filter, the color material used in the present invention preferably satisfies at least one of the following requirements (1) to (3).

[0309] (1): Two or more color colorants are included and a combination of the two or more color colorants forms black. Preferably, a combination of two or more colorants selected from red colorants, blue colorants, yellow colorants, violet colorants, and green colorants forms black.

[0310] (2): Contains organic black colorant.

[0311] (3): The above (1) or (2), further comprising an infrared absorbing dye.

[0312] Examples of preferred combinations of the above-mentioned aspect (1) include the following.

[0313] (1-1) A mode in which a red colorant and a blue colorant are contained.

[0314] (1-2) A form containing a red colorant, a blue colorant, and a yellow colorant.

[0315] (1-3) A mode containing a red colorant, a blue colorant, a yellow colorant, and a violet colorant.

[0316] (1-4) A mode containing a red colorant, a blue colorant, a yellow colorant, a violet colorant, and a green colorant.

[0317] (1-5) A mode containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.

[0318] (1-6) A mode containing a red colorant, a blue colorant, and a green colorant.

[0319] (1-7) A mode containing a yellow colorant and a purple colorant.

[0320] In the above-mentioned embodiment (2), it is also preferred to further contain a color colorant. By using an organic black colorant and a color colorant in combination, excellent spectral characteristics can be easily obtained. As a color colorant used in combination with an organic black colorant, for example, a red colorant, a blue colorant, a purple colorant, etc. can be mentioned, preferably a red colorant and a blue colorant. These can be used alone or in combination of two or more. In addition, the mixing ratio of the color colorant and the organic black colorant is preferably 10 to 200 parts by mass, and more preferably 15 to 150 parts by mass, relative to 100 parts by mass of the organic black colorant.

[0321] In the above embodiment (3), the content of the infrared absorbing pigment in the total mass of the color material is preferably 5 to 40 mass %, the upper limit is preferably 30 mass % or less, more preferably 25 mass % or less, and the lower limit is preferably 10 mass % or more, more preferably 15 mass % or more.

[0322] Resin

[0323] The photosensitive composition of the present invention may contain a resin. In addition, in the present invention, the resin refers to an organic compound other than a color material and an organic compound having a molecular weight of 2000 or more. The resin is blended for purposes such as dispersing particles such as pigments in the composition or for purposes such as an adhesive. In addition, a resin mainly used to disperse particles such as pigments is also referred to as a dispersant. However, this use of the resin is an example, and the resin may also be used for purposes other than this use. In addition, a resin having a free radical polymerizable group is also a component equivalent to the above-mentioned free radical polymerizable compound.

[0324] The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 5,000 or more.

[0325] As resin, (meth) acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin etc. can be cited. One can be used alone from these resins, or two or more can be mixed and used. As cyclic olefin resin, from the viewpoint of improving heat resistance, norbornene resin can be preferably used. As a commercial product of norbornene resin, for example, ARTON series (for example, ARTON F4520) manufactured by JSR Corporation etc. can be cited. Furthermore, the resin described in the examples of International Publication No. WO2016 / 088645, the resin described in Japanese Patent Application Publication No. 2017-057265, the resin described in Japanese Patent Application Publication No. 2017-032685, the resin described in Japanese Patent Application Publication No. 2017-075248, and the resin described in Japanese Patent Application Publication No. 2017-066240 can also be used as the resin, and these contents are incorporated into this specification.

[0326] In the present invention, a resin having an acid group is preferably used as the resin. According to this mode, the developability of the photosensitive composition can be improved, thereby easily forming pixels with excellent rectangularity. As the acid group, carboxyl, phosphoric acid, sulfonic acid, phenolic hydroxyl, etc. can be cited, preferably carboxyl. The resin having an acid group can be used as an alkali-soluble resin, for example.

[0327] The resin having an acid group preferably contains a repeating unit having an acid group in a side chain, and more preferably contains 5 to 70 mol% of the repeating unit having an acid group in the side chain in the total repeating units of the resin. The upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, more preferably 20 mol% or more.

[0328] The resin having an acid group also preferably contains repeating units derived from a monomer component containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as “ether dimers”).

[0329] [Chemical formula 25]

[0330]

[0331] In formula (ED1), R 1 and R 2 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[0332] [Chemical formula 26]

[0333]

[0334] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED2), reference can be made to the description of Japanese Unexamined Patent Publication No. 2010-168539, the contents of which are incorporated herein.

[0335] As specific examples of the ether dimer, reference can be made to, for example, paragraph 0317 of Japanese Patent Application Laid-Open No. 2013-029760, the contents of which are incorporated herein.

[0336] The resin used in the present invention also preferably contains a repeating unit derived from a compound represented by the following formula (X).

[0337] [Chemical formula 27]

[0338]

[0339] In formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 2 to 10 carbon atoms, and R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1 to 15.

[0340] Examples of the resin having an acid group include resins having the following structures. Among the resins listed in the following specific examples, resins having a radical polymerizable group also correspond to the above-mentioned radical polymerizable compound.

[0341] [Chemical formula 28]

[0342]

[0343] Regarding the resin having an acid group, reference can be made to the description in paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (paragraphs 0685 to 0700 of the corresponding specification of US Patent Application Publication No. 2012 / 0235099), and the contents are incorporated into the present specification. In addition, the copolymer (B) described in paragraphs 0029 to 0063 of Japanese Patent Application Publication No. 2012-032767 and the alkali-soluble resin used in the examples, the binder resin described in paragraphs 0088 to 0098 of Japanese Patent Application Publication No. 2012-208474 and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of Japanese Patent Application Publication No. 2012-137531 and the binder resin used in the examples, the binder resin described in paragraphs 0132 to 0143 of Japanese Patent Application Publication No. 2013-024934 and the binder resin used in the examples, the binder resin described in paragraphs 0092 to 0098 of Japanese Patent Application Publication No. 2011-242752 and the binder resin used in the examples, and the binder resin described in paragraphs 0030 to 0072 of Japanese Patent Application Publication No. 2012-032770 can also be used. These contents are incorporated into this manual.

[0344] The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, further preferably 70 mgKOH / g or more, and particularly preferably 80 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 250 mgKOH / g or less.

[0345] The weight average molecular weight (Mw) of the resin having an acid group is preferably 5000 to 100000. Also, the number average molecular weight (Mn) of the resin having an acid group is preferably 1000 to 20000.

[0346] The photosensitive composition of the present invention may also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and an alkaline dispersant (alkaline resin). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of alkaline groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of acid groups and the amount of alkaline groups is set to 100 mol%, and more preferably a resin containing essentially only acid groups. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and further preferably 60 to 105 mgKOH / g. In addition, the alkaline dispersant (alkaline resin) refers to a resin in which the amount of alkaline groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin having a basic group content exceeding 50 mol % when the total of the acid group content and the basic group content is 100 mol %. The basic group possessed by the basic dispersant is preferably an amino group.

[0347] The resin used as a dispersant preferably contains a repeating unit having an acid group. When the resin used as a dispersant contains a repeating unit having an acid group, the residue generated on the pixel base can be reduced when forming pixels by photolithography, thereby making it possible to prepare a photosensitive composition with excellent developability.

[0348] The resin used as the dispersant is also preferably a graft copolymer. The graft copolymer has affinity with the solvent through the graft chain, so the dispersibility of the pigment and the dispersion stability after time are excellent. The details of the graft copolymer can refer to the records in paragraphs 0025 to 0094 of Japanese Patent Publication No. 2012-255128, which are incorporated into this specification. In addition, specific examples of the graft copolymer include the following resins. The following resins are also resins with acid groups (alkali-soluble resins). In addition, as graft copolymers, the resins described in paragraphs 0072 to 0094 of Japanese Patent Publication No. 2012-255128 can be cited, and the contents are incorporated into this specification.

[0349] [Chemical formula 30]

[0350]

[0351] In addition, in the present invention, it is also preferred to use an oligoimine copolymer containing a nitrogen atom in at least one of the main chain and the side chain as a resin (dispersant). As an oligoimine copolymer, it is preferred to have the following structural units and a side chain containing a side chain Y with an atomic number of 40 to 10,000, and a resin having a basic nitrogen atom in at least one of the main chain and the side chain, and the structural unit contains a partial structure X with a functional group of pKa 14 or less. There is no particular restriction on the basic nitrogen atom as long as it is a basic nitrogen atom. Regarding the oligoimine copolymer, reference can be made to the records of paragraphs 0102 to 0166 of Japanese Patent Publication No. 2012-255128, which are incorporated into this specification. As an oligoimine copolymer, a resin having the following structure or a resin described in paragraphs 0168 to 0174 of Japanese Patent Publication No. 2012-255128 can be used.

[0352] [Chemical formula 31]

[0353]

[0354] Furthermore, the above-mentioned alkali-soluble resin can also be used as a dispersant.

[0355] Furthermore, the resin used as the dispersant is preferably a resin containing repeating units having ethylenically unsaturated bond groups in the side chains. The content of repeating units having ethylenically unsaturated bond groups in the side chains is preferably 10 mol% or more, more preferably 10 to 80 mol%, and further preferably 20 to 70 mol% in the total repeating units of the resin.

[0356] The dispersant may also be a commercially available product, for example, the product described in paragraph 0129 of Japanese Patent Application Publication No. 2012-137564 may also be used as a dispersant. For example, the DISPERBYK series (for example, DISPERBYK-161, etc.) manufactured by BYK Chemical GmbH may be cited. In addition, the resin described as the above-mentioned dispersant may also be used for purposes other than the dispersant. For example, it may also be used as a binder.

[0357] 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 (when the radical polymerizable compound contains a radical polymerizable polymer, the content of the radical polymerizable polymer is also included) is preferably 5 to 50% by mass. The lower limit is 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.

[0358] Furthermore, the content of the resin having an acid group in the total solid content of the photosensitive composition (when the radical polymerizable compound includes a radical polymerizable polymer having an acid group, the content of the radical polymerizable polymer having an acid group is also included) is preferably 5 to 50% by mass. The lower limit is preferably 10% by mass or more, 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.

[0359] Furthermore, from the perspective of easily obtaining excellent developability, the content of the resin having an acid group in the total amount of the resin is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit can be 100% by mass, 95% by mass, or 90% by mass or less.

[0360] In addition, from the perspective of easy consideration of curability, developability, and coating properties, the total content of the radical polymerizable monomer and the resin in the total solid content of the photosensitive composition is preferably 15 to 65% by mass. The lower limit is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less. In addition, relative to 100 parts by mass of the radical polymerizable monomer, it is preferred to contain 30 to 300 parts by mass of the resin. 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.

[0361] 《Compounds having cyclic ether groups》

[0362] The photosensitive composition of the present invention may contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group, an oxetanyl group, and the like. The compound having a cyclic ether group is preferably a compound having an epoxy group. Examples of the compound having an epoxy group include a compound having one or more epoxy groups in one molecule, and preferably a compound having two or more epoxy groups. It is preferred that there are 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy group can be, for example, set to 10 or less, or can be set to 5 or less. The lower limit of the epoxy group is preferably two or more. As the compound having an epoxy group, compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, paragraphs 0085 to 0092 of JP-A-2014-089408, and compounds described in JP-A-2017-179172 can also be used. These contents are incorporated into this specification.

[0363] The compound having an epoxy group may be a low molecular weight compound (e.g., a molecular weight of less than 2000, and further a molecular weight of less than 1000), or a macromolecule (e.g., in the case of a polymer having a molecular weight of 1000 or more, a weight average molecular weight of 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100000, and more preferably 500 to 50000. The upper limit of the weight average molecular weight is preferably 10000 or less, more preferably 5000 or less, and further preferably 3000 or less.

[0364] As the compound having an epoxy group, an epoxy resin can be preferably used. As the epoxy resin, there can be mentioned an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolac resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, a glycidyl ester epoxy resin, a glycidyl amine epoxy resin, an epoxy resin obtained by glycidylating halogenated phenols, a condensate of a silicon compound having an epoxy group and a silicon compound other than this, a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds other than this, etc. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and further preferably 310 to 1000 g / eq.

[0365] Commercially available products of the compound having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), MARPROOF G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOC Corporation and containing epoxy groups).

[0366] 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 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 further preferably 10% by mass or less. The compound having a cyclic ether group may be only one or more than two. In the case of two or more, it is preferred that the total amount is within the above range.

[0367] 《Silane coupling agent》

[0368] The photosensitive composition of the present invention can contain a silane coupling agent. According to this mode, the adhesion of the obtained film to the support can be improved. In the present invention, the coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than the hydrolyzable group. In addition, the hydrolyzable group refers to a substituent that is directly connected to the silicon atom and can produce a siloxane bond by performing at least any one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, etc. can be cited, preferably an alkoxy group. That is, the silane coupling agent preferably has an alkoxysilyl compound. In addition, as a functional group other than hydrolyzable, for example, a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetane group, an amino group, a urea group, a thioether group, an isocyanate group, a phenyl group, etc. can be cited, preferably an amino group, a (meth) acryloyl group and an epoxy group. Specific examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraphs 0056 to 0066 of JP-A-2009-242604, and the contents thereof are incorporated into the present specification.

[0369] 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 or more than two. In the case of two or more, the total amount is preferably within the above range.

[0370] Pigment derivatives

[0371] The photosensitive composition of the present invention may further include a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a portion of the pigment is substituted with an acid group, a basic group, a group having a salt structure, or a phthalimide methyl group. The pigment derivative is preferably a compound represented by formula (B1).

[0372] [Chemical formula 32]

[0373]

[0374] In formula (B1), P represents a pigment structure, L represents a single bond or a linking group, X represents an acid group, a basic group, a group having a salt structure or a phthalimide methyl group, m represents an integer greater than 1, and n represents an integer greater than 1. When m is greater than 2, multiple Ls and Xs may be different from each other, and when n is greater than 2, multiple Xs may be different from each other.

[0375] The pigment structure represented by P is preferably selected from at least one of a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, a quinacridone pigment structure, anthraquinone pigment structure, a dianthraquinone pigment structure, a benzisoindole pigment structure, a thiazine indigo pigment structure, an azo pigment structure, a quinophthalone pigment structure, a phthalocyanine pigment structure, a naphthalocyanine pigment structure, a dioxazine pigment structure, a perylene pigment structure, a perinone pigment structure, a benzimidazolone pigment structure, a benzothiazole pigment structure, a benzimidazole pigment structure and a benzoxazole pigment structure, and more preferably selected from at least one of a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, a quinacridone pigment structure and a benzimidazolone pigment structure.

[0376] Examples of the linking group represented by L include a hydrocarbon group, a heterocyclic group, -NR-, -SO2-, -S-, -O-, -CO-, or a group consisting of a combination thereof. R represents a hydrogen atom, an alkyl group, or an aryl group.

[0377] Examples of the acid group represented by X include a carboxyl group, a sulfonic acid group, a carboxylic acid amide group, a sulfonic acid amide group, and an imidic acid group. X1 As the sulfonic acid amide group, preferably -NHSO2R X2 As the imidic acid group, preferably -SO2NHSO2R X3 、-CONHSO2R X4 、-CONHCOR X5 or-SO2NHCOR X6 Represents a group. X1 ~R X6 R each independently represents a hydrocarbon group or a heterocyclic group. X1 ~R X6 The hydrocarbon group and heterocyclic group represented by X may further have a substituent. As a further substituent, a halogen atom is preferred, and a fluorine atom is more preferred. As a basic group represented by X, an amino group may be mentioned. As a salt structure represented by X, a salt of the above-mentioned acidic group or basic group may be mentioned.

[0378] As the pigment derivative, compounds of the following structures can be mentioned. In addition, Japanese Patent Publication No. 56-118462, Japanese Patent Publication No. 63-264674, Japanese Patent Publication No. 01-217077, Japanese Patent Publication No. 03-009961, Japanese Patent Publication No. 03-026767, Japanese Patent Publication No. 03-153780, Japanese Patent Publication No. 03-045662, Japanese Patent Publication No. 04-285669, Japanese Patent Publication No. 06-145546, Japanese Patent Publication No. 06-212088, Japanese Patent Publication No. 06-240158, Japanese Patent Publication No. 10-030063, Japanese Patent Publication No. 10-195326, International Publication No. WO201 The compounds described in paragraphs 0086 to 0098 of International Publication No. 1 / 024896, paragraphs 0063 to 0094 of International Publication No. WO2012 / 102399, paragraph 0082 of International Publication No. WO2017 / 038252, etc., the contents of which are incorporated into the present specification.

[0379] [Chemical formula 33]

[0380]

[0381] The content of the pigment derivative is preferably 1 to 50 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. If the content of the pigment derivative is within the above range, the dispersibility of the pigment can be improved and the aggregation of the pigment can be effectively suppressed. Only one type of pigment derivative can be used, or two or more types can be used. When two or more types are used, the total amount is preferably within the above range.

[0382] Solvents

[0383] The photosensitive composition of the present invention may contain a solvent. As the solvent, an organic solvent may be mentioned. As long as the solvent satisfies the solubility of each component or the coating property of the composition, there is basically no particular limitation. Examples of organic solvents include esters, ethers, ketones, aromatic hydrocarbons, etc. For details of these, reference may be made to paragraph 0223 of the International Publication No. WO2015 / 166779, which is incorporated into this specification. In addition, cyclic alkyl substituted ester solvents and cyclic alkyl substituted ketone solvents may also be preferably used. As the specific example of organic solvent, polyethylene glycol monomethyl ether, methylene chloride, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy methyl propionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate etc. can be mentioned. In the present invention, organic solvent can be used alone or in combination of two or more. And, from the viewpoint of improving solubility, 3-methoxy-N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide are also preferred. However, sometimes for environmental reasons, it is advisable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as solvents (for example, relative to the total amount of the organic solvent, it can be set to 50 mass ppm (parts per million) or less, it can also be set to 10 mass ppm or less, or it can also be set to 1 mass ppm or less).

[0384] In the present invention, it is preferred to use a solvent with a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a mass ppt (parts per trillion) level solvent may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

[0385] As a method for removing impurities such as metals from a solvent, for example, distillation (molecular distillation or thin film distillation, etc.) and filtering using a filter can be cited. The filter pore size of the filter used in the filtration is preferably below 10 μm, more preferably below 5 μm, and further preferably below 3 μm. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

[0386] The solvent may contain isomers (compounds having the same number of atoms but different structures). Also, the isomers may contain only one type or multiple types.

[0387] In the present invention, the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0388] The content of the solvent in the photosensitive composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 30 to 90% by mass.

[0389] Furthermore, from the perspective of environmental regulation, the photosensitive composition of the present invention preferably does not substantially contain environmentally regulated substances. In addition, in the present invention, substantially not containing environmentally regulated substances means that the content of environmentally regulated substances in the photosensitive composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, etc. These are registered as environmentally regulated substances according to REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, PRTR (Pollutant Release and Transfer Register) law, VOC (Volatile Organic Compounds) regulation, etc., and the amount of use and operation methods are strictly regulated. When manufacturing the various components used in the photosensitive composition of the present invention, these compounds are sometimes used as solvents, and sometimes mixed into the photosensitive composition as residual solvents. From the perspective of safety for people and consideration for the environment, it is preferred to reduce these substances as much as possible. As a method for reducing environmentally controlled substances, there can be cited a method of heating or reducing the inside of the system to a boiling point above the boiling point of the environmentally controlled substances and distilling the environmentally controlled substances from the inside of the system to reduce them. In addition, in the case of distilling a small amount of environmentally controlled substances, it is also useful to azeotropize with a solvent having a boiling point equal to that of the solvent in order to improve efficiency. In addition, in the case of containing compounds with free radical polymerizability, in order to suppress the free radical polymerization reaction during the reduced pressure distillation and cross-link between molecules, a polymerization inhibitor or the like can also be added to perform reduced pressure distillation. These distillation methods can be performed at any stage of the raw material stage, the stage of the product of the raw material reaction (such as a resin solution or a multifunctional monomer solution after polymerization), or the stage of mixing these compounds to make a composition.

[0390] 《Polymerization Inhibitors》

[0391] The photosensitive composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, benzoquinone, and N-nitrosophenylhydroxylamine salts (ammonium salts, cerium salts, 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.

[0392] Surfactants

[0393] The photosensitive composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicon-based surfactants may be used. For surfactants, reference may be made to paragraphs 0238 to 0245 of International Publication No. WO2015 / 166779, which is incorporated into this specification.

[0394] In the present invention, the surfactant is preferably a fluorine-based surfactant. By including a fluorine-based surfactant in the photosensitive composition, the solution properties (especially fluidity) are further improved, and the liquid saving can be further improved. In addition, a film with less uneven thickness can be formed.

[0395] 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. Fluorine-based surfactants having a fluorine content within this range are effective from the perspective of uniformity of the thickness of the coating film or liquid saving, and also have good solubility in the composition.

[0396] Examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of JP-A-2014-041318 (equivalent to paragraphs 0060 to 0064 of WO-2014 / 017669), and the surfactants described in paragraphs 0117 to 0132 of JP-A-2011-132503, and the contents of these are incorporated into the present specification. Examples of commercially available fluorine-based surfactants include MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS-330 (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (all 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 (all manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA Solutions Inc.), etc.

[0397] In addition, the fluorine-based surfactant can also be appropriately used as an acrylic compound, which has a molecular structure having a functional group containing a fluorine atom and a portion of the functional group containing a fluorine atom is cut off and the fluorine atom is volatilized when heat is applied. As such a fluorine-based surfactant, the MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Industry News, February 23, 2016) can be cited, such as MEGAFACE DS-21.

[0398] In addition, the fluorine-based surfactant is preferably a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl or fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Regarding this fluorine-based surfactant, reference can be made to the description of Japanese Patent Publication No. 2016-216602, which is incorporated into this specification.

[0399] The fluorine-based surfactant can also use block polymers. For example, the compounds described in Japanese Patent Publication No. 2011-89090 can be cited. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, which contains a repeating unit derived from a (meth) acrylate compound having a fluorine atom and a repeating unit derived from a (meth) acrylate compound having two or more (preferably 5 or more) alkylene oxides (preferably ethylene oxide, propylene oxide). The following compounds can also be exemplified as the fluorine-based surfactant used in the present invention.

[0400] [Chemical formula 34]

[0401]

[0402] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compound, % indicating the ratio of the repeating unit is mol %.

[0403] In addition, the fluorine-based surfactant can also use a fluorine-containing polymer having an ethylenically unsaturated bond group in the side chain. As a specific example, the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965, such as MEGAFACERS-101, RS-102, RS-718K, RS-72-K manufactured by DIC Corporation, etc. The fluorine-based surfactant can also use the compounds described in paragraphs 0015 to 0158 of Japanese Patent Publication No. 2015-117327.

[0404] Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Limited.), 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.), Olfine F1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

[0405] As the silicon-based surfactant, for example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., LTD.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie Corporation), etc. Furthermore, as the silicon-based surfactant, compounds having the following structures can also be used.

[0406] [Chemical formula 35]

[0407]

[0408] 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 one or more. In the case of two or more, the total amount is preferably within the above range.

[0409] 《UV absorber》

[0410] The photosensitive composition of the present invention can contain an ultraviolet absorber. The ultraviolet absorber can use a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyl triazine compound, an indole compound, a triazine compound, etc. For details, reference can be made to paragraphs 0052 to 0072 of Japanese Patent Publication No. 2012-208374, paragraphs 0317 to 0334 of Japanese Patent Publication No. 2013-068814, and paragraphs 0061 to 0080 of Japanese Patent Publication No. 2016-162946, which are incorporated into this specification. As a specific example of an ultraviolet absorber, compounds of the following structures can be cited. As a commercially available product of an ultraviolet absorber, for example, UV-503 (manufactured by DAITO CHEMICAL CO., LTD.) can be cited. In addition, examples of the benzotriazole compound include the MYUA series manufactured by MIYOSHIOIL & FAT CO., LTD. (Chemical Industry Daily, February 1, 2016).

[0411] [Chemical formula 36]

[0412]

[0413] The content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

[0414] 《Other ingredients》

[0415] As required, the photosensitive composition of the present invention may contain a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension regulators, chain transfer agents, etc.). By appropriately containing these ingredients, the properties of the film and the like can be adjusted. For example, these ingredients can refer to the records of paragraphs 0183 and later of Japanese Patent Application Publication No. 2012-003225 (equivalent to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, paragraphs 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, etc., and these contents are incorporated into this specification. In addition, as required, the photosensitive composition of the present invention may also contain a potential antioxidant. As potential antioxidants, compounds in which the part that functions as an antioxidant is protected by a protecting group and heated at 100 to 250 ° C or heated at 80 to 200 ° C in the presence of an acid / base catalyst to remove the protecting group and function as an antioxidant can be cited. As potential antioxidants, compounds described in International Publication WO2014 / 021023, International Publication WO2017 / 030005, and Japanese Patent Publication 2017-008219 can be cited. As commercially available products, ADEKA ARKLS SGPA-5001 (manufactured by ADEKA CORPORATION) and the like can be cited.

[0416] For example, when forming a film 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 further preferably 3 mPa·s or more. The upper limit is more preferably 50 mPa·s or less, further preferably 30 mPa·s or less, and particularly preferably 15 mPa·s or less.

[0417] <Container>

[0418] The container for the photosensitive composition of the present invention is not particularly limited, and a known container can be used. In addition, as the container, it is also preferred to use a multilayer bottle having an inner wall of the container composed of six types of six layers of resin or a bottle having a seven-layer structure of six types of resin in order to suppress the mixing of impurities into the raw materials or the composition. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

[0419] <Method for preparing photosensitive composition>

[0420] The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photosensitive composition, all the components can be dissolved or dispersed in a solvent at the same time to prepare the photosensitive composition, or two or more solutions or dispersions of the components can be prepared in advance as needed, and then mixed to prepare the photosensitive composition when used (when applied).

[0421] Furthermore, in the case where the photosensitive composition of the present invention includes particles such as pigments, it is preferred to include a process for dispersing the particles. In the process of dispersing the particles, compression, extrusion, impact, shearing, cavitation, etc. can be cited as mechanical forces for dispersing the particles. As specific examples of these processes, bead milling, sand milling, roller milling, ball milling, paint agitator, micro jet, high-speed impeller, sand mixing, jet stream mixing, high-pressure wet micronization, ultrasonic dispersion, etc. can be cited. Furthermore, in the pulverization of particles in sand milling (bead milling), it is preferred to process under the following conditions: by using micro beads with a smaller diameter and increasing the filling rate of micro beads, etc. to improve the pulverization efficiency. Furthermore, it is preferred to remove coarse particles by filtering, centrifugation, etc. after the pulverization process. Furthermore, regarding the process and disperser for dispersing the particles, it is preferred to use the process and disperser described in paragraph 0022 of "Dispersion Technology Encyclopedia, Information Organization Co., Ltd., July 15, 2005" or "Comprehensive Data Collection of Dispersion Technology and Practical Industrial Applications of Suspensions (Solid / Liquid Dispersion Systems), Business Development Center Publishing Department, October 10, 1978", and Japanese Patent Publication No. 2015-157893. Furthermore, in the process of dispersing the particles, the particles can also be refined in the salt milling process. Regarding the raw materials, equipment, processing conditions, etc. used in the salt milling process, for example, reference can be made to the records in Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629.

[0422] When preparing the photosensitive composition of the present invention, in order to remove foreign matter or reduce defects, it is preferred to filter the photosensitive composition using a filter. As a filter, as long as it is a filter used for filtering purposes in the past, it can be used without particular restrictions. For example, filters using raw materials such as fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (such as nylon-6, nylon-6,6), polyethylene, polypropylene (PP) and other polyolefin resins (including high-density, ultra-high molecular weight polyolefin resins) can be cited. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore size of the filter is preferably 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. If the pore size of the filter is within the above range, fine foreign matter can be reliably removed. In addition, it is also preferred to use a fibrous filter material. As a fibrous filter material, for example, polypropylene fiber, nylon fiber, glass fiber, etc. can be cited. Specifically, the filter elements of the SBP series (SBP008, etc.), TPR series (TPR002, TPR005, etc.), and SHPX series (SHPX003, etc.) manufactured by ROKI TECHNO CO., LTD. can be cited. When using a filter, different filters (for example, a first filter and a second filter, etc.) can be combined. In this case, the filtration in each filter may be performed only once or twice or more. Furthermore, filters of different pore sizes may be combined within the above range. Furthermore, the filtration in the first filter is performed only on the dispersion, and after mixing other components, filtration may be performed by the second filter.

[0423] <Optical filter manufacturing method>

[0424] Next, a method for producing an optical filter using the photosensitive composition of the present invention will be described. Examples of the types of optical filters include color filters and infrared transmission filters.

[0425] The method for producing an optical filter in the present invention preferably includes the steps of applying the photosensitive composition of the present invention on a support to form a photosensitive composition layer (photosensitive composition layer forming step), irradiating the photosensitive composition layer with light in a pulsed manner to expose it in a pattern (pulse exposure) (exposure step), and developing and removing the unexposed portion of the photosensitive composition layer to form pixels (development step). Each step is described below.

[0426] (Photosensitive Composition Layer Formation Step)

[0427] In the photosensitive composition layer forming process, the above-mentioned photosensitive composition of the present invention is applied on a support to form a photosensitive composition layer. As a support, for example, a substrate composed of materials such as silicon, alkali-free glass, soda glass, PYREX (registered trademark) glass, quartz glass, etc. can be cited. In addition, an InGaAs substrate, etc. are also preferably used. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. can be formed on the support. In addition, a black matrix (black matrix) is sometimes formed on the support to isolate each pixel. In addition, a primer layer can be provided on the support as needed in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or planarize the substrate surface.

[0428] As a method for applying the photosensitive composition on the support, a known method can be used. For example, a drop method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method (spin coating method); a cast coating method; a slit spin coating method; a pre-wetting method (for example, the method described in Japanese Patent Publication No. 2009-145395); various printing methods such as inkjet (for example, on-demand method, piezoelectric method, thermal method), nozzle jetting, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.; a transfer method using a mold, etc.; a nanoimprint method, etc. There is no particular limitation on the application method based on inkjet, and examples thereof include the method described in "Inkjet that can be promoted and used - Infinite possibilities appearing in patents -, published in February 2005, Sumitbe Techon Research Co., Ltd." (especially pages 115 to 133), or Japanese Patent Publication No. 2003-262716, Japanese Patent Publication No. 2003-185831, Japanese Patent Publication No. 2003-261827, Japanese Patent Publication No. 2012-126830, Japanese Patent Publication No. 2006-169325, etc. In addition, the descriptions of International Publication No. WO2017 / 030174 and International Publication No. WO2017 / 018419 can be used for the application method of the photosensitive composition, and these contents are incorporated into this specification.

[0429] After applying the photosensitive composition on the support, drying (prebaking) can be further performed. When prebaking is performed, the prebaking temperature is preferably below 150°C, more preferably below 120°C, and further preferably below 110°C. The lower limit can be set to above 50°C, for example, and can also be set to above 80°C. The prebaking time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and further preferably 80 to 2200 seconds. Drying can be performed using a hot plate, an oven, etc.

[0430] (Exposure process)

[0431] Next, the photosensitive composition layer on the support formed as described above is exposed to light in a pulsed manner (pulse exposure) in a pattern. The photosensitive composition layer is pulse-exposed through a mask having a predetermined mask pattern, thereby making it possible to pulse-expose the photosensitive composition layer in a pattern. Thus, the exposed portion of the photosensitive composition layer can be cured.

[0432] The light used in pulse exposure may be light having a wavelength exceeding 300nm or light having a wavelength below 300nm, but from the perspective of easily obtaining a more excellent curability, light having a wavelength below 300nm is preferred, light having a wavelength below 270nm is more preferred, and light having a wavelength below 250nm is further preferred. Furthermore, the aforementioned light is preferably light having a wavelength of 180nm or more. Specifically, KrF rays (wavelength 248nm), ArF rays (wavelength 193nm), etc. may be cited, and KrF rays (wavelength 248nm) are preferred from the perspective of easily obtaining a more excellent curability.

[0433] The pulse exposure conditions are preferably the following conditions. From the viewpoint of easily generating a large number of active species such as free radicals instantaneously, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and further preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but can be set to 1 femtosecond (fs) or more, and can also be set to 10 femtoseconds or more. From the viewpoint of curability, the frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and further preferably 4 kHz or more. From the reason that it is easy to suppress deformation of the substrate caused by exposure heat, the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and further preferably 10 kHz or less. From the viewpoint of curability, the maximum instantaneous illumination is preferably 50000000 W / m 2 More preferably 100000000 W / m 2 More preferably, 200000000 W / m 2 Furthermore, from the perspective of suppressing high-intensity failure, the upper limit of the maximum instantaneous illuminance is preferably 1000000000 W / m 2 Below, more preferably 800000000W / m 2 Below, more preferably 500000000 W / m 2 The exposure amount is preferably 1 to 1000 mJ / cm 2 The upper limit is preferably 500 mJ / cm 2 Below, more preferably 200mJ / cm 2 The lower limit is preferably 10 mJ / cm 2 More preferably, 20 mJ / cm 2More preferably, 30 mJ / cm 2 above.

[0434] The oxygen concentration during exposure can be appropriately selected. In addition to exposure in the atmosphere, exposure can be performed in a low oxygen environment with an oxygen concentration of less than 19 volume % (for example, 15 volume %, 5 volume %, or essentially oxygen-free), or in a high oxygen environment with an oxygen concentration exceeding 21 volume % (for example, 22 volume %, 30 volume %, or 50 volume %).

[0435] (Development Process)

[0436] Next, the photosensitive composition layer of the unexposed portion in the photosensitive composition layer after the exposure step is developed to form pixels (patterns). The development and removal of the photosensitive composition layer of the unexposed portion can be performed using a developer. Thus, the photosensitive composition layer of the unexposed portion is dissolved in the developer, and only the photocured portion in the above-mentioned exposure step remains on the support. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. In addition, in order to improve the removability of the residue, the process of shaking off the developer every 60 seconds and further supplying a new developer can be repeated multiple times.

[0437] The developer is preferably an alkaline aqueous solution obtained by diluting an alkali agent in pure water. As the alkali agent, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and other organic alkaline compounds or inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate. Alkali agents are preferably compounds with larger molecular weights in terms of environmental and safety aspects. The concentration of the alkali agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. In addition, the developer may further contain a surfactant. As the surfactant, the above-mentioned surfactants may be mentioned, preferably nonionic surfactants. From the perspective of convenient transportation or storage, the developer can be temporarily prepared as a concentrated solution and diluted to a desired concentration when used. The dilution ratio is not particularly limited, and can be set in a range of 1.5 to 100 times, for example. In addition, when a developer including such an alkaline aqueous solution is used, it is preferred to wash (rinse) with pure water after development.

[0438] After development, additional exposure treatment and heating treatment (post-baking) can also be performed after drying. Additional exposure treatment and post-baking are post-development treatments for completely curing the film. When additional exposure treatment is performed, the light used in the exposure is preferably light with a wavelength of 400nm or less.

[0439] The film thickness of the pixel (pattern) to be formed is preferably appropriately selected according to the type of pixel. For example, it is preferably 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.3 to 1.0 μm. The upper limit is preferably 0.8 μm or less, more preferably 0.6 μm or less. The lower limit is preferably 0.4 μm or more.

[0440] Furthermore, the size (line width) of the pixel (pattern) to be formed is preferably appropriately selected according to the purpose or the type of pixel. For example, it is preferably 2.0 μm or less. The upper limit is preferably 1.0 μm or less, and more preferably 0.9 μm or less. The lower limit is preferably 0.4 μm or more.

[0441] When manufacturing a filter having multiple pixels, at least one pixel may be formed through the above process, and preferably the first pixel (first pixel) is formed through the above process. The second and subsequent pixels (second and subsequent pixels) may be formed through the same process as above, or may be formed by exposure to continuous light.

[0442] Example

[0443] Below, give embodiment and the present invention is further specifically described.The material, usage amount, ratio, processing content, processing sequence etc. shown in the following embodiment can be appropriately changed as long as it does not depart from the purpose of the present invention.Therefore, the scope of the present invention is not limited to the specific example shown below.

[0444] <Measurement of Weight Average Molecular Weight (Mw) of Resin>

[0445] The weight average molecular weight of the resin was measured by gel permeation chromatography (GPC) under the following conditions.

[0446] Column type: Columns that connect TOSOH TSKgel Super HZM-H, TOSOH TSKgel SuperHZ4000, and TOSOH TSKgel Super HZ2000

[0447] Developing solvent: tetrahydrofuran

[0448] Column temperature: 40℃

[0449] Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1 mass %)

[0450] Device name: HLC-8220GPC manufactured by TOSOH CORPORATION

[0451] Detector: RI (refractive index) detector

[0452] Calibration curve base resin: polystyrene resin

[0453] <Preparation of Photosensitive Composition>

[0454] After mixing the raw materials described in the following table, the mixture was filtered through a nylon filter (manufactured by NIHONPALL LTD.) with a pore size of 0.45 μm to prepare a photosensitive composition (compositions 1 to 26, R1 to R3) having a solid content concentration of 20% by mass. In addition, the solid content concentrations of compositions 1 to 8, 10 to 26, and R1 to R3 were adjusted by changing the blending amount of propylene glycol monomethyl ether acetate (PGM EA). In addition, the solid content concentration of composition 9 was adjusted by changing the blending amount of a mixed solvent of PGMEA and polyethylene glycol monomethyl ether (PGMEA: polyethylene glycol monomethyl ether = 9:1 (mass ratio)). The numerical values ​​in the blending amount column shown in the following table are parts by mass.

[0455] [Table 1]

[0456]

[0457] The raw materials described in the above table are as follows.

[0458] (Pigment dispersion)

[0459] A1: Pigment dispersion prepared by the following method

[0460] 230 parts by mass of zirconium oxide microbeads with a diameter of 0.3 mm were added to a mixed solution of 10.7 parts by mass of CI Pigment Green 58, 2.7 parts by mass of CI Pigment Yellow 185, 1.3 parts by mass of pigment derivative 1, 5.3 parts by mass of dispersant 1, and 80 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and the mixture was dispersed for 3 hours using a paint shaker, and the microbeads were separated by filtration to prepare pigment dispersion A1. The solid content concentration of the pigment dispersion A1 was 20% by mass, and the pigment content was 13.4% by mass.

[0461] Pigment derivative 1: a compound having the following structure.

[0462] [Chemical formula 37]

[0463]

[0464] Dispersant 1: Resin with the following structure (Mw=26000, the numerical value marked on the main chain is the molar ratio, and the numerical value marked on the side chain is the number of repeating units.)

[0465] [Chemical formula 38]

[0466]

[0467] A2: Pigment dispersion prepared by the following method

[0468] 230 parts by mass of zirconium oxide microbeads with a diameter of 0.3 mm were added to a mixed solution of 11.8 parts by mass of CI Pigment Blue 15:6, 3.0 parts by mass of CI Pigment Violet 23, 5.2 parts by mass of dispersant 2, and 80 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and the mixture was dispersed for 3 hours using a paint shaker, and the microbeads were separated by filtration to prepare a pigment dispersion A2. The pigment dispersion A2 had a solid content concentration of 20% by mass and a pigment content of 14.8% by mass.

[0469] Dispersant 2: Resin with the following structure (the numerical value marked on the main chain is the molar ratio, and the numerical value marked on the side chain is the number of repeating units. Mw: 20000, C=C value: 0.7 mmol / g, acid value: 72 mgKOH / g).

[0470] [Chemical formula 39]

[0471]

[0472] A3: Pigment dispersion prepared by the following method

[0473] 230 parts by mass of zirconium oxide microbeads with a diameter of 0.3 mm were added to a mixed solution of 11.8 parts by mass of CI Pigment Red 254, 3.0 parts by mass of CI Pigment Yellow 139, 5.2 parts by mass of dispersant 2, and 80 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and the mixture was dispersed for 3 hours using a paint shaker, and the microbeads were separated by filtration to prepare a pigment dispersion A3. The solid content concentration of the pigment dispersion A3 was 20% by mass, and the pigment content was 14.8% by mass.

[0474] (resin)

[0475] B1: Resin with the following structure (the numerical value marked on the main chain is the molar ratio. Mw: 10,000, acid value: 70 mgKOH / g)

[0476] B2: Acrybase FF-426 (manufactured by FUJIKURA KASEI CO., LTD., alkali-soluble resin)

[0477] [Chemical formula 40]

[0478]

[0479] (Free radical polymerizable monomer)

[0480] M1: Compound of the following structure (acrylate monomer, free radical polymerizable group value: 11.4 mmol / g)

[0481] [Chemical formula 41]

[0482]

[0483] M2: OGSOL EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., a (meth)acrylate monomer having a fluorene skeleton)

[0484] (Photoradical polymerization initiator)

[0485] I1: IRGACURE-OXE01 (manufactured by BASF, oxime compound)

[0486] I2: Compound of the following structure (oxime compound)

[0487] [Chemical formula 42]

[0488]

[0489] I3: IRGACURE-379 (manufactured by BASF, α-aminoalkylphenone compound)

[0490] (Surfactant)

[0491] W1: KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0492] W2: Compound having the following structure (Mw: 14000, the numerical value of % indicating the ratio of repeating units is mol %)

[0493] [Chemical formula 43]

[0494]

[0495] (Chain transfer agent)

[0496] CT1: Pentaerythritol tetrakis (3-mercaptopropionate)

[0497] CT2: 2,4-diphenyl-4-methyl-1-pentene

[0498] CT3: Cyanomethyldodecyl trithiocarbonate

[0499] CT4: SANCELER M (manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD., thiol compound)

[0500] CT5: 2-Cyano-2-propyldodecyl trithiocarbonate

[0501] CT6: Karenz MT BD1 (manufactured by SHOWA DENKO KK, thiol compound)

[0502] (Free Radical Scavenger)

[0503] RT1: 2,2,6,6-Tetramethylpiperidinyl 1-oxygen

[0504] RT2: 2,2-Diphenyl-1-picrylhydrazyl

[0505] RT3: ADK STAB AO-20 (manufactured by ADEKA Corporation)

[0506] RT4: ADK STAB LA-52 (manufactured by ADEKA Corporation)

[0507] RT5: Triphenyl tetrazide

[0508] RT6: ADK STAB AO-60G (manufactured by ADEKA Corporation)

[0509] (additive)

[0510] UV1: UV-503 (manufactured by DAITO CHEMICAL CO., LTD., ultraviolet absorber)

[0511] <Evaluation>

[0512] Each of the photosensitive compositions obtained above was applied to an 8-inch (203.2 mm) silicon wafer with a primer layer by spin coating so that the film thickness after coating was 0.5 μm. Then, it was post-baked at 100°C for 2 minutes using a hot plate. Then, pulse exposure was performed under the following conditions using a KrF scanning exposure machine through a mask with a Bayer pattern of 0.9 μm squares. Then, spin immersion development was performed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, it was rinsed by rotary spraying and then washed with pure water. Then, it was heated (post-baked) at 200°C for 5 minutes using a hot plate to form pixels (patterns). The pulse exposure conditions are as follows.

[0513] Exposure light: KrF rays (wavelength 248nm)

[0514] Exposure: 200 mJ / cm in Test Examples 1 to 26 2 , 200 mJ / cm in test examples R1 to R3 2 , 250 or 300 mJ / cm 2

[0515] Maximum instantaneous illumination: 250000000W / m 2 (Average illumination: 30000W / m 2 )

[0516] Pulse width: 30 nanoseconds

[0517] Frequency: 4kHz

[0518] The formed pixels (patterns) were observed with a scanning electron microscope, and the line widths of the pixels were measured. The following table shows the line widths of the formed pixels (patterns) at each exposure amount.

[0519] [Table 2]

[0520]

[0521] As shown in the above table, in Test Examples 1 to 3, 7, 9, 11 to 22 using Compositions 1 to 3, 7, 9, 11 to 22 containing chain transfer agents, the line width of the pixel (pattern) can be made thicker than in Test Examples R1 to R3. In addition, in Test Examples 4 to 6, 8, 10, 23 to 26 using Compositions 4 to 6, 8, 10, 23 to 26 containing radical scavengers, the line width of the pixel (pattern) can be made thinner than in Test Examples R1 to R3. As described above, according to the present invention, the line width of the obtained pattern can be adjusted even without changing the opening size of the mask.

[0522] Furthermore, the pixels obtained in Test Examples 1 to 26 were sufficiently cured to the bottom, and had excellent properties such as adhesion and solvent resistance equivalent to those of the pixels obtained in Test Examples R1 to R3.

[0523] On the other hand, regarding Test Examples R1 to R3, even if the exposure amount was changed, the line width of the obtained pattern hardly changed.

[0524] In Compositions 1 to 26, even when a composition prepared using Pigment Dispersion Liquid A100 prepared by the following method was used instead of Pigment Dispersion Liquid A1, the same effects as those of Test Examples 1 to 26 were obtained.

[0525] (Pigment dispersion A100)

[0526] To a mixed solution of 10.7 parts by mass of CI Pigment Green 36, 2.7 parts by mass of CI Pigment Yellow 185, 1.3 parts by mass of pigment derivative 1, 5.3 parts by mass of dispersant 1, and 80 parts by mass of PGMEA, 230 parts by mass of zirconium oxide microbeads having a diameter of 0.3 mm were added, and a dispersion treatment was performed for 3 hours using a paint shaker. The microbeads were separated by filtration to prepare pigment dispersion A100.

Claims

1. A photosensitive composition for pulse exposure, comprising: Free radical polymerizable compounds; Photo radical polymerization initiator; and Chain transfer agent. 2 . The photosensitive composition according to claim 1 , further comprising a coloring material.

3. The photosensitive composition according to claim 1 or 2, wherein The chain transfer agent is at least one selected from the group consisting of a thiol compound, a thiocarbonylsulfide compound, and a dimer of an aromatic α-methylalkenyl.

4. The photosensitive composition according to claim 1 or 2, wherein The content of the chain transfer agent in the total solid content of the photosensitive composition is 0.01% by mass to 10% by mass.

5. The photosensitive composition according to claim 1 or 2, wherein The chain transfer agent is contained in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the radical polymerizable compound.

6. The photosensitive composition according to claim 1 or 2, wherein The chain transfer agent is contained in an amount of 0.2 to 200 parts by mass based on 100 parts by mass of the photoradical polymerization initiator.

7. The photosensitive composition according to claim 1 or 2, wherein Also contains free radical scavengers. 8 . The photosensitive composition according to claim 1 , comprising a resin having an acid group. 9 . The photosensitive composition according to claim 1 , which is a photosensitive composition for pulse exposure using light having a wavelength of 300 nm or less.

10. The photosensitive composition according to claim 1 or 2, which is used for a maximum instantaneous illumination of 50000000 W / m 2 The photosensitive composition was subjected to pulse exposure under the above conditions. 11 . The photosensitive composition according to claim 1 or 2 , which is a photosensitive composition for a solid imaging element. 12 . The photosensitive composition according to claim 1 , which is a photosensitive composition for color filters.

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