KR20200122349A - Photosensitive composition - Google Patents

Abstract

It is a photosensitive composition for pulse exposure containing a color material and a radical polymerizable monomer. The radical polymerizable monomer is a compound having a radical polymerizable group, and the radical polymerizable group contained in the compound includes compound M1 which is at least one selected from allyl group, metalyl group, styrene group, styryl group and methacrylamide group. It relates to a photosensitive composition.

Description

Photosensitive composition

The present invention relates to a photosensitive composition containing a color material. More specifically, it relates to a photosensitive composition used for a solid-state imaging device, a color filter, or the like.

In video cameras, digital still cameras, and mobile phones with a camera function, solid-state imaging devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor) are used. In addition, a film containing a colorant such as a color filter is used for the solid-state imaging device. A film containing a colorant such as a color filter is manufactured using, for example, a photosensitive composition containing a colorant and a radically polymerizable monomer. (See Patent Documents 1 and 2).

Patent Document 1: Japanese Patent Publication No. 2012-532334 Patent Document 2: KR101573937B

Since the (meth)acrylate monomer has good reactivity due to radical polymerization, a (meth)acrylate monomer is generally used in the photosensitive composition used for production of a color filter or the like.

On the other hand, the photosensitive composition used for manufacturing a film containing a color material, such as a color filter, may be used after long-term storage. When the present inventor intensively studied a photosensitive composition using a (meth)acrylate monomer as a radical polymerizable monomer, it was found that foreign substances and the like were easily generated. Particularly, when the photosensitive composition is stored for a long period under a high temperature environment, it has been found that foreign matter is more easily generated. Moreover, also in the photosensitive composition described in Patent Documents 1 and 2, it was found that storage stability was insufficient, and foreign matter was easily generated during storage.

Accordingly, an object of the present invention is to provide a photosensitive composition excellent in storage stability.

When the present inventor intensively studied the photosensitive composition, it was found that the above object could be achieved by setting it as the following configuration, and the present invention was completed. Accordingly, the present invention provides the following.

<1> It is a photosensitive composition for pulse exposure containing a color material and a radical polymerizable monomer,

The radical polymerizable monomer is a compound having a radical polymerizable group, and the radical polymerizable group contained in the compound includes compound M1 which is at least one selected from allyl group, metalyl group, styrene group, styryl group and methacrylamide group, Photosensitive composition.

<2> The photosensitive composition according to <1>, wherein the radical polymerizable value of the compound M1 is 1 mmol/g or more.

The photosensitive composition according to <1> or <2>, wherein the content of the compound M1 in the total solid content of the <3> photosensitive composition is 0.05 to 50% by mass.

The photosensitive composition according to any one of <1> to <3>, wherein the content of the compound M1 in the total amount of the <4> radical polymerizable monomer is 1% by mass or more.

The <5> radical polymerizable monomer is the photosensitive composition in any one of <1> to <4> containing compound M1 and a (meth)acrylate monomer.

The photosensitive composition in any one of <1> to <5> which further contains a <6> photoradical polymerization initiator.

The photosensitive composition in any one of <1>-<6> containing <7> resin further.

<8> The photosensitive composition according to <7>, in which the resin described above contains an alkali-soluble resin.

<9> The photosensitive composition in any one of <1> to <8> in which the color material mentioned above contains a pigment.

<10> The photosensitive composition in any one of <1> to <9>, which is a photosensitive composition for pulse exposure in light having a wavelength of 300 nm or less.

<11> The photosensitive composition according to any one of <1> to <10>, which is a photosensitive composition for pulse exposure under conditions of 50000000 W/m ² or more of maximum instantaneous illuminance.

The photosensitive composition in any one of <1>-<11> which is a <12> photosensitive composition for solid-state imaging devices.

The photosensitive composition in any one of <1>-<11> which is a <13> photosensitive composition for color filters.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive composition excellent in storage stability can be provided.

Hereinafter, the content of the present invention will be described in detail.

In this specification, "~" is used as a meaning including numerical values described before and after it as a lower limit value and an upper limit value.

In the notation of the group (atomic group) in the present specification, the notation in which substitution or unsubstituted is not described includes a group having a substituent (atom group) as well as a group not having a substituent (atom group). For example, the "alkyl group" includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, "(meth)acrylate" represents both or any one of acrylate and methacrylate, and "(meth)acrylic" represents both or any one of acrylic and methacrylate, "(Meth)acryloyl" represents both or any one of acryloyl and methacryloyl.

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

In this specification, infrared means light with a wavelength of 700 to 2500 nm.

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

In the present specification, the term "step" is included in the term as long as the desired action of the step is achieved even when not only an independent step but also a case that cannot be clearly distinguished from another step.

<Photosensitive composition>

The photosensitive composition of the present invention,

It is a photosensitive composition for pulse exposure containing a coloring material and a radical polymerizable monomer,

The radical polymerizable monomer is a compound having a radical polymerizable group, and the radical polymerizable group contained in the compound includes compound M1 which is at least one selected from allyl group, metalyl group, styrene group, styryl group and methacrylamide group. It features.

The compound M1 having the above-described predetermined group as a radical polymerizable group has a relatively low reactivity due to radical polymerization, and thus it is difficult to react during storage of the photosensitive composition. Therefore, by using the thing containing the compound M1 as the radical polymerizable monomer, the reaction of the radical polymerizable monomer during storage can be suppressed, and a photosensitive composition having excellent storage stability can be obtained. Moreover, even when a radical polymerizable monomer other than the compound M1 such as a (meth)acrylate monomer is contained in addition to the aforementioned compound M1 as the radical polymerizable monomer, a photosensitive composition having excellent storage stability can be obtained. Compared to the formulation not using the compound M1, since it is possible to reduce the amount of the radical polymerizable monomer that is liable to cause dark polymerization (dark reaction), it is assumed that the stability during storage is increased.

In addition, the photosensitive composition of the present invention is a photosensitive composition for pulse exposure, and by pulse exposure to the photosensitive composition of the present invention, radicals are instantaneously generated in large quantities from components such as radical polymerizable monomers contained in the photosensitive composition in the exposed portion. I can make it. Since radicals are instantaneously generated in a large amount in the exposed portion, the radical polymerizable monomer can be efficiently cured due to effects such as suppressing deactivation by oxygen. For this reason, the photosensitive composition of this invention can be used as a photosensitive composition excellent in curability and storage stability. In addition, pulse exposure is an exposure method in which light is repeatedly irradiated and paused in a cycle for a short period of time (for example, at the level of milliseconds or less).

The photosensitive composition of the present invention is a photosensitive composition for pulse exposure. The light used for exposure may be light with a wavelength of more than 300 nm or light with a wavelength of 300 nm or less, but it is preferably light with a wavelength of 300 nm or less, more preferably light with a wavelength of 270 nm or less for reasons such as easy to obtain excellent curability. It is preferable, and it is more preferable that it is light with a wavelength of 250 nm or less. Moreover, it is preferable that the above-described light is light having a wavelength of 180 nm or more. Specifically, a KrF line (wavelength 248 nm), an ArF line (wavelength 193 nm), and the like are exemplified, and a KrF line (wavelength 248 nm) is preferable for reasons such as ease of obtaining more excellent curability.

It is preferable that the exposure conditions of pulse exposure are the following conditions. The pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less from the reason that radicals are easily generated in a large amount instantaneously. The lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, and may be 10 femtosecond or more. The frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and even more preferably 4 kHz or more from the viewpoint of curability. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and still more preferably 10 kHz or less, because it is easy to suppress deformation of the substrate or the like due to exposure heat. The maximum instantaneous intensity is not less than 50000000W / m ² preferably from the viewpoint of curability, and more preferably at least 100000000W / m ^2, and is more preferably not less than 200000000W / m ^2. In addition, the upper limit of the maximum instantaneous intensity is heightened even reciprocity law failing (不軌) and 1000000000W / m ² or less in view of suppression is preferred, more preferably 800000000W / m ² or less, and more preferably 500000000W / m ² or less. In addition, the pulse width is the length of time during which light is irradiated in a pulse period. In addition, the frequency is the number of pulse cycles per second. In addition, the maximum instantaneous illuminance is an average illuminance within a time period during which light is irradiated in a pulse period. In addition, the pulse period is a period in which light irradiation and pause in pulse exposure are made one cycle.

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, or the like. Examples of the color filter include a filter having a colored pixel that transmits light of a specific wavelength, and at least one colored pixel selected from a red pixel, a blue pixel, a green pixel, a yellow pixel, a cyan pixel, and a magenta pixel It is preferably a filter having. The infrared transmission filter is a filter that transmits at least a part of infrared rays. As an infrared transmission filter, the maximum value of the transmittance in the range of 400 to 640 nm wavelength is 20% or less (preferably 15% or less, more preferably 10% or less), and the transmittance in the range of 1100 to 1300 nm wavelength. A filter or the like that satisfies the spectral characteristics with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) can be mentioned. It is preferable that the infrared transmission filter is a filter satisfying the spectral characteristics in any one of the following (1) to (4).

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

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

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

(4): The maximum value of the transmittance in the range of the wavelength 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), the minimum value of the transmittance in the range of the wavelength 1100 to 1300 nm A filter of 70% or more (preferably 75% or more, more preferably 80% or more).

When using the photosensitive composition of the present invention as a composition for an infrared transmission filter, the photosensitive composition of the present invention has a minimum value Amin of absorbance in a range of 400 to 640 nm and a maximum value Bmax of absorbance in a range of 1100 to 1300 nm. It is preferable that Amin/Bmax, which is the ratio of, satisfies the spectral characteristics of 5 or more. Amin/Bmax is more preferably 7.5 or more, more preferably 15 or more, and particularly preferably 30 or more.

The absorbance Aλ at a predetermined wavelength λ is defined by the following equation (1).

Aλ=-log(Tλ/100) … (One)

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

In the present invention, the value of absorbance may be a value measured in the state of a solution, or may be a value in a film formed using the photosensitive composition. In the case of measuring the absorbance in the state of the film, a photosensitive composition is applied 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 dried using a hot plate at 100°C for 120 seconds. It is preferable to measure using the prepared membrane.

When using the photosensitive composition of the present invention as a composition for an infrared transmission filter, it is more preferable that the photosensitive composition of the present invention satisfies the spectral properties of any one of the following (11) to (14).

(11): Amin1/Bmax1, which is the ratio of the minimum value Amin1 of absorbance in the range of wavelength 400 to 640 nm and the maximum value Bmax1 of absorbance in the range of wavelength 800 to 1300 nm, is 5 or more, preferably 7.5 or more, and 15 or more. More preferably, it is more preferably 30 or more. According to this aspect, it is possible to form a film capable of transmitting light having a wavelength of 720 nm or more by blocking light in a range of 400 to 640 nm in wavelength.

(12): Amin2/Bmax2, which is a ratio of the minimum value Amin2 of absorbance in the range of wavelength 400 to 750 nm and the maximum value Bmax2 of absorbance in the range of wavelength 900 to 1300 nm, is 5 or more, preferably 7.5 or more, and 15 or more More preferably, it is more preferably 30 or more. According to this aspect, it is possible to form a film capable of transmitting light having a wavelength of 850 nm or more by blocking light in a range of 400 to 750 nm.

(13): Amin3/Bmax3, which is a ratio of the minimum value Amin3 of absorbance in the range of wavelength 400 to 850 nm and the maximum value Bmax3 of absorbance in the range of wavelength 1000 to 1300 nm, is 5 or more, preferably 7.5 or more, and 15 or more. More preferably, it is more preferably 30 or more. According to this aspect, it is possible to form a film capable of transmitting light having a wavelength of 940 nm or more by blocking light in a range of 400 to 850 nm in wavelength.

(14): Amin4/Bmax4 which is the ratio of the minimum value Amin4 of absorbance in the range of wavelength 400 to 950 nm and the maximum value Bmax4 of absorbance in the range of wavelength 1100 to 1300 nm is 5 or more, preferably 7.5 or more, and 15 or more. More preferably, it is more preferably 30 or more. According to this aspect, it is possible to form a film capable of transmitting light having a wavelength of 1040 nm or more by blocking light in a range of 400 to 950 nm in wavelength.

The photosensitive composition of the present invention can be preferably used as a photosensitive composition for solid-state imaging devices. Moreover, the photosensitive composition of this invention can be used suitably as a photosensitive composition for color filters. Specifically, it can be preferably used as a photosensitive composition for pixel formation of a color filter, and more preferably as a photosensitive composition for pixel formation of a color filter used in a solid-state imaging device.

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

<< colorant >>

The photosensitive composition of this invention contains a color material. As a color material, a chromatic colorant, a black colorant, an infrared absorbing dye, etc. are mentioned. It is preferable that the color material used for the photosensitive composition of this invention contains at least a chromatic colorant.

(Chromic colorant)

Examples of the chromatic colorant include a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant. The chromatic colorant may be a pigment or a dye. It is preferably a pigment. The average particle diameter (r) of the pigment is preferably 20 nm≦r≦300 nm, more preferably 25 nm≦r≦250 nm, and still more preferably 30 nm≦r≦200 nm. The "average particle diameter" as used herein refers to the average particle diameter of the secondary particles collected by the primary particles of the pigment. In addition, as for the particle size distribution of the secondary particles of the pigment that can be used (hereinafter, simply referred to as “particle size distribution”), the secondary particles included in the range of the average particle diameter ±100 nm are preferably 70% by mass or more of the total, and 80 It is more preferable that it is mass% or more.

It is preferable that the pigment is an organic pigment. The following are mentioned as an organic pigment.

Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35 :1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 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. (over, yellow pigment),

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 (above, orange pigment),

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4 , 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. Red pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc.(over, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (over, purple pigment),

C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. (more, blue pigment).

These organic pigments can be used alone or in various combinations.

In addition, as a yellow pigment, a metal azo pigment containing at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure, two or more metal ions, and a melamine compound is used. May be.

[Formula 1]

In the formula, R ¹ and R ² are each independently -OH or -NR ⁵ R ⁶ , R ³ and R ⁴ are each independently =O or =NR ⁷ , and R ⁵ to R ⁷ are each independently , A hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group represented by R ⁵ to R ⁷ is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The alkyl group may be linear, branched or cyclic, and linear or branched is preferable, and linear is more preferable. The alkyl group may have a substituent. The substituent is preferably a halogen atom, a hydroxy group, an alkoxy group, a cyano group, and an amino group.

In formula (I), it is preferable that R ¹ and R ² are -OH. Moreover, it is preferable that R ³ and R ⁴ are =O.

It is preferable that the melamine compound in a metal azo pigment is a compound represented by following formula (II).

[Formula 2]

In the formula, R ¹¹ to R ¹³ are each independently a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The alkyl group may be linear, branched or cyclic, and linear or branched is preferable, and linear is more preferable. The alkyl group may have a substituent. The substituent is preferably a hydroxy group. At least one of R ¹¹ to R ¹³ is preferably a hydrogen atom, and more preferably all of R ¹¹ to R ¹³ are hydrogen atoms.

The metal azo pigment described above includes at least one anion selected from an azo compound represented by the above formula (I) and an azo compound having a tautomeric structure, and a metal ion containing at least Zn ²⁺ and Cu ²⁺ , It is preferable that it is a metal azo pigment of the aspect containing a melamine compound. In this aspect, it is preferable to contain 95 to 100 mol% of Zn ²⁺ and Cu ²⁺ in total, based on 1 mol of all metal ions of the metal azo pigment, more preferably 98 to 100 mol%. It is preferable, it is more preferable that it contains 99.9-100 mol%, and it is especially preferable that it is 100 mol%. In addition, the molar ratio of Zn ²⁺ and Cu ²⁺ in the metallic azo pigment is preferably Zn ²⁺ :Cu ²⁺ =199:1 to 1:15, more preferably 19:1 to 1:1, It is more preferable that it is 9:1-2:1. Further, in this aspect, the metal azo pigment may further contain divalent or trivalent metal ions other than Zn ²⁺ and Cu ²⁺ (hereinafter, also referred to as metal ion Me1). As the metal ion Me1, 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⁺ , Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ³⁺ , Er ³⁺ , Tm ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Mn ²⁺ and Y ³⁺ is preferably at least one 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⁺ It is more preferable that it is at least one selected from, Al ³⁺ , Fe ²⁺ , Fe ³ It is particularly preferred that it is at least one selected from ⁺ , Co ²⁺ and Co ³⁺ . The content of the metal ion Me1 is preferably 5 mol% or less, more preferably 2 mol% or less, further preferably 0.1 mol% or less, based on 1 mol of all metal ions of the metal azo pigment.

Regarding the above metal azo pigments, paragraph numbers 0011 to 062, 0137 to 0276 of JP 2017-171912 A, paragraph numbers 0010 to 062, 0138 to 0295 of JP 2017-171913 A, and JP 2017- Reference may be made to the description of paragraphs 0011 to 062, 0139 to 0190 of 171914, paragraphs 0010 to 0065, and 0142 to 0222 of Japanese Laid-Open Patent Application No. 2017-171915, and these contents are incorporated herein by reference.

Further, as the red pigment, a compound having a structure in which an aromatic ring group into which an oxygen atom, a sulfur atom, or a nitrogen atom bonded group is introduced is bonded to a diketopyrrolopyrrole skeleton may be used. As such a compound, it is preferable that it is a compound represented by Formula (DPP1), and it is more preferable that it is a compound represented by Formula (DPP2).

[Formula 3]

In the above formula, R ¹¹ and R ¹³ each independently represent a substituent, R ¹² and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and n11 and n13 are each independently of 0-4 Represents an integer, X ¹² and X ¹⁴ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, and when X ¹² is an oxygen atom or a sulfur atom, m12 represents 1, and when X ¹² is a nitrogen atom , m12 represents 2, when X ¹⁴ is an oxygen atom or a sulfur atom, m14 represents 1, and when X ¹⁴ is a nitrogen atom, m14 represents 2. Examples of the substituent represented by R ¹¹ and R ¹³ include an alkyl group, aryl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, amide group, cyano group, nitro group, trifluoro A lomethyl group, a sulfoxide group, a sulfo group, etc. are mentioned as a preferable specific example.

Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14 per molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms can also be used. As a specific example, the compound described in International Publication No. WO2015/118720 can be mentioned.

Moreover, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue pigment. As specific examples, the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraph 0047 of JP2011-157478A may be mentioned.

There is no restriction|limiting in particular as a dye, A well-known dye can be used. For example, pyrazole azo system, anilino azo system, triarylmethane system, anthraquinone system, anthrapyridone system, benzylidene system, oxonol system, pyrazole triazole azo system, pyridone azo system, cyanine system, phenothiazine Dyes such as pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethane. Moreover, you may use a multimer of these dyes. In addition, the dyes described in JP 2015-028144 A and JP 2015-034966 A can also be used.

(Black colorant)

Examples of the black colorant include inorganic black colorants such as carbon black, metal oxynitrides (such as titanium black), and metal nitrides (such as titanium nitride), and bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds. And organic black colorants. The organic black colorant is preferably a bisbenzofuranone compound and a perylene compound. Examples of the bisbenzofuranone compound include compounds described in JP 2010-534726 A, JP 2012-515233 A, JP 2012-515234 A, etc. For example, "Irgaphor Black" manufactured by BASF It is available as ". As a perylene compound, C. I. Pigment Black 31, 32, etc. are mentioned. Examples of the azomethine compound include those described in Japanese Laid-Open Patent Publication No. Hei1-170601, Japanese Laid-Open Patent Publication No. Hei 2-034664, etc., for example, available as "Cromo Fine Black A1103" manufactured by Dainichi Seika. I can. The bisbenzofuranone compound is preferably a compound represented by any one of the following formulas or a mixture thereof.

[Formula 4]

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

Substituents represented by R ¹ to R ⁴ are halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkyneyl group, aralkyl group, aryl group, 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 , -SO ₂ R ³¹⁴ , -SO ₂ OR ³¹⁵ ,- NHSO ₂ R ³¹⁶ or -SO ₂ NR ³¹⁷ R ³¹⁸ is represented, and R ³⁰¹ to R ³¹⁸ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.

For details of the bisbenzofuranone compound, reference can be made to the description of paragraphs 0014 to 0037 of Japanese Laid-Open Patent Publication No. 2010-534726, the contents of which are incorporated herein by reference.

(Infrared absorbing pigment)

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

In the present invention, as the infrared absorbing dye, a compound having a ?-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 of the infrared absorbing dye is preferably 14 or more, more preferably 20 or more, still more preferably 25 or more, and particularly preferably 30 or more. As for the upper limit, it is preferable that it is 80 or less, and it is more preferable that it is 50 or less, for example. The π-conjugated plane of the infrared absorbing dye preferably contains two or more monocyclic or condensed aromatic rings, more preferably three or more of the aforementioned aromatic rings, and four or more of the aforementioned aromatic rings. It is more preferable to do, and it is particularly preferable to contain 5 or more of the above-described aromatic rings. As for the upper limit, 100 or less are preferable, 50 or less are more preferable, and 30 or less are still more preferable. As the aromatic ring mentioned above, a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, a quaterylene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, Chrysene ring, triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring , Oxazole ring, benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazin ring, triazine ring, pyrrole ring, indole ring, isoindole ring, carbazole ring, and Condensed rings having these rings are mentioned.

The infrared absorbing dye is a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterylene compound, a merocyanine compound, a chromonium compound, an oxonol compound, and a diimo At least one selected from nium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, azomethine compounds, anthraquinone compounds and dibenzofuranone compounds is preferred, and pyrrolopyrrole compounds, cyanine compounds, At least one selected from a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, and a dimonium compound is more preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound and a squarylium compound is More preferred, and pyrrolopyrrole compounds are particularly preferred.

As a pyrrolopyrrole compound, a compound described in paragraphs 0016 to 0058 of JP 2009-263614 A, a compound described in paragraphs 0037 to 0052 of JP 2011-068731 A, and paragraph number 0010 of WO2015/166873 The compounds described in to 0033, etc. can be mentioned, and these contents are incorporated in the present specification.

As the squarylium compound, the compound described in paragraphs 0044 to 0049 of JP 2011-208101 A, the compound described in paragraphs 0060 to 0601 of JP 605169 A, and the compound described in paragraph 0040 of WO2016/181987 The compound, the compound described in WO2013/133099, the compound described in WO2014/088063, the compound described in JP 2014-126642, the compound described in JP 2016-146619 A, JP The compound described in Patent Publication No. 2015-176046, the compound described in JP 2017-025311 A, the compound described in International Publication No. WO2016/154782, the compound described in JP 5884953 A, the compound described in JP 6036689 A , The compound described in JP 5810604 A, the compound described in JP 2017-068120 A, and the like, and these contents are incorporated herein by reference.

As the cyanine compound, the compounds described in paragraphs 0044 to 0045 of JP 2009-108267 A, the compounds described in paragraphs 0026 to 0030 of JP 2002-194040, and the compounds described in JP 2015-172004 , The compounds described in JP 2015-172102 A, the compounds described in JP 2008-088426 A, the compounds described in JP 2017-031394 A, and the like, the contents of which are incorporated herein by reference. .

Examples of the dimonium compound include compounds described in Japanese Laid-Open Patent Publication No. 2008-528706, and the contents are incorporated herein by reference. As the phthalocyanine compound, for example, the compound described in paragraph No. 0093 of JP 2012-077153 A, the oxytitanium phthalocyanine described in JP 2006-343631 A, and JP 2013-195480 A The compounds described in paragraphs 0013 to 0029 can be mentioned, and these contents are incorporated in the present specification. As a naphthalocyanine compound, the compound described in Paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153 is mentioned, for example, The content is incorporated in this specification.

In the present invention, a commercial item may be used as the infrared absorbing dye. For example, SDO-C33 (manufactured by Arimoto Chemical Industry 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.), ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, ShigenoxNIA-839 (made by Hakko Chemical), EpoliteV-63, Epolight3801, Epolight3036 (made by EPOLIN), PRO-JET825LDI (Fujifilm Co., Ltd. product), NK-3027, NK-5060 (Hayashibara Co., Ltd. product), YKR-3070 (Mitsui Chemical Co., Ltd. product), etc. are mentioned.

The content of the colorant in the total solid content of the photosensitive composition is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly 60% by mass or more from the viewpoint of thinning of the resulting film. desirable. When the content of the coloring material is 40% by mass or more, it is easy to form a thin film and a film having good spectral properties. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less from the viewpoint of film-forming properties.

It is preferable that the color material used for the photosensitive composition of this invention contains at least 1 type selected from chromatic colorants and black colorants. Further, 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 still more preferably 70% by mass or more. The upper limit can be set to 100% by mass and may be set to 90% by mass or less.

Moreover, it is preferable that the color material used for the photosensitive composition of this invention contains at least a green colorant. Moreover, it is preferable that it is 30 mass% or more, and, as for content of the green coloring agent in the total mass of a color material, it is more preferable that it is 40 mass% or more, and it is still more preferable that it is 50 mass% or more. The upper limit can be set to 100% by mass and may be set to 75% by mass or less.

In the color material used in the photosensitive composition of the present invention, the content of the pigment in the total mass of the color material is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. When the content of the pigment in the total mass of the colorant is within the above range, it is easy to obtain a film in which spectral fluctuations due to heat are suppressed.

In the case of using the photosensitive composition of the present invention as a composition for color filters (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. , It is more preferable that it is 50 mass% or more, It is more preferable that it is 55 mass% or more, It is especially preferable that it is 60 mass% or more. Further, the content of the chromatic colorant in the total mass of the colorant is preferably 25% by mass or more, more preferably 45% by mass or more, and still more preferably 65% by mass or more. The upper limit can be set to 100% by mass and may be set to 75% by mass or less. Moreover, it is preferable that the said color material contains at least a green colorant. Further, the content of the green colorant in the total mass of the color material is preferably 35% by mass or more, more preferably 45% by mass or more, and still more preferably 55% by mass or more. The upper limit can be set to 100% by mass and may be set to 80% by mass or less.

In the case of using the photosensitive composition of the present invention as a composition for forming a light-shielding film, the content of the black colorant (preferably inorganic black colorant) in the total solid content of the photosensitive composition is preferably 40% by mass or more, and 50% by mass or more. It is more preferable, it is more preferable that it is 55 mass% or more, and it is especially preferable that it is 60 mass% or more. Further, the content of the black coloring agent in the total mass of the colorant is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more. The upper limit can be set to 100% by mass and may be set to 90% by mass or less.

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

(1): Two or more types of chromatic colorants are contained, and black is formed by a combination of two or more types of chromatic colorants. It is preferable to form black by a combination of two or more kinds of colorants selected from red colorants, blue colorants, yellow colorants, purple colorants and green colorants.

(2): An organic black colorant is included.

(3): In the above (1) or (2), an infrared absorbing dye is further included.

As a preferable combination of the aspect of said (1), the following is mentioned, for example.

(1-1) An aspect containing a red colorant and a blue colorant.

(1-2) An aspect containing a red colorant, a blue colorant, and a yellow colorant.

(1-3) An aspect containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.

(1-4) An aspect containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.

(1-5) An aspect containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.

(1-6) An aspect containing a red colorant, a blue colorant, and a green colorant.

(1-7) An aspect containing a yellow colorant and a purple colorant.

In the aspect of the above (2), it is also preferable to further contain a chromatic colorant. By using an organic black colorant and a chromatic colorant together, it is easy to obtain excellent spectral characteristics. Examples of the chromatic colorant used in combination with the organic black colorant include a red colorant, a blue colorant, and a purple colorant, and a red colorant and a blue colorant are preferable. These may be used independently and may use 2 or more types together. In addition, the mixing ratio of the chromatic colorant and the organic black colorant is preferably 10 to 200 parts by mass, and more preferably 15 to 150 parts by mass, with respect to 100 parts by mass of the organic black colorant.

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

<<radical polymerizable monomer>>

The photosensitive composition of this invention contains a radical polymerizable monomer. It is preferable that it is 2000 or less, and, as for the molecular weight of a radical polymerizable monomer, it is more preferable that it is 1500 or less. The lower limit is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more.

(Compound M1)

The radical polymerizable monomer used in the photosensitive composition of the present invention is a compound having a radical polymerizable group, and the radical polymerizable group contained in the compound is at least selected from allyl groups, metalyl groups, styrene groups, styryl groups, and methacrylamide groups. One containing one type of compound M1 is used. That is, in the photosensitive composition of the present invention, as the radical polymerizable monomer, one containing the aforementioned compound M1 is used.

The number of radical polymerizable groups contained in the compound M1 may be one or two or more. When the number of radical polymerizable groups contained in the compound M1 is one (that is, when the compound M1 is a monofunctional monomer), more excellent storage stability is likely to be obtained. Moreover, when the number of radical polymerizable groups contained in compound M1 is 2 or more (that is, when compound M2 is a polyfunctional monomer), it is easy to obtain more excellent curability. Moreover, when compound M1 contains two or more radical polymerizable groups, the number of radical polymerizable groups contained in compound M1 is preferably 2 to 20 pieces. From the viewpoint of storage stability, the upper limit is preferably 15 or less, more preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less.

Moreover, it is preferable that it is 2000 or less, and, as for the molecular weight of compound M1, it is more preferable that it is 1500 or less. The lower limit is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more.

The radical polymerizable value of the compound M1 is preferably 1 mmol/g or more, more preferably 2 mmol/g or more, and still more preferably 3 mol/g or more. When the radical polymerizable value of the compound M1 is 1 mmol/g or more, the curability of the film after exposure and post-baking can be further improved. In addition, the radical polymerizable value of compound M1 is a value calculated by dividing the number of the above-described radical polymerizable groups contained in one molecule of compound M1 by the molecular weight of compound M1.

In addition to the radical polymerizable group described above, the compound M1 may further have at least one group selected from an acid group and a hydroxy group. According to this aspect, developability of the photosensitive composition, etc. can be improved, and a photosensitive composition excellent in pattern formation can be obtained. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable.

Compound M1 may have an alkyleneoxy group. As carbon number of the alkyleneoxy group, 1-10 are preferable, 1-5 are more preferable, 1-3 are more preferable, 2 or 3 are especially preferable, and 2 is the most preferable. The number of alkyleneoxy groups contained in compound M1 is preferably 1 to 40. As for the lower limit, 2 or more are preferable and 3 or more are more preferable. As for the upper limit, 30 or less are preferable, 20 or less are more preferable, and 10 or less are still more preferable.

It is preferable that compound M1 does not contain a group represented by the following formula (S1).

-Si(Rs ¹ )(Rs ² )(Rs ³ )… (S)

In the above formula, Rs ¹ to Rs ³ each independently represent a halogen atom, an alkoxy group, and an acyloxy group.

It is preferable that compound M1 is a compound represented by following formula (M1a).

L ¹ -(A ¹ ) _n … Equation (M1a)

(In formula (M1a), A ¹ represents an allyl group, a metalyl group, a styrene group, a styryl group or a methacrylamide group, L ¹ represents an n-valent group, and n represents an integer of 1 or more)

In formula (M1a), examples of the n-valent group represented by L ¹ include a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR-, -CO-, -COO-, -OCO-, -SO ₂ -Or a group consisting of a combination of these is mentioned. R represents a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom is preferable. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Moreover, the aliphatic hydrocarbon group may be cyclic or may be acyclic. Further, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent and does not need to have a substituent. Further, the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be monocyclic or condensed. 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 preferable. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Moreover, a nitrogen atom, an oxygen atom, a sulfur atom, etc. are mentioned as a hetero atom which comprises a heterocyclic group. The number of carbon atoms constituting L ¹ is preferably 3 to 100, and more preferably 6 to 50.

In formula (M1a), n represents an integer of 1 or more. The upper limit of n is preferably 15 or less, more preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less.

Specific examples of the compound M1 include allyl acetate, triallyl trimellitic acid, allyl butyrate, pentaerythritol triallyl ether, trimethylolpropanediallyl ether, allyl glycidyl ether, glycerin monoallyl ether, Allyl monomers such as diallyldimethyl ammonium chloride; Metalyl monomers such as β-metalyl acetate and 3-chloro-2-methyl-1-propene; Styryl monomers such as 4-styrylpyridine and 1,3-bisstyrylbenzene; Styrene monomers such as styrene, 2,4,6-trimethylstyrene, and methylstyrene; Methacrylamide, N-tert-butylmethacrylamide, N-[4-cyano-3-(trifluoromethyl)phenyl]methacrylamide, N,N-dimethylmethacrylamide, N-(3- Dimethylaminopropyl)methacrylamide, N-(4-hydroxyphenyl)methacrylamide, N-methylmethacrylamide, N,N'-methylenebismethacrylamide, N-(methoxymethyl)methacrylamide And methacrylamide monomers such as 3-methacrylamide phenylboronic acid and N-phenyl methacrylamide.

(Compound M2)

The photosensitive composition of the present invention may contain, as a radical polymerizable monomer, a radical polymerizable monomer other than the above-described compound M1 (hereinafter, also referred to as compound M2). The compound M2 is preferably a compound having a group selected from acryloyloxy group, methacryloyloxy group and acryloylamide group as a radical polymerizable group from the viewpoint of reactivity. Specifically, as the compound M2, it is preferable that it is a (meth)acrylate monomer or an acrylamide monomer, and it is more preferable that it is a (meth)acrylate monomer.

In addition, compound M2 is preferably a compound having two or more of the above-described groups such as acryloyloxy group (a compound having two or more functionalities), more preferably a compound having 2 to 15 (a compound having a function of 2 to 15), , It is more preferable that it is a compound which has 2-10 pieces (a compound of 2-10 functions), and it is especially preferable that it is a compound which has 2-6 pieces (a compound of 2-6 functions). More specifically, it is preferable that it is a bifunctional or more (meth)acrylate monomer, it is more preferable that it is a 2-15 functional (meth)acrylate monomer, and it is more that it is a 2-10 functional (meth)acrylate monomer It is preferable, and it is especially preferable that it is a 2-6 functional (meth)acrylate monomer.

It is preferable that it is 2000 or less, and, as for the molecular weight of compound M2, it is more preferable that it is 1500 or less. The lower limit is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more.

The radical polymerizable value of the compound M2 is preferably 1 mmol/g or more, more preferably 2 mmol/g or more, and still more preferably 3 mol/g or more. When the radical polymerizable value of the compound M2 is 1 mmol/g or more, the curability of the film after exposure and post-baking can be improved. In addition, the radical polymerizable value of compound M2 is a value calculated by dividing the number of the above-described radical polymerizable groups contained in one molecule of compound M2 by the molecular weight of compound M2.

As compound M2, ethyleneoxy-modified pentaerythritol tetraacrylate (as a commercial product, NK ester ATM-35E; Shin-Nakamura Chemical Co., Ltd. product), dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; Nippon Kayaku Co., Ltd.), Dipentaerythritol tetraacrylate (commercially available, KAYARAD D-320; Nippon Kayaku Co., Ltd. product), Dipentaerythritol penta (meth)acrylate (commercially available KAYARAD D-) 310; Nippon Kayaku Co., Ltd. product), dipentaerythritol hexa(meth)acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Co., Ltd. product, A-DPH-12E; Shinnakamura Chemical Co., Ltd.) A), and a compound having a structure in which these (meth)acryloyl groups are bonded through an ethylene glycol residue and/or a propylene glycol residue, Paragraph No. 0477 of Japanese Laid-Open Patent Application 2012-208494 (corresponding US The polymerizable monomers described in Paragraph No. 0585 of Patent Application Publication No. 2012/0235099) can be mentioned. In addition, diglycerin EO (ethylene oxide) modified (meth)acrylate (M-460 as a commercial product; manufactured by Toa Kosei Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shinnakamura Chemical Co., Ltd., A-TMMT) ), 1,6-hexanediol diacrylate (made by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (made by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (Toa Kosei Co., Ltd.) Article), etc. can also be used.

As the compound M2, a compound having an acid group such as a carboxyl group, a sulfo group, and a phosphoric acid group can also be used. As a commercial item, Aronix M-305, M-510, M-520 (above, Toa Kosei Co., Ltd. product) etc. are mentioned. As the compound M2, a compound having a caprolactone structure can also be used.

As the compound M2, a radically polymerizable monomer having a fluorene skeleton can also be used. The radical polymerizable monomer having a fluorene skeleton is preferably a compound having a partial structure represented by the following formula (Fr). Further, the radical polymerizable monomer having a fluorene skeleton is a radical polymerizable group (preferably, a group selected from acryloyloxy group, methacryloyloxy group, and acryloyl amide group, more preferably acryloyl oxide). It is preferable that it is a compound having 2 or more radicals or a methacryloyloxy group), more preferably a compound having 2 to 15 radical polymerizable groups described above, and a compound having 2 to 10 radical polymerizable groups described above. It is more preferable, and it is especially preferable that it is a compound which has 2-6 radical polymerizable groups mentioned above.

[Formula 5]

In the formula, a broken line represents a bond hand, R ^f1 and R ^f2 each independently represent a substituent, and m and n each independently represent an integer of 0 to 5. when m is 2 or more, two R ^f1 may be the same m is different and, respectively, by a combination of m R ^f1 of the two R ^f1 together may form a ring. When n is 2 or more, and n number of R ^f2 may be the same or different and, respectively, by a combination of n R ^f2 of the two R ^f2 together it may form a ring. As a substituent represented by R ^f1 and R ^f2 , 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, -SO 2 R f24, -SO 2 oR f25, -NHSO 2 R f26 or ^f27 -SO ₂ NR R ^f28 is mentioned. Each of R ^f11 to R ^f28 independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

As a specific example of the radical polymerizable monomer having a fluorene skeleton, a compound of the following structure is mentioned. Moreover, as a commercial item of a radical polymerizable monomer having a fluorene skeleton, Ogsol EA-0200, EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (meth)acrylate monomer having a fluorene skeleton), etc. are mentioned. .

[Formula 6]

As the compound M2, a radically polymerizable monomer having a caprolactone structure can also be used. As the compound having a caprolactone structure, description of paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents are incorporated herein. Examples of the radical polymerizable monomer having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, and DPCA-120 commercially available from Nippon Kayaku Co. as the KAYARAD DPCA series.

As the compound M2, a radically polymerizable monomer having an alkyleneoxy group can also be used. The radical polymerizable monomer having an alkyleneoxy group is preferably a radical polymerizable monomer having an ethyleneoxy group and/or a propyleneoxy group, more preferably a radical polymerizable monomer having an ethyleneoxy group, and 4 to 20 ethyleneoxy groups. It is more preferable that it is a 3-6 functional (meth)acrylate monomer which it has. Commercially available products of radical polymerizable monomers having an alkyleneoxy group include, for example, SR-494, a tetrafunctional (meth)acrylate having 4 ethyleneoxy groups manufactured by Sartomer, and a trifunctional (meth)acrylate having 3 isobutyleneoxy groups (meth ) KAYARAD TPA-330 which is an acrylate, etc. are mentioned.

As the compound M2, the compound described in JP 2017-048367 A, JP 6057891 A, and JP 6031807 A, the compound described in JP 2017-194662 A, 8UH-1006, 8UH-1012 (above, made by Daisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (made by Kyoeisha Chemical Co., Ltd.), etc. can also be used.

The content of the radical polymerizable monomer in the total solid content of the photosensitive composition is preferably 0.05 to 50% by mass. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass or more. It is preferable that it is 40 mass% or less, and, as for an upper limit, it is more preferable that it is 30 mass% or less.

It is preferable that the content of the compound M1 in the total solid content of the photosensitive composition is 0.05 to 50% by mass. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass or more from the reason that a film having a sufficient crosslinking density is easily obtained by photopolymerization. It is preferable that it is 40 mass% or less, and, as for an upper limit, it is more preferable that it is 30 mass% or less.

In addition, the content of the compound M1 in the total amount of the radical polymerizable monomer contained in the photosensitive composition is preferably 1% by mass or more, more preferably 10% by mass, and still more preferably 20% by mass or more, It is more preferably 30% by mass or more, particularly preferably 40% by mass or more, and most preferably 50% by mass or more. The upper limit can also be set to 100 mass%. Further, the radical polymerizable monomer contained in the photosensitive composition may be substantially only the compound M1. According to this aspect, the aging stability of the photosensitive composition can be further improved by further suppressing dark polymerization (dark reaction) over time. In addition, when the radical polymerizable monomer is substantially only the compound M1, it means that the content of the compound M1 in the total amount of the radical polymerizable monomer is 99% by mass or more, preferably 99.9% by mass, and It is more preferable that the polymerizable monomer is only the compound M1.

Further, when the photosensitive composition contains the aforementioned compound M2 as a radical polymerizable monomer, the content of the compound M2 in the total solid content of the photosensitive composition is preferably 50% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more from the reason that more excellent curability is easily obtained. It is preferable that it is 50 mass% or less, and, as for an upper limit, it is more preferable that it is 40 mass% or less.

In addition, when the radical polymerizable monomer contained in the photosensitive composition contains the aforementioned compound M2, the content of the compound M2 is preferably 10000 parts by mass or less based on 100 parts by mass of the compound M1. When the ratio of the compound M1 and the compound M2 is within the above range, it is possible to suppress dark polymerization (dark reaction) during storage, while having excellent curability by photopolymerization, and a photosensitive composition having excellent curability and stability over time.

<<Optical radical polymerization initiator>>

It is preferable that the photosensitive composition of this invention contains a photoradical polymerization initiator. When the photosensitive composition of the present invention contains a photo radical polymerization initiator, more excellent curability is obtained. It is preferable that the photoradical polymerization initiator is a compound that generates radicals by reacting to light having a wavelength of 300 nm or less.

It is also preferable that the photoradical polymerization initiator is a compound that is easily absorbed by two photons. In addition, two-photon absorption is an excitation process that absorbs two photons at the same time.

The photo-radical polymerization initiator is preferably at least one compound selected from an alkylphenone compound, an acylphosphine compound, a benzophenone compound, a thioxanthone compound, a triazine compound, and an oxime compound, and more preferably an oxime compound. .

Examples of the alkylphenone compound include a benzyldimethylketal compound, an α-hydroxyalkylphenone compound, and an α-aminoalkylphenone compound.

Examples of the benzyl dimethyl ketal compound include 2,2-dimethoxy-2-phenylacetophenone. As a commercial item, IRGACURE-651 (made by BASF) etc. are mentioned.

As an α-hydroxyalkylphenone compound, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxy Ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl) -Benzyl]phenyl}-2-methyl-propan-1-one, and the like. As a commercial item of an α-hydroxyalkylphenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, product made by BASF), etc. are mentioned.

As an α-aminoalkylphenone compound, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-mo Polynophenyl)-1-butanone, 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and the like. have. As commercially available products of the α-aminoalkylphenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (above, manufactured by BASF), and the like can be mentioned.

As an acylphosphine compound, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. are mentioned. As a commercial item of an acylphosphine compound, IRGACURE-819, IRGACURE-TPO (above, product made by BASF), etc. are mentioned.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(t-butylperoxycarbo Nyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy And thioxantone.

As a triazine compound, 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(trichloro To methyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl) Tenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

As the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-080068 A, the compound described in JP 2006-342166 A, JCS Perkin II (1979, pp. 1653). -1660), JCS Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Laid-Open Patent Publication 2000- The compound described in 066385, the compound described in JP 2000-080068, the compound described in JP 2004-534797, the compound described in JP 2006-342166, JP 2017-019766 A The compound described in, the compound described in Japanese Patent Publication No. 605596, the compound described in International Publication No. WO2015/152153, the compound described in International Publication No. WO2017/051680, and the like are mentioned. Specific examples of the oxime compound include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane- 3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2- On, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. As commercial products of oxime compounds, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Optomer N -1919 (manufactured by ADEKA Co., Ltd., photopolymerization initiator 2 described in JP 2012-014052 A) can be mentioned. In addition, it is also preferable to use a compound having no colorability or a compound having high transparency and difficult to discolor other components as the oxime compound. As a commercial item, Adeka Arcles NCI-730, NCI-831, NCI-930 (above, manufactured by ADEKA Co., Ltd.), etc. are mentioned.

Further, as the oxime compound, an oxime compound having a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound described in Unexamined-Japanese-Patent No. 2014-137466 can be mentioned. This content is incorporated in this specification.

Further, as the oxime compound, an oxime compound having a fluorine atom can also be used. As specific examples of the oxime compound having a fluorine atom, the compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in JP 2014-500852 A, and the compounds described in JP 2013-164471 A. (C-3), etc. are mentioned. This content is incorporated in this specification.

Further, as the oxime compound, an oxime compound having a nitro group can be used. It is also preferable to use the oxime compound which has a nitro group as a dimer. Specific examples of the oxime compound having a nitro group include compounds described in Japanese Patent Application Laid-Open No. 2013-114249, paragraphs 0031 to 0047, Japanese Patent Application Laid-Open No. 2014-137466, paragraphs 0008 to 0012, and 0070 to 0079, The compounds described in paragraphs 0007 to 0025 of 4223071, Adeka Arcles NCI-831 (manufactured by ADEKA Co., Ltd.) can be mentioned.

Further, as the oxime compound, an oxime compound having a benzofuran skeleton can also be used. As a specific example, OE-01 to OE-75 described in International Publication No. WO2015/036910 can be mentioned.

Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

[Formula 7]

[Formula 8]

In the present invention, as a photo radical polymerization initiator, a bifunctional or trifunctional or higher photo radical polymerization initiator may be used. By using such a photo-radical polymerization initiator, since two or more radicals are generated from one molecule of the photo-radical polymerization initiator, good sensitivity is obtained. In addition, when a compound having an asymmetric structure is used, crystallinity decreases, solubility in a solvent or the like is improved, it becomes difficult to precipitate over time, and the stability over time of the photosensitive composition can be improved. As a specific example of a bifunctional or a trifunctional or higher photoradical polymerization initiator, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. WO2015/004565, and Japanese Patent Publication No. 2016-532675 Paragraph No. 0407 to 0412, the dimer of the oxime compound described in paragraphs 0039 to 0055 of WO2017/033680, the compound (E) and the compound (G) described in Japanese Patent Publication No. 2013-522445, International Publication Cmpd 1 to 7 described in Publication No. WO2016/034963, oxime esters photoinitiator described in paragraph No. 0007 of Japanese Laid-Open Patent Publication 2017-523465, and described in paragraph No. 0020 to 0033 of Japanese Laid-Open Patent Publication 2017-167399 A photo-radical polymerization initiator, and a photo-polymerization initiator (A) described in paragraphs 0017 to 0026 of JP 2017-151342 A.

In the present invention, a pinacol compound can also be used as a photo radical polymerization initiator. As a pinacol compound, 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(trimethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tri Ethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(t-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2 -Trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t -Butyldimethylsiloxy-1,1,2,2-tetraphenylethane, etc. are mentioned. In addition, for the pinacol compound, reference can be made to the descriptions of JP 2014-521772, JP 2014-523939, and JP 2014-521772, the contents of which are incorporated herein by reference. .

In the present invention, it is preferable to use a photo radical polymerization initiator containing a photo radical polymerization initiator b1 that satisfies the following condition 1 as the photo radical polymerization initiator.

Condition 1: For a propylene glycol monomethyl ether acetate solution containing 0.035 mmol/L of a photo radical polymerization initiator b1, light with a wavelength of 355 nm, maximum instantaneous illumination of 375000000 W/m ² , pulse width of 8 nanoseconds, and frequency of 10 Hz. The quantum yield q ₃₅₅ after pulse exposure under conditions was 0.05 or more.

The quantum yield q ₃₅₅ of the photoradical polymerization initiator b1 is preferably 0.10 or more, more preferably 0.15 or more, more preferably 0.25 or more, even more preferably 0.35 or more, and particularly preferably 0.45 or more.

In the present specification, the quantum yield q ₃₅₅ of the photo radical polymerization initiator b1 is obtained by dividing the number of decomposed molecules of the photo radical polymerization initiator b1 after pulse exposure under the condition of condition 1 by the number of absorbed photons of the photo radical polymerization initiator b1. Value. Regarding the number of absorbed photons, the number of irradiated photons is calculated from the exposure time by pulse exposure under the condition 1, and the average of the absorbance at 355 nm before and after exposure is converted into transmittance, and the number of irradiated photons is (1-transmittance). The number of absorbed photons was obtained by multiplying by. Regarding the number of decomposed molecules, the decomposition rate of the photoradical polymerization initiator b1 was calculated from the absorbance of the photoradical polymerization initiator b1 after exposure, and the number of decomposed molecules was obtained by multiplying the decomposition rate by the number of molecules present in the photoradical polymerization initiator b1. In addition, as for the absorbance of the photo radical polymerization initiator b1, a propylene glycol monomethyl ether acetate solution containing 0.035 mmol/L of the photo radical polymerization initiator b1 was placed in an optical cell of 1 cm×1 cm×4 cm, and a spectrophotometer was used. Can be measured. As the spectrophotometer, for example, HP8453 manufactured by Agilent can be used. Examples of the photo-radical polymerization initiator b1 satisfying the above condition 1 include IRGACURE-OXE01, OXE02, OXE03 (above, manufactured by BASF). Further, a compound having the following structure can also be preferably used as a photoradical polymerization initiator b1 that satisfies the above condition 1. Among them, IRGACURE-OXE01 and OXE02 are preferably used from the viewpoint of adhesion. Moreover, from the viewpoint of curability, a compound represented by the following formula (I3) is preferably used.

[Formula 9]

Moreover, it is preferable that the photo-radical polymerization initiator b1 satisfies the following condition 2 further.

Condition 2: For a film having a thickness of 1.0 μm containing 5% by mass of a photo radical polymerization initiator b1 and 95% by mass of a resin, light with a wavelength of 265 nm, maximum instantaneous illumination of 375000000 W/m ² , pulse width of 8 nanoseconds, and frequency of 10 Hz. The quantum yield q ₂₆₅ after pulse exposure under conditions was 0.05 or more.

The quantum yield q ₂₆₅ of the photoradical polymerization initiator b1 is preferably 0.10 or more, more preferably 0.15 or more, and still more preferably 0.20 or more.

In the present specification, the quantum yield q ₂₆₅ of the photoradical polymerization initiator b1 is the number of decomposed molecules of the photoradical polymerization initiator b1 per 1 cm ^{2 of the} film after pulse exposure under the condition 2, and the number of absorbed photons of the photo radical polymerization initiator b1 It is the value obtained by dividing by. About the number of absorbed photons, the number of irradiated photons was obtained from the exposure time by pulse exposure under the condition 2, and the number of absorbed photons was obtained by multiplying the number of irradiated photons per 1 cm ^{2 of} film by (1-transmittance). Regarding the number of decomposition molecules of the photoradical polymerization initiator b1 per 1 cm ² of the film after exposure, the decomposition rate of the photo radical polymerization initiator b1 is obtained from the change in absorbance of the film before and after exposure, and photoradical polymerization in the film per 1 cm ² of the decomposition rate of the photo radical polymerization initiator b1 It was determined by multiplying the number of molecules present in the initiator b1. 1cm ^2, the presence of a photoradical polymerization initiator of b1 per membrane molecules, the film to obtain a film with a film weight per surface area 1cm ² to a 1.2g / cm ³ density, "((1cm × 5% by weight per weight of the film ² (photoradical It calculated|required as content rate of polymerization initiator b1)/molecular weight of optical radical polymerization initiator b1) x 6.02 x 10 ²³ pieces (Avogadro's number))".

In addition, it is preferable that the photo radical polymerization initiator b1 used in the present invention satisfies Condition 3 below.

Condition 3: For a film containing 5% by mass of the photo-radical polymerization initiator b1 and a resin, a maximum instantaneous irradiance of 625000000 W/m ² , a pulse width of 8 nanoseconds, and a frequency of 10 Hz for any one wavelength in the range of 248 to 365 nm. After exposure of one pulse under conditions, the radical concentration in the film reaches 0.000000001 mmol or more per 1 cm ² of film.

In the condition 3, the radical concentration in the membrane is preferably 0.000000005 mmol or more per 1 cm ² of the membrane, more preferably 0.00000001 mmol or more, more preferably 0.00000003 mmol or more, and 0.0000001 It is particularly preferred to reach more than mmol.

In addition, in the present specification, the radical concentration in the film is calculated by multiplying the quantum yield of the initiator b1 in the light of the measured wavelength by (1-membrane transmittance) to calculate the decomposition rate per incident photon count, and "1 pulse From the number of moles per photon "x" decomposition rate of initiator b1 per incident photon number", the concentration of the photoradical polymerization initiator b1 decomposed per 1 cm ^{2 of the} film was calculated and calculated. In addition, in the calculation of the radical concentration, it is a value calculated by assuming that all of the photoradical polymerization initiators b1 decomposed by light irradiation become radicals (reacted in the process and do not disappear).

The resin used in the measurement under the above conditions 2 and 3 is not particularly limited as long as it is compatible with the photoradical polymerization initiator b1. For example, resin (A) having the following structure is preferably used. The numerical value added to the repeating unit is a molar ratio, the weight average molecular weight is 40000, and the dispersion degree (Mn/Mw) is 5.0.

Resin (A)

[Formula 10]

The photoradical polymerization initiator b1 is preferably an alkylphenone compound and an oxime compound, and more preferably an oxime compound because it is easy to generate a large amount of radicals instantaneously by pulse exposure. Further, the photoradical polymerization initiator b1 is preferably a compound that is easily absorbed by two photons. In addition, two-photon absorption is an excitation process that absorbs two photons at the same time.

The photo-radical polymerization initiator used in the present invention may be only one type or may contain two or more photo-radical polymerization initiators. When the photo-radical polymerization initiator contains two or more types of photo-radical polymerization initiators, each photo-radical polymerization initiator may be a photo-radical polymerization initiator b1 that satisfies Condition 1 described above. Further, a photo radical polymerization initiator b1 that satisfies the above-described condition 1 and a photo radical polymerization initiator b2 that does not satisfy the above-described condition 1 may each be included. When two or more types of photo-radical polymerization initiators included in the photo-radical polymerization initiator are only the photo-radical polymerization initiator b1 that satisfies the above-described condition 1, the amount of radicals required for curing the radical polymerizable monomer is instantaneously exposed by pulse exposure. It is easy to occur. Two or more types of photo-radical polymerization initiators included in the photo-radical polymerization initiator include at least one photo-radical polymerization initiator b1 that satisfies the above-described condition 1, and at least one photo-radical polymerization initiator b2 that does not satisfy the above-described condition 1. In this case, it is easy to suppress the sensation of time due to pulse exposure.

It is preferable that the photo-radical polymerization initiator used in the present invention contains two or more types of photo-radical polymerization initiators for easy sensitivity adjustment. In addition, when the photo-radical polymerization initiator used in the present invention contains two or more types of photo-radical polymerization initiators, the photo-radical polymerization initiator preferably satisfies the following condition 1a from the viewpoint of curability.

Condition 1a: For a propylene glycol monomethyl ether acetate solution containing 0.035 mmol/L of a mixture of two or more types of photoradical polymerization initiators mixed at a ratio included in the photosensitive composition, light having a wavelength of 355 nm, maximum instantaneous illumination The quantum yield q ₃₅₅ after pulse exposure under conditions of 375000000 W/m ² , a pulse width of 8 nanoseconds and a frequency of 10 Hz is preferably 0.05 or more, more preferably 0.10 or more, further preferably 0.15 or more, and even more preferably 0.25 or more. And it is particularly preferably 0.35 or more, and most preferably 0.45 or more.

In addition, when the photo-radical polymerization initiator used in the present invention contains two or more types of photo-radical polymerization initiators, the photo-radical polymerization initiator preferably satisfies the following condition 2a from the viewpoint of curability.

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

In addition, when the photo-radical polymerization initiator used in the present invention contains two or more types of photo-radical polymerization initiators, the photo-radical polymerization initiator preferably satisfies the following condition 3a from the viewpoint of curability.

Condition 3a: 5% by mass of a mixture of two or more types of photo-radical initiators mixed at a ratio included in the photosensitive composition, and light having a wavelength in the range of 248 to 365 nm for a film containing a resin is irradiated at a maximum instantaneous intensity of 625000000 W /m ² , pulse width 8 nanoseconds, after pulse exposure for 0.1 seconds under the conditions of a frequency of 10 Hz, the radical concentration in the film preferably reaches 0.000000001 mmol or more per 1 cm ² of the film, more preferably 0.000000005 mmol or more, , It is more preferable to reach 0.00000001mmol or more, particularly preferably to reach 0.00000003mmol or more, and most preferably to reach 0.0000001mmol or more.

When the photosensitive composition of the present invention contains a photo-radical polymerization initiator, the content of the photo-radical 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 7% by mass. % Or less is more preferable. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. Moreover, it is preferable that content of a photo radical polymerization initiator is 10 to 200 mass parts with respect to 100 mass parts of a radical polymerizable monomer from a curable viewpoint. It is preferable that it is 100 mass parts or less, and, as for an upper limit, it is more preferable that it is 50 mass parts or less. It is preferable that it is 20 mass parts or more, and, as for a lower limit, it is more preferable that it is 30 mass parts or more. When the photosensitive composition of the present invention contains two or more kinds of photoradical polymerization initiators, it is preferable that the total amount thereof falls within the above range.

Moreover, the content of the above-described 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 still more preferably 7% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. Moreover, it is preferable that the content of the above-described photoradical polymerization initiator b1 is 10 to 200 parts by mass based on 100 parts by mass of the radical polymerizable monomer from the viewpoint of curability. It is preferable that it is 100 mass parts or less, and, as for an upper limit, it is more preferable that it is 50 mass parts or less. It is preferable that it is 20 mass parts or more, and, as for a lower limit, it is more preferable that it is 30 mass parts or more. When the photosensitive composition of the present invention contains two or more types of photoradical polymerization initiators b1, it is preferable that the total amount thereof falls within the above range.

<< resin >>

The photosensitive composition of the present invention may contain a resin. The resin is blended, for example, for a use of dispersing a pigment or the like in a composition or a use of a binder. In addition, resins mainly used to disperse pigments and the like are also referred to as dispersants. However, such a use of a resin is an example, and a resin may be used for purposes other than such use.

As resin, (meth)acrylic resin, (meth)acrylamide resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin , Polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, and the like. These resins may be used alone or in combination of two or more. As the cyclic olefin resin, a norbornene resin can be preferably used from the viewpoint of improving heat resistance. As a commercial item of norbornene resin, JSR Corporation ARTON series (for example, ARTON F4520) etc. are mentioned, for example. Moreover, it is also possible to use the resin described in the example of WO2016/088645 as the resin.

The weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000. The upper limit is preferably 1000000 or less, and more preferably 500000 or less. As for the lower limit, 3000 or more are preferable and 5000 or more are more preferable.

It is preferable that the photosensitive composition of this invention contains an alkali-soluble resin. When the photosensitive composition of the present invention contains an alkali-soluble resin, developability can be improved. As the alkali-soluble resin, it can be appropriately selected from resins having a group that promotes alkali dissolution. Examples of the group that promotes alkali dissolution (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxyl group, and a carboxyl group is preferable. The type of the acid group which the alkali-soluble resin has may be one type or two or more types.

The alkali-soluble resin is preferably a (meth)acrylic resin, a (meth)acrylamide resin, a siloxane resin, and a styrene resin, more preferably a (meth)acrylic resin and a (meth)acrylamide resin from the viewpoint of heat resistance. And (meth)acrylic resin is more preferable.

The alkali-soluble resin preferably includes a repeating unit having an acid group, and more preferably 5 to 70 mol% of the repeating unit having an acid group in the total repeating units of the resin. It is preferable that it is 50 mol% or less, and, as for the upper limit of the content of the repeating unit which has an acidic group, it is more preferable that it is 30 mol% or less. The lower limit of the content of the repeating unit having an acid group is preferably 10 mol% or more, and more preferably 20 mol% or more.

In addition, examples of the alkali-soluble resin include benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate copolymer, and benzyl (meth) Polypolymers composed of acrylate/(meth)acrylic acid/other monomers can be preferably used. In addition, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth)acrylate and other monomers, described in Japanese Laid-Open Patent Publication No. Hei 7-140654, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzylmetha Acrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropylacrylate/polymethylmethacrylate macromonomer/benzylmethacrylate/methacrylic acid copolymer, 2-hydroxyethylmethacrylate/ Polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer and the like can also be preferably used. Moreover, as a commercial item, FF-426 (made by Fujikura Kasei) etc. can also be used, for example.

As the alkali-soluble resin, an alkali-soluble resin having a polymerizable group can also be used. As a polymerizable group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned. The alkali-soluble resin having a polymerizable group is preferably an alkali-soluble resin having a polymerizable group in the side chain. Specific examples of the alkali-soluble resin having a polymerizable group include, for example, resins having the following structures. As commercial items of alkali-soluble resin having a polymerizable group, Diamond NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), and Biscoat R -264, KS resist 106 (all manufactured by Osaka Yuki Chemical Industry Co., Ltd.), Cyclomer P series (e.g. ACA230AA), Flaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl3800 (Daisel Yushibi) Co., Ltd.), Aclique RD-F8 (made by Nippon Shokubai Co., Ltd.), DP-1305 (made by Fuji Fine Chemicals Co., Ltd.), etc. are mentioned.

[Formula 11]

Alkali-soluble resin is a repeating unit 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 are sometimes referred to as "ether dimers") It is also preferable to include.

[Formula 12]

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

[Formula 13]

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

As a specific example of the ether dimer, paragraph number 0317 of Japanese Unexamined Patent Application Publication No. 2013-029760 can be referred to, for example, and the contents are incorporated herein.

It is also preferable that the alkali-soluble resin contains a repeating unit derived from a compound represented by the following formula (X).

[Formula 14]

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

In the formula (X), the number of carbon atoms of the alkylene group of R ₂ is preferably 2 to 3. Moreover, the number of carbon atoms of the alkyl group of R ₃ is preferably 1 to 10. The alkyl group of R ₃ may contain a benzene ring. Examples of the alkyl group containing the benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso)propyl group.

For the alkali-soluble resin, reference can be made to the description of Japanese Patent Application Laid-Open No. 2012-208494, Paragraph Nos. 0558 to 0571 (corresponding U.S. Patent Application Publication No. 2012/0235099, Paragraph Nos. 0685 to 0700). It is used in the specification. In addition, the copolymer (B) described in Japanese Patent Application Laid-Open No. 2012-032767, paragraphs 0029 to 0063, the alkali-soluble resin used in Examples, and the binder resins described in Japanese Patent Application Laid-Open No. 2012-208474, paragraphs 0088 to 0098 And the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP 2012-137531 A, and the binder resin used in the examples, paragraphs 0132 to 0143 of JP 2013-024934 A. The binder resin described in and the binder resin used in the examples, paragraphs 0092 to 0098 of JP 2011-242752 A, and the binder resin used in the examples, paragraphs 0030 to 072 of JP 2012-032770 A The binder resin described in can also be used. These contents are incorporated in this specification.

The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, more 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, and still more preferably 250 mgKOH/g or less.

As for the weight average molecular weight (Mw) of an alkali-soluble resin, 5,000-100000 are preferable. Moreover, as for the number average molecular weight (Mn) of an alkali-soluble resin, 1000-20000 are preferable.

The photosensitive composition of the present invention may contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acidic groups is larger than the amount of basic groups. As for the acidic dispersant (acidic resin), when the total amount of the amount of acidic groups and the amount of basic groups is 100 mol%, a resin in which the amount of acidic groups accounts for 70 mol% or more is preferable, and a resin substantially consisting of only acidic groups is more preferable. . 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 still more preferably 60 to 105 mgKOH/g. In addition, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of the basic group exceeds 50 mol% when the total amount of the amount of the acid group and the amount of the basic group is 100 mol%. It is preferable that the basic group which the basic dispersant has is an amino group.

It is preferable that the resin used as a dispersing agent contains a repeating unit which has an acidic group. When the resin used as the dispersant contains a repeating unit having an acidic group, when a pixel is formed by a photolithography method, residues generated on the base of the pixel can be further reduced, and a photosensitive composition having excellent developability can be obtained.

It is also preferable that the resin used as a dispersant is a graft copolymer. Since the graft copolymer has affinity with the solvent due to the graft chain, it is excellent in dispersibility of the pigment and dispersion stability after aging. For details of the graft copolymer, reference can be made to the description of paragraphs 0025 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein by reference. Moreover, the following resin is mentioned as a specific example of a graft copolymer. The following resins are also resins (alkali-soluble resins) having an acid group. In addition, examples of the graft copolymer include resins described in paragraphs 0072 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein by reference.

[Formula 15]

In addition, in the present invention, it is also preferable to use an oligoimine copolymer containing a nitrogen atom in at least one of the main chain and the side chain as the resin (dispersant). As the oligoimine copolymer, a resin having a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain having 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and the side chain is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom showing basicity. For the oligoimine-based copolymer, reference can be made to the description of paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated herein by reference. As the oligoimine-based copolymer, a resin having the following structure or a resin described in paragraphs 0168 to 0174 of JP 2012-255128 A can be used.

[Formula 16]

Moreover, the alkali-soluble resin mentioned above can also be used as a dispersing agent.

Moreover, it is also preferable that the resin used as a dispersing agent is a resin containing a repeating unit which has an ethylenic unsaturated bond group in a side chain. The content of the repeating unit having an ethylenically unsaturated bond group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and still more preferably 20 to 70 mol% in the total repeating units of the resin.

A commercially available product can also be used as a dispersing agent. For example, the product described in Paragraph No. 0129 of JP 2012-137564 A can also be used as a dispersant. For example, BYK Chemie's DISPERBYK series (for example, DISPERBYK-161, etc.) etc. are mentioned. Further, the resin described as the dispersant may be used for applications other than the dispersant. For example, it can also be used as a binder.

When the photosensitive composition of the present invention contains a resin, the content of the resin in the total solid content of the photosensitive composition is preferably 5 to 50% by mass. The lower limit is 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 still more preferably 30% by mass or less.

Further, the content of the alkali-soluble resin in the total solid content of the photosensitive composition 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 still more preferably 30% by mass or less.

In addition, the content of the alkali-soluble resin in the total amount of the resin is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more, because excellent developability is easily obtained. , 80 mass% or more is particularly preferable. The upper limit can be set to 100 mass%, 95 mass%, or 90 mass% or less.

In addition, the total content of the radical polymerizable monomer and the resin in the total solid content of the photosensitive composition is preferably 10 to 65% by mass from the reason that curability, developability, and filmability are easily combined. The lower limit is preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more, because a film having excellent film properties is easily obtained. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass or less because it is easy to achieve both curability and developability. Moreover, it is preferable to contain 30-300 mass parts of resin with respect to 100 mass parts of a radical polymerizable monomer. The lower limit is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more. The upper limit is preferably 250 parts by mass or less, and more preferably 200 parts by mass or less.

<<compound having a cyclic ether group>>

The photosensitive composition of the present invention can contain a compound having a cyclic ether group. As a cyclic ether group, an epoxy group, an oxetanyl group, etc. are mentioned. It is preferable that the compound which has a cyclic ether group is a compound which has an epoxy group. Examples of the compound having an epoxy group include compounds having one or more epoxy groups in one molecule, and a compound having two or more epoxy groups is preferable. It is preferable to have 1-100 epoxy groups in 1 molecule. The upper limit of the epoxy groups may be, for example, 10 or less, and may be 5 or less. The lower limit of the epoxy group is preferably two or more. As the compound having an epoxy group, the compounds described in paragraphs 0034 to 0036 of JP 2013-011869 A, paragraphs 0147 to 0156 of JP 2014-043556 A, and paragraphs 0085 to 0092 of JP 2014-089408 A In addition, the compound described in Japanese Unexamined Patent Application Publication No. 2017-179172 can also be used. These contents are used in this specification.

The compound having an epoxy group may be a low molecular weight compound (e.g., a molecular weight of less than 2000, and furthermore a molecular weight of less than 1000), or a macromolecule (e.g., a molecular weight of 1000 or more, in the case of a polymer, a weight average molecular weight of 1000 Any of the above) may be used. As for the weight average molecular weight of the compound which has an epoxy group, 200-100000 are preferable, and 500-500,000 are more preferable. The upper limit of the weight average molecular weight is preferably 10000 or less, more preferably 5000 or less, and still more preferably 3000 or less.

As the compound having an epoxy group, an epoxy resin can be preferably used. As an epoxy resin, for example, an epoxy resin that is a glycidyl ether product of a phenol compound, an epoxy resin that is a glycidyl ether product of various novolac resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, Glycidyl ester-based epoxy resin, glycidyl amine-based epoxy resin, an epoxy resin obtained by glycidylating halogenated phenols, a silicon compound having an epoxy group and a condensation product of other silicon compounds, and a polymerizable unsaturated compound having an epoxy group And copolymers of other polymerizable unsaturated compounds and the like. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g/eq, more preferably 310 to 1700 g/eq, and still more preferably 310 to 1000 g/eq.

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

When the photosensitive composition of the present invention contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less, for example. The number of compounds having a cyclic ether group may be one or two or more. In the case of two or more types, it is preferable that the total amount thereof falls within the above range.

<<Silane coupling agent>>

The photosensitive composition of the present invention may contain a silane coupling agent. According to this aspect, the adhesion of the resulting film to the support can be improved. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than that. In addition, the hydrolyzable group refers to a substituent that is directly connected to a silicon atom and capable of generating a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, as functional groups other than the hydrolyzable group, for example, vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, isocyanate Group, a phenyl group, and the like, and an amino group, a (meth)acryloyl group, and an epoxy group are preferable. Specific examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP 2009-288703 A, and compounds described in paragraphs 0056 to 0066 of JP 2009-242604 A. It is used in the specification.

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. One type of silane coupling agent may be sufficient, and two or more types may be used. In the case of two or more types, it is preferable that the total amount falls within the above range.

<<pigment derivative>>

The photosensitive composition of the present invention may further contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acid group, a basic group, a group having a salt structure, or a phthalimidemethyl group. As a pigment derivative, a compound represented by formula (B1) is preferable.

[Formula 17]

In formula (B1), P represents a dye 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 phthalimidemethyl group, and m represents an integer of 1 or more, n represents an integer of 1 or more, and when m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of Xs may be different from each other.

As a dye structure represented by P, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, a quinacridone dye structure, an anthraquinone dye structure, a dianthraquinone dye structure, a benzisoindole dye structure, a thiazine indigo dye structure, Azo dye structure, quinophthalone dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, dioxazine dye structure, perylene dye structure, perinone dye structure, benzimidazolone dye structure, benzothiazole dye At least one selected from structure, benzimidazole dye structure, and benzoxazole dye structure is preferred, and selected from pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure, and benzimidazoleone dye structure At least one of these is more preferable.

Examples of the linking group represented by L include a hydrocarbon group, a heterocyclic group, -NR-, -SO ₂ -, -S-, -O-, -CO-, or a group consisting of a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group.

Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imide acid group. As the carboxylic acid amide group, a group represented by -NHCOR ^X1 is preferable. As the sulfonic acid amide group, a group represented by -NHSO ₂ R ^X2 is preferable. As the imide acid group, a group represented by -SO ₂ NHSO ₂ R ^X3 , -CONHSO ₂ R ^X4 , -CONHCOR ^X5 or -SO ₂ NHCOR ^X6 is preferable. Each of R ^X1 to R ^X6 independently represents a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group represented by R ^X1 to R ^X6 may further have a substituent. As an additional substituent, it is preferable that it is a halogen atom, and it is more preferable that it is a fluorine atom. The basic group represented by X includes an amino group. Examples of the salt structure represented by X include salts of the acid group or basic group described above.

As a pigment derivative, the compound of the following structure is mentioned. In addition, JP-A-56-118462, JP-A-63-264674, JP-A-1-217077, JP-A-3-009961, JP-A-3-026767 No., Japanese Unexamined Patent Application Publication No. Hei 3-153780, Japanese Unexamined Patent Publication No. 3-045662, Japanese Unexamined Patent Publication No. 4-285669, Japanese Unexamined Patent Publication No. 6-145546, Japanese Unexamined Patent Publication No. 6-212088 No., JP-A6-240158, JP-A-10-030063, JP-A-10-195326, International Publication No. WO2011/024896, paragraphs 0086 to 0098, International Publication WO2012/ The compounds described in paragraphs 0063 to 0094 of 102399, paragraph number 0082 of WO2017/038252, and the like can also be used, the contents of which are incorporated herein by reference.

[Formula 18]

The content of the pigment derivative is preferably 1 to 50 parts by mass per 100 parts by mass of the pigment. 3 mass parts or more are preferable and, as for a lower limit, 5 mass parts or more are more preferable. As for the upper limit, 40 parts by mass or less are preferable, and 30 parts by mass or less are more preferable. When the content of the pigment derivative is within the above range, the dispersibility of the pigment can be improved, and aggregation of the pigment can be effectively suppressed. As for the pigment derivative, only 1 type may be used and 2 or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.

<< solvent >>

The photosensitive composition of this invention can contain a solvent. As a solvent, an organic solvent is mentioned. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons. For these details, reference may be made to paragraph number 0223 of International Publication No. WO2015/166779, the contents of which are incorporated herein by reference. Further, an ester-based solvent in which a cyclic alkyl group is substituted and a ketone-based solvent in which a cyclic alkyl group is substituted can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl Ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and And propylene glycol monomethyl ether acetate. In the present invention, the organic solvent may be used alone or in combination of two or more. Moreover, 3-methoxy-N,N-dimethylpropaneamide and 3-butoxy-N,N-dimethylpropaneamide are also preferable from the viewpoint of improving solubility. However, in some cases, it is better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent for reasons such as environmental reasons (e.g., 50 mass ppm with respect to the total amount of the organic solvent). (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use a solvent having a small metal content, and the metal content of the solvent is preferably 10 parts per billion (ppb) or less, for example. If necessary, a solvent with a mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided by Toyo Kosei, for example (Kagaku High School Nippo, November 13, 2015).

As a method of removing impurities such as metal from the solvent, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter may be mentioned, for example. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only 1 type may be contained and multiple types may be contained as an isomer.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol/L or less, and more preferably does not substantially contain a peroxide.

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

Moreover, it is preferable that the photosensitive composition of this invention does not contain an environmental regulation substance substantially from a viewpoint of environmental regulation. In addition, in the present invention, the term "substantially free of environmental control substances" means that the content of the environmental control substances in the photosensitive composition is 50 mass ppm or less, preferably 30 mass ppm or less, and 10 mass ppm or less. It is more preferable and it is especially preferable that it is 1 mass ppm or less. Environmentally regulated substances include, for example, benzene; Alkylbenzenes such as toluene and xylene; And halogenated benzenes such as chlorobenzene. These are registered as environmentally regulated substances based on REACH (Registration Evaluation Authorization and Restriction of CHemicals) rules, PRTR (Pollutant Release and Transfer Register) laws, and VOC (Volatile Organic Compounds) regulations, and their usage and handling methods are strictly It is regulated. These compounds may be used as a solvent when preparing each component or the like used in the photosensitive composition of the present invention, and may be mixed in the photosensitive composition as a residual solvent. From the viewpoint of safety for humans and consideration for the environment, it is desirable to reduce these substances as much as possible. As a method of reducing the environmentally regulated substance, a method of reducing by distilling off the environmentally regulated substance from the system by heating or reducing the pressure in the system to make it above the boiling point of the environmentally regulated substance is mentioned. In addition, in the case of distilling off a small amount of environmental control substances, it is also useful to make azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase efficiency. Further, when a compound having radical polymerizable properties is contained, a polymerization inhibitor or the like may be added and evaporated under reduced pressure to prevent radical polymerization reaction from proceeding and crosslinking between molecules during vacuum distillation. These distillation and removal methods can be performed at any stage of the raw material, the reaction of the raw material (for example, a polymerized resin solution or a polyfunctional monomer solution), or a composition prepared by mixing these compounds.

<< polymerization inhibitor >>

The photosensitive composition of the present invention can contain a polymerization inhibitor. As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6) -tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.) are mentioned. . 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.

<<surfactant>>

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 silicone surfactants can be used. For surfactants, reference may be made to paragraphs 0238 to 0245 of WO2015/166779, the contents of which are incorporated herein by reference.

In the present invention, it is preferable that the surfactant is a fluorine-based surfactant. By containing a fluorine-based surfactant in the photosensitive composition, liquid properties (especially, fluidity) are further improved, and liquid saving properties can be further improved. In addition, a film having a small thickness unevenness can also be formed.

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

Examples of the fluorine-based surfactant include surfactants described in JP 2014-041318, paragraphs 0060 to 0064 (corresponding International Publication 2014/017669, paragraphs 0060 to 0064), and the like, and JP 2011-132503, paragraphs 0117 The surfactant described in -0132 can be mentioned, and these contents are incorporated in the present specification. As a commercial product of the fluorine-based surfactant, for example, Megapak F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS-330 ( Above, DIC Corporation make), Fluorad FC430, FC431, FC171 (above, Sumitomo 3M Corporation make), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC -1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), and the like. .

Further, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off when heat is applied and the fluorine atom is volatilized can also be suitably used. As such a fluorine-based surfactant, DIC Corporation's MegaPak DS series (Kagaku Kogyo Nippo, February 22, 2016) (Nikkei Sangyo new class, February 23, 2016), for example MegaPak DS- 21 is mentioned.

Further, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. For such a fluorine-based surfactant, the description of Japanese Unexamined Patent Application Publication No. 2016-216602 can be referred to, and the contents are incorporated herein.

Block polymer can also be used as a fluorine-type surfactant. For example, the compound described in Japanese Unexamined Patent Application Publication No. 2011-089090 can be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) of 2 or more (preferably 5 or more). ) A fluorinated polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 19]

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

Further, as the fluorine-based surfactant, a fluorinated polymer having an ethylenically unsaturated bond group in the side chain can also be used. As a specific example, the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, for example, Megapak RS-101, RS-102, RS-718K, RS manufactured by DIC Corporation -72-K, etc. are mentioned. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327A can also be used.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol 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 ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspurs 20000 (Nihon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wako Junyaku Co., Ltd. product), Pionin D-6112, D-6112-W, D-6315 (Takemoto Yushi) (Manufactured by Co., Ltd.), Olpin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.), etc. are mentioned.

Examples of silicone surfactants include Toray Silicon DC3PA, Toray Silicon SH7PA, Toray Silicon DC11PA, Toray Silicon SH21PA, Toray Silicon SH28PA, Toray Silicon SH29PA, Toray Silicon SH30PA, Toray Silicon SH8400 (above, Toray Dow Corning Co., Ltd.) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, Shin-Etsu) Silicone Co., Ltd.), BYK307, BYK323, BYK330 (above, made by Bicchemi), etc. are mentioned. Moreover, as a silicone surfactant, you can also use a compound of the following structure.

[Formula 20]

The content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001% by mass to 5.0% by mass, and more preferably 0.005% by mass to 3.0% by mass. One type of surfactant may be sufficient, and two or more types may be used. In the case of two or more types, it is preferable that the total amount falls within the above range.

<<Ultraviolet absorber>>

The photosensitive composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, and the like can be used. I can. For these details, see paragraphs 0052 to 0072 of JP 2012-208374 A, paragraph numbers 0317 to 0334 of JP 2013-068814, and paragraphs 0061 to 0080 of JP 2016-162946 A. Reference may be made, and these contents are incorporated herein by reference. As a specific example of an ultraviolet absorber, the compound etc. of the following structure are mentioned. As a commercial item of an ultraviolet absorber, UV-503 (made by Daito Chemical Co., Ltd.) etc. is mentioned, for example. Moreover, as a benzotriazole compound, the MYUA series (Kagaku Kogyo Nippo, February 1, 2016) made by Miyoshi Yushi is mentioned.

[Formula 21]

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, it is preferable that the total amount falls within the above range.

<<Antioxidant>>

The photosensitive composition of the present invention can contain an antioxidant. As an antioxidant, a phenol compound, a phosphorous acid ester compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. A compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-described substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, the antioxidant is also preferably a compound having a phenol group and a phosphorous acid ester group in the same molecule. Moreover, as an antioxidant, a phosphorus antioxidant can also be used suitably. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6- Yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl) Oxy]ethyl]amine, ethyl bis phosphite (2,4-di-tert-butyl-6-methylphenyl), and the like. As commercially available products of antioxidants, for example, adeca stave AO-20, adeca stave AO-30, adeca stave AO-40, adeca stave AO-50, adeca stave AO-50F, a Deca Stave AO-60, Adeka Stave AO-60G, Adeka Stave AO-80, Adeka Stave AO-330 (above, ADEKA Co., Ltd.), etc. are mentioned.

The content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, and two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.

<<other ingredients>>

The photosensitive composition of the present invention, if necessary, a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, and other preparations (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, fragrances , A surface tension adjusting agent, a chain transfer agent, etc.) may be contained. By appropriately containing these components, properties such as film properties can be adjusted. These components are described in, for example, paragraph No. 0183 of JP 2012-003225 (paragraph No. 0237 of the corresponding U.S. Patent Application Publication No. 2013/0034812), paragraph No. 0101 of JP 2008-250074 A. Reference can be made to descriptions such as -0104, 0107-0109, and the like, and these contents are incorporated herein by reference. Moreover, the photosensitive composition of this invention may contain a latent antioxidant as needed. As a latent antioxidant, a compound in which a site functioning as an antioxidant is protected by a protecting group, and the protecting group is removed by heating at 100 to 250°C or by heating at 80 to 200°C in the presence of an acid/base catalyst, which functions as an antioxidant. And compounds. As the latent antioxidant, the compounds described in International Publication No. WO2014/021023, International Publication No. WO2017/030005, and Japanese Unexamined Patent Publication No. 2017-008219 can be mentioned. As a commercial item, Adeka Arcles GPA-5001 (made by ADEKA Co., Ltd.), etc. are mentioned.

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

<receiving container>

There is no restriction|limiting in particular as a container for the photosensitive composition of this invention, A well-known container can be used. In addition, for the purpose of suppressing the incorporation of impurities into the raw material or composition, as the housing container, a multi-layer bottle composed of 6 types of 6 layers of resin or a bottle of 6 types of resin in a 7-layer structure is also used. desirable. As such a container, the container described in Japanese Unexamined Patent Application Publication No. 2015-123351 is mentioned, for example.

<Preparation method of photosensitive composition>

The photosensitive composition of the present invention can be prepared by mixing the above-described components. When preparing a photosensitive composition, all components may be simultaneously dissolved or dispersed in a solvent to prepare a photosensitive composition.If necessary, two or more solutions or dispersions in which each component is appropriately blended are prepared in advance, and when used (application You may mix these in time), and you may prepare as a photosensitive composition.

Moreover, when the photosensitive composition of this invention contains particles, such as a pigment, it is preferable to include a process of dispersing the particles. In the process of dispersing particles, the mechanical force used for dispersing the particles includes compression, compression, impact, shear, and cavitation. Specific examples of these processes include bead mill, sand mill, roll mill, ball mill, paint shaker, microfluidizer, high-speed impeller, sand grinder, flow jet mixer, high pressure wet atomization, ultrasonic dispersion, and the like. In addition, in the pulverization of particles in a sand mill (bead mill), it is preferable to use beads having a small diameter, or to increase the filling rate of the beads, and to perform treatment under conditions in which the pulverization efficiency is increased. Further, it is preferable to remove coarse particles by filtration or centrifugation after the pulverization treatment. In addition, the process and dispersing machine for dispersing particles are “Dispersion Technology Daejeon, published by Joho Kiko Co., Ltd., July 15, 2005” or “Suspension (high/liquid dispersion system) based dispersion technology and practical synthesis of industrial applications. The process and disperser described in the document collection, published by Keii Kaihatsu Center Press, October 10, 1978", paragraph number 0022 of Japanese Unexamined Patent Application Publication No. 2015-157893 can be suitably used. In addition, in the process of dispersing the particles, a refinement treatment of the particles may be performed in the salt milling process. For materials, equipment, processing conditions, and the like used in the salt milling process, for example, reference may be made to descriptions in Japanese Unexamined Patent Publication No. 2015-194521 and Japanese Unexamined Patent Publication 2012-046629.

In the preparation of the photosensitive composition of the present invention, it is preferable to filter the photosensitive composition with a filter for the purpose of removing foreign matters or reducing defects. The filter can be used without any particular limitation as long as it is a filter conventionally used for filtration applications or the like. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) Filters using materials such as (including high-density and ultra-high molecular weight polyolefin resins) are mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter 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. When the pore diameter of the filter is within the above range, fine foreign matter can be reliably removed. Moreover, it is also preferable to use a fibrous filter medium. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Specifically, filter cartridges of the SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) manufactured by Rocky Techno, and the SHPX type series (SHPX003, etc.) can be mentioned. When using a filter, other filters (eg, a first filter and a second filter, etc.) may be combined. In that case, filtration using each filter may be performed only once or may be performed twice or more. Further, filters having different pore diameters may be combined within the above-described range. Moreover, filtration by the 1st filter may be performed only with respect to a dispersion liquid, and after mixing another component, filtration may be performed by a 2nd filter.

<Method of manufacturing optical filter>

Next, a method of manufacturing an optical filter using the photosensitive composition of the present invention will be described. As a kind of optical filter, a color filter, an infrared transmission filter, etc. are mentioned.

The manufacturing method of the optical filter in the present invention includes the step of forming a photosensitive composition layer by applying the photosensitive composition of the present invention described above on a support (photosensitive composition layer forming step), and pulsed light to the photosensitive composition layer. It is preferable to include a step (exposure step) of irradiating and exposing in a pattern (pulse exposure) and a step (development step) of developing and removing a photosensitive composition layer of an unexposed portion to form a pixel. Hereinafter, each process is demonstrated.

(Photosensitive composition layer formation process)

In the photosensitive composition layer forming step, the photosensitive composition layer is formed by applying the photosensitive composition of the present invention described above on a support. Examples of the support include a substrate made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. It is also preferable to use an InGaAs substrate or the like. Further, a charge-coupled device (CCD), a complementary metal oxide film semiconductor (CMOS), a transparent conductive film, and the like may be formed on the support. In addition, in some cases, a black matrix for separating each pixel is formed on the support. Further, if necessary, an undercoat layer may be provided on the support to improve adhesion with the upper layer, to prevent diffusion of substances, or to planarize the surface of the substrate.

As a method of applying the photosensitive composition to the support, a known method can be used. For example, dropping method (drop cast); Slit coat method; Spray method; Roll coat method; Rotation coating method (spin coating); Casting method; Slit and spin method; The pre-wet method (for example, the method described in Japanese Unexamined Patent Publication No. 2009-145395); Various printing methods such as ink jet (for example, on-demand, piezo, thermal), nozzle jet, and other ejection-based printing, flexo printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; Transfer method using a mold or the like; Nanoimprint method, etc. are mentioned. The method of application in the inkjet is not particularly limited, and for example, the method shown in "Diffusion and usable inkjet-infinite possibility seen as a patent -, published in February 2005, Sumibetechno Research" (especially 115~ 133 pages), Japanese Unexamined Patent Publication No. 2003-262716, Japanese Unexamined Patent Publication 2003-185831, Japanese Unexamined Patent Publication 2003-261827, Japanese Unexamined Patent Publication 2012-126830, Japanese Unexamined Patent Publication 2006-169325, etc. The described method is mentioned. In addition, as for the application method of the photosensitive composition, the method described in International Publication No. WO2017/030174 and International Publication No. WO2017/018419 may be used, and these contents are incorporated herein by reference.

After applying the photosensitive composition to the support, further drying (pre-baking) may be performed. In the case of performing prebaking, the prebaking temperature is preferably 150°C or less, more preferably 120°C or less, and still more preferably 110°C or less. The lower limit can be, for example, 50°C or higher, or 80°C or higher. The prebaking time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and still more preferably 80 to 2200 seconds. Drying can be performed by a hot plate, an oven, or the like.

(Exposure process)

Next, the photosensitive composition layer on the support formed as described above is irradiated with light in a pulsed manner and exposed in a pattern (pulse exposure). With respect to the photosensitive composition layer, by pulse exposure through a mask having a predetermined mask pattern, the photosensitive composition layer can be pulse exposed in a pattern shape. Thereby, the exposed portion of the photosensitive composition layer can be cured.

The light used at the time of pulse exposure may be light with a wavelength of more than 300 nm or light with a wavelength of 300 nm or less, but it is preferably light with a wavelength of 300 nm or less for reasons such as ease of obtaining better curability, and a light having a wavelength of 270 nm or less. It is more preferable that it is light with a wavelength of 250 nm or less. Moreover, it is preferable that the above-described light is light having a wavelength of 180 nm or more. Specifically, a KrF line (wavelength 248 nm), an ArF line (wavelength 193 nm), and the like are exemplified, and a KrF line (wavelength 248 nm) is preferable for reasons such as ease of obtaining more excellent curability.

It is preferable that the pulse exposure conditions are the following conditions. The pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less from the viewpoint of being easy to generate a large amount of active species such as radicals instantly. The lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, and may be 10 femtosecond or more. The frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and even more preferably 4 kHz or more from the viewpoint of curability. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and still more preferably 10 kHz or less, because it is easy to suppress deformation of the substrate or the like due to exposure heat. The maximum instantaneous intensity is not less than 50000000W / m ² preferably from the viewpoint of curability, and more preferably at least 100000000W / m ^2, and is more preferably not less than 200000000W / m ^2. In addition, the upper limit of the maximum instantaneous intensity is heightened, and it is also 1000000000W / m ² or less desirable in terms of reciprocity law failing inhibition, and more preferably 800000000W / m ² or less, more preferably 500000000W / m ² or less. The exposure amount is preferably 1 to 1000 mJ/cm ² . The upper limit is preferably 500 mJ/cm ² or less, and more preferably 200 mJ/cm ² or less. The lower limit is preferably 10 mJ/cm ² or more, more preferably 20 mJ/cm ² or more, and still more preferably 30 mJ/cm ² or more.

The oxygen concentration at the time of exposure can be appropriately selected, and in addition to performing in the atmosphere, for example, in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, substantially oxygen free) Exposure may be performed in or under a high oxygen atmosphere in which the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume, and 50% by volume).

(Development process)

Next, the photosensitive composition layer of the unexposed part in the photosensitive composition layer after the exposure step is developed and removed to form a pixel (pattern). The development and removal of the photosensitive composition layer in the unexposed part can be performed using a developer. As a result, the photosensitive composition layer of the unexposed portion is eluted into the developer, and only the portion photocured in the above exposure step remains on the support. The temperature of the developer is preferably 20 to 30°C, for example. The developing time is preferably 20 to 180 seconds. Further, in order to improve the residue removal property, the step of shaking off the developer every 60 seconds and further supplying the developer may be repeated several times.

The developing solution is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water. As the alkali agent, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Side, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole , Piperidine, and organic alkaline compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, etc. And inorganic alkaline compounds. As for the alkali agent, a compound having a large molecular weight is preferable from the viewpoint of environment and safety. 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. Examples of the surfactant include the surfactant described above, and a nonionic surfactant is preferable. The developer may be prepared as a concentrated solution once from the viewpoint of convenience of transportation and storage, and then diluted to a concentration required at the time of use. The dilution ratio is not particularly limited, but can be set in the range of 1.5 to 100 times, for example. In addition, when an alkaline aqueous solution is used as a developer, it is preferable to wash (rinse) with pure water after development.

After development and drying, additional exposure treatment or heat treatment (post-baking) may be performed. Further exposure treatment and post-baking are treatments after development to complete curing of the film. When performing additional exposure treatment, it is preferable that light used for exposure is light having a wavelength of 400 nm or less.

It is preferable to appropriately select the film thickness of the pixel (pattern) to be formed according to the type of the pixel. For example, 2.0 μm or less is preferable, 1.0 μm or less is more preferable, and 0.3 to 1.0 μm is still more preferable. The upper limit is preferably 0.8 µm or less, and more preferably 0.6 µm or less. The lower limit is preferably 0.4 μm or more.

In addition, as the size (line width) of the pixel (pattern) to be formed, it is preferable to appropriately select it according to the application and the type of pixel. For example, 2.0 μm or less is preferable. 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.

In the case of manufacturing an optical filter having a plurality of types of pixels, at least one type of pixel may be formed through the above-described process, and it is preferable to form the first pixel (first type of pixel) through the above-described process. . The pixels formed after the second (second type and subsequent pixels) may be formed through the same process as above, or may be formed by performing exposure with continuous light.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. Materials, usage, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Measurement of the weight average molecular weight (Mw) of the resin>

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

Column type: A column connecting TOSOH TSKgel Super HZM-H and TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000

Developing solvent: tetrahydrofuran

Column temperature: 40°C

Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1% by mass)

Device name: Toso HLC-8220GPC

Detector: RI (refractive index) detector

Calibration curve base resin: Polystyrene resin

<Preparation of photosensitive composition>

After mixing the raw materials shown in the following table, it was filtered with a nylon filter (manufactured by Nihon Paul Co., Ltd.) with a pore diameter of 0.45 μm, to prepare a photosensitive composition (compositions 1 to 14, R1) having a solid content concentration of 20% by mass. In addition, the solid content concentration of compositions 1-7, 9-14, and R1 was adjusted by changing the compounding amount of propylene glycol monomethyl ether acetate (PGMEA). In addition, the solid content concentration of the composition 8 was adjusted by changing the blending amount of the mixed solvent of PGMEA and polyethylene glycol monomethyl ether (PGMEA: polyethylene glycol monomethyl ether = 9: 1 (mass ratio)). In addition, the numerical value in the column of the compounding amount in the following table is a mass part.

[Table 1]

The raw materials listed in the above table are as follows.

(Pigment dispersion)

A1: Pigment dispersion prepared by the following method

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) To the mixed liquid mixture, 230 parts by mass of zirconia beads having a diameter of 0.3 mm were added, dispersion treatment was performed for 3 hours using a paint shaker, and the beads were separated by filtration to prepare a pigment dispersion liquid A1. This pigment dispersion liquid A1 had a solid content concentration of 20 mass% and a pigment content of 13.4 mass%.

Pigment derivative 1: a compound of the following structure.

[Formula 22]

Dispersant 1: Resin of the following structure (Mw=26000, the value added to the main chain is a molar ratio, and the value added to the side chain is the number of repeating units)

[Formula 23]

A2: Pigment dispersion prepared by the following method

To a mixture 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), diameter 230 parts by mass of 0.3 mm zirconia beads were added, dispersion treatment was performed for 3 hours using a paint shaker, and the beads were separated by filtration to prepare a pigment dispersion liquid A2. This pigment dispersion liquid had a solid content concentration of 20 mass% and a pigment content of 14.8 mass%.

Dispersant 2: Resin of the following structure (the value added to the main chain is a molar ratio, and the value added to the side chain is the number of repeating units. Mw: 20000, C=C value: 0.7 mmol/g, acid value: 72 mgKOH/g)

[Formula 24]

A3: Pigment dispersion prepared by the following method

To a mixture 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), a diameter of 0.3 mm 230 parts by mass of zirconia beads were added, dispersion treatment was performed for 3 hours using a paint shaker, and the beads were separated by filtration to prepare a pigment dispersion liquid A3. This pigment dispersion liquid had a solid content concentration of 20 mass% and a pigment content of 14.8 mass%.

(Suzy)

B1: Resin of the following structure (the value added to the main chain is a molar ratio. Mw: 10,000, acid value: 70mgKOH/g)

B2: ACRYBASE FF-426 (Fujikura Kasei Co., Ltd. product, alkali-soluble resin)

[Formula 25]

(Radical polymerizable monomer)

M1-1: allyl acetate

M1-2: 4-styrylpyridine

M1-3: methacrylamide

M1-4: Styrene

M1-5: Triallyl trimellitic acid

M1-6: β-metalyl acetate

M2-1: Compound of the following structure (acrylate monomer, radical polymerizable value: 11.4 mmol/g)

[Formula 26]

M2-2: Ogsol EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (meth)acrylate monomer having a fluorene skeleton)

(Photopolymerization initiator)

I1: IRGACURE-OXE01 (manufactured by BASF, an oxime compound)

I2: Compound of the following structure (oxime compound)

[Formula 27]

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

(Surfactants)

W1: KF-6002 (manufactured by Shin-Etsu Silicone Co., Ltd.)

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

[Formula 28]

(additive)

UV1: UV-503 (made by Daito Chemical Co., Ltd., ultraviolet absorber)

<Evaluation>

Each of the photosensitive compositions (compositions 1 to 14, R1) obtained above was filled into a light-shielding container and stored at a temperature of 7°C (condition 1) or 45°C (condition 2) for 12 months.

Each photosensitive composition after storage was applied onto an 8-inch (203.2 mm) silicon wafer by spin coating so that the film thickness after application was 0.5 μm. Subsequently, it was post-baked at 100 degreeC for 2 minutes using a hot plate. Subsequently, a film was formed by performing pulse exposure under the following conditions using a KrF scanner exposure machine. Pulse exposure conditions are as follows.

Exposure light: KrF line (wavelength 248 nm)

Exposure amount: 200mJ/cm ²

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

Pulse width: 30 nanoseconds

Frequency: 4kHz

The number of defects in the obtained film was inspected using a defect inspection apparatus (ComPLUS, manufactured by AMAT). Further, foreign matters (aggregates) having a size of 0.5 μm or more were counted as defects.

[Table 2]

As shown in the above table, Test Examples 1 to 14 using compositions 1 to 14 containing radical polymerizable monomers containing compound M1 according to the present invention are Test Examples using a composition R1 not containing compound M1 A film with fewer defects than R1 could be formed. In this respect, it can be seen that the compositions 1 to 14 containing the radical polymerizable monomer containing the compound M1 described above according to the present invention have excellent storage stability.

In addition, the films of Test Examples 1 to 14 were sufficiently cured to the bottom, and had film properties superior in adhesion and solvent resistance compared to the film of Test Example R1.

In the compositions 1 to 14, the same effects as in Test Examples 1 to 14 are obtained even when a composition prepared by using the pigment dispersion liquid A100 prepared by the following method is used instead of the pigment dispersion liquid A1.

(Pigment dispersion A100)

In a mixture 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, zirconia beads having a diameter of 0.3 mm 230 parts by mass was added, dispersion treatment was performed for 3 hours using a paint shaker, and the beads were separated by filtration to prepare a pigment dispersion liquid A100.

Claims (13)

It is a photosensitive composition for pulse exposure containing a coloring material and a radical polymerizable monomer,
The radical polymerizable monomer is a compound having a radical polymerizable group, and the radical polymerizable group included in the compound includes a compound M1 of at least one selected from allyl group, metalyl group, styrene group, styryl group and methacrylamide group. , Photosensitive composition. The method according to claim 1,
The radical polymerizable value of the compound M1 is 1 mmol / g or more, photosensitive composition. The method according to claim 1 or 2,
The photosensitive composition, wherein the content of the compound M1 in the total solid content of the photosensitive composition is 0.05 to 50% by mass. The method according to any one of claims 1 to 3,
The photosensitive composition, wherein the content of the compound M1 in the total amount of the radical polymerizable monomer is 1% by mass or more. The method according to any one of claims 1 to 4,
The radical polymerizable monomer includes the compound M1 and a (meth)acrylate monomer, a photosensitive composition. The method according to any one of claims 1 to 5,
A photosensitive composition further comprising a photo radical polymerization initiator. The method according to any one of claims 1 to 6,
A photosensitive composition further comprising a resin. The method of claim 7,
The photosensitive composition, wherein the resin contains an alkali-soluble resin. The method according to any one of claims 1 to 8,
The photosensitive composition, wherein the color material contains a pigment. The method according to any one of claims 1 to 9,
A photosensitive composition, which is a photosensitive composition for pulse exposure in light having a wavelength of 300 nm or less. The method according to any one of claims 1 to 10,
A photosensitive composition, which is a photosensitive composition for pulse exposure under conditions of a maximum instantaneous illumination of 50000000 W/m ² or more. The method according to any one of claims 1 to 11,
A photosensitive composition which is a photosensitive composition for solid-state imaging devices. The method according to any one of claims 1 to 11,
A photosensitive composition which is a photosensitive composition for color filters.