WO2022085485A1 - Resin composition, method for producing resin composition, method for producing film, method for producing optical filter, a method for producing solid-state imaging element, and method for producing image display device - Google Patents

Abstract

Provided is a resin composition exhibiting suppressed variations in pigment average particle diameter even after long-term storage at a low temperature. The resin composition contains a pigment, a resin, and a solvent, and the solvent contains an ether-based solvent represented by formula (1). In formula (1), R1 is a hydrocarbon group and R2 through R6 are each independently a hydrogen atom or a hydrocarbon group.

Description

A resin composition, a method for manufacturing a resin composition, a method for manufacturing a film, a method for manufacturing an optical filter, a method for manufacturing a solid-state image sensor, and a method for manufacturing an image display device.

The present invention relates to a resin composition containing a pigment. The present invention also relates to a method for manufacturing a resin composition, a film, an optical filter, a solid-state image sensor, and an image display device.

Optical filters such as color filters are manufactured using resin compositions containing pigments.

For example, Patent Document 1 describes a colorant (A) such as an organic pigment or an inorganic pigment, a binder polymer (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a propylene glycol monomethyl. It is described that a color filter is produced using a resin composition containing a solvent (E) containing ether acetate and 4-hydroxy-4-methyl-2-pentanone.

Japanese Unexamined Patent Publication No. 2004-199040

When forming a film using a resin composition, a film may be formed using a resin composition stored at a low temperature for a long period of time.

However, if the dispersity of the pigment in the resin composition is low, the pigment in the resin composition aggregates during storage of the resin composition even if the average particle size of the pigment is small in the resin composition immediately after production. The average particle size of the pigment tends to be large. When the average particle size of the pigment present in the resin composition becomes large, the viscosity of the resin composition increases and the coatability tends to decrease. Therefore, as the storage period of the resin composition becomes longer, the thickness unevenness of the obtained film tends to increase. Further, since the average particle size of the pigment increases during storage of the resin composition, a film formed by using the resin composition immediately after production and a film formed by using the resin composition after long-term storage are used. There may also be differences in performance such as the spectral characteristics of the film.

When the present inventor examined the resin composition described in Patent Document 1, it was found that there is room for further improvement in the dispersibility of the pigment.

Therefore, an object of the present invention is to provide a resin composition in which fluctuations in the average particle size of the pigment are suppressed even after long-term storage at a low temperature. The present invention also provides a method for manufacturing a resin composition, a film, an optical filter, a solid-state image sensor, and an image display device.

According to the study of the present inventor, it has been found that the above object can be achieved by adopting the following configuration, and the present invention has been completed. Therefore, the present invention provides the following.
<1> Containing a pigment, a resin, and a solvent,
The solvent is a resin composition containing an ether solvent represented by the formula (1);

In formula (1), R ¹ represents a hydrocarbon group, and R ² to R ⁶ independently represent a hydrogen atom or a hydrocarbon group, respectively.
<2> The ether solvent represented by the above formula (1) is at least one selected from anisole, phenetol, 4-methylanisole, 3-methylanisole and 2-methylanisole, according to <1>. Resin composition.
<3> The resin composition according to <1> or <2>, wherein the solvent contains 1 to 100% by mass of an ether solvent represented by the above formula (1).
<4> The resin composition according to <1> or <2>, wherein the solvent contains 1 to 50% by mass of an ether solvent represented by the above formula (1).
<5> The resin composition according to any one of <1> to <4>, wherein the resin composition contains 0.5% by mass or more of an ether solvent represented by the above formula (1).
<6> The solvent is any one of <1> to <5>, which comprises an ether solvent represented by the above formula (1) and a solvent other than the ether solvent represented by the above formula (1). The resin composition according to one.
<7> The resin composition according to <6>, wherein the solvent other than the ether solvent represented by the above formula (1) contains propylene glycol monomethyl ether acetate.
<8> The resin composition according to <7>, which contains 100 to 9900 parts by mass of propylene glycol monomethyl ether acetate with respect to 100 parts by mass of the ether solvent represented by the above formula (1).
<9> The resin composition according to any one of <6> to <8>, wherein the solvent other than the ether solvent represented by the above formula (1) contains a ketone solvent.
<10> The resin composition according to any one of <1> to <9>, wherein the pigment contains at least one selected from a chromatic pigment and a near-infrared absorbing pigment.
<11> The method for producing a resin composition according to any one of <1> to <10>, wherein the pigment is a resin and a solvent containing an ether solvent represented by the formula (1). A method for producing a resin composition, which comprises a step of dispersing below;

In formula (1), R ¹ represents a hydrocarbon group, and R ² to R ⁶ independently represent a hydrogen atom or a hydrocarbon group, respectively.
<12> A method for producing a film, which comprises a step of applying the resin composition according to any one of <1> to <10> to a support.
<13> A method for manufacturing an optical filter, which comprises the method for manufacturing a film according to <12>.
<14> A method for manufacturing a solid-state image sensor, which comprises the method for manufacturing a film according to <12>.
<15> A method for manufacturing an image display device including the method for manufacturing a film according to <12>.

According to the present invention, it is possible to provide a resin composition in which fluctuations in the average particle size of the pigment are suppressed even after long-term storage at a low temperature. Further, it is possible to provide a method for manufacturing a resin composition, a film, an optical filter, a solid-state image pickup device, and an image display device.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, "to" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Acryloyl "represents both acryloyl and / or methacryloyl.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, Pr represents a propyl group, and Ph represents a phenyl group.
In the present specification, the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by a GPC (gel permeation chromatography) method.
In the present specification, the near infrared ray means light having a wavelength of 700 to 2500 nm.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent.
In the present specification, the pigment means a coloring material that is difficult to dissolve in a solvent. For example, the solubility of the pigment in 100 g of water at 23 ° C. and 100 g of propylene glycol monomethyl ether acetate at 23 ° C. is preferably 0.1 g or less, and more preferably 0.01 g or less.
In the present specification, the dye means a coloring material that is easily dissolved in a solvent.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..

<Resin composition>
The resin composition of the present invention contains a pigment, a resin, and a solvent, and the solvent is characterized by containing an ether solvent represented by the formula (1).

In formula (1), R ¹ represents a hydrocarbon group, and R ² to R ⁶ independently represent a hydrogen atom or a hydrocarbon group, respectively.

It is presumed that the ether solvent contained in the resin composition of the present invention has a high affinity with pigments and can weaken the cohesiveness between pigments. Therefore, the resin composition of the present invention can suppress fluctuations in the average particle size of the pigment even after being stored at a low temperature (for example, 5 ° C.) for a long period of time. It is presumed that the ether solvent represented by the formula (1) can interact with the conjugated system of the organic pigment to further enhance the affinity with the organic pigment. Therefore, when an organic pigment is used as the pigment, the fluctuation of the average particle size can be suppressed more effectively.

Further, by using the resin composition of the present invention, it is possible to form a film having excellent film thickness uniformity. It is presumed that the reason why such an effect is obtained is that the thixotropic property of the resin composition can be reduced by suppressing the aggregation of the pigment.

The resin composition of the present invention is preferably used as a resin composition for an optical filter. Examples of the optical filter include a color filter, a near-infrared transmission filter, a near-infrared cut filter, and the like, and a color filter is preferable. Further, the resin composition of the present invention is preferably used for a solid-state image sensor. More specifically, it is preferably used as a resin composition for an optical filter used in a solid-state image sensor, and more preferably used as a resin composition for forming colored pixels of a color filter used in a solid-state image sensor.

Examples of the color filter include a filter having colored pixels that transmit light of a specific wavelength. Examples of the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta pixel, a cyan pixel, a yellow pixel, and the like, and a green pixel or a cyan pixel is preferable, and a green pixel is more preferable. The colored pixels of the color filter can be formed by using a resin composition containing a chromatic pigment.

The maximum absorption wavelength of the near-infrared cut filter is preferably in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. .. Further, the transmittance of the near-infrared cut filter in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. Further, the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less. The ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm (absorbance Amax / absorbance A550) is preferably 20 to 500, more preferably 50 to 500. , 70 to 450, more preferably 100 to 400, and particularly preferably 100 to 400. The near-infrared cut filter can be formed by using a resin composition containing a near-infrared absorbing pigment.

The near-infrared ray transmission filter is a filter that transmits at least a part of near-infrared rays. The near-infrared transmission filter may be a filter (transparent film) that transmits both visible light and near-infrared light, and is a filter that shields at least a part of visible light and transmits at least a part of near-infrared light. May be good. As a near-infrared transmissive filter, the maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the transmittance in the wavelength range of 1100 to 1300 nm. A filter satisfying the spectral characteristics having a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more) is preferably mentioned. The near-infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).
(1): The maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 800 to 1500 nm is. A filter of 70% or more (preferably 75% or more, more preferably 80% or more).
(2): The maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 900 to 1500 nm is. A filter of 70% or more (preferably 75% or more, more preferably 80% or more).
(3): The maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1500 nm is. A filter of 70% or more (preferably 75% or more, more preferably 80% or more).
(4): The maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1500 nm is. A filter of 70% or more (preferably 75% or more, more preferably 80% or more).
(5): The maximum value of the transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1200 to 1500 nm is. A filter of 70% or more (preferably 75% or more, more preferably 80% or more).

The resin composition of the present invention can also be used as a light-shielding film or the like.

The solid content concentration of the resin composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

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

<< Pigment >>
The resin composition of the present invention contains a pigment. Examples of the pigment include a white pigment, a black pigment, a chromatic pigment, and a near-infrared absorbing pigment. In the present specification, the white pigment includes not only pure white but also light gray (for example, grayish white, light gray, etc.) pigment close to white.

When the resin composition is used for a color filter, a chromatic pigment is used as the pigment. The chromatic pigment may be only one kind or may contain two or more kinds. When the resin composition is used for forming a near-infrared cut filter, a near-infrared absorbing pigment is used as the pigment. The near-infrared absorbing pigment may be only one kind, or may contain two or more kinds. Further, when forming pixels for a near-infrared transmission filter from a resin composition, two or more kinds of chromatic pigments are used in combination as pigments, or black pigments are used.

The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less. In the present invention, the primary particle size of the pigment can be obtained from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle size in the present invention is an arithmetic average value of the primary particle size for the primary particles of 400 pigments. Further, the primary particles of the pigment refer to independent particles without aggregation.

The pigment used in the present invention is preferably an organic pigment because the effect of the present invention is more prominent, and is preferably a phthalocyanine pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, an isoindrin pigment, an azo pigment, and an azomethine. It is more preferably at least one selected from pigments, quinophthalone pigments, dioxazine pigments and pteridine pigments, and even more preferably phthalocyanine pigments. The phthalocyanine pigment is a green pigment, Color Index (CI). Pigment Green7, 36, 58, 59, 62, 63, etc., which is a blue pigment, C.I. I. Pigment Blue 15: 3, 15: 4, 15: 6, 16 and the like are preferable. The diketopyrrolopyrrole pigment is a red pigment, C.I. I. Pigment Red 254, 264, 272, 291 and the like are preferable. As the anthraquinone pigment, C.I. I. Pigment Red 177 and the like are preferable. The isoindoline pigment is C.I. I. Pigment Yellow 139, 185 and the like are preferable. As the azo pigment, C.I. I. Pigment Yellow 150, a red pigment, C.I. I. Pigment Red 269 and the like are preferable. Further, as the azo pigment, an azobarbituric acid nickel complex pigment having the following structure can also be used. The quinophthalone pigment is a yellow pigment, C.I. I. Pigment Yellow 138, 231 and 233 are preferable. The dioxazine pigment is a purple pigment, C.I. I. Pigment Violet23 and the like are preferable. The pteridine pigment is a yellow pigment, C.I. I. Pigment Yellow 215 and the like are preferable. The azomethine pigment is a yellow pigment, C.I. I. Pigment Yellow 129 and the like are preferable.

Hereinafter, the pigment used in the present invention will be described in more detail.

(Color pigment)
The chromatic pigment is not particularly limited, and a known chromatic pigment can be used. Examples of the chromatic pigment include pigments having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, yellow pigments, orange pigments, red pigments, green pigments, purple pigments, blue pigments and the like can be mentioned. The chromatic pigment is preferably an organic pigment. Specific examples of these include those shown below.

C. I. Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35: 1,36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97, 98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139, 147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179, 180,181,182,185,187,188,193,194,199,213,214,215,228,231,232,233,234,235,236 etc. (above, yellow pigment),
C. I. Pigment Orange 2,5,13,16,17: 1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73, etc. (The above is orange pigment),
C. I. 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, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291 294,295,296,297 etc. (above, red pigment),
C. I. Pigment Green 7,10,36,37,58,59,62,63,64,65,66 etc. (above, green pigment),
C. I. Pigment Violet 1,19,23,27,32,37,42,60,61 etc. (above, purple pigment),
C. I. Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,29,60,64,66,79,80,87,88 etc. , Blue pigment).

Further, as a green pigment, a halogen having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5. Halogenated zinc phthalocyanine pigments can also be used. Specific examples include the phthalocyanine pigment described in International Publication No. 2015/118720. Further, as a green pigment, a compound described in Chinese Patent Application No. 106900927, a phthalocyanine compound having a phosphate ester described in International Publication No. 2012/102395 as a ligand, and Japanese Patent Application Laid-Open No. 2019-008014. Phthalocyanine compounds, phthalocyanine compounds described in JP-A-2018-180023, compounds described in JP-A-2019-038958, core-shell pigments described in JP-A-2020-076955, and the like can also be used.

Further, as the blue pigment, an aluminum phthalocyanine pigment having a phosphorus atom can also be used. Specific examples thereof include the compounds described in paragraph numbers 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A.

Further, as the yellow pigment, a nickel azobarbiturate complex pigment having the above-mentioned structure can also be used. Further, as the yellow pigment, the compounds described in JP-A-2017-201003, the compounds described in JP-A-2017-197719, and paragraph numbers 0011 to 0062 and 0137-0276 of JP-A-2017-171912 are described. Compounds, compounds described in paragraphs 0010 to 0062, 0138 to 0295 of JP-A-2017-171913, compounds described in paragraph numbers 0011 to 0062, 0139-0190 of JP-A-2017-171914, JP-A-2017- The compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of JP-A-171915, the quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP2013-054339, paragraph numbers 0013 to 0058 of JP-A-2014-026228. The quinophthalone compound described in JP-A-2018-062644, the quinophthalone compound described in JP-A-2018-203798, the quinophthalone compound described in JP-A-2018-062578, Patent No. 6432076. The quinophthalone compound described in JP-A-2018-155881, the quinophthalone compound described in JP-A-2018-11175, the quinophthalone compound described in JP-A-2018-040835, the quinophthalone compound described in JP-A-2018-040835, JP-A-2017- The quinophthalone compound described in JP-A-197640, the quinophthalone compound described in JP-A-2016-145282, the quinophthalone compound described in JP-A-2014-0855565, the quinophthalone compound described in JP-A-2014-021139, JP-A-B. The quinophthalone compound described in Japanese Patent Application Laid-Open No. 2013-209614, the quinophthalone compound described in JP-A-2013-209435, the quinophthalone compound described in JP-A-2013-181015, the quinophthalone compound described in JP-A-2013-061622, The quinophthalone compound described in JP2013-032486, the quinophthalone compound described in JP2012-226110, the quinophthalone compound described in JP2008-074987, and the quinophthalone described in JP2008-081565. Compounds, quinophthalone compounds described in JP-A-2008-074986, quinophthalone compounds described in JP-A-2008-074985, quinophthalone compounds described in JP-A-2008-050420, JP-A-2. The quinophthalone compound described in Japanese Patent Application Laid-Open No. 008-031281, the quinophthalone compound described in JP-A-48-032765, the quinophthalone compound described in JP-A-2019-008014, the quinophthalone compound described in Patent No. 6607427, the following formula. Compound represented by (QP1), compound represented by the following formula (QP2), compound described in Korean Publication No. 10-2014-0034963, compound described in JP-A-2017-095706, Taiwan Patent Publication No. The compound described in Japanese Patent Application Laid-Open No. 201920495, the compound described in Japanese Patent Application Laid-Open No. 6607427, the compound described in JP-A-2020-033525, the compound described in JP-A-2020-033524, and JP-A-2020-0335223. The compound described in JP-A, the compound described in JP-A-2020-033522, the compound described in JP-A-2020-033521, the compound described in International Publication No. 2020/045200, International Publication No. 2020/045199. , The compound described in International Publication No. 2020/045197, the perylene compound described in JP-A-2020-083982, the perylene compound described in International Publication No. 2020/105346, JP-A-2020-517791. The quinophthalone compound described in 1 can also be used. Further, a multimerized version of these compounds is also preferably used from the viewpoint of improving the color value.

In the formula (QP1), X ¹ to X ¹⁶ independently represent a hydrogen atom or a halogen atom, and Z ¹ represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP1) include the compound described in paragraph No. 0016 of Japanese Patent No. 6443711.

^In the formula (QP2), Y1 to ^Y3 independently represent halogen atoms. n and m represent integers of 0 to 6, and p represents an integer of 0 to 5. (N + m) is 1 or more. Specific examples of the compound represented by the formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.

As the red pigment, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, and a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838. The diketopyrrolopyrrole compound described in WO2012 / 102399, the diketopyrrolopyrrole compound described in WO2012 / 117965, the naphtholazo compound described in JP-A-2012-229344, Patent No. 6516119. The red pigment described in Japanese Patent Application Laid-Open No. 6525101, the red pigment described in Japanese Patent Application Laid-Open No. 2020-090632, the brominated diketopyrrolopyrrole compound described in paragraph No. 0229 of JP-A-2020-090632, Korean Publication No. 10-2019-0140741. Anthraquinone compound described in JP-A, anthraquinone compound described in Korean Publication No. 10-2019-0140744, perylene compound described in JP-A-2020-079396, paragraph numbers 0025 to 0041 of JP-A-2020-066702. The diketopyrrolopyrrole compound described in the above can also be used. Further, as the red pigment, a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. can.

Further, it is also preferable to use a halogenated zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6474002 as the pigment from the viewpoint of enhancing the spectral characteristics. Further, it is also preferable to use a dioxazine pigment having a controlled contact angle described in International Publication No. 2019/107166 as the pigment from the viewpoint of viscosity adjustment.

Regarding the diffraction angles that are preferably possessed by various pigments, the descriptions of Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, and Japanese Patent Application Laid-Open No. 2020-026503 can be referred to. Incorporated herein. In addition, the pyrolopyrrolop pigment shall have a crystallite size of 140 Å or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes (± 1 ± 1 ± 1) of the crystal lattice planes. Is also preferable. Further, it is also preferable to set the physical characteristics of the pyrrolopyrrole pigment as described in paragraphs 0028 to 0073 of JP-A-2020-097744.

Two or more kinds of chromatic pigments may be used in combination. For example, when the resin composition of the present invention is used for forming green pixels of a color filter, it is preferable to use a green pigment and a yellow pigment in combination. Further, when the resin composition of the present invention is used for forming red pixels of a color filter, it is preferable to use a red pigment and a yellow pigment in combination. Further, when the resin composition of the present invention is used for forming blue pixels of a color filter, it is preferable to use a blue pigment and a purple pigment in combination.

The pigment used in the coloring composition of the present invention preferably contains a green pigment, and more preferably contains a green pigment and a yellow pigment, respectively. Further, the green pigment is preferably a phthalocyanine pigment (also referred to as a phthalocyanine green pigment). The phthalocyanine green pigment tends to have high cohesiveness and low dispersibility of the pigment, but according to the resin composition of the present invention, excellent dispersibility can be obtained even when the phthalocyanine green pigment is used. The effect of the present invention is remarkably exhibited when the phthalocyanine green pigment is used. The phthalocyanine green pigment is preferably a phthalocyanine pigment having a central metal (also referred to as a metal phthalocyanine pigment). Examples of the metal phthalocyanine pigment include copper phthalocyanine pigments, zinc phthalocyanine pigments and aluminum phthalocyanine pigments, and copper phthalocyanine pigments and zinc phthalocyanine pigments are preferable.

Further, when two or more kinds of chromatic color pigments are used in combination, black may be formed by a combination of two or more kinds of chromatic color pigments. Examples of such a combination include the following aspects (1) to (7). When the resin composition contains two or more chromatic pigments and the combination of the two or more chromatic pigments exhibits black color, the resin composition of the present invention is used for forming a near-infrared transmission filter. It can be preferably used as a resin composition.
(1) An embodiment containing a red pigment and a blue pigment.
(2) An embodiment containing a red pigment, a blue pigment, and a yellow pigment.
(3) An embodiment containing a red pigment, a blue pigment, a yellow pigment, and a purple pigment.
(4) An embodiment containing a red pigment, a blue pigment, a yellow pigment, a purple pigment, and a green pigment.
(5) An embodiment containing a red pigment, a blue pigment, a yellow pigment, and a green pigment.
(6) An embodiment containing a red pigment, a blue pigment, and a green pigment.
(7) An embodiment containing a yellow pigment and a purple pigment.

(White pigment)
White pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow. Examples include resin particles and zinc sulfide. The white pigment is preferably particles having a titanium atom, and more preferably titanium oxide. Further, the white pigment is preferably particles having a refractive index of 2.10 or more with respect to light having a wavelength of 589 nm. The above-mentioned refractive index is preferably 2.10 to 3.00, and more preferably 2.50 to 2.75.

Further, as the white pigment, titanium oxide described in "Titanium Oxide Physical Properties and Applied Technology, by Manabu Kiyono, pp. 13-45, published on June 25, 1991, published by Gihodo Publishing" can also be used.

The white pigment is not limited to a single inorganic substance, but particles compounded with other materials may be used. For example, particles having pores or other materials inside, particles in which a large number of inorganic particles are attached to core particles, core particles composed of polymer particles and shell layers composed of inorganic nanoparticles are used, and core and shell composite particles are used. Is preferable. As the core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles, for example, the description in paragraphs 0012 to 0042 of JP2015-047520 can be referred to. This content is incorporated herein.

Hollow inorganic particles can also be used as the white pigment. Hollow inorganic particles are inorganic particles having a structure having cavities inside, and refer to inorganic particles having cavities surrounded by an outer shell. Examples of the hollow inorganic particles include the hollow inorganic particles described in JP-A-2011-075786, International Publication No. 2013/06621, JP-A-2015-164881, and the like, and the contents thereof are incorporated in the present specification. Is done.

(Black pigment)
The black pigment is not particularly limited, and known ones can be used. For example, carbon black, titanium black, graphite and the like can be mentioned, with carbon black and titanium black being preferable, and titanium black being more preferable. Titanium black is black particles containing a titanium atom, and low-order titanium oxide or titanium oxynitride is preferable. Titanium black can modify the surface as needed for the purpose of improving dispersibility and suppressing cohesion.
For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, it is also possible to treat with a water-repellent substance as shown in Japanese Patent Application Laid-Open No. 2007-302836. As a black pigment, C.I. I. Pigment Black 1, 7 and the like can be mentioned. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles and having a content ratio of Si atoms and Ti atoms in the dispersion adjusted to be in the range of 0.20 to 0.50 can be mentioned. Regarding the above dispersion, the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification. Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13RN, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D (Tilack) D (trade name: manufactured by Mitsubishi Materials Corporation). Product name: Ako Kasei Co., Ltd.) and the like.

(Near infrared absorber pigment)
The near-infrared absorbing pigment is preferably an organic pigment. Further, the near-infrared absorbing pigment preferably has a maximum absorption wavelength in a range of more than 700 nm and 1400 nm or less. The maximum absorption wavelength of the near-infrared absorbing pigment is preferably 1200 nm or less, more preferably 1000 nm or less, and further preferably 950 nm or less. Further, the near-infrared absorbing pigment preferably has A ₅₅₀ / A _max , which is the ratio of the absorbance A ₅₅₀ at a wavelength of 550 nm and the absorbance A _max at the maximum absorption wavelength, to be 0.1 or less, preferably 0.05 or less. Is more preferable, 0.03 or less is further preferable, and 0.02 or less is particularly preferable. The lower limit is not particularly limited, but may be, for example, 0.0001 or more, or 0.0005 or more. When the above-mentioned absorbance ratio is in the above range, a near-infrared absorbing pigment having excellent visible transparency and near-infrared shielding property can be obtained. In the present invention, the maximum absorption wavelength of the near-infrared absorbing pigment and the value of the absorbance at each wavelength are values obtained from the absorption spectrum of the film formed by using the resin composition containing the near-infrared absorbing pigment.

The near-infrared absorbing pigment is not particularly limited, but is a pyrolopyrrole compound, a lilene compound, an oxonol compound, a squarylium compound, a cyanine compound, a croconium compound, a phthalocyanine compound, a naphthalocyanine compound, a pyrylium compound, an azurenium compound, an indigo compound and a pyrromethene compound. It is preferable that it is at least one selected from a pyrolopyrrole compound, a squarylium compound, a cyanine compound, a phthalocyanine compound and a naphthalocyanine compound, and more preferably a pyrolopyrrole compound or a squarylium compound, which is a pyrolopyrrole compound. Is particularly preferred. Specific examples of the near-infrared absorbing pigment include the compounds described in Examples described later.

The content of the pigment in the total solid content of the resin composition is preferably 30 to 80% by mass. The lower limit is preferably 35% by mass or more, and more preferably 40% by mass or more. The upper limit is preferably 75% by mass or less, and more preferably 70% by mass or less.
The content of the organic pigment in the pigment is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and further preferably 70 to 100% by mass.
The content of the chromatic pigment in the pigment is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass.

<< Dye >>
The resin composition of the present invention may contain a dye. The dye is not particularly limited, and known dyes can be used. Examples of the dye include chromatic dyes, black dyes, and near-infrared absorbing dyes. As the dye, a known dye can be used. Further, the methine dye described in JP-A-2019-073695, the methine dye described in JP-A-2019-073696, the methine dye described in JP-A-2019-073697, and JP-A-2019-073698 are described. The methine dye of No. 2020, the azo dye described in JP-A-2020-09394, and the like can also be used. Further, as the dye, a dye multimer can also be used. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures contained in one molecule may have the same dye structure or may have different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. For dye multimers, JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, JP-A-2016-102191, International Publication No. 2016 / The compounds described in 031442 and the like can also be used.

The content of the dye in the total solid content of the resin composition is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. The content of the dye in the resin composition is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 60 parts by mass or less with respect to 100 parts by mass of the pigment. preferable.

It is also preferable that the resin composition of the present invention contains substantially no dye. According to this aspect, the ratio of the pigment in the resin composition can be increased, and the effect of the present invention is more remarkable. In the present specification, the case where the dye is substantially not contained means that the content of the dye in the total solid content of the resin composition is 0.1% by mass or less, and is 0.01% by mass. The following is preferable, and it is more preferable that the dye is not contained.

<< Resin >>
The resin composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing a pigment or the like in a resin composition or for a binder. The resin mainly used for dispersing the pigment is also referred to as a dispersant. However, such use of the resin is an example, and it can be used for purposes other than such use.

The weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

Examples of the resin include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamideimide resin. , Polyimine resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more thereof may be mixed and used. Further, the resin described in paragraph numbers 0041 to 0060 of JP-A-2017-206689, the resin described in paragraph numbers 0022-0071 of JP-A-2018-010856, and the block poly described in JP-A-2016-222891. Isocyanate resin can also be used.

The resin composition of the present invention preferably contains a resin having an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable. The resin having an acid group can be used, for example, as an alkali-soluble resin.

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

The resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable to include repeating units derived from the components.

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

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For the details of the formula (ED2), the description in JP-A-2010-168539 can be referred to, and the contents thereof are incorporated in the present specification.

As a specific example of the ether dimer, for example, the description in paragraph No. 0317 of JP2013-209760A can be referred to, and this content is incorporated in the present specification.

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

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 a hydrogen atom or a benzene ring having 1 to 20 carbon atoms. Represents the alkyl group of. n represents an integer from 1 to 15.

Regarding the resin having an acid group, the description in paragraph numbers 0558 to 0571 of JP2012-208494A (paragraph numbers 0685 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408 The description of paragraphs 0076 to 0999 of the publication can be taken into consideration, and these contents are incorporated in the present specification. Further, as the resin having an acid group, the resin described in paragraph Nos. 0107 to 0111 of JP-A-2010-0024557 and the resin described in paragraph numbers 0995 to 0098 of JP-A-2010-406655 can also be used.

The acid value of the resin having an acid group is preferably 5 to 200 mgKOH / g. The upper limit is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less. The lower limit is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and even more preferably 20 mgKOH / g or more. The weight average molecular weight (Mw) of the resin having an acid group is preferably 3000 to 35000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. The lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.

As the resin composition of the present invention, a resin having a basic group can also be used. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in the side chain, and has both a repeating unit having a basic group in the side chain and a repeating unit not containing a basic group. A polymer is more preferable, and a block copolymer having a repeating unit having a basic group in the side chain and a repeating unit not containing a basic group is further preferable. A resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 300 mgKOH / g. The lower limit is preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more. The upper limit is preferably 200 mgKOH / g or less, and more preferably 100 mgKOH / g or less. Examples of the resin having a basic group are described in the block copolymers (B) described in paragraphs 0063 to 0112 of JP2014-219665A and paragraphs 0046 to 0076 of JP-A-2018-156021. The block copolymer A1 can be mentioned.

Commercially available products of resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919, BYK-LPN21116 (all manufactured by Big Chemie), SOLPERSE11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000 , 53095, 56000, 7100 (above, manufactured by Japan Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (above, manufactured by BASF) and the like.

The resin composition of the present invention preferably contains a graft resin having an acid group (hereinafter, also referred to as an acidic graft resin). The acidic graft resin can be preferably used as a dispersant. Here, the graft resin means a resin containing a repeating unit having a graft chain. Further, the graft chain means a polymer chain that branches and extends from the main chain of the repeating unit.

The graft chain is preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure, and is preferably a polyester structure or a poly structure. More preferably, it is a polymer chain containing at least one structure selected from an ether structure and a poly (meth) acrylic structure.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, a hydroxy group, an amino group and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable, from the viewpoint of improving the dispersibility of pigments and the like. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched is preferable.

The weight average molecular weight of the graft chain is preferably 500 to 10000. The upper limit is preferably 5000 or less, and more preferably 3000 or less. The lower limit is preferably 800 or more, and more preferably 1000 or more. In the present specification, the weight average molecular weight of the graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the repeating unit having the graft chain. For example, repeating units with graft chains can be formed by polymerizing macromonomers. Here, the macromonomer means a polymer compound having a polymerizable group introduced at the end of the polymer. Further, as the value of the weight average molecular weight of the raw material monomer, the polystyrene-equivalent value measured by the GPC (gel permeation chromatography) method is used.

Examples of the acid group contained in the acidic graft resin include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable. The acid value of the acidic graft resin is preferably 20 to 150 mgKOH / g. The upper limit is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less. The lower limit is preferably 25 mgKOH / g or more, more preferably 30 mgKOH / g or more, and even more preferably 35 mgKOH / g or more.

The weight average molecular weight of the acidic graft resin is preferably 3000 to 35000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. The lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.

Examples of the acidic graft resin include a resin containing a repeating unit having a graft chain and a repeating unit having an acid group, and a resin having a repeating unit represented by the following formula (Ac-2). The acidic graft resin may further contain other repeating units such as repeating units having a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated bond-containing group and a cyclic ether group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group.

When the acidic graft resin is a resin containing a repeating unit having a graft chain and a repeating unit having an acid group, the acidic graft resin contains 1 mol of the repeating unit having a graft chain in all the repeating units of the acidic graft resin. % Or more is preferable, 2 mol% or more is more preferable, and 3 mol% or more is further preferable. The upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. can. Further, the acidic graft resin preferably contains 1 mol% or more of the repeating units having an acid group in all the repeating units of the acidic graft resin, more preferably 2 mol% or more, and 3 mol% or more. Is more preferable. The upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. can.

Next, the repeating unit represented by the equation (Ac-2) will be described.

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

Examples of the group containing an aromatic carboxyl group represented by Ar ¹⁰ in the formula (Ac-2) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like. Examples of the aromatic tricarboxylic acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures.

In the above formula, Q ¹ is represented by a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO _2- , -C (CF ₃ ) _2- , and the following formula (Q-1). Represents a group to be used or a group represented by the following formula (Q-2).

The group containing an aromatic carboxyl group represented by Ar ¹⁰ may have a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group. Specific examples of the group containing an aromatic carboxyl group represented by Ar ¹⁰ include a group represented by the formula (Ar-11), a group represented by the formula (Ar-12), and a group represented by the formula (Ar-13). Examples include the base.

In the formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
In the formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
In the formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
In the formula (Ar-13), Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO _2- , -C (CF ₃ ) _2- , the above formula (Q-). It represents a group represented by 1) or a group represented by the above formula (Q-2).
In the formulas (Ar-11) to (Ar-13), * 1 represents the bonding position with L ¹¹ .

In formula (Ac-2), L ¹¹ is preferably —COO−.

The trivalent linking group represented by L ¹² in the formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two of these. A group that combines species or more can be mentioned. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group and the like. The trivalent linking group represented by L ¹² is preferably a group represented by the formula (L12-1), and more preferably a group represented by the formula (L12-2).

In the formula (L12-1), L ^12b represents a trivalent linking group, X ¹ represents S, * 1 represents the bonding position with L 11 in the formula (Ac-2), and * 2 represents the bonding position with L ¹¹ in the formula (Ac-2). It represents the binding position of Ac- ² ) with P10. The trivalent linking group represented by L ^12b includes a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined, and a hydrocarbon group or a group in which a hydrocarbon group and —O— are combined is preferable.

In the formula (L12-2), L ^12c represents a trivalent linking group, X ¹ represents S, * 1 represents the bonding position with L ¹¹ of the formula (Ac-2), and * 2 represents the binding position of the formula (L12-2). It represents the binding position of Ac- ² ) with P10. The trivalent linking group represented by L ^12c includes a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined, and a hydrocarbon group is preferable.

The polymer chain represented by P10 of the formula (Ac- ² ) is a polymer containing at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure. The chain is mentioned and is preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure and a poly (meth) acrylic structure. The weight average molecular weight of the polymer chain represented by P ¹⁰ is preferably 500 to 10000. The upper limit is preferably 5000 or less, and more preferably 3000 or less. The lower limit is preferably 800 or more, and more preferably 1000 or more.

The polymer chain represented by P ¹⁰ may contain a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated bond-containing group and a cyclic ether group. The ratio of the repeating unit containing the polymerizable group in all the repeating units constituting P ¹⁰ is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more. More preferred. The upper limit can be 100% by mass, preferably 90% by mass or less, and more preferably 60% by mass or less.

It is also preferable that the polymer chain represented by P ¹⁰ contains a repeating unit containing an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. The ratio of the repeating unit containing an acid group in all the repeating units constituting P ¹⁰ is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and 3 to 10% by mass. Is even more preferable.

Further, as the acidic graft resin, a polyimine resin containing a nitrogen atom in at least one of the main chain and the side chain can also be used. The polyimine resin has a main chain having a partial structure having a functional group of pKa14 or less, a side chain having 40 to 10,000 atoms, and 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 exhibiting basicity.

Specific examples of the acidic graft resin include resins B-1 to B-5 described in Examples described later. Further, as the acidic graft resin, the resin described in paragraphs 0025 to 0094 of JP2012-255128 and the polyimine resin described in paragraphs 0102 to 0166 of JP2012-255128 may be used. can.

The resin composition of the present invention preferably contains 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) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acid dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially acid. A resin consisting only of a group is more preferable. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g. Further, the basic dispersant (basic resin) represents 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 basic groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. The basic group of the basic dispersant is preferably an amino group.

It is also preferable that the resin used as the dispersant is a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.

Further, as the dispersant, a resin such as the above-mentioned block copolymer or acidic graft resin can also be used.

Further, as the dispersant, the resin described in JP-A-2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraph numbers 0219 to 0221 of Patent No. 6432077, and the like. Polyethylenimine having a polyester side chain described in WO2016 / 104803, a block copolymer described in WO2019 / 125940, and a block polymer having an acrylamide structural unit described in JP-A-2020-06667. , Block polymers having an acrylamide structural unit described in JP-A-2020-066688 can also be used.

Dispersants are also available as commercial products, and specific examples thereof include BYK series and DISPERBYK series manufactured by Big Chemie, SOLSERSE series manufactured by Japan Lubrizol Co., Ltd., and Efka series manufactured by BASF. Can be mentioned. Further, the pigment dispersants described in paragraphs 0041 to 0130 of JP2014-130338A can also be used, and the contents thereof are incorporated in the present specification. The resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.

The content of the resin in the total solid content of the resin composition is preferably 5 to 40% by mass. The lower limit is preferably 10% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
Further, the content of the resin having an acid group in the total solid content of the resin composition is preferably 5 to 40% by mass. The lower limit is preferably 10% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
The content of the resin as a dispersant is preferably 10 to 60 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.

<< Solvent >>
The resin composition of the present invention contains a solvent. The solvent is preferably a liquid at 20 ° C.
The solvent contained in the resin composition of the present invention includes an ether solvent represented by the formula (1) (hereinafter, also referred to as solvent SA). Only one type of solvent SA may be used, or two or more types may be used in combination.

In formula (1), R ¹ represents a hydrocarbon group, and R ² to R ⁶ independently represent a hydrogen atom or a hydrocarbon group, respectively.

Examples of the hydrocarbon group represented by R ¹ to R ⁶ of the formula (1) include an alkyl group, an alkenyl group and an alkynyl group, and an alkyl group is preferable, and a methyl group is more preferable.

The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1. The alkyl group is preferably a linear or branched alkyl group, preferably a linear alkyl group.
The alkenyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. The alkenyl group is preferably a linear or branched alkenyl group, preferably a linear alkenyl group.
The alkynyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. The alkynyl group is preferably a linear or branched alkynyl group, preferably a linear alkynyl group.

Of ^R2 to R6 of the formula ( ¹ ), one or more are preferably hydrogen atoms, two or more are more preferably hydrogen atoms, and three or more are more preferably hydrogen atoms. .. ^R2 to R6 of the formula (1) are preferably any of the following embodiments (R ^- 1) to (R-3), and in the embodiment (R-1) or (R-2). It is more preferable that there is, and it is further preferable that it is the aspect of (R-1).
(R ^- 1): Aspect in which all of ^R2 to R6 are hydrogen atoms (R ^{- 2} ): Aspect in which any one of R2 to R6 is an alkyl group and the rest are hydrogen atoms (R-1). -3): A mode in which any ^two of ^R2 to R6 are alkyl groups and the rest are hydrogen atoms.

The molecular weight of the solvent SA is preferably 108 to 200, more preferably 108 to 180, and even more preferably 108 to 160.

The boiling point of the solvent SA is preferably 100 to 220 ° C, more preferably 120 to 180 ° C, and even more preferably 140 to 180 ° C.

The solubility parameter (SP value) of the solvent SA at 25 ° C. is preferably 15 to 24 (MPa) ^0.5 , more preferably 17 to 22 (MPa) ^0.5 , and 19 to 20 (MPa). ) ^0.5 is more preferable. The viscosity of the solvent SA at 25 ° C. is preferably 0.5 to 2.0 mPa · s, more preferably 0.6 to 1.7 mPa · s, and 0.7 to 1.4 mPa · s. Is more preferable.

Specific examples of the solvent SA include anisole, phenetol, 4-methylanisole, 3-methylanisole, 2-methylanisole, 4-ethylanisole, 3-ethylanisole, 2-ethylanisole, isopropoxybenzene, propoxybenzene, 2 , 4-Dimethylanisole, 2,5-dimethylanisole, 2,6-dimethylanisole, 3,5-dimethylanisole, butylphenyl ether, 4-ethylphenetol, 4-tert-butylanisole, etc. It is preferably at least one selected from anisole, phenetol, 4-methylanisole, 3-methylanisole and 2-methylanisole because it is possible to obtain a resin composition having excellent film thickness uniformity at the time. , Anisole is more preferred.

The solvent contained in the resin composition preferably contains 1 to 100% by mass of the solvent SA, more preferably 1 to 99% by mass, and even more preferably 1 to 50% by mass. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.

The solvent contained in the resin composition may be only the solvent SA, but the solvent solubility of the polymerizable compound, the resin, the photopolymerization initiator, etc. used in the resin composition can be improved, or the resin composition can be produced. In order to control the drying rate at the time of the film, it is preferable to contain a solvent other than the ether solvent represented by the formula (1) (hereinafter, also referred to as solvent SB). Examples of the solvent SB include an ether solvent, an ester solvent, and a ketone solvent. Only one type of solvent SB may be used, or two or more types may be used in combination.

Examples of the ether-based solvent used as the solvent SB include propylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. It is preferably propylene glycol monomethyl ether.

Examples of the ester-based solvent used as the solvent SB include propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethyl acetate, and acetate-n-. Butyl, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. , Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetoacetic acid Methyl, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, cyclohexyl acetate, 1-methyl-2-methoxyethyl propionate and the like can be mentioned, such as propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate. Is preferable.

Ketone-based solvents used as the solvent SB include 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-. Examples thereof include nonanonone, 4-nonanonone, 5-nonanonone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cyclopentanone, diacetone alcohol, methylethylketone, methylisoamylketone, methylisobutylketone, and the like. , Cyclopentanone, 2-octanone, diacetone alcohol is preferred.

The solvent SB preferably contains at least one selected from an ester solvent and a ketone solvent, more preferably contains an ester solvent, and further preferably contains propylene glycol monomethyl ether acetate.

When the solvent contained in the resin composition contains the solvent SA and the solvent SB, the content of the solvent SB is preferably 100 to 9900 parts by mass with respect to 100 parts by mass of the solvent SA. The lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. The upper limit is preferably 3500 parts by mass or less, and more preferably 2000 parts by mass or less.

When an ester solvent (hereinafter, also referred to as solvent SB ¹ ) is used as the solvent SB, the content of the solvent SB ¹ is preferably 100 to 9900 parts by mass with respect to 100 parts by mass of the solvent SA. The lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. The upper limit is preferably 3500 parts by mass or less, and more preferably 2000 parts by mass or less.

When propylene glycol monomethyl ether acetate is used as the solvent SB, the content of propylene glycol monomethyl ether acetate is preferably 100 to 9900 parts by mass with respect to 100 parts by mass of the solvent SA. The lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. The upper limit is preferably 3500 parts by mass or less, and more preferably 2000 parts by mass or less.
The total content of the solvent SA and the propylene glycol monomethyl ether acetate in the solvent contained in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass. The above is more preferable. The upper limit may be 100% by mass or less, 90% by mass or less, or 80% by mass or less.

When a ketone solvent (hereinafter, also referred to as solvent SB ² ) is used as the solvent SB, the content of the solvent SB ² is preferably 10 to 900 parts by mass with respect to 100 parts by mass of the solvent SA. The lower limit is preferably 25 parts by mass or more, and more preferably 40 parts by mass or more. The upper limit is preferably 400 parts by mass or less, more preferably 250 parts by mass or less.

When an ester solvent (solvent SB ¹ ) and a ketone solvent (solvent SB ² ) are used in combination as the solvent SB, the solvent contained in the resin composition has a solvent SA content of 1 to 50% by mass. It is preferable that the content of the solvent SB ¹ is 20 to 95% by mass and the content of the solvent SB ² is 1 to 40% by mass. In this case, the content of the solvent SA is preferably 3 to 45% by mass, more preferably 5 to 40% by mass. The content of the solvent SB ¹ is preferably 25 to 90% by mass, more preferably 30 to 85% by mass. The content of the solvent SB ² is preferably 3 to 35% by mass, more preferably 5 to 30% by mass.
Further, the total content of the solvent SA, the solvent SB ¹ and the solvent SB ² in the solvent contained in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, 70. It is more preferably mass% or more. The upper limit may be 100% by mass or less, 90% by mass or less, or 80% by mass or less.

The content of the solvent in the resin composition is preferably 50 to 95% by mass. The upper limit is preferably 92.5% by mass or less, and more preferably 90% by mass or less. The lower limit is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and further preferably 80% by mass or more.
The content of the solvent SA in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more. The content of the solvent SA in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less.

Further, it is preferable that the resin composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations. In the present invention, substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the resin composition is 50 mass ppm or less, and preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of the environmentally regulated substance include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are REACH (Registration Evolution Analysis and Restriction of Chemicals) rules, PRTR (Pollutant Release and Transfer Register) method, VOC (Volatile and Transfer Registor) method, VOC (Volatile Organic Compounds), and VOC (Volatile Organic Compounds). The method is strictly regulated. These compounds may be used as a solvent in producing each component used in the resin composition, and may be mixed in the resin composition as a residual solvent. From the viewpoint of human safety and consideration for the environment, it is preferable to reduce these substances as much as possible. As a method for reducing the environmentally regulated substance, there is a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance or higher and distilling off the environmentally regulated substance from the system to reduce the amount. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to improve efficiency. When a compound having radical polymerization property is contained, a polymerization inhibitor or the like is added and the mixture is distilled off under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. May be. These distillation methods are the stage of the raw material, the stage of the product obtained by reacting the raw material (for example, the resin solution after polymerization or the polyfunctional monomer solution), or the stage of the resin composition prepared by mixing these compounds. It is possible at any stage such as.

<< Polyalkylene imine >>
The resin composition of the present invention may also contain polyalkyleneimine. Polyalkyleneimine is used, for example, as a dispersion aid. The dispersion aid is a material for enhancing the dispersibility of the pigment in the resin composition. The polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and has a branched structure containing a primary amino group, a secondary amino group and a tertiary amino group, respectively. The carbon number of the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

The molecular weight of polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, further preferably 10,000 or less, and particularly preferably 2000 or less. When the molecular weight of polyalkyleneimine can be calculated from the structural formula, the molecular weight of polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. If the measurement cannot be performed by the boiling point elevation method or is difficult to measure, the value of the number average molecular weight measured by the viscosity method is used. If it cannot be measured by the viscosity method or it is difficult to measure by the viscosity method, the value of the number average molecular weight in the polystyrene conversion value measured by the GPC (gel permeation chromatography) method is used.

The amine value of polyalkyleneimine is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.

Specific examples of the alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and the like, preferably ethyleneimine or propyleneimine, and more preferably ethyleneimine. preferable. The polyalkyleneimine is particularly preferably polyethyleneimine. Further, polyethyleneimine preferably contains a primary amino group in an amount of 10 mol% or more, more preferably 20 mol% or more, based on the total of the primary amino group, the secondary amino group and the tertiary amino group. , 30 mol% or more is more preferable. Examples of commercially available polyethyleneimine products include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).

The content of alkyleneimine in the total solid content of the resin composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less. The content of alkyleneimine is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, and more preferably 8 parts by mass or less. As the alkyleneimine, only one kind may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is in the above range.

<< Pigment derivative >>
The resin composition of the present invention can contain a pigment derivative. Pigment derivatives are used, for example, as dispersion aids. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.

The pigment skeletons constituting the pigment derivative include quinoline pigment skeleton, benzoimidazolone pigment skeleton, benzoisoindole pigment skeleton, benzothiazole pigment skeleton, iminium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, and pyrolopyrrole pigment. Skeleton, diketopyrrolopyrrole pigment skeleton, azo pigment skeleton, azomethine pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, anthraquinone pigment skeleton, quinacridone pigment skeleton, dioxazine pigment skeleton, perinone pigment skeleton, perylene pigment skeleton, thioindigo pigment skeleton, Examples thereof include an isoindrin pigment skeleton, an isoindolinone pigment skeleton, a quinophthalone pigment skeleton, an iminium pigment skeleton, a dithiol pigment skeleton, a triarylmethane pigment skeleton, and a pyrromethene pigment skeleton.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imic acid group and salts thereof. As the atoms or atomic groups constituting the salt, alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ , etc.), alkaline earth metal ions (Ca ²⁺ , Mg ²⁺ , etc.), ammonium ions, imidazolium ions, pyridinium ions, etc. Examples include phosphonium ion. As the carboxylic acid amide group, a group represented by -NHCOR ^X1 is preferable. As the sulfonamide group, a group represented by -NHSO ₂ ^RX2 is preferable. As the imidic 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, and -SO ₂ NHSO ₂ R ^X3 is more preferable. ^{RX1 to RX6 independently} represent an alkyl group or an aryl group, respectively. The alkyl group and aryl group represented by ^{RX1 to RX6 may} have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.

Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimidemethyl group. Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.

As the pigment derivative, a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative) can be used. The maximum molar extinction coefficient (εmax) of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L · mol ^-1 · cm ^-1 or less, and 1000 L · mol ^-1 · cm ^-1 or less. Is more preferable, and 100 L · mol ^-1 · cm ^-1 or less is further preferable. The lower limit of εmax is, for example, 1 L · mol ^-1 · cm ^-1 or more, and may be 10 L · mol ^-1 · cm ^-1 or more.

Specific examples of the pigment derivative include the compounds described in Examples described later, JP-A-56-118462, JP-A-63-246674, JP-A-01-217077, and JP-A-03-009961. , Japanese Patent Laid-Open No. 03-026767, Japanese Patent Application Laid-Open No. 03-153780, Japanese Patent Application Laid-Open No. 03-045662, Japanese Patent Application Laid-Open No. 04-285669, Japanese Patent Application Laid-Open No. 06-145546, Japanese Patent Application Laid-Open No. 06-212088, Kaihei 06-240158, Japanese Patent Laid-Open No. 10-030063, Japanese Patent Laid-Open No. 10-195326, Paragraph Nos. 0086 to 0998 of International Publication No. 2011/024896, Paragraph Nos. 0063 to 0094 of International Publication No. 2012/102399. , International Publication No. 2017/038252, paragraph No. 802, JP-A-2015-151530, paragraph No. 0171, JP-A-2011-52065, paragraph numbers 0162 to 0183, JP-A-2003-081972, Patent No. 5299151. No., JP-A-2015-172732, JP-A-2014-199308, JP-A-2014-085562, JP-A-2014-035351, JP-A-2008-081565, International Publication No. Examples thereof include the diketopyrrolopyrrole compound having a thiol linking group according to 2020/002106.

The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, still more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the pigment. As the pigment derivative, only one kind may be used, or two or more kinds may be used in combination. When two or more types are used in combination, the total amount thereof is preferably in the above range.

<< Polymerizable compound >>
The resin composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a known compound that can be crosslinked by radicals, acids or heat can be used. In the present invention, the polymerizable compound is preferably, for example, a compound having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.

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

The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and more preferably an ethylenically unsaturated bond. It is more preferable that the compound contains 3 to 6 containing groups. Further, the polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities. Specific examples of the polymerizable compound include paragraph numbers 0995 to 0108 of JP2009-288705, paragraphs 0227 of JP2013-029760, paragraphs 0254 to 0257 of JP2008-292970, and JP-A. The compounds described in paragraph numbers 0034 to 0038 of Japanese Patent Application Laid-Open No. 2013-253224, paragraph numbers 0477 of Japanese Patent Application Laid-Open No. 2012-208494, Japanese Patent Application Laid-Open No. 2017-048637, Japanese Patent No. 6057891 and Japanese Patent Application Laid-Open No. 6031807 are These contents are incorporated herein by reference.

As the polymerizable compound, dipentaerythritol tri (meth) acrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetra (meth) acrylate (commercially available KAYARAD D-320). ; Nippon Kayaku Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available) KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol and / or propylene glycol residues. Compounds with a bound structure (eg, SR454, SR499 commercially available from Sartmer) are preferred. As the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toa Synthetic), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK ester A) -TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toa Synthetic Co., Ltd.) , NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINK-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. are used. You can also do it.

The polymerizable compounds include trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanuric acid ethyleneoxy-modified tri (meth). Trifunctional (meth) acrylate compounds such as acrylate and pentaerythritol tri (meth) acrylate can also be used. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.

Further, as the polymerizable compound, a compound having an acid group can also be used. By using a polymerizable compound having an acid group, the polymerizable compound in the unexposed portion can be easily removed during development, and the generation of development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable. Examples of the polymerizable compound having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate. Examples of commercially available products of the polymerizable compound having an acid group include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). The preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling.

Further, as the polymerizable compound, a compound having a caprolactone structure can also be used. Examples of commercially available products of the polymerizable compound having a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.) and the like.

Further, as the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. As the polymerizable compound having an alkyleneoxy group, a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group is preferable, a polymerizable compound having an ethyleneoxy group is more preferable, and 3 to 3 having 4 to 20 ethyleneoxy groups. A hexafunctional (meth) acrylate compound is more preferred. Commercially available products of the polymerizable compound having an alkyleneoxy group include, for example, SR-494 (manufactured by Sartmer), which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups, and trifunctional (manufactured by Sartmer) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330 (manufactured by Nippon Kayaku Co., Ltd.), which is a meta) acrylate.

Further, as the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. The polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound. Examples of the polymerizable compound having a fluorene skeleton include compounds having a partial structure represented by the following formula (Fr).

The wavy line in the equation represents a bond, 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, m R ^f1s may be the same or different from each other, and two R ^f1s out of m R ^f1s are bonded to each other to form a ring. May be good. When n is 2 or more, the n R ^f2s may be the same or different from each other, and two R ^f2s out of the n R ^f2s are bonded to each other to form a ring. May be good. The substituents represented by R ^f1 and R ^f2 include 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 , and -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 -SO ₂ NR ^f27 R ^f28 can be mentioned. R ^{f11 to R f28 each} independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.

Specific examples of the polymerizable compound having a fluorene skeleton include compounds having the following structures. Examples of commercially available products of the polymerizable compound having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (meth) acrylate monomer having a fluorene skeleton).

As the polymerizable compound, it is also preferable to use a compound that does not substantially contain an environmentally restrictive substance such as toluene. Examples of commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

The content of the polymerizable compound in the total solid content of the resin composition is preferably 0.1 to 50% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less. The polymerizable compound may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total of them is within the above range.

<< Photopolymerization Initiator >>
The resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole. It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl substituted coumarin compound, preferably an oxime compound and an α-hydroxyketone compound. , Α-Aminoketone compound, and a compound selected from an acylphosphine compound are more preferable, and an oxime compound is further preferable. Further, as the photopolymerization initiator, the compound described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol. 19, No. Peroxide-based photopolymerization initiator described in 3, 2019, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, JP-A-2019-043864. The photopolymerization initiator described in JP-A-2019-044030, the peroxide-based initiator described in JP-A-2019-167313, JP-A-2020-055992. Examples thereof include the above-mentioned aminoacetophenone-based initiators having an oxazolidine group, the oxime-based photopolymerization initiators described in JP-A-2013-190459, and the contents thereof are incorporated in the present specification.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure27, Irgacure29. (Manufactured by the company) and the like. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369, Irger Made) and so on. Examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).

Examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No. 2017. The compound described in / 051680, the compound described in JP-A-2017-198865, the compound described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, the compound described in International Publication No. 2013/167515, etc. Can be mentioned. Specific examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like. 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropane-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, manufactured by BASF), TR-PBG-304, TR-PBG-3057 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA PTOMER N. -1919 (manufactured by ADEKA Corporation, Photopolymerization Initiator 2) described in Japanese Patent Application Laid-Open No. 2012-014052). Further, as the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and difficult to discolor. Examples of commercially available products include ADEKA ARCLUS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.

As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.

As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like can be mentioned.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARCULDS NCI-831 (manufactured by ADEKA Corporation).

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

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

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. Examples of the electron-attracting group of the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferable, and an acyl group is more preferable, and a benzoyl group is further preferable because it is easy to form a film having excellent light resistance. The benzoyl group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group. It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.

The oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.

In the formula, ^RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group. A group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group, and ^RX2 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, Heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group or amino group, and ^{RX3 to RX14 are} independent hydrogen atoms. Alternatively, it represents a substituent; however, at least one of ^RX10 to ^RX14 is an electron-attracting group.

Examples of the electron-attracting group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group, preferably an acyl group and a nitro group, and lightfast resistance. An acyl group is more preferable, and a benzoyl group is further preferable, because it is easy to form a film having excellent properties.

In the above formula, it is preferable that ^RX12 is an electron-withdrawing group and ^RX10 , ^RX11 , ^RX13 , and ^RX14 are hydrogen atoms.

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

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

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Further, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, still more preferably 2000 to 300,000, and more preferably 5000 to 200,000. It is particularly preferable to have. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photopolymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. Further, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the resin composition with time can be improved. .. Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Dimerics of oxime compounds described in paragraphs 0407 to 0412, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds described in JP-A-2013-522445. G), Cmpd1-7 described in International Publication No. 2016/034943, Oxime Esters Photoinitiator described in paragraph No. 0007 of JP-A-2017-523465, JP-A-2017-167399. The photoinitiator described in paragraphs 0020 to 0033, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, is described in Japanese Patent No. 6469669. Examples include oxime ester photoinitiators.

The content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less. The photopolymerization initiator may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total of them is within the above range.

<< Compound with cyclic ether group >>
The resin composition of the present invention can contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter, also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferable. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy group contained in the epoxy compound may be, for example, 10 or less, or 5 or less. The lower limit of the epoxy group contained in the epoxy compound is preferably two or more. Examples of the epoxy compound are described in paragraphs 0034 to 0036 of JP2013-011869, paragraph numbers 0147 to 0156 of JP2014-0435556, and paragraph numbers 0083 to 0092 of JP2014-089408. Compounds, compounds described in JP-A-2017-179172 can also be used. These contents are incorporated in the present specification.

The epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 2000, further, a molecular weight of less than 1000), or a polymer compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). It may be any of. The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5000 or less, and even more preferably 3000 or less.

As the epoxy compound, an epoxy resin can be preferably used. Examples of the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester. Epoxy resin, glycidylamine epoxy resin, glycidylated epoxy resin of halogenated phenols, condensate of silicon compound having epoxy group and other silicon compounds, polymerizable unsaturated compound having epoxy group and others Examples thereof include a copolymer with another polymerizable unsaturated compound. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and even more preferably 310 to 1000 g / eq.

Commercially available products of compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G. -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all manufactured by NOF CORPORATION, epoxy group-containing polymer) and the like can be mentioned.

The content of the compound having a cyclic ether group in the total solid content of the resin composition is preferably 0.1 to 20% by mass. The lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is, for example, more preferably 15% by mass or less, further preferably 10% by mass or less. As the compound having a cyclic ether group, only one kind may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

<< Curing Accelerator >>
The resin composition of the present invention may contain a curing accelerator. Examples of the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidin salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds and the like. Specific examples of the curing accelerator include the compound described in paragraph Nos. 0094 to 0097 of International Publication No. 2018/056189, the compound described in paragraph numbers 0246 to 0253 of JP-A-2015-034963, and JP-A-2013-041165. Compounds described in Japanese Patent Laid-Open No. 0186-0251, ionic compounds described in JP-A-2014-0551114, compounds described in paragraphs 0071-0080 of JP-A-2012-150180, JP-A-2011-253504. Examples thereof include the alkoxysilane compound described in JP-A, the compounds described in paragraphs 805 to 0092 of Patent No. 5765059, and the carboxyl group-containing epoxy curing agent described in JP-A-2017-036379. The content of the curing accelerator in the total solid content of the resin composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.

<< Surfactant >>
The resin composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant. As for the surfactant, the surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.

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

Examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of the corresponding International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-. The surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-008634 are mentioned, and the contents thereof are incorporated in the present specification. Commercially available products of fluorine-based surfactants include, for example, Megafax F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560. , F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40, R-40-LM, R-41, R -141-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, Sumitomo) 3M Co., Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Surfactant 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710F ,
(The above is manufactured by NEOS Co., Ltd.) 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 and the fluorine atom volatilizes when heat is applied. Can be suitably used. Examples of such a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be 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. Examples of such a fluorine-based surfactant include the fluorine-based surfactants described in JP-A-2016-216602, the contents of which are incorporated in the present specification.

As the fluorine-based surfactant, a block polymer can also be used. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.

The weight average molecular weight of the above compounds is preferably 3000 to 50,000, for example 14000. Among the above compounds,% indicating the ratio of the repeating unit is mol%.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K, manufactured by DIC Corporation. RS-72-K and the like can be mentioned. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

It is also preferable from the viewpoint of environmental regulation to use the surfactant described in International Publication No. 2020/088454 as a substitute for the surfactant having a perfluoroalkyl group having 6 or more carbon atoms.

It is also preferable to use a fluorine-containing imide salt compound represented by the formula (fi-1) as a surfactant.

In the formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, α represents 1 or 2, and X ^{α +} represents an α-valent metal ion, a primary ammonium ion, and a first. Represents a secondary ammonium ion, a tertiary ammonium ^ion , a quaternary ammonium ion or NH ₄₊ .

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. 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 (BASF) , Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm sum) Kojunyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) ) And so on.

Examples of the silicone-based surfactant include DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400, SH 8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Addive, SF84 and above. -Toray Specialty Materials Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Co., Ltd.), KP-341, KF- 6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK -UV3510 (above, manufactured by Big Chemie) and the like.

The content of the surfactant in the total solid content of the resin composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005 to 3.0% by mass. Only one type of surfactant 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 thereof is within the above range.

<< Silane Coupling Agent >>
The resin composition of the present invention can contain a silane coupling agent. As used herein, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form 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, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group and an isocyanate group. , A phenyl group and the like, preferably an amino group, a (meth) acryloyl group and an epoxy group. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-amino. Propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxy There are propylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503) and the like. Specific examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. , These contents are incorporated herein.

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

<< UV absorber >>
The resin 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. Examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraph numbers 0052 to 0072 of JP2012-208374A, and paragraph numbers 0317 to 0334 of JP2013-066814. The compounds described in paragraphs 0061 to 0080 of JP 2016-162946 are mentioned, the contents of which are incorporated herein by reference. Examples of commercially available ultraviolet absorbers include UV-503 manufactured by Daito Kagaku Co., Ltd., Tinuvin series manufactured by BASF, and Uvinul series manufactured by BASF. Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016). Further, the ultraviolet absorber is a compound described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967, a compound described in paragraph numbers 0059 to 0076 of International Publication No. 2016/181987, and International Publication No. 2020/137819. The thioaryl group-substituted benzotriazole type ultraviolet absorber described in 1 can also be used. The content of the ultraviolet absorber in the total solid content of the resin composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one kind of ultraviolet absorber may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

<< Antioxidant >>
The resin composition of the present invention can contain an antioxidant. Examples of the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. Further, as the antioxidant, the compound described in Korean Patent Publication No. 10-2019-0059371 can also be used. The content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.

<< Polymerization inhibitor >>
The resin composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, etc.). Of these, p-methoxyphenol is preferable. The content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass. The polymerization inhibitor may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount is within the above range.

<< Other ingredients >>
In the present invention, the resin composition is, if necessary, a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent). , Flame retardant, leveling agent, peeling accelerator, fragrance, surface tension modifier, chain transfer agent, etc.) may be contained. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The description of numbers 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification. Further, the resin composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation). Further, the resin composition of the present invention may contain an aromatic group-containing phosphonium salt described in JP-A-2020-079833.

The resin composition of the present invention may contain a light resistance improving agent. Examples of the light resistance improving agent include the compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, the compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, and JP-A-2017-129774. The compounds described in paragraphs 0036 to 0037 and 0049 to 0052, the compounds described in paragraphs 0031 to 0034 and 0058 to 0059 of JP-A-2017-129674, paragraph numbers 0036 to 0037 of JP-A-2017-122803. , 0051 to 0054, the compounds described in paragraphs 0025 to 0039 of International Publication No. 2017/164127, the compounds described in paragraphs 0034 to 0047 of JP-A-2017-186546, the compounds of JP-A-2015-025116. The compounds described in paragraph numbers 0019 to 0041 of JP-A, the compounds described in paragraph numbers 0101 to 0125 of JP2012-145604, the compounds described in paragraph numbers 0018 to 0021 of JP-A-2012-103475, the present invention. The compounds described in paragraphs 0015 to 0018 of JP-A-2011-257591, the compounds described in paragraph numbers 0017 to 0021 of JP-A-2011-191483, and paragraph numbers 0108 to 0116 of JP-A-2011-145668. , And the compounds described in paragraphs 0103 to 0153 of JP-A-2011-253174.

The resin composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, which is not bonded or coordinated with a pigment or the like. , It is particularly preferable that it is not substantially contained. According to this aspect, stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable components, suppression of conductivity fluctuation due to elution of metal atoms / metal ions, Effects such as improvement of display characteristics can be expected. In addition, JP-A-2012-153996, JP-A-2000-34585, JP-A-2005-2005, JP-A-08-043620, JP-A-2004-145878, JP-A-2014-119487, Described in JP-A-2010-083979, JP-A-2017-090930, JP-A-2018-025612, JP-A-2018-025797, JP-A-2017-155228, JP-A-2018-036521 and the like. The effect that was done is also obtained. Examples of the types of free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, and the like. Examples thereof include Cs, Ni, Cd, Pb and Bi. Further, the resin composition of the present invention preferably has a content of free halogen not bonded or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, and more preferably 10 ppm or less. It is more preferable, and it is particularly preferable that it is not substantially contained. Examples of the halogen include F, Cl, Br, I and their anions. Examples of the method for reducing free metals and halogens in the resin composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.

It is also preferable that the resin composition of the present invention does not substantially contain a terephthalic acid ester. Here, "substantially free" means that the content of the terephthalic acid ester is 1000 mass ppb or less in the total amount of the resin composition, and more preferably 100 mass ppb or less. Zero is particularly preferred.

From the viewpoint of environmental regulation, the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be restricted. In the resin composition of the present invention, when the content of the above-mentioned compound is reduced, the perfluoroalkyl sulfonic acid (particularly the perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group), a salt thereof, and a per. The content of the fluoroalkylcarboxylic acid (particularly the perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01 ppb to 1,000 ppb with respect to the total solid content of the resin composition. It is preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb. The resin composition of the present invention may be substantially free of perfluoroalkyl sulfonic acid and salts thereof, as well as perfluoroalkyl carboxylic acid and salts thereof. For example, by using a compound that can substitute for perfluoroalkylsulfonic acid and its salt, and a compound that can substitute for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid can be used. And a resin composition that is substantially free of salts thereof may be selected. Examples of compounds that can substitute for the regulated compound include compounds excluded from the regulation due to the difference in the number of carbon atoms of the perfluoroalkyl group. However, the above-mentioned contents do not prevent the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt. The resin composition of the present invention may contain a perfluoroalkyl sulfonic acid and a salt thereof, and a perfluoroalkyl carboxylic acid and a salt thereof within the maximum allowable range.

<< Storage container >>
The storage container for the resin composition is not particularly limited, and a known storage container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into raw materials and resin compositions, a multi-layer bottle having a container inner wall composed of 6 types and 6 layers of resin and a bottle having 6 types of resin having a 7-layer structure. It is also preferable to use. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351. Further, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, improving the storage stability of the resin composition, and suppressing the deterioration of the components.

<Manufacturing method of resin composition>
The resin composition of the present invention can be produced by mixing the above-mentioned materials. In the production of the resin composition, all the components may be simultaneously dissolved and / or dispersed in a solvent to produce the resin composition, or each material may be appropriately used as two or more solutions or dispersions as required. Then, these may be mixed at the time of use (at the time of application) to produce a resin composition.

The method for producing a resin composition of the present invention includes a step (dispersion step) of dispersing a pigment in the presence of a resin and a solvent containing an ether solvent (solvent SA) represented by the above formula (1). Is preferable. According to this aspect, the dispersibility of the pigment in the resin composition can be further improved, and the average particle size of the pigment in the resin composition can be further reduced. The detailed reason why such an effect is obtained is unknown, but it is presumed to be due to the following. It is presumed that the solvent SA has a high affinity with the pigment and can weaken the cohesiveness between the pigments. Therefore, by dispersing the pigment in the presence of the resin and the solvent containing the solvent SA, the reaggregation of the pigment at the time of dispersion can be effectively suppressed, and the average particle size of the pigment in the resin composition can be made smaller. can do. Further, it is presumed that the solvent SA can interact with the conjugated system of the organic pigment to further enhance the affinity with the organic pigment. Therefore, when an organic pigment is used as the pigment, the reaggregation of the pigment at the time of dispersion can be suppressed more effectively, and the average particle size of the pigment in the resin composition can be further reduced.

The solvent used in the dispersion step is other than solvent SA from the viewpoints of solubility of the resin used at the time of dispersion, solvent solubility of polymerizable compounds, resins, photopolymerization initiators, etc., and control of the drying speed at the time of film formation of the resin composition. It is preferable to contain the solvent (solvent SB) of the above. Examples of the solvent SB include the above-mentioned solvents, preferably those containing at least one selected from an ester solvent and a ketone solvent, more preferably those containing an ester solvent, and containing propylene glycol monomethyl ether acetate. It is more preferable that it is a solvent.

The solvent used in the dispersion step preferably contains 1% by mass or more of the solvent SA, more preferably 3% by mass or more, and further preferably 5% by mass or more. The upper limit may be 100% by mass or less, 50% by mass or less, or 30% by mass or less.
When the solvent used in the dispersion step further contains the solvent SB, the content of the solvent SB is preferably 1 to 99% by mass, more preferably 30 to 90% by mass, and 50 to 70% by mass. It is more preferable to have. The content of the solvent SB is preferably 10 to 3000 parts by mass with respect to 100 parts by mass of the solvent SA. The lower limit is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more. The upper limit is preferably 2000 parts by mass or less, and more preferably 1000 parts by mass or less.
The solvent used in the dispersion step preferably contains 1 to 99% by mass of propylene glycol monomethyl ether acetate, more preferably 30 to 90% by mass, and even more preferably 50 to 70% by mass. The content of propylene glycol monomethyl ether acetate is preferably 10 to 3000 parts by mass with respect to 100 parts by mass of the solvent SA. The lower limit is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more. The upper limit is preferably 2000 parts by mass or less, and more preferably 1000 parts by mass or less.

Mechanical forces used to disperse pigments include compression, squeezing, impact, shearing, cavitation, etc. Specific means include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, ultrasonic dispersion, and the like. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter and to perform the treatment under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. In addition, the process and disperser for dispersing pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial". Practical application The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used. Further, in the process of dispersing the pigment, the particles may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.

It is preferable to use a resin composition material (particularly, a dispersion liquid, a polymerizable compound, a photopolymerization initiator, etc.) that has been refrigerated at a temperature of 5 to 10 ° C. In addition, when manufacturing the resin composition, the refrigerated material is stored in an environment with a temperature of 17 to 27 ° C and a relative humidity of 40 to 80% for 12 hours or more, and the temperature of the material is returned to 17 to 27 ° C. It is preferable to mix it with other materials.

Further, when a resin, a polymerizable compound, a photopolymerization initiator, or the like is further added to the dispersion liquid produced through the above dispersion step, the order of addition of each material is not particularly limited, but the dissolution rate and handleability are improved. After mixing the polymerizable compound, the resin, and the solvent for the purpose, a photopolymerization initiator, a polymerization inhibitor, and other additives are further mixed to produce a monomer liquid, and then the monomer liquid is added to the dispersion liquid. It is also preferable.

Further, it is preferable to manufacture the resin composition in an environment of a temperature of 17 to 27 ° C. and a relative humidity of 40 to 80% from the viewpoint of preventing excessive water from being mixed into the resin composition.

It is preferable that the method for producing the resin composition includes a step of filtering the resin composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP). Examples thereof include filters using materials such as (including high-density, ultra-high molecular weight polyethylene resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore diameter of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the hole diameter value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used. ..

It is also preferable to use a fiber-like filter medium as the filter. Examples of the fiber-like filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd.

When using a filter, different filters (for example, a first filter and a second filter) may be combined. At that time, the filtration with each filter may be performed only once or twice or more. Further, filters having different pore diameters may be combined within the above-mentioned range. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.

It is also preferable to fill the produced resin composition (particularly when it contains a green pigment) in a light-shielded container from the viewpoint of imparting stability. Further, it is preferable that the gas occupying the void inside the container has an oxygen concentration of 23% or more from the viewpoint of imparting stability.

<Membrane manufacturing method>
Next, the method for producing the film of the present invention will be described. The method for producing a film of the present invention includes a step of applying the resin composition of the present invention to a support.

According to the film manufacturing method of the present invention, the film thickness of the manufactured film can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more.

The film produced by the film manufacturing method of the present invention can be used as a color filter, a near-infrared transmission filter, a near-infrared cut filter, a black matrix, a light-shielding film, and the like.

The film manufacturing method of the present invention preferably further includes a step of forming a pattern (pixel). Examples of the pattern (pixel) forming method include a photolithography method and a dry etching method, and the photolithography method is preferable.

The pattern formation by the photolithography method includes a step of forming a resin composition layer on a support using the resin composition of the present invention, a step of exposing the resin composition layer in a pattern, and a step of exposing the resin composition layer in a pattern. It is preferable to include a step of developing and removing the exposed portion to form a pattern (pixel). If necessary, a step of baking the resin composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

In the step of forming the resin composition layer, the resin composition layer of the present invention is used to form the resin composition layer on the support. The support is not particularly limited and may be appropriately selected depending on the intended use. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable. Further, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, a black matrix that separates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with a base layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate. The surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the coating property of the resin composition is good. The surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.

As a method for applying the resin composition, a known method can be used. For example, a drop method (drop cast); a slit coat method; a spray method; a roll coat method; a rotary coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; transfer method using a mold or the like; nanoinprint method and the like can be mentioned. The method of application in inkjet is not particularly limited, and is, for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). Page 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned.
Further, regarding the method of applying the resin composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in the present specification.

The resin composition layer formed on the support may be dried (prebaked). When the membrane is manufactured by a low temperature process, prebaking may not be performed. When prebaking is performed, the prebake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher. The prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, still more preferably 80 to 220 seconds. Pre-baking can be performed on a hot plate, an oven, or the like.

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

Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm) and the like, and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.

Further, at the time of exposure, light may be continuously irradiated for exposure, or pulsed irradiation may be performed for exposure (pulse exposure). The pulse exposure is an exposure method of a method in which light irradiation and pause are repeated in a cycle of a short time (for example, a millisecond level or less).

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J / cm ² , more preferably 0.05 to 1.0 J / cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment (for example, 22% by volume, 30% by volume, or 50% by volume) in a high oxygen atmosphere having an oxygen concentration of more than 21% by volume. The exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m ² to 100,000 W / m ² (for example, 5000 W / m ² , 15,000 W / m ² , or 35,000 W / m ² ). Can be done. The oxygen concentration and the exposure illuminance may be appropriately combined with each other. For example, the illuminance may be 10,000 W / m ² at an oxygen concentration of 10% by volume, an illuminance of 20,000 W / m ² at an oxygen concentration of 35% by volume, and the like.

Next, the unexposed portion of the resin composition layer is developed and removed to form a pattern (pixel). The unexposed portion of the resin composition layer can be developed and removed using a developing solution. As a result, the resin composition layer in the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains. The temperature of the developer is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, etc. Examples thereof include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the alkaline agent, a compound having a large molecular weight is preferable in terms of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Further, the developer may further contain a surfactant. From the viewpoint of convenience of transfer and storage, the developer may be once produced as a concentrated solution and diluted to a concentration required for use. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the rinsing liquid to the developed resin composition layer while rotating the support on which the developed resin composition layer is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of the rinse can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion of the support to the peripheral portion.

It is preferable to perform additional exposure treatment or heat treatment (post-baking) after development and drying. Additional exposure processing and post-baking are post-development curing treatments to complete the curing. The heating temperature in the post-bake is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C. Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so as to meet the above conditions. .. When the additional exposure process is performed, the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

The pattern formation by the dry etching method includes a step of forming a resin composition layer on a support using the resin composition of the present invention and curing the entire resin composition layer to form a cured product layer. A step of forming a photoresist layer on the cured product layer, a step of exposing the photoresist layer in a pattern and then developing to form a resist pattern, and a step of etching the cured product layer using this resist pattern as a mask. It is preferable to include a step of dry etching with a gas. In forming the photoresist layer, it is preferable to further perform a prebaking treatment. In particular, as a process for forming the photoresist layer, it is desirable to carry out a heat treatment after exposure and a heat treatment (post-baking treatment) after development. Regarding the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP2013-064993 can be referred to, and this content is incorporated in the present specification.

<Manufacturing method of optical filter>
The method for manufacturing an optical filter of the present invention includes the above-mentioned method for manufacturing a film of the present invention. That is, the method for manufacturing an optical filter of the present invention includes the step of applying the above-mentioned resin composition of the present invention to a support. Examples of the type of optical filter include a color filter, a near-infrared cut filter, a near-infrared transmission filter, and the like, and a color filter is preferable. The color filter preferably has the film of the present invention as its pixel, more preferably has the film of the present invention as a colored pixel, and further preferably has the film of the present invention as a green pixel.

In the optical filter, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more.

The width of the pixels included in the optical filter is preferably 0.1 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and further preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, further preferably 1.0 μm or less, and even more preferably 0.8 μm or less.

<Manufacturing method of solid-state image sensor>
The method for manufacturing a solid-state image sensor of the present invention includes the above-mentioned method for manufacturing a film of the present invention. That is, the method for manufacturing a solid-state image sensor of the present invention includes the step of applying the above-mentioned resin composition of the present invention to a support. The configuration of the solid-state image sensor is not particularly limited as long as it functions as a solid-state image sensor, and examples thereof include the following configurations.

On the substrate, there are a plurality of photodiodes constituting the light receiving area of a solid-state image pickup device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like. A device protective film made of silicon nitride or the like formed on the photodiode and the transfer electrode so as to have a light-shielding film in which only the light-receiving part of the photodiode is open, and to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode on the light-shielding film. And has a color filter on the device protective film. Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective film under the color filter (near the substrate), a configuration having a condensing means on the color filter, and the like. There may be. Further, the color filter may have a structure in which each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478, JP-A-2014-179757, and International Publication No. 2018/043654. Further, as shown in Japanese Patent Application Laid-Open No. 2019-21159, an ultraviolet absorbing layer may be provided in the structure of the solid-state image sensor to improve the light resistance. The image pickup device provided with the solid-state image pickup device of the present invention can be used not only for digital cameras and electronic devices having an image pickup function (mobile phones and the like), but also for in-vehicle cameras and surveillance cameras.

<Manufacturing method of image display device>
The method for manufacturing an image display device of the present invention includes the above-mentioned method for manufacturing a film of the present invention. That is, the method for manufacturing an image display device of the present invention includes the step of applying the above-mentioned resin composition of the present invention to a support. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For details on the definition of image display devices and the details of each image display device, see, for example, "Electronic Display Devices (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", "Display Devices (Junaki Ibuki, Industrial Books). Co., Ltd. (issued in 1989) ”. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".

The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Measurement conditions of weight average molecular weight and number average molecular weight by gel permeation chromatography method>
Column type: Column in which TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 are linked Developing solvent: Tetrahydrofuran Column temperature: 40 ° C.
Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1% by mass)
Device name: Tosoh HLC-8220GPC
Detector: RI (refractive index) detector Calibration curve base resin: Polystyrene resin

<Manufacturing of dispersion>
(Dispersion prescription 1)
A mixed solution of 13.3 parts by mass of the pigment, 0.7 parts by mass of the dispersion aid, 4.9 parts by mass of the resin, and 81.1 parts by mass of the solvent was mixed with a bead mill (zirconia beads 0.1 mm diameter). ) Was mixed and dispersed for 3 hours to prepare a dispersion. Then, a dispersion treatment was performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under the conditions of a pressure of 2000 kg / cm ³ and a flow rate of 500 g / min. This dispersion treatment was repeated up to a total of 10 times to obtain a dispersion liquid. The materials shown in the table below were used for the pigment, dispersion aid, resin and solvent.

(Dispersion prescription 2)
A mixed solution of 13.3 parts by mass of the pigment, 0.7 parts by mass of the dispersion aid, 3.5 parts by mass of the resin, and 82.5 parts by mass of the solvent was mixed with a bead mill (zirconia beads 0.1 mm diameter). ) Was mixed and dispersed for 3 hours to prepare a dispersion. Then, a dispersion treatment was performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under the conditions of a pressure of 2000 kg / cm ³ and a flow rate of 500 g / min. This dispersion treatment was repeated up to a total of 10 times to obtain a dispersion liquid. The materials shown in the table below were used for the pigment, dispersion aid, resin solution, and solvent.

The details of the materials indicated by the abbreviations in the table showing the formulation of the above dispersion are as follows.

(Pigment)
P-1: C.I. I. Pigment Green7 (green pigment)
P-2: C.I. I. Pigment Green36 (green pigment)
P-3: C.I. I. Pigment Green58 (green pigment)
P-4: C.I. I. Pigment Green59 (green pigment)
P-5: C.I. I. Pigment Green63 (green pigment)
P-6: C.I. I. Pigment Yellow 129 (yellow pigment)
P-7: C.I. I. Pigment Yellow 138 (yellow pigment)
P-8: C.I. I. Pigment Yellow 139 (yellow pigment)
P-9: C.I. I. Pigment Yellow 150 (yellow pigment)
P-10: C.I. I. Pigment Yellow 185 (yellow pigment)
P-11: C.I. I. Pigment Yellow 215 (yellow pigment)
P-12: C.I. I. Pigment Yellow 231 (yellow pigment)
P-13: C.I. I. Pigment Yellow233 (yellow pigment)
P-14: C.I. I. Pigment Red177 (red pigment)
P-15: C.I. I. Pigment Red 254 (red pigment)
P-16: C.I. I. Pigment Red 264 (red pigment)
P-17: C.I. I. Pigment Red272 (red pigment)
P-18: C.I. I. Pigment Red 291 (red pigment)
P-19: C.I. I. Pigment Blue 15: 4 (blue pigment)
P-20: C.I. I. Pigment Blue 15: 6 (blue pigment)
P-21: C.I. I. Pigment Blue16 (blue pigment)
P-22: C.I. I. Pigment Violet23 (purple pigment)
P-23: TiO ₂ (pigment containing titanium atom, white pigment)
P-24: TiON (pigment containing titanium atom, black pigment)
P-25: Compound with the following structure (near infrared absorber pigment)

P-26: Compound with the following structure (near infrared absorber pigment)

(Dispersion aid)
Syn-1: Compound (pigment derivative) having the following structure

Syn-2: Compound (pigment derivative) with the following structure

Syn-3: Compound (pigment derivative) having the following structure

Syn-4: Compound (pigment derivative) having the following structure

Syn-5: Polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd.)

Syn-6: Compound (pigment derivative) with the following structure

Syn-7: Compound (pigment derivative) having the following structure

Syn-8: Compound (pigment derivative) having the following structure

Syn-9: Compound (pigment derivative) having the following structure

Syn-10: Compound (pigment derivative) having the following structure

Syn-111: Compound (pigment derivative) with the following structure

(resin)
B-1: Resin B-1 synthesized by the following method
50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of (3-ethyloxetane-3-yl) methyl methacrylate, and 45.4 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were charged into the reaction vessel to create an atmosphere. The gas was replaced with nitrogen gas. The inside of the reaction vessel is heated to 70 ° C., 6 parts by mass of 3-mercapto-1,2-propanediol is added, and 0.12 parts by mass of AIBN (azobisisobutyronitrile) is further added, and the reaction is carried out for 12 hours. I let you. It was confirmed by solid content measurement that 95% had reacted. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added. , 120 ° C. for 7 hours. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value and terminating the reaction, the acid value is 43 mgKOH / g and the weight average molecular weight is 9000. Resin B-1 of the above was obtained.

B-2: Resin B-2 synthesized by the following method
108 parts by mass of 1-thioglycerol, 174 parts by mass of pyromellitic anhydride, 650 parts by mass of methoxypropyl acetate, and 0.2 parts by mass of monobutyltin oxide as a catalyst were charged in a reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The reaction was carried out at 120 ° C. for 5 hours (first step). By measuring the acid value, it was confirmed that 95% or more of the acid anhydride was half-esterified. Next, the compound obtained in the first step is 160 parts by mass in terms of solid content, 200 parts by mass of 2-hydroxypropyl methacrylate, 200 parts by mass of ethyl acrylate, 150 parts by mass of t-butyl acrylate, and 200 parts by mass of 2-methoxyethyl acrylate. Parts, 200 parts by mass of methyl acrylate, 50 parts by mass of methacrylic acid, and 663 parts by mass of PGMEA are charged in a reaction vessel, and the inside of the reaction vessel is heated to 80 ° C. to 2,2'-azobis (2,4-dimethylvaleronitrile) 1 .2 parts by mass was added and reacted for 12 hours (second step). It was confirmed by solid content measurement that 95% had reacted. Finally, 500 parts by mass of a 50% by mass PGMEA solution, 27.0 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part by mass of hydroquinone of the compound obtained in the second step were charged into the reaction vessel to form an isocyanate group. The reaction was carried out until the disappearance of the peak of 2270 cm ^-1 based on the above was confirmed (third step). After confirming the disappearance of the peak, the reaction solution is cooled and then dried to remove the solvent. The resin having an acid value of 68 mgKOH / g, an ethylenically unsaturated bond base value of 0.62 mmol / g, and a weight average molecular weight of 13000 has the following structure. Obtained B-2.

B-3: Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 16000, acid value 67 mgKOH / g)

B-4: Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 24000, acid value 52.5 mgKOH / g)

B-5: Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 21000, acid value 58.4 mgKOH / g)

B-6: A material obtained by drying BYK-LPN21116 (quaternary ammonium salt type acrylic block copolymer manufactured by Big Chemie) and adjusting the non-volatile content (solid content concentration) to 100% by mass.

B-7: Resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 11000, acid value 69.2 mgKOH / g)

B-8: Resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 21000)

B-9: Resin B-9 synthesized by the following method
A flask equipped with a cooling tube and a stirrer was charged with 100 parts by mass of PGMEA and replaced with nitrogen. Heated to 80 ° C. and at the same temperature, 100 parts by mass of PGMEA, 15 parts by mass of methacrylic acid, 15 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, N. -A mixed solution of 12 parts by mass of phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) succinate and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour. , This temperature was maintained and polymerization was carried out for 2 hours. After that, the temperature of the reaction solution was raised to 100 ° C.
The resin B-9 (weight average molecular weight 12000, acid value 137 mgKOH / g) was obtained by further polymerizing for 1 hour and drying to remove the solvent.

B-10: Resin B-10 synthesized by the following method
A flask equipped with a cooling tube and a stirrer was charged with 100 parts by mass of PGMEA and replaced with nitrogen. Heated to 80 ° C. and at the same temperature, 100 parts by mass of PGMEA, 7 parts by mass of methacrylic acid, 15 parts by mass of styrene, 10 parts by mass of benzyl methacrylate, 20 parts by mass of 2-hydroxyethyl methacrylate, 28 parts by mass of 2-ethylhexyl methacrylate, N. -A mixed solution of 15 parts by mass of phenylmaleimide, 5 parts by mass of mono (2-acryloyloxyethyl) succinate and 4 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour. , This temperature was maintained and polymerization was carried out for 2 hours. Then, the temperature of the reaction solution was raised to 100 ° C., polymerized for another hour, and dried to remove the solvent to obtain resin B-10 (weight average molecular weight 18500, acid value 59 mgKOH / g).

B-11: Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 20000, acid value 77 mgKOH / g)

(solvent)
[Ether-based solvent represented by the formula (1)]

[Solvents other than the ether solvent represented by the formula (1)]
SB-1: Propylene glycol monomethyl ether acetate (PGMEA)
SB-2: Propylene glycol monomethyl ether (PGME)
SB-3: Ethyl 3-ethoxypropionate SB-4: 2-octanone SB-5: Cyclopentanone SB-6: Diacetone alcohol

<Manufacturing of resin composition>
Each material was mixed at a ratio according to the following formulations 1 to 4 to produce each resin composition. Some of the dispersions, polymerizable compounds, and photopolymerization initiators listed in the table below were refrigerated at 5 to 10 ° C. Refrigerated dispersions, polymerizable compounds and photopolymerization initiators were taken out of the refrigerator 12 hours or more before the production of the resin composition and controlled to a temperature of 17 to 27 ° C. and a relative humidity of 40 to 80%. It was temporarily stored indoors and used after returning the temperature of these materials to the indoor temperature.
In addition, each resin composition was produced by the following procedure. That is, a polymerizable compound, a resin, and a solvent were added to a mixing tank equipped with stirring blades installed in a room controlled at a temperature of 17 to 27 ° C. and a relative humidity of 40 to 80%, and stirring was started. Then, a photopolymerization initiator, a polymerization inhibitor, and an additive were added, and the mixture was stirred until the total stirring time was 30 minutes or more. A monomer solution was produced by such a procedure. Next, the dispersion liquid was added to a mixing tank equipped with stirring blades installed in a room controlled by the temperature and humidity, then the above-mentioned monomer liquid was added, and then a surfactant was added and the mixture was stirred for 10 minutes or more. A resin composition was produced by such a procedure. Finally, the obtained resin composition is filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm, filled in a storage container, and then filled in the voids of the storage container with a gas having an oxygen concentration of 30% by volume. Was stored in a filled state.

In the table below, the value of the pigment content in the total solid content of the resin composition is described in the "Pigment concentration" column.

(Prescription 1)
Dispersions listed in the table below ... 54.1 parts by mass Polymerizable compounds listed in the table below ... 3.6 parts by mass Resins listed in the table below ... 3.3 parts by mass Described in the table below Photopolymerization initiator ・ ・ ・ 0.9 parts by mass Surface active agent listed in the table below ・ ・ ・ 0.02 parts by mass Polymerization inhibitor listed in the table below ・ ・ ・ 0.0002 parts by mass Solvent listed in the table below ... 38.1 parts by mass

(Prescription 2)
Dispersions listed in the table below ... 67.7 parts by mass Polymerizable compounds listed in the table below 2.7 parts by mass Resins listed in the table below 1.6 parts by mass Photopolymerization initiator ・ ・ ・ 0.9 parts by mass Surface active agent listed in the table below ・ ・ ・ 0.02 parts by mass Polymerization inhibitor listed in the table below ・ ・ ・ 0.0002 parts by mass Solvent listed in the table below ... 27.1 parts by mass

(Prescription 3)
Dispersions listed in the table below ... 81.2 parts by mass Polymerizable compounds listed in the table below ... 0.9 parts by mass Resins listed in the table below ... 1.2 parts by mass Listed in the table below Photopolymerization initiator ・ ・ ・ 0.5 parts by mass Surface active agent listed in the table below ・ ・ ・ 0.02 parts by mass Polymerization inhibitor listed in the table below ・ ・ ・ 0.0002 parts by mass Solvent listed in the table below ... 16.1 parts by mass

(Prescription 4)
Dispersions listed in the table below ・ ・ ・ 88.0 parts by mass Polymerizable compounds listed in the table below ・ ・ ・ 0.9 parts by mass Resins listed in the table below ・ ・ ・ 1.1 parts by mass Photopolymerization initiator ・ ・ ・ 0.5 parts by mass Surface active agent listed in the table below ・ ・ ・ 0.02 parts by mass Polymerization inhibitor listed in the table below ・ ・ ・ 0.0002 parts by mass Solvent listed in the table below ... 9.4 parts by mass

Among the materials indicated by the abbreviations in the table showing the formulation of the above resin composition, the details other than the dispersion liquid are as follows. The above-mentioned dispersion was used as the dispersion.

(Polymerizable compound)
M-1: Compound with the following structure

M-2: Compound with the following structure

M-3: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
M-4: Compound with the following structure

(Photopolymerization initiator)
I-1: Irgure OXE02 (Oxime compound manufactured by BASF)
I-2 to I-5: Compounds with the following structure

(resin)
B-1 to B-10: Resins B-1 to B-10 described above

(Surfactant)
W-1: FZ-2122 (Silicone-based surfactant manufactured by Dow Corning Toray Specialty Materials Co., Ltd.)
W-2: BYK-330 (Silicone-based surfactant manufactured by Big Chemie)
W-3: KF-6001 (Silicone-based surfactant manufactured by Shin-Etsu Chemical Co., Ltd.)
W-4: PolyFox PF6320 (OMNOVA, fluorine-based surfactant)
W-5: Megafuck F-554 (manufactured by DIC Corporation, fluorine-based surfactant)

(Polymerization inhibitor)
In-1: p-methoxyphenol

(solvent)
SA-1, SA-2, SA-3, SA-4, SA-5, SB-1, SB-2, SB-3, SB-4, SB-5, SB-6: Solvent SA-1 described above. , SA-2, SA-3, SA-4, SA-5, SB-1, SB-2, SB-3, SB-4, SB-5, SB-6

<Evaluation of pigment dispersibility>
(Initial average particle size)
For the resin composition immediately after production, the average particle size of the pigment was measured using a particle size distribution meter (MT3300EXII, manufactured by Microtrac Bell Co., Ltd., measurement principle: laser diffraction / scattering method). The initial average particle size was evaluated according to the following criteria. Practically, it is preferable that it is 3 or more according to the following criteria.
-Evaluation criteria-
5: Average particle size of pigment ≤ 70 nm
4: 70 nm <average particle size of pigment ≤ 100 nm
3: 100 nm <average particle size of pigment ≤ 150 nm
2: 150 nm <average particle size of pigment ≤ 200 nm
1: Average particle size of pigment> 200 nm

(Volatility of average particle size)
For the resin composition immediately after production, use a particle size distribution meter (MT3300EXII, manufactured by Microtrac Bell Co., Ltd., measurement principle: laser diffraction / scattering method) to determine the average particle size of the pigment (hereinafter referred to as average particle size 1). It was measured.
Next, after storing each resin composition at 5 ° C. for 9 months, the average particles of the pigment were again used using a particle size distribution meter (MT3300EXII, manufactured by Microtrac Bell Co., Ltd., measurement principle: laser diffraction / scattering method). The diameter (hereinafter referred to as average particle diameter 2) was measured. The volatility of the average particle size was calculated from the following formula, and the volatility of the average particle size was evaluated according to the following criteria. Practically, it is preferable that it is 3 or more according to the following criteria.
Volatility of average particle size (%) = ((average particle size 2 / average particle size 1) -1) × 100
-Evaluation criteria-
5: Volatility of average particle size <10%
4: 10% ≤ average particle size volatility <20%
3: 20% ≤ average particle size volatility <50%
2: 50% ≤ volatility of average particle size <100%
1: Volatility of average particle size ≧ 100%

<Evaluation of film thickness uniformity>
The resin composition immediately after production was applied onto an 8-inch (203.2 mm) silicon wafer by a spin coating method so that the average film thickness was 400 nm to form a film. The film thickness of the film formed on the silicon wafer was measured using an optical film thickness meter F-50 (manufactured by Philmetrics Co., Ltd.). Measured at 10 points from one end of the silicon wafer to the other, | value of | average film thickness-maximum film thickness | (absolute value of difference between average film thickness and maximum film thickness), | value of | average film thickness-minimum film thickness | (Absolute value of the difference between the average film thickness and the minimum film thickness) was calculated respectively. The film thickness uniformity was evaluated according to the following criteria using the larger value of | average film thickness-maximum film thickness | and | average film thickness-minimum film thickness | (hereinafter referred to as Δt). .. Practically, it is preferable that it is 3 or more according to the following criteria.
5: Δt <3 nm
4: 3 nm ≤ Δt <5 nm
3: 5 nm ≤ Δt <10 nm
2:10 nm ≤ Δt <20 nm
1: Δt ≧ 20nm

As shown in the above table, the resin composition of the example had good dispersibility and film thickness uniformity.

(Example 1001)
The composition for forming an underlayer film is applied on a support having a diameter of 8 inches (= 203.2 mm) on which a silicon photodiode is formed by a spin coating method, and heated at 220 ° C. for 5 minutes using a hot plate to form a film thickness. A 5 nm underlayer film was formed. The green resin composition was applied onto the support with the underlayer film by a spin coating method so that the film thickness after film formation was 0.4 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed with an exposure amount of 1000 mJ / cm ² through a mask having a Bayer pattern on each side of 1.4 μm square. Then, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. Then, the green resin composition was patterned to form green pixels by heating at 200 ° C. for 5 minutes using a hot plate. Similarly, the red resin composition and the blue resin composition are patterned in the same process via a mask having a dot pattern of 1.4 μm square on each side to sequentially form red pixels and blue pixels to form green pixels, red pixels and the like. A color filter having blue pixels was formed. In this color filter, green pixels are formed by a Bayer pattern, and red pixels and blue pixels are formed by a dot pattern in an adjacent region thereof. The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability. As the green resin composition, the resin composition of Example 141 was used. As the red resin composition, the resin composition of Example 75 was used. As the blue resin composition, the resin composition of Example 82 was used.

In the above, using a KrF scanner exposure apparatus (FPA-6300ES6a, manufactured by Canon Inc.), light having a wavelength of 248 nm is irradiated with an exposure amount of 200 mJ / cm ² through a mask having a side of 0.7 μm for exposure. Even in this case, a solid-state image sensor with good image performance was obtained as described above.

(Composition for forming a lower layer film)
The composition for forming an underlayer film was produced by mixing the following materials in the ratio shown below and filtering with a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm. I used a thing.
-Composition of composition for forming underlayer film-
Resin A: 0.7 parts by mass Surfactant A: 0.8 parts by mass Propylene glycol monomethyl ether acetate (PGMEA): 98.5 parts by mass

The details of each material are as follows.
Resin A: Cyclomer P (ACA) 230AA (manufactured by Daicel Corporation, acid value = 30 mgKOH / g, weight average molecular weight 15000, PGME solution having a solid content concentration of 54% by mass)
-Surfactant A: 0.2% by mass PGMEA solution of a compound having the following structure (weight average molecular weight 14000, the numerical value of% indicating the ratio of repeating units is mol%. Fluorosurfactant)

Claims (15)

1. Contains pigments, resins, and solvents,
   The solvent is a resin composition containing an ether solvent represented by the formula (1);
   

   

   In formula (1), R ¹ represents a hydrocarbon group, and R ² to R ⁶ independently represent a hydrogen atom or a hydrocarbon group, respectively.
2. The resin composition according to claim 1, wherein the ether solvent represented by the formula (1) is at least one selected from anisole, phenetol, 4-methylanisole, 3-methylanisole and 2-methylanisole. ..
3. The resin composition according to claim 1 or 2, wherein the solvent contains 1 to 100% by mass of an ether-based solvent represented by the formula (1).
4. The resin composition according to claim 1 or 2, wherein the solvent contains 1 to 50% by mass of an ether solvent represented by the formula (1).
5. The resin composition according to any one of claims 1 to 4, wherein the resin composition contains 0.5% by mass or more of an ether solvent represented by the formula (1).
6. The solvent according to any one of claims 1 to 5, wherein the solvent includes an ether solvent represented by the formula (1) and a solvent other than the ether solvent represented by the formula (1). Resin composition.
7. The resin composition according to claim 6, wherein the solvent other than the ether solvent represented by the formula (1) contains propylene glycol monomethyl ether acetate.
8. The resin composition according to claim 7, which contains 100 to 9900 parts by mass of propylene glycol monomethyl ether acetate with respect to 100 parts by mass of the ether solvent represented by the formula (1).
9. The resin composition according to any one of claims 6 to 8, wherein the solvent other than the ether solvent represented by the formula (1) contains a ketone solvent.
10. The resin composition according to any one of claims 1 to 9, wherein the pigment contains at least one selected from a chromatic pigment and a near-infrared absorbing pigment.
11. The method for producing a resin composition according to any one of claims 1 to 10, wherein the pigment is dispersed in the presence of a resin and a solvent containing an ether solvent represented by the formula (1). Method for producing a resin composition including
    

    

    In formula (1), R ¹ represents a hydrocarbon group, and R ² to R ⁶ independently represent a hydrogen atom or a hydrocarbon group, respectively.
12. A method for producing a film, which comprises a step of applying the resin composition according to any one of claims 1 to 10 to a support.
13. A method for manufacturing an optical filter, including the method for manufacturing a film according to claim 12.
14. A method for manufacturing a solid-state image sensor, including the method for manufacturing a film according to claim 12.
15. A method for manufacturing an image display device including the method for manufacturing a film according to claim 12.