WO2022024970A1 - Resin composition, film, optical filter, solid-state imaging element, and image display device - Google Patents

Abstract

Provided is a resin composition comprising: a resin; a compound A having a molecular weight of 300 or less and represented by formula (1); and an organic solvent. Further provided are an optical filter, a solid-state imaging element, an image display device, and a film obtained using the resin composition. In formula (1), Q¹ represents an ethylenically-unsaturated bond-containing group, and L¹ represents a divalent linking group.

Description

Resin composition, film, optical filter, solid-state image sensor and image display device

The present invention relates to a resin composition. The present invention also relates to a film using a resin composition, an optical filter, a solid-state image pickup device, and an image display device.

Solid-state image sensors such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor) are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. Further, the solid-state image sensor is provided with an optical filter such as a color filter. The optical filter is manufactured by using, for example, a resin composition (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2020-086222

In recent years, the pattern size of optical filters used in solid-state image sensors and the like has been miniaturized. However, as the pattern size becomes finer, the adhesion to the support tends to be insufficient.

Further, when the present inventor examined the composition described in Patent Document 1, it was found that there is room for improvement in the adhesion of the obtained film to the support.

Therefore, an object of the present invention is to provide a resin composition, a film, an optical filter, a solid-state image pickup device, and an image display device capable of forming a film having excellent adhesion to a support.

According to the study of the present inventor, it has been found that the above object can be achieved by the resin composition described later, and the present invention has been completed. Therefore, the present invention provides the following.
<1> A resin composition containing a resin, a compound A having a molecular weight of 300 or less represented by the formula (1), and an organic solvent;

In the formula (1), Q ¹ represents an ethylenically unsaturated bond-containing group, and L ¹ represents a divalent linking group.
<2> The resin composition according to <1>, wherein the content of the compound A in the total solid content of the resin composition is 0.1 to 2000 mass ppm.
<3> The compound A is a compound represented by the formula (1-1), a compound represented by the formula (1-2), a compound represented by the formula (1-3), or a compound represented by the formula (1-3). The resin composition according to <1> or <2>, which is a compound represented by 4).

<4> Further, any one of <1> to <3>, which contains 0.1 to 300 mass ppm of compound B represented by the formula (2) and having a molecular weight of 300 or less in the total solid content of the resin composition. The resin composition according to one;

In the formula (2), Q ² represents an ethylenically unsaturated bond-containing group, and L ² represents a divalent linking group.
<5> The compound B is a compound represented by the formula (2-1), a compound represented by the formula (2-2), a compound represented by the formula (2-3), or a compound represented by the formula (2-3). The resin composition according to <1> or <2>, which is a compound represented by 4).

<6> The resin composition according to <4> or <5>, which contains 0.1 to 120 parts by mass of the compound B with respect to 100 parts by mass of the compound A.
<7> The invention according to any one of <4> to <6>, wherein the total content of the compound A and the compound B in the total solid content of the resin composition is 1 to 300 mass ppm. Resin composition.
<8> The resin composition according to any one of <1> to <7>, wherein the resin contains a group represented by the formula (3);

In formula (3), Q ³¹ represents an ethylenically unsaturated bond-containing group, L ³¹ represents a divalent linking group, R ³¹ represents a hydrogen atom or a substituent, and * represents a linking hand.
<9> The resin composition according to any one of <1> to <8>, wherein the resin contains a resin containing a repeating unit represented by the formula (3-1);

In formula (3-1), Q ³¹ represents an ethylenically unsaturated bond-containing group, L ³¹ and L ³² each independently represent a divalent linking group, and R ³¹ represents a hydrogen atom or a substituent. R ³² represents a hydrogen atom or a methyl group.
<10> The resin composition according to any one of <1> to <9>, wherein the resin composition contains 0.3 to 2.0% by mass of water.
<11> The resin composition according to any one of <1> to <10>, further comprising a coloring material.
<12> The resin composition according to any one of <1> to <11>, further comprising a polyfunctional polymerizable monomer having two or more ethylenically unsaturated bond-containing groups and a photopolymerization initiator.
<13> A film obtained by using the resin composition according to any one of <1> to <12>.
<14> An optical filter containing the film according to <13>.
<15> A solid-state image sensor including the film according to <13>.
<16> An image display device including the film according to <13>.

According to the present invention, it is possible to provide a resin composition, a film, an optical filter, a solid-state image pickup device, and an image display device capable of forming a film having excellent adhesion to a support.

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, 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 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 is characterized by containing a resin, a compound A having a molecular weight of 300 or less represented by the formula (1), and an organic solvent.

According to the resin composition of the present invention, it is possible to form a film having excellent adhesion to a support. Although the detailed reason why such an effect is obtained is unknown, when the resin composition contains the above-mentioned compound A, the hydroxy group of the compound A and the silanol group (SiOH) present on the surface of the support at the time of film formation and the like are unknown. It is presumed that the compound A undergoes a dehydration condensation reaction to form a chemical bond, and the ethylenically unsaturated bond-containing group of compound A reacts with a component in the membrane such as a resin to form a chemical bond. Therefore, it is presumed that a film having excellent adhesion to the support can be formed.

Further, when the resin composition of the present invention further contains the above-mentioned compound B, the adhesion of the obtained film to the support can be further improved.

Further, the resin composition of the present invention preferably contains 0.3 to 2.0% by mass of water. According to this aspect, the adhesion of the obtained membrane to the support can be further improved. The detailed reason why such an effect is obtained is unknown, but it is presumed as follows. That is, it is presumed that the water contained in the resin composition is not completely volatilized at the stage immediately after being applied with a spin coater or the like, and remains in the film. At the time of prebaking, the water remaining in this film contains the hydroxy group of compound A (in the case of further containing compound B, the hydroxy group of compound A or the epoxy group of compound B) and the silanol group existing on the surface of the support ( It is presumed that it functions as a catalyst when forming a chemical bond by causing a dehydration condensation reaction with SiOH) or the like. On the other hand, when the amount of water contained in the resin composition exceeds a predetermined amount, the amount of water remaining in the film immediately after application also increases. If the amount of water remaining in the membrane is too large, the hydroxy group of compound A (or the hydroxy group of compound A or the epoxy group of compound B when compound B is further contained) is present on the surface of the support at the time of prebaking. The reverse reaction of the dehydration condensation reaction that forms a chemical bond with the silanol group (SiOH), that is, the hydrolysis reaction becomes predominant, and the chemical bond formed between the surface of the support and compound A or the like is dissociated. It is presumed that it will be difficult to obtain sufficient adhesion. For this reason, it is presumed that better adhesion was obtained by including water in the above range.

The upper limit of the water content (moisture content) in the resin composition is preferably 1.5% by mass or less, more preferably 1.3% by mass or less. The lower limit of the water content is preferably 0.4% by mass or more, more preferably 0.5% by mass or more. In the present specification, the water content of the resin composition is a value measured by the Karl Fischer measuring method.

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 color pixel, a cyan color pixel, and a yellow pixel. The colored pixels of the color filter can be formed by using a resin composition containing a chromatic color material.

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 is more preferable, and 100 to 400 is particularly preferable. The near-infrared cut filter can be formed by using a resin composition containing a near-infrared absorbing color material.

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 850 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 be used as a resin composition for forming a transparent film, a light-shielding film, or the like.

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

<< 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 and the resin described in paragraph numbers 0022-0071 of JP-A-2018-010856 can also be used.

The resin composition of the present invention preferably contains a resin containing a group represented by the formula (3) (hereinafter, also referred to as a resin (3)). According to this aspect, it is possible to form a film having excellent adhesion to the support.

In formula (3), Q ³¹ represents an ethylenically unsaturated bond-containing group, L ³¹ represents a divalent linking group, R ³¹ represents a hydrogen atom or a substituent, and * represents a linking hand.

Examples of the ethylenically unsaturated bond-containing group represented by Q ³¹ of the formula (3) include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamide group. The (meth) allyl group, the (meth) acryloyl group and the (meth) acryloyloxy group are preferable, and the (meth) acryloyloxy group is more preferable.

As the divalent linking group represented by L ³¹ of the formula (3), an alkylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two or more of these are used. Examples include combined groups. The alkylene group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. The alkylene group may be linear, branched or cyclic, but is preferably linear or cyclic. The alkylene group may have a substituent. Examples of the substituent include a hydroxy group and the like. The divalent linking group represented by L ³¹ is preferably an alkylene group or a group in which two or more alkylene groups are bonded via a linking group, and more preferably an alkylene group. Examples of the linking group that binds the alkylene groups to each other include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.

R ³¹ of the formula (3) represents a hydrogen atom or a substituent. Examples of the substituent represented by R ³¹ include residues of various acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. It is preferable that R ³¹ of the formula (3) is a hydrogen atom. According to this aspect, it is possible to form a film having excellent adhesion to the support.

The resin (3) is preferably a resin containing a repeating unit represented by the formula (3-1).

In formula (3-1), Q ³¹ represents an ethylenically unsaturated bond-containing group, L ³¹ and L ³² each independently represent a divalent linking group, and R ³¹ represents a hydrogen atom or a substituent. R ³² represents a hydrogen atom or a methyl group.

Q ^{31, L 31 and R 31 of the formula (3-1) are synonymous with Q 31 , L 31 and R 31 of} the formula (3), respectively.

The divalent linking group represented by L ³² in the formula (3-1) 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, and an aliphatic hydrocarbon group is preferable. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The aliphatic hydrocarbon group may be linear, branched or cyclic, but is preferably linear 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 divalent linking group represented by L ³¹ is preferably a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a linking group. Examples of the linking group that binds the hydrocarbon groups to each other include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.

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 (3) may be a resin having an acid group. That is, the resin (3) may further have an acid group.

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, a commercially available product 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.

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 a 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 the polyester structure, More preferably, it is a polymer chain containing at least one structure selected from a polyether 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.

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 bonding position of Ac- ² ) with P10. The trivalent linking group represented by L ^12b is 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 with, 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 bonding position of Ac- ² ) with P10. The trivalent linking group represented by L ^12c is 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 ) contains 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 polymer 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 preferably contains a repeating unit containing an ethylenically unsaturated bond-containing group in the side chain. Further, the ratio of the repeating unit containing the ethylenically unsaturated bond ^- containing group in the side chain in all the repeating units constituting P10 is preferably 5% by mass or more, and more preferably 10% by mass or more. , 20% by mass or more is more preferable. 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.

Specific examples of the acidic graft resin include resins B-1 to B-7 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 a resin 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, a resin such as the above-mentioned acidic graft resin can also be used as a dispersant.

Dispersants are also available as commercial products, and specific examples thereof include DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111, 161 etc.) and Solsparse series manufactured by Japan Lubrizol Co., Ltd. (for example, DISPERBYK-111, 161 etc.). For example, Solsparse 76500) and the like. 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 1 to 45% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.

<< Compound A >>
The resin composition of the present invention contains a compound A having a molecular weight of 300 or less (hereinafter, also referred to as compound A) represented by the formula (1).

In the formula (1), Q ¹ represents an ethylenically unsaturated bond-containing group, and L ¹ represents a divalent linking group.

Examples of the ethylenically unsaturated bond-containing group represented by ^Q1 of the formula (1) include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamide group. The (meth) allyl group, the (meth) acryloyl group and the (meth) acryloyloxy group are preferable, and the (meth) acryloyloxy group is more preferable.

As the divalent linking group represented by L ¹ of the formula (1), an alkylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two or more of these are used. Examples include combined groups. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. The aliphatic hydrocarbon group may be linear, branched or cyclic, but is preferably linear 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. Examples of the divalent linking group represented by L ¹ include a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a linking group, and a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is preferable. Is more preferable. Examples of the linking group that binds the hydrocarbon groups to each other include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.

Specific examples of the compound A include compounds having the following structures. The compound represented by the formula (1-1) is glycerin monomethacrylate, the compound represented by the formula (1-2) is glycerin monoacrylate, and the compound represented by the formula (1-3) is 4-. It is (2,3-dihydroxypropoxy) butyl methacrylate, and the compound represented by the formula (1-4) is 4- (2,3-dihydroxypropoxy) butyl acrylate.

The compound A is a compound represented by the formula (1-1), a compound represented by the formula (1-2), a compound represented by the formula (1-3), or a compound represented by the formula (1-4). It is preferably a compound represented by the formula (1-1), more preferably a compound represented by the formula (1-4), and a compound represented by the formula (1-1). Is more preferable.

The content of compound A in the total solid content of the resin composition is preferably 0.1 to 2000 mass ppm. The upper limit is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and particularly preferably 250 mass ppm or less. The lower limit is preferably 10 mass ppm or more, more preferably 25 mass ppm or more, and further preferably 50 mass ppm or more.

<< Compound B >>
The resin composition of the present invention preferably contains compound B having a molecular weight of 300 or less (hereinafter, also referred to as compound B) represented by the formula (2). By using the compound A and the compound B in combination, a film having better adhesion can be formed.

In the formula (2), Q ² represents an ethylenically unsaturated bond-containing group, and L ² represents a divalent linking group.

Examples of the ethylenically unsaturated bond-containing group represented by ^Q2 of the formula (2) include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamide group. The (meth) allyl group, the (meth) acryloyl group and the (meth) acryloyloxy group are preferable, and the (meth) acryloyloxy group is more preferable.

As the divalent linking group represented by L ² in the formula (2), an alkylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two or more of these are used. Examples include combined groups. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. The aliphatic hydrocarbon group may be linear, branched or cyclic, but is preferably linear 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. Examples of the divalent linking group represented by L ² include a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a linking group, and a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is preferable. Is more preferable. Examples of the linking group that binds the hydrocarbon groups to each other include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.

Specific examples of the compound B include compounds having the following structures. The compound represented by the formula (2-1) is glycidyl methacrylate, the compound represented by the formula (2-2) is glycidyl acrylate, and the compound represented by the formula (2-3) is 4-hydroxybutyl. It is a methacrylate glycidyl ether, and the compound represented by the formula (2-4) is 4-hydroxybutyl acrylate glycidyl ether.

The compound B is a compound represented by the formula (2-1), a compound represented by the formula (2-2), a compound represented by the formula (2-3), or a compound represented by the formula (2-4). It is preferably a compound represented by the formula (2-1), more preferably a compound represented by the formula (2-4), and a compound represented by the formula (2-1). Is more preferable.

The content of compound B in the total solid content of the resin composition is preferably 0.1 to 300 mass ppm. The upper limit is preferably 100 mass ppm or less, and more preferably 10 mass ppm or less. The lower limit is preferably 0.2 mass ppm or more, and more preferably 0.3 mass ppm or more.

Further, it is preferable to contain 0.1 to 120 parts by mass of compound B with respect to 100 parts by mass of compound A. The upper limit of the content is preferably 60 parts by mass or less, more preferably 30 parts by mass or less, further preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less. The lower limit of the content is preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. According to this aspect, it is possible to form a film having better adhesion. Furthermore, the generation of development residue can be suppressed more effectively.

Further, the total content of the compound A and the compound B in the total solid content of the resin composition is preferably 1 to 300 mass ppm. The upper limit is preferably 250 mass ppm or less, more preferably 200 mass ppm or less, further preferably 100 mass ppm or less, and even more preferably 15 mass ppm or less. The lower limit is preferably 2 mass ppm or more, more preferably 3 mass ppm or more, and further preferably 5 mass ppm or more.

<< Polyfunctional polymerizable monomer >>
The resin composition of the present invention can contain a polyfunctional polymerizable monomer having two or more ethylenically unsaturated bond-containing groups (hereinafter, also referred to as a polyfunctional polymerizable monomer). Examples of the ethylenically unsaturated bond-containing group of the polyfunctional polymerizable monomer include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamide group. A (meth) allyl group, a (meth) acryloyl group and a (meth) acryloyloxy group are preferable, and a (meth) acryloyloxy group is more preferable. The polyfunctional polymerizable monomer used in the present invention is preferably a radically polymerizable monomer.

The molecular weight of the polyfunctional polymerizable monomer 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 polyfunctional polymerizable monomer 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 is not ethylenically. It is more preferable that the compound contains 3 to 6 saturated bond-containing groups. Further, the polyfunctional polymerizable monomer 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 polyfunctional polymerizable monomer include paragraph numbers 0995 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-029760A, and paragraph numbers 0254 to 0257 of JP2008-292970. Japanese Patent Laid-Open Nos. 2013-253224, Paragraph Nos. 0034 to 0038, Japanese Patent Laid-Open No. 2012-208494, Paragraph Nos. 0477, Japanese Patent Laid-Open No. 2017-048637, Japanese Patent No. 6057891, Japanese Patent No. 6031807, Japanese Patent Application Laid-Open No. 2017- Examples include the compounds described in Japanese Patent Publication No. 194662, the contents of which are incorporated herein by reference.

As the polyfunctional polymerizable monomer, dipentaerythritol tri (meth) acrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), 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 contain ethylene glycol and / or propylene glycol residues. Compounds having a structure bound to each other (for example, SR454 and SR499 commercially available from Sartmer) are preferable. As the polymerizable monomer, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toa Synthetic Co., Ltd.), 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 (Toa Synthetic Co., Ltd.) ), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. Can also be used.

Examples of the polyfunctional polymerizable monomer include trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, and isocyanuric acid ethylene oxide modified tri (meth) acrylate. It is also preferable to use a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. 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 Toa Synthetic 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.

As the polyfunctional polymerizable monomer, a polymerizable monomer having an acid group can also be used. By using a polymerizable monomer having an acid group, the resin composition 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 commercially available products of the polymerizable monomer having an acid group include Aronix M-305, M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). The acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g.

As the polyfunctional polymerizable monomer, a polymerizable monomer having a caprolactone structure can also be used. The polymerizable monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

As the polyfunctional polymerizable monomer, a polymerizable monomer having an alkyleneoxy group can also be used. As the polymerizable monomer having an alkyleneoxy group, a polymerizable monomer having an ethyleneoxy group and / or a propyleneoxy group is preferable, a polymerizable monomer 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 monomer having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartmer, and a trifunctional (meth) having three isobutyleneoxy groups. ) KAYARAD TPA-330, which is an acrylate, and the like.

As the polyfunctional polymerizable monomer, a polymerizable monomer having a fluorene skeleton can also be used. Examples of commercially available products of the polymerizable monomer 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 polyfunctional polymerizable monomer, it is also preferable to use a compound that does not substantially contain an environmentally regulatory 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.).

Examples of the polyfunctional polymerizable monomer include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765. Further, urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, it is also preferable to use a polymerizable monomer having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A No. 01-105238. The polyfunctional polymerizable monomers are 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- Commercially available products such as 600, T-600, AI-600, and LINK-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

The polyfunctional polymerizable monomer used in the resin composition of the present invention contains a trifunctional or lower polymerizable monomer C1 containing two or three ethylenically unsaturated bond-containing groups and four ethylenically unsaturated bond-containing groups. It is preferable to contain the above-mentioned tetrafunctional or higher polymerizable monomer C2. According to this aspect, the curing shrinkage of the film is appropriately suppressed and the adhesion to the support is improved, so that the effect of the present invention is more remarkably exhibited. When the polymerizable monomer C1 and the polymerizable monomer C2 are used in combination, the ratio of the two is preferably 10 to 1000 parts by mass, preferably 30 to 300 parts by mass, based on 100 parts by mass of the polymerizable monomer C1. It is more preferably parts, and even more preferably 50 to 200 parts by mass.

The content of the polyfunctional polymerizable monomer in the total solid content of the resin composition is preferably 0.1 to 40% 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 30% by mass or less, more preferably 20% by mass or less.

<< Photopolymerization Initiator >>
The resin composition of the present invention can contain 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 light 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-2004-534977, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-109766, compounds described in Japanese Patent Application Laid-Open No. 6065596, International Publication No. 2015. The compound described in / 152153, the compound described in International Publication No. 2017/051680, the compound described in JP-A-2017-198865, the compound described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, Examples thereof include the compounds described in International Publication No. 2013/167515. 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 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA PTOMER N-1919 (Co., Ltd.). Examples thereof include a photopolymerization initiator 2) manufactured by ADEKA and described in JP2012-014552A. 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. Represents a group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group or sulfamoyl group.
^RX2 contains 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 and an aryl. Represents a sulfonyl group, an acyloxy group or an amino group
^{RX3 to RX14 independently} represent hydrogen atoms or substituents;
However, at least one of ^RX10 to ^RX14 is an electron-withdrawing group.

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 functional 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 an organic solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the resin composition with time is improved. can. 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 30% 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 20% by mass or less, more preferably 15% by mass or less. In the resin composition of the present invention, only one type of photopolymerization initiator 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.

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

The coloring material preferably contains at least one selected from the group consisting of a chromatic color material, a black color material, and a near-infrared absorbing color material, and more preferably contains a chromatic color material. Further, the content of the chromatic color material in the color material is preferably 60% by mass or more, and more preferably 80% by mass or more. Such a resin composition can be preferably used as a resin composition for forming colored pixels of a color filter.

The coloring material may be a pigment or a dye. Pigments and dyes may be used in combination. Further, the pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, an inorganic pigment or a material in which a part of the organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing the inorganic pigment or the organic-inorganic pigment with an organic chromophore, the hue design can be facilitated.

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. When the average primary particle size of the pigment is in the above range, the dispersion stability of the pigment in the photosensitive composition is good. In the present invention, the primary particle size of the pigment can be obtained from an image 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.

It is preferable to use a coloring material containing a pigment. The content of the pigment in the coloring material is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and preferably 90% by mass or more. Especially preferable.

(Coloring material)
Examples of the chromatic color material include a color material having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, a yellow color material, an orange color material, a red color material, a green color material, a purple color material, a blue color material, and the like can be mentioned. Specific examples of the chromatic color material include those shown below.

Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35,35: 1,36,36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86, 93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128, 129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,215,228,231,232 (methine type), 233 (quinoline type), 234 ( Yellow pigments such as (aminoketone type), 235 (aminoketone type), 236 (aminoketone type).
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. 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 Red pigments such as 294 (xanthene type, Ultramarine, Blush Red), 295 (monoazo type), 296 (diazo type), 297 (aminoketone type).
C. I. Pigment Green 7,10,36,37,58,59,62,63,64 (phthalocyanine type), 65 (phthalocyanine type), 66 (phthalocyanine type) and other green pigments.
C. I. Pigment Violet 1,19,23,27,32,37,42,60 (triarylmethane type), 61 (xanthene type) and other purple pigments.
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 (monoazo system), A blue pigment such as 88 (methine type).

Further, as a green color material, halogenated zinc phthalocyanine having an average number of halogen atoms in one molecule of 10 to 14, a bromine atom of 8 to 12, and a chlorine atom of 2 to 5 on average. Pigments can also be used. Specific examples include the compounds described in International Publication No. 2015/118720. Further, as a green color material, the compound described in Chinese Patent Application No. 1069090227, the phthalocyanine compound having a phosphoric acid ester described in International Publication No. 2012/102395 as a ligand, and Japanese Patent Application Laid-Open No. 2019-008014. , The phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, and the like can also be used.

Further, as the blue color material, an aluminum phthalocyanine compound 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 color material, a nickel azobarbiturate complex having the following structure can also be used.

Further, as the yellow color material, 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. , The compounds described in paragraphs 0010 to 0062, 0138 to 0295 of JP-A-2017-171913, the compounds described in paragraphs 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 JP-A-2014-0226228. The quinophthalone compound described in 0058, the isoindolin 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. -Kinophthalone compound described in JP-A-197640, quinophthalone compound described in JP-A-2016-145282, quinophthalone compound described in JP-A-2014-0856565, quinophthalone compound described in JP-A-2014-021139, special The quinophthalone compound described in JP2013-209614, the quinophthalone compound described in JP2013-209435, the quinophthalone compound described in JP2013-181015, and the quinophthalone compound described in JP2013-061622. , A quinophthalone compound described in JP2013-032486, a quinophthalone compound described in JP2012-226110A, a quinophthalone compound described in JP-A-2008-074987, and a quinophthalone compound described in JP-A-2008-081565. Kinophthalone compound, quinophthalone compound described in JP-A-2008-074986, quinophthalone compound described in JP-A-2008-074985, quinophthalone compound described in JP-A-2008-054020, 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 Japanese Patent Application Laid-Open No. 6607427, and JP-A. Metin dyes described in JP-A-2019-073695, Metin dyes described in JP-A-2019-073696, Metin dyes described in JP-A-2019-073697, Metin dyes described in JP-A-2019-073698, Compounds described in Korean Publication No. 10-2014-0034963, compounds described in JP-A-2017-095076, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Patent No. 6607427. , The quinophthalone dimer described in JP-A-2020-033521 can also be used. Further, a multimerized version of these compounds is also preferably used from the viewpoint of improving the color value. Further, a compound represented by the following formula (QP1) and a compound represented by the following formula (QP2) can also be used.

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 a red color material, 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 Patent No. 6248838. , Diketopyrrolopyrrole compound described in WO2012 / 102399, diketopyrrolopyrrole compound described in WO2012 / 117965, naphtholazo compound described in JP2012-229344, patent No. 6516119. The red color material described in Japanese Patent No. 6525101, the red color material described in Japanese Patent No. 6525101, and the like 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, the diarylmethane compound described in Japanese Patent Publication No. 2020-504758 can also be used as the coloring material.

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.

Also, a dye can be used as a chromatic color material. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo compound, anilino azo compound, triarylmethane compound, anthraquinone compound, anthrapyridone compound, benzylidene compound, oxonol compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyrrolopyrazole azomethine compound, xanthene compound, Examples thereof include phthalocyanine compounds, benzopyran compounds, indigo compounds and pyromethene compounds. 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 chromatic color material may be used in combination of two or more. For example, C.I. I. Pigment Green7 and C.I. I. Pigment Green36 and C.I. I. Pigment Yellow 139 and C.I. I. A green color may be formed in combination with Pigment Yellow 185, and C.I. I. Pigment Green58 and C.I. I. Pigment Yellow150 and C.I. I. A green color may be formed in combination with Pigment Yellow 185.

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

(White color material)
White coloring materials 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, Examples thereof include hollow resin particles and inorganic pigments (white pigments) such as 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 core particles composed of polymer particles, and core and shell composite particles composed of a shell layer composed of inorganic nanoparticles 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 color material)
The black color material is not particularly limited, and known materials can be used. For example, examples of the inorganic black coloring material include carbon black, titanium black, graphite and the like, 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. Examples of the black color material include Color Index (CI) Pigment Black 1, 7 and the like. Titanium black preferably has a small primary particle size and an average primary particle size of each particle. Specifically, it is preferable that the average primary particle size is 10 to 45 nm. 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), Tilak D (Tilak) D (trade name: manufactured by Mitsubishi Materials Corporation). Product name: Ako Kasei Co., Ltd.) and the like. Examples of the organic black coloring material include a bisbenzofuranone compound, an azomethine compound, a perylene compound, an azo compound and the like, and a bisbenzofuranone compound and a perylene compound are preferable. Examples of the bisbenzofuranone compound are described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, International Publication No. 2014/208348, Japanese Patent Publication No. 2015-525260 and the like. Compounds are mentioned and are available, for example, as "Irgaphor Black" manufactured by BASF. Examples of the perylene compound include C.I. I. Pigment Black 31, 32 and the like can be mentioned. Examples of the azomethin compound include the compounds described in JP-A No. 01-17601, JP-A-02-0346664, and the like, and can be obtained as, for example, "Chromofine Black A1103" manufactured by Dainichiseika. Further, as the organic black color material, perylene black (Lumogen Black FK4280 or the like) described in paragraphs 0016 to 0020 of JP-A-2017-226821 may be used.

(Near infrared absorbing color material)
The near-infrared absorbing color material is preferably a pigment, more preferably an organic pigment. Further, the near-infrared absorbing color material is preferably a compound having a maximum absorption wavelength in the range of more than 700 nm and 1400 nm or less. The maximum absorption wavelength of the near-infrared absorbing color material is preferably 1200 nm or less, more preferably 1000 nm or less, and further preferably 950 nm or less. Further, the near-infrared absorbing color material 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. It is more preferably 0.03 or less, and particularly preferably 0.02 or less. 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 color material having excellent visible transparency and near-infrared shielding property can be obtained. The maximum absorption wavelength of the near-infrared absorbing color material and the value of the absorbance at each wavelength are values obtained from the absorption spectrum of the film formed by using the photosensitive composition containing the near-infrared absorbing color material.

The near-infrared absorbing color material is not particularly limited, but is limited to pyrolopyrrole compound, cyanine compound, squarylium compound, phthalocyanine compound, naphthalocyanine compound, quaterylene compound, merocyanine compound, croconium compound, oxonol compound, iminium compound, dithiol compound, and tria. Examples thereof include a reelmethane compound, a pyrromethene compound, an azomethin compound, an anthraquinone compound, a dibenzofuranone compound, and a dithiolene metal complex. Examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614, the compounds described in paragraphs 0037-0052 of JP2011-066731A, and International Publication No. 2015/166783. Examples thereof include the compounds described in paragraphs 0010 to 0033. Examples of the squarylium compound include the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraph numbers 0040 of International Publication No. 2016/181987. , The compound described in JP-A-2015-176046, the compound described in paragraph No. 0072 of International Publication No. 2016/190162, the compound described in paragraph No. 0196-0228 of JP-A-2016-0734649. , The compound described in paragraph No. 0124 of JP-A-2017-066963, the compound described in International Publication No. 2017/135359, the compound described in JP-A-2017-114956, the compound described in Japanese Patent Application Laid-Open No. 6197940, Examples thereof include the compounds described in International Publication No. 2016/120166. Examples of the cyanine compound include the compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, the compounds described in paragraph numbers 0026-0030 of JP-A-2002-194040, and JP-A-2015-172004. , The compound described in JP-A-2015-172102, the compound described in JP-A-2008-084246, the compound described in paragraph No. 0090 of International Publication No. 2016/190162, JP-A-2017-031394. Examples thereof include the compounds described in. Examples of the croconium compound include the compounds described in JP-A-2017-082029. Examples of the iminium compound include the compound described in JP-A-2008-528706, the compound described in JP-A-2012-02239, the compound described in JP-A-2007-09260, and International Publication No. 2018/043564. Examples thereof include the compounds described in paragraphs 0048 to 0063 of. Examples of the phthalocyanine compound include the compound described in paragraph No. 0093 of JP2012-077153, the oxytitanium phthalocyanine described in JP2006-343631, and paragraphs 0013 to 0029 of JP2013-195480. , The vanadium phthalocyanine compound described in Japanese Patent No. 6081771, and the compound described in International Publication No. 2020/071470. Examples of the naphthalocyanine compound include the compound described in paragraph No. 0093 of JP2012-07715. Examples of the dithiolene metal complex include the compounds described in Japanese Patent No. 5733804.

Examples of the near-infrared absorbing color material include a squarylium compound described in JP-A-2017-197437, a squarylium compound described in JP-A-2017-025311, a squarylium compound described in International Publication No. 2016/154782, and Patent No. 5884953. Squarylium compound described in Japanese Patent Publication No. 6036689, Squalylium compound described in Japanese Patent No. 581604, Squalylium compound described in International Publication No. 2017/213047, Squarylium compound described in paragraphs 0090 to 0107 of International Publication No. 2017/213047, The pyrrole ring-containing compound described in paragraphs 0019 to 0075 of Japanese Patent Application Laid-Open No. 2018-054760, the pyrrol ring-containing compound described in paragraph numbers 0078 to 0082 of JP-A-2018-040955, paragraphs of JP-A-2018-002773. Pyrrole ring-containing compounds described in Nos. 0043 to 0069, squarylium compounds having an aromatic ring at the amide α position described in paragraphs 0024 to 0086 of JP-A-2018-041047, and amides described in JP-A-2017-179131. Concatenated squalylium compound, compound having a pyrrolbis-type squalylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole-type squalylium compound described in JP-A-2017-082029, JP-A-2017-066120 Asymmetric compound described in paragraphs 0027 to 0114 of Japanese Patent Application Laid-Open No. 2017-067963, pyrrol ring-containing compound (carbazole type) described in JP-A-2017-066963, phthalocyanine compound described in Japanese Patent No. 6251530, international publication. The vanadium phthalocyanine compound described in No. 2020/071486, the phthalocyanine compound described in International Publication No. 2020/071470, and the like can also be used.

The content of the coloring material in the total solid content of the resin composition is preferably 20 to 90% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less.
Further, the content of the pigment in the total solid content of the resin composition is preferably 20 to 90% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less.
The content of the dye in the coloring material is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

<< Pigment derivative >>
The resin composition of the present invention preferably contains a pigment derivative. 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 derivatives 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, dianthraquinone pigment skeleton, quinacridone pigment skeleton, dioxazine pigment skeleton, perinone pigment skeleton, perylene pigment skeleton , Thiadine indigo pigment skeleton, thioindigo pigment skeleton, isoindolin pigment skeleton, isoindolinone pigment skeleton, quinophthalone pigment skeleton, iminium pigment skeleton, dithiol pigment skeleton, triarylmethane pigment skeleton, pyrromethene pigment skeleton, etc. Skeleton, diketopyrrolopyrrole pigment skeleton, pyrolopyrrole pigment skeleton, benzoisoindole pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, thiazineindigo pigment skeleton, azo pigment skeleton, quinophthalone pigment skeleton or quinacridone pigment skeleton preferable. Examples of the acid group include a sulfo group, a carboxyl group, a phosphoric 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. 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 contained. 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 Application Laid-Open No. 10-195326, paragraph numbers 0086 to 0998 of International Publication No. 2011/024896, paragraph numbers 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. Examples thereof include the compounds described in JP-A-2015-172732, JP-A-2014-199308, JP-A-2014-085562, JP-A-2014-055351, and JP-A-2008-081565.

The content of the pigment derivative in the total solid content of the resin composition is preferably 0.3 to 20% by mass. The lower limit is preferably 0.6% by mass or more, and more preferably 0.9% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 12.5% by mass or less, and further preferably 10% by mass or less. The content of the pigment derivative is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15% by mass or less. In the resin composition of the present invention, only one pigment derivative may be used, or two or more pigment derivatives may be used in combination. When two or more types are used in combination, the total amount thereof is preferably in the above range.

<< Specific amine compound >>
The resin composition of the present invention contains a compound having three or more basic groups in one molecule, an amine value of 2.7 mmol / g or more, and a molecular weight of 100 or more (hereinafter, also referred to as a specific amine compound). You can also.

The molecular weight of the specific amine compound 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 the specific amine compound can be calculated from the structural formula, the molecular weight of the specific amine compound 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 the specific amine compound is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and further preferably 15 mmol / g or more.

The number of basic groups contained in the specific amine compound is preferably 4 or more, more preferably 6 or more, and further preferably 10 or more.

The basic group of the specific amine compound is preferably an amino group. Further, the specific amine compound is preferably a compound having a primary amino group, more preferably a compound containing a primary amino group and a tertiary amino group, respectively, and a primary amino group and a secondary amino. It is more preferable that the compound contains a group and a tertiary amino group, respectively.

Further, the amino group contained in the specific amine compound may be a cyclic amino group. The cyclic amino group may be an aliphatic cyclic amino group such as a piperidino group or an aromatic cyclic amino group such as a pyridyl group. The cyclic amino group is preferably a cyclic amino group having a 5-membered ring or a 6-membered ring structure, more preferably a cyclic amino group having a 6-membered ring structure, and an aliphatic cyclic amino having a 6-membered ring structure. It is more preferably a group. The cyclic amino group preferably has a hindered amine structure, and particularly preferably has a 6-membered ring hindered amine structure. As the hindered amine structure, it is preferable that the two carbon atoms in the ring structure adjacent to the nitrogen atom of the cyclic amino group have a substituent such as an alkyl group. Examples of the cyclic amino group having a hindered amine structure include 1,2,2,6,6-pentamethylpiperidyl group, 2,2,6,6-tetramethylpiperidyl group and 1,2,6,6-trimethylpiperidyl. Group, 2,6-dimethylpiperidyl group, 1-methyl-2,6-di (t-butyl) piperidyl group, 2,6-di (t-butyl) piperidyl group, 1,2,2,5,5- Examples thereof include a pentamethylpyrrolidyl group and a 2,2,5,5-tetramethylpyrrolidyl group. Of these, 1,2,2,6,6-pentamethylpiperidyl group or 2,2,6,6-tetramethylpiperidyl group is preferable, and 1,2,2,6,6-pentamethylpiperidyl group is preferable. More preferred.

The specific amine compound is preferably polyalkyleneimine because it can further improve the storage stability of 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 number of carbon atoms of the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2. 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 the specific amine compound 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.

Further, the content of the specific amine compound is preferably 0.5 to 10 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 8 parts by mass or less, more preferably 7% by mass or less, and further preferably 5 parts by mass or less.

Further, the content of the specific amine compound is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the graft resin having an acid group. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more. The upper limit is preferably 45 parts by mass or less, more preferably 40% by mass or less, and further preferably 30 parts by mass or less.

<< 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 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). But it may be. The weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more 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 type. Epoxy resin, glycidylamine-based epoxy resin, epoxy resin obtained by glycidylizing halogenated phenols, condensate of silicon compound having an epoxy group and other silicon compounds, polymerizable unsaturated compound having an epoxy group and other 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 Dicelle Co., Ltd.), 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 Nichiyu Co., Ltd., 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, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 15% by mass or less, and more preferably 10% by mass or less. The compound having a cyclic ether group may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount thereof is within the above range.

<< Organic Solvent >>
The resin composition of the present invention contains an organic solvent. Examples of the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and the like. For these details, paragraph No. 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol acetate, butylcarbi Tall acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methylethylketone, Gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane diacetate-1,3-diyl, dipropylene glycol methyl ether acetate, diacetone alcohol and the like can be mentioned. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 parts by mass (parts) with respect to the total amount of organic solvent. Per millision) or less, 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, an organic solvent at the mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).

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

The organic solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.

The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.

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

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 corresponding 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 include a raw material stage, a product obtained by reacting the raw materials (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a resin composition stage prepared by mixing these compounds. It is possible at any stage of.

<< 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 an alkoxysilane compound having an epoxy group described in Japanese Patent No. 5, a compound described in paragraphs 805 to 0092 of Japanese Patent No. 5765059, and a carboxyl group-containing epoxy curing agent described in JP-A-2017-036379. When the curing accelerator is contained, 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.

<< 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. Details thereof are described in paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-066814, and paragraph numbers 0061 to 0080 of JP2016-162946. These compounds are incorporated herein by reference. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016). Further, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 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. In the resin composition of the present invention, 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. When the polymerization inhibitor is contained, 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.

<< Silane Coupling Agent >>
The resin composition of the present invention can contain a silane coupling agent. In the present invention, 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 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. When a silane coupling agent is contained, the content of the silane coupling agent in the total solid content of the resin composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. preferable. The silane coupling agent 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.

<< 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 silicon-based surfactant can be used. 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.

In the present invention, the liquid characteristic (particularly, fluidity) is further improved by containing the fluorine-based surfactant in the resin composition in which the surfactant is preferably a fluorine-based surfactant, and the liquid saving property is further improved. Can be improved. It is also possible to form a film having a small thickness unevenness.

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, Megafuck 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-41, R-41-LM, R-01, R-40, R -40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Co., Ltd.), Fluorard 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 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (manufactured by NEOS), etc. Can be mentioned.

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. For such a fluorine-based surfactant, the description in JP-A-2016-216602 can be referred to, and the content thereof is incorporated in the present specification.

As the fluorine-based surfactant, a block polymer can also be used. For example, the compounds described in JP-A-2011-089090 can be mentioned. 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 compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, for example, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. , RS-72-K and the like. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and the like. 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 (Fuji Film Japanese) Kojunyaku Kogyo), Pionin D-6112, D-6112-W, D-6315 (Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (Nisshin Chemical Industry Co., Ltd.), etc. Can be mentioned.

Examples of the silicon-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all of which are Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, (Shinetsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all 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. In the resin composition of the present invention, 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.

<< Other ingredients >>
The resin composition of the present invention may be used as a sensitizer, a curing accelerator, a thermosetting accelerator, a plasticizer and other auxiliaries (for example, conductive particles, a filler, an antifoaming agent, a flame retardant), if necessary. , Leveling agent, peeling accelerator, fragrance, surface tension adjusting agent, 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 descriptions of Nos. 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification. In addition, 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).

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, compounds described in paragraph numbers 0025 to 0039 of International Publication No. 2017/164127, compounds described in paragraphs 0034 to 0047 of JP-A-2017-186546, 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. , The compounds described in paragraph Nos. 0103 to 0153 of JP2011-253174A, and the like.

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. Further, JP-A-2012-153796, 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 perfluoroalkyl sulfonic acid and its salt, and a compound that can substitute for perfluoroalkyl carboxylic acid and its salt, perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic 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 JP-A-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.

<Preparation method of resin composition>
The resin composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the resin composition, all the components may be simultaneously dissolved and / or dispersed in an organic solvent to prepare a resin composition, or if necessary, each component may be appropriately dissolved in two or more solutions or dispersions. However, these may be mixed at the time of use (at the time of application) to prepare a resin composition.

Further, when preparing the resin composition, it is preferable to include a process of dispersing the organic pigment. In the process of dispersing the organic pigment, the mechanical force used for dispersing the organic pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes 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 organic pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter and to process 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 organic pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology and industry centered on suspension (solid / liquid dispersion system)". Practical application The process and disperser described in Section 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 organic 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.

When preparing the resin composition, it is preferable to filter 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.

<Membrane>
The film of the present invention is a film obtained from the above-mentioned resin composition of the present invention. The film thickness of the film of the present invention can be appropriately adjusted according to the intended 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 of the present invention can be used for a color filter, a near-infrared transmission filter, a near-infrared cut filter, a black matrix, a light-shielding film, and the like. The film of the present invention can be preferably used as a colored pixel of a color filter. Examples of the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta color pixel, a cyan color pixel, and a yellow pixel.

<Membrane manufacturing method>
Next, the method for producing the film of the present invention will be described. The film of the present invention can be produced through a step of applying the resin composition of the present invention. The film manufacturing method 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) and ArF line (wavelength 193 nm), 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 oxygen concentration performed 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, and for example, the illuminance may be 10,000 W / m ² when the oxygen concentration is 10% by volume, the illuminance may be 20000 W / m ² when the oxygen concentration is 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.

<Optical filter>
The optical filter of the present invention has the above-mentioned film of the present invention. Examples of the type of the 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.

The optical filter can be used for solid-state image pickup devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), image display devices, and the like.

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 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 width of the pixels included in the optical filter is preferably 0.4 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. The Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.

It is preferable that each pixel included in the optical filter has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less. The lower limit is not specified, but it is preferably 0.1 nm or more, for example. The surface roughness of the pixel can be measured using, for example, an AFM (atomic force microscope) Measurement 3100 manufactured by Veeco. Further, the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110 °. The contact angle can be measured using, for example, a contact angle meter CV-DT · A type (manufactured by Kyowa Interface Science Co., Ltd.). Further, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably ^{109 Ω · cm or more, and more preferably 10 11 Ω} · cm or more. The upper limit is not specified, but it is preferably 10 ¹⁴ Ω · cm or less, for example. The volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).

In the optical filter, a protective layer may be provided on the surface of the film of the present invention. By providing the protective layer, various functions such as oxygen blocking, low reflection, prohydrophobicization, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of the method for forming the protective layer include a method of applying a resin composition for forming a protective layer to form the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. The components constituting the protective layer include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and polyimide. Resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples thereof include resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ , and the like, and two or more of these components may be contained. For example, in the case of a protective layer for the purpose of blocking oxygen, it is preferable that the protective layer contains a polyol resin, SiO ₂ , and Si ₂ N ₄ . Further, in the case of a protective layer for the purpose of reducing reflection, it is preferable that the protective layer contains a (meth) acrylic resin and a fluororesin.

The protective layer may be an additive such as organic / inorganic fine particles, an absorber for light of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjusting agent, an antioxidant, an adhesive, and a surfactant, if necessary. May be contained. Examples of organic / inorganic fine particles include polymer fine particles (for example, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , Magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate and the like. A known absorber can be used as the absorber of light having a specific wavelength. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer.

Further, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.

The optical filter may have a base layer. 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. The surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.

The optical 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.

<Solid image sensor>
The solid-state image sensor of the present invention has the above-mentioned film of the present invention. The configuration of the solid-state image pickup device of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state image pickup device, 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.

<Image display device>
The image display device of the present invention has the above-mentioned film of the present invention. 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 specifically described below with reference to examples. 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.

<Evaluation of resin>
(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) of the resin was calculated by GPC (Gel Permeation Chromatography) measurement under the following measurement conditions.
Equipment: HLC-8220GPC (manufactured by Tosoh Corporation)
Detector: Differential refractometer (RI detector)
Pre-column: TSKGUARD COLUMN MP (XL) 6 mm x 40 mm (manufactured by Tosoh Corporation)
Sample side column: The following 4 columns are directly connected [all manufactured by Tosoh Corporation]
TSK-GEL Multipore-HXL-M 7.8mm x 300mm
Reference side column: Same as sample side column Constant temperature bath temperature: 40 ° C
Mobile phase: tetrahydrofuran Sample side mobile phase flow rate: 1.0 mL / min Reference side mobile phase flow rate: 0.3 mL / min Sample concentration: 0.1% by mass
Sample injection amount: 100 μL
Data collection time: 16 to 46 minutes after sample injection Sampling pitch: 300 ms (milliseconds)

(Acid value)
The acid value of the resin was determined by neutralization titration using an aqueous sodium hydroxide solution. Specifically, the obtained resin is dissolved in a solvent and titrated with an aqueous solution of sodium hydroxide using a potential difference measurement method to calculate the number of millimoles of the acid contained in 1 g of the solid content of the resin, and then the number of millimoles is calculated. , The value was determined by multiplying the molecular weight of potassium hydroxide (KOH) by 56.1.

<Measurement method of C = C value (base value containing ethylenically unsaturated bond)>
The C = C value (base value containing ethylenically unsaturated bond) of the resin was calculated from the raw materials used for the synthesis of the resin.

<Manufacturing of resin solution>
[Production Example 1-1] Production of resin solutions (B-1-1) to (B-1-6), (B-1-c) A separable flask equipped with a cooling tube is prepared as a reaction tank, and the other , 176.5 parts by mass of benzyl methacrylate (hereinafter referred to as "BzMA"), 40.0 parts by mass of methacrylic acid (hereinafter referred to as "MAA"), t-butylperoxy-2-ethylhexa as a monomer dropping tank. A mixture of 4 parts by mass of Noate (“Perbutyl O” manufactured by Nippon Oil &Fats; hereinafter referred to as “PBO”) and 60 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) was prepared by stirring. As a chain transfer agent dropping tank, 8 parts by mass of n-dodecanethiol (hereinafter referred to as "n-DM") and 32 parts by mass of PGMEA were well stirred and mixed. After charging 375 parts by mass of PGMEA into the reaction vessel and substituting with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction vessel became stable at 90 ° C., dropping from the monomer dropping tank and the chain transfer agent dropping tank to the reaction tank was started. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, the reaction solution was cooled to room temperature. 1000 parts by mass of water was added to the cooled reaction solution, the precipitated solid (polymer) was collected by filtration, and the collected solid was washed twice with 100 parts by mass of ethanol and once with 500 parts by mass of water. The resin B-1 having the following structure was obtained. The weight average molecular weight (Mw) of the obtained resin B-1 was 18,500, and the acid value was 106 mgKOH / g.

After dissolving the purified resin B-1 obtained by the above procedure in PGMEA, glycerin monomethacrylate (compound (1-1) having the following structure, hereinafter referred to as "GLA") PGMEA solution and glycidyl methacrylate ( A PGMEA solution of a compound (2-1) having the following structure (hereinafter referred to as “GMA”) is added, and the resin concentration (solid content concentration) of the finally obtained resin solution is 30%, and each component Resin solutions (B-1-1) to (B-1-6) were produced so that the content was as shown in the table below.
Further, the purified resin B-1 obtained by the above procedure was dissolved in PGMEA to adjust the resin concentration (solid content concentration) to 30% by mass to produce a resin solution (B-1-c). The resin solution (B-1-c) is one to which neither GLA nor GMA component is added.

In the table below, the contents of GLA and GMA in each resin solution are the results quantified by liquid high performance chromatography (HPLC). Since the lower limit of detection of each component by the HPLC method was 0.1 mass ppm, when it was lower than the lower limit of detection, it was described as "<0.1" in the table below. Further, among the components corresponding to compound A contained in each resin solution, the components other than GLA were below the lower limit of detection. Therefore, the content of GLA corresponds to the content of compound A. Further, among the components corresponding to compound B contained in each resin composition, the components other than GMA were below the lower limit of detection. Therefore, the total amount of GMA corresponds to the content of compound B.

[Production Example 1-2] Production of resin solution (B-2-1) A separable flask equipped with a cooling tube is prepared as a reaction tank, while dimethyl-2,2'-[oxybis (Oxybis) is used as a monomer dropping tank. Methylene)] 30.7 parts by mass of bis-2-propenoate, 43.1 parts by mass of MAA, 14.3 parts by mass of methyl methacrylate (hereinafter abbreviated as "MMA"), 113.5 parts by mass of BzMA, Prepare a mixture of 4 parts by mass of PBO and 60 parts by mass of diethylene glycol dimethyl ether (hereinafter referred to as "DMDG") by stirring, and prepare 8 parts by mass of n-DM and 32 parts by mass of DMDG as a chain transfer agent dropping tank. A mixture was prepared by stirring. After charging 375 parts by mass of DMDG into the reaction vessel and substituting with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction vessel became stable at 90 ° C., dropping from the monomer dropping tank and the chain transfer agent dropping tank to the reaction tank was started. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 50.9 parts by mass of GMA, 0.4 parts by mass of 2,2'-methylenebis (4-methyl-6-t-butylphenol) (hereinafter referred to as "MBMTB"), and triethylamine (hereinafter referred to as "TEA") were added to the reaction vessel. It was charged with 0.8 parts by mass and reacted at 110 ° C. for 3 hours as it was. After confirming the completion of the reaction by measuring the acid value of the reaction solution, 155 parts by mass of DMDG was added to the reaction solution and the mixture was cooled to room temperature. 1000 parts by mass of water was added to the cooled reaction solution, the precipitated solid (polymer) was collected by filtration, and the collected solid was washed twice with 100 parts by mass of ethanol and once with 500 parts by mass of water. , Resin B-2 having the following structure was obtained. The weight average molecular weight (Mw) of the obtained resin B-2 was 18,000, and the acid value was 32 mgKOH / g.

After dissolving the purified polymer powder obtained by the above procedure in PGMEA, the PGMEA solution of GLA and the PGMEA solution of GMA are further added, and the resin concentration (solid content) of the finally obtained resin solution is added. A resin solution (B-2-1) was produced so that the concentration) was 30% and the content of each component was the amount shown in the table below.
Of the components corresponding to compound A contained in the resin solution (B-2-1), the components other than GLA were below the lower limit of detection. Therefore, the content of GLA corresponds to the content of compound A. Further, among the components corresponding to compound B contained in the resin solution (B-2-1), the components other than GMA were below the lower limit of detection. Therefore, the total amount of GMA corresponds to the content of compound B.

[Production Example 1-3] Production of resin solution (B-3-1) In a three-necked flask, 30.4 parts by mass of a macromonomer represented by the following formula (MM), ω-carboxy-polycaprolactone monoacrylate (Toa). 51 parts by mass of Aronix M-5300 (manufactured by Synthetic Co., Ltd.) and PGMEA were introduced to obtain a mixture. The above mixture was stirred while blowing nitrogen.

Next, the temperature of the mixture was raised to 75 ° C. while flowing nitrogen gas into the flask. Next, 0.82 parts by mass of n-DM and then 0.43 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., V-601) were added to the mixture. Was added, and the polymerization reaction was started. After heating the mixture at 75 ° C. for 2 hours, an additional 0.43 parts by weight of 2,2'-azobis (methyl 2-methylpropionate) was added to the mixture. After 2 hours, an additional 0.43 parts by weight of 2,2'-azobis (methyl 2-methylpropionate) was added to the mixture. After the reaction for another 2 hours, the temperature of the mixture was raised to 90 ° C. and the mixture was stirred for 3 hours. By the above operation, the polymerization reaction was completed. After completion of the polymerization reaction, 9.6 parts by mass of dimethyldodecylamine as an amine compound and 0.3 parts by mass of 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) as a polymerization inhibitor under air. After the addition, 9 parts by mass of 4-hydroxybutyl acrylate glycidyl ether (compound (2-4) having the following structure, hereinafter referred to as 4HBAGE) was added dropwise.

After completion of the dropping, the reaction was continued at 90 ° C. for 24 hours under air, the completion of the reaction was confirmed by acid value measurement, and the reaction solution was cooled to room temperature. 1000 parts by mass of water was added to the cooled reaction solution, the precipitated solid (polymer) was collected by filtration, and the collected solid was washed twice with 100 parts by mass of ethanol and once with 500 parts by mass of water. The resin B-3 having the following structure was obtained. The weight average molecular weight (Mw) of the obtained resin B-3 was 17,200, and the acid value was 70 mgKOH / g.

After dissolving the purified resin B-3 powder obtained by the above procedure in PGMEA, further 4- (2,3-dihydroxypropoxy) butyl acrylate (compound (1-4) having the following structure, the following The PGMEA solution (referred to as "4HBAGE-O") and the PGMEA solution of 4HBAGE are added, and the resin concentration (solid content concentration) of the finally obtained resin solution is 30%, and the content of each component is high. A resin solution (B-3-1) was produced so that the amount of the resin solution was as shown in the table below.

Of the components corresponding to compound A contained in the resin solution (B-3-1), the components other than 4HBAGE-O were below the lower limit of detection. Therefore, the content of 4HBAGE-O corresponds to the content of compound A. Further, among the components corresponding to compound B contained in the resin solution (B-3-1), the components other than 4HBAGE were below the lower limit of detection. Therefore, the total amount of 4HBAGE corresponds to the content of compound B.

[Production Example 1-4] Production of resin solution (B-4-1) 8 parts by mass of 3-mercapto-1,2-propanediol in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer. , 12 parts by mass of pyromellitic anhydride, 80 parts by mass of PGMEA, and 0.2 parts by mass of monobutyltin oxide as a catalyst were charged, replaced with nitrogen gas, and then reacted 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, 30 parts by mass of methyl methacrylate, 10 parts by mass of t-butyl acrylate, 10 parts by mass of ethyl acrylate, 5 parts by mass of methacrylic acid, 10 parts by mass of benzyl methacrylate, and 35 parts by mass of 2-hydroxyethyl methacrylate. After charging, the inside of the reaction vessel was heated to 80 ° C., 1 part by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). It was confirmed by solid content measurement that 95% had reacted. Next, the inside of the flask was replaced with air, and 35.0 parts by mass of 2-methacryloyloxyethyl isocyanate and 0.1 part by mass of hydroquinone were charged and reacted at 70 ° C. for 4 hours (third step). After confirming that the peak of 2270 cm ^-1 based on the isocyanate group disappeared by infrared absorption spectroscopy, the reaction solution was cooled to obtain a resin B-4 having the following structure. The acid value of the obtained resin B-4 was 40 mgKOH / g, the weight average molecular weight was 12000, and the double bond equivalent was 692 g / mol.

In formula (B-4), one of * 1 and * 2 is bonded to * 5 or * 6 to form a polyester main chain, and the other is bonded to * 3 or * 4 to form a polyester main chain. Is forming. In * 3 and * 4, one of them is bonded to * 1 or * 2 to form a polyester main chain, and the other is integrated with an OH group to form a carboxylic acid. One of * 5 and * 6 is bonded to * 1 or * 2 to form a polyester main chain, and the other is integrated with an OH group to form a carboxylic acid.

<Manufacturing of refined pigments>
[Manufacturing Example 2-1]
(Manufacturing of refined pigment (PR254M))
C. I. 100 parts by mass of Pigment Red 254 (“B-CF” manufactured by BASF), 1200 parts by mass of sodium chloride, and 120 parts by mass of diethylene glycol were charged in a 1-gallon kneader made of stainless steel (manufactured by Inoue Seisakusho) and 4 at 60 ° C. Time kneaded. The obtained kneaded composition was put into 3000 parts by mass of warm water, stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours to make a fine pigment. (PR254M) was obtained.

[Manufacturing Examples 2-2-2-23]
In Production Example 2-1 above, the same treatment as in Production Example 2-1 was carried out except that the pigment used was changed from Pigment Red 254 to the pigment shown in the table below to obtain each miniaturized pigment.

<Manufacturing of pigment dispersion>
[Manufacturing Example 3-1]
(Manufacturing of Pigment Dispersion Liquid (GB-1))
The raw materials shown below were mixed by the mass parts shown below, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 3 hours using zirconia beads having a diameter of 0.5 mm. Then, the obtained mixture was filtered through a filter having a pore size of 5.0 μm to produce a pigment dispersion liquid (GB-1).
Micronized pigment (PG36M): 11.0 parts by mass Derivative 1: 0.7 parts by mass Resin solution (B-5-1): 6.7 parts by mass Resin solution (B-1-1): 6.7 parts by mass PGMEA: 74.9 parts by mass

Here, the derivative 1 is a compound represented by the following structural formula. The resin solution B-5-1 is a 30% by mass PGMEA solution of resin B-5 (weight average molecular weight 23000, acid value 50 mgKOH / g) having the following structure.

[Manufacturing Examples 3-2 to 3-45]
Each dispersion was prepared by the same method as in Production Example 3-1 above, except that the types and amounts (parts by mass) of the finely divided pigments, derivatives, resin solutions, and solvents used were changed as shown in the table below. Manufactured.

In the above table, TiB is titanium oxynitride particles (manufactured by Mitsubishi Materials Electronics Co., Ltd.), CB is carbon black particles (manufactured by Cabot, average primary particle diameter 15 nm), and ZrO ₂ is zirconium oxide particles (manufactured by Shin Nihon Denko Co., Ltd., average 1). (Secondary particle diameter 20 nm), TiO ₂ is titanium oxide particles (manufactured by Ishihara Sangyo Co., Ltd., TTO-51 (C), average primary particle diameter 10 to 30 nm, surface alumina / stearic acid treated product). Derivatives 2 to 7 are compounds represented by the following structural formulas.

<Manufacturing of resin composition>
[Manufacturing Example 4-1]
(Manufacturing of resin composition (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1 μm to produce a resin composition (GR-1).
Pigment dispersion (GB-1): 44.5 parts by mass Pigment dispersion (YB-1): 40.5 parts by mass Resin solution (B-1-1): 2.3 parts by mass Polymerizable monomer (M-1) ): 1.2 parts by mass Photopolymerization initiator (I-1): 0.6 parts by mass Ultraviolet absorber (U-1): 0.4 parts by mass Surface active agent (S-1): 4.2 parts by mass Polymerization Initiator (IN-1): 0.005 parts by mass PGMEA: 6.3 parts by mass

Here, the abbreviations of various materials represent the following, respectively.
Polymerizable Monomer (M-1): 7: 3 Mixture of Dipentaerythritol Hexaacrylate (DPHA) and Dipentaerythritol Pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku)
Photopolymerization Initiator (I-1): Irgacure OXE-01 (manufactured by BASF)
UV absorber (U-1): Triazine-based UV absorber "Tinuvin 477" (manufactured by BASF)
Surfactant (S-1): A 1% by mass PGMEA solution of a compound having the following structure (Mw = 14000, the numerical value of% indicating the ratio of repeating units is mol%).

Polymerization inhibitor (IN-1): p-methoxyphenol

[Manufacturing Examples 4-2 to 4-48]
(Manufacturing of polymerizable composition)
A resin composition was produced by the same method as in Production Example 4-1 above, except that the material used was changed to the material shown in the table below.

[Manufacturing Example 4-49]
The resin composition (GR-9) obtained in Production Example 4-9 was dehydrated by adding Molecular Sieve 3A (manufactured by Nacalai Tesque) to produce a resin composition (GR-9dh).

In the above table, the abbreviations of various materials represent the following, respectively.
Polymerizable Monomer (M-2): Trimethylolpropane Triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMPT)
Polymerizable monomer (M-3): Compound represented by the following formula (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH-12E)

Photopolymerization Initiator (I-2): Irgacure OXE-02 (manufactured by BASF)
Photopolymerization initiator (I-3): A compound having the following structure

Photopolymerization Initiator (I-4): Omnirad 369 (manufactured by IGM Resins B.V.)
Photopolymerization initiator (I-5): A compound having the following structure

Additive (AD-1): Pionin D6112W (Made by Takemoto Oil & Fat, aryl phenyl ether type nonionic surfactant)
Additive (AD-2): Ultrapure water

<Evaluation of resin composition>
(Measurement of content and water content of GLA, GMA, 4HBAGE-O and 4HBAGE)
High performance liquid chromatography (HPLC) was used to quantify the contents of GLA, GMA, 4HBAGE-O and 4HBAGE contained in each of the prepared resin compositions. The quantitative results are summarized in the table below. Since the lower limit of detection of each component by the HPLC method was 0.1 mass ppm, when it was lower than the lower limit of detection, it was described as "<0.1" in the table below.
In addition, the amount of water contained in each resin composition was quantified by the Karl Fischer measurement method. The measurement results of the water content are also shown in the table below.

(Evaluation of adhesion)
A spin coater was used to make each resin composition 4 μm in thickness after prebaking each resin composition on a silicon wafer with a diameter of 8 inches (203.2 mm) having a 400 nm-thick thermal oxide film (SiO ₂ film) formed on the surface. And heat-treated (pre-baked) for 120 seconds using a hot plate at 110 ° C.
Next, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), exposure (exposure amount) of 365 nm wavelength light is performed through a pattern mask forming 25 lines having a width of 100 μm and a length of 1000 μm. 50 to 1700 mJ / cm ² ).
Next, the composition layer after exposure was developed using a developing device (Act8 manufactured by Tokyo Electron Limited). A 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used as a developing solution, and shower development was performed at 23 ° C. for 60 seconds. Then, rinsing was performed in a spin shower using pure water, then spin-dried, and then heat-treated (post-baked) for 5 minutes using a hot plate at 200 ° C. to obtain a pattern.
The difference ΔE (E2-E1) between the minimum exposure amount E1 required to form a pattern having a width of 100 μm and a length of 1000 μm and the minimum exposure amount E2 required to make all the above-mentioned patterns adhere to each other was obtained and described below. Adhesion was evaluated based on the criteria. The smaller ΔE is, the better the adhesion is. The fact that the patterns were in close contact with each other and the size of the patterns were observed using an optical microscope (magnification: 200 times).
-Evaluation criteria-
5: ΔE is 0 mJ / cm ² .
4: ΔE is more than 0 mJ / cm ² and 100 mJ / cm ² or less.
3: ΔE exceeds 100 mJ / cm ² .
At an exposure rate of 2: 50 to 1700 mJ / cm ² , at least one pattern of lines having a width of 100 μm and a length of 1000 μm could be formed, but not all 25 patterns could be formed.
With an exposure amount of 1: 50 to 1700 mJ / cm ² , a pattern having a width of 100 μm and a length of 1000 μm could not be formed. (All peeled off)

(Evaluation of development residue)
Each resin composition is placed on a silicon wafer having a diameter of 8 inches (203.2 mm) having a 400 nm-thick thermal oxide film (SiO ₂ film) formed on the surface so that the film thickness after post-baking is 0.6 μm. Was applied by the spin coating method. Then, using a hot plate, it was post-baked at 100 ° C. for 2 minutes. Next, using a KrF scanner exposure machine, light was irradiated through a mask having a Bayer pattern formed in a pixel (pattern) size of 1.1 μm square, and pulse exposure was performed under the following conditions. 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, using a hot plate, the pixels (patterns) were formed by heating at 200 ° C. for 5 minutes. The pulse exposure conditions by the KrF scanner exposure machine are as follows.

-Pulse exposure conditions-
Exposure light: KrF line (wavelength 248 nm)
Maximum instantaneous illuminance: 250,000,000,000 W / m ² (Average illuminance: 30,000 W / m ² )
Pulse width: 30 nanoseconds Frequency: 4 kHz

Of the pixel patterns obtained above, the region where the cured pixel pattern does not remain was observed with a scanning electron microscope (scanning electron microscope, trade name: S-9260, manufactured by Hitachi High-Technologies Corporation), and the degree of residue in this region was observed. Was evaluated on the following five stages.

-Evaluation criteria-
5: No residue is observed 4: 1 to 5 residues with a size (width of the longest axis) of 0.05 μm or less are observed 3: Size (width of the longest axis) is 0 6 to 10 residues of 0.05 μm or less are observed 2: More than 10 residues of size (width of the longest axis) or less are observed and the size is 0.05 μm. No residue exceeding the size is observed 1: More than 10 residues with a size (width of the longest axis) of 0.05 μm or less are observed, and residues with a size exceeding 0.05 μm are also observed.

The evaluation results evaluated by the above procedure are shown in the table below.

As shown in the above table, the examples had a good evaluation of adhesion.

1.0% by mass of the surfactants (S-2) to (S-32) shown in the table below instead of the surfactant (S-1) in the resin compositions of Production Examples 4-1 to 4-47. The same effect as described above was also obtained when the resin composition replaced with the PGMEA solution was used.
S-2: Futergent 710FM (manufactured by NEOS Co., Ltd.)
S-3: Futergent 610FM (manufactured by NEOS Co., Ltd.)
S-4: Futergent 601AD (manufactured by NEOS Co., Ltd.)
S-5: Futergent 601ADH2 (manufactured by NEOS Co., Ltd.)
S-6: Futergent 602A (manufactured by NEOS Co., Ltd.)
S-7: Futergent 215M (manufactured by NEOS Co., Ltd.)
S-8: Futergent 245F (manufactured by NEOS Co., Ltd.)
S-9: Megafuck F-556 (manufactured by DIC Corporation)
S-10: Megafuck F-557 (manufactured by DIC Corporation)
S-11: Megafuck F-563 (manufactured by DIC Corporation)
S-12: Megafuck F-560 (manufactured by DIC Corporation)
S-13: Megafuck F-575 (manufactured by DIC Corporation)
S-14: Megafuck R-41 (manufactured by DIC Corporation)
S-15: Megafuck R-41-LM (manufactured by DIC Corporation)
S-16: Megafuck R-01 (manufactured by DIC Corporation)
S-17: Megafuck R-40 (manufactured by DIC Corporation)
S-18: Megafuck R-40-LM (manufactured by DIC Corporation)
S-19: Megafuck RS-43 (manufactured by DIC Corporation)
S-20: Megafuck TF-1956 (manufactured by DIC Corporation)
S-21: Megafuck R-94 (manufactured by DIC Corporation)
S-22: Megafuck F-558 (manufactured by DIC Corporation)
S-23: Megafuck F-561 (manufactured by DIC Corporation)
S-24: Megafuck F-477 (manufactured by DIC Corporation)
S-25: Megafuck F-554 (manufactured by DIC Corporation)
S-26: Megafuck F-565 (manufactured by DIC Corporation)
S-27: Megafuck F-568 (manufactured by DIC Corporation)
S-28: Megafuck F-559 (manufactured by DIC Corporation)
S-29: Mega Fuck F-555-A (manufactured by DIC Corporation)
S-30: Megafuck RS-90 (manufactured by DIC Corporation)
S-31: Megafuck RS-72-K (manufactured by DIC Corporation)
S-32: Megafuck DS-21 (manufactured by DIC Corporation)

In the resin composition G-9, a non-photosensitive resin composition was prepared in which the entire amount of the polymerizable monomer and the photopolymerization initiator was replaced with an epoxy compound (EHPE-3150, manufactured by Daicel Corporation). Using this resin composition, a green pattern (green pixel) was formed by the same method as described in paragraph Nos. 0460 to 0468 of JP2013-06499, and the adhesion of the pixel pattern was evaluated. However, it was confirmed that good adhesion was obtained.

In Examples 1 to 48, the i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) is used instead of the KrF scanner exposure machine, and the pixel (pattern) size is formed in an array of 0.7 μm square. Pixels were formed in the same manner as above except that light having a wavelength of 365 nm was irradiated at an exposure amount of 500 mJ / cm ² through a mask having a Bayer pattern to evaluate adhesion and development residue. However, the same results as in Examples 1 to 47 were obtained.

(Example 1001)
The green coloring composition was applied onto the silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 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 via a mask of a 2 μm square dot pattern. 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 coloring composition was patterned to form green pixels by heating at 200 ° C. for 5 minutes using a hot plate. Similarly, the red coloring composition and the blue coloring composition were patterned by the same process to sequentially form red pixels and blue pixels to form a color filter having green pixels, red pixels and blue pixels. In this color filter, green pixels are formed by a Bayer pattern, and red pixels and blue pixels are formed by an island 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 coloring composition, a resin composition (GR-21) was used. As the red coloring composition, a resin composition (RR-1) was used. As the blue coloring composition, a resin composition (BR-1) was used.

Claims (16)

1. A resin composition containing a resin, a compound A having a molecular weight of 300 or less represented by the formula (1), and an organic solvent;
   

   

   In the formula (1), Q ¹ represents an ethylenically unsaturated bond-containing group, and L ¹ represents a divalent linking group.
2. The resin composition according to claim 1, wherein the content of the compound A in the total solid content of the resin composition is 0.1 to 2000 mass ppm.
3. The compound A is a compound represented by the formula (1-1), a compound represented by the formula (1-2), a compound represented by the formula (1-3), or a compound represented by the formula (1-4). The resin composition according to claim 1 or 2, which is the compound represented.
   

   
4. The resin according to any one of claims 1 to 3, further comprising the compound B having a molecular weight of 300 or less represented by the formula (2) in the total solid content of the resin composition in an amount of 0.1 to 300 mass ppm. Composition;
   

   

   In the formula (2), Q ² represents an ethylenically unsaturated bond-containing group, and L ² represents a divalent linking group.
5. The compound B is a compound represented by the formula (2-1), a compound represented by the formula (2-2), a compound represented by the formula (2-3), or a compound represented by the formula (2-4). The resin composition according to claim 1 or 2, which is a compound represented by the present invention.
   

   
6. The resin composition according to claim 4 or 5, which contains 0.1 to 120 parts by mass of the compound B with respect to 100 parts by mass of the compound A.
7. The resin composition according to any one of claims 4 to 6, wherein the total content of the compound A and the compound B in the total solid content of the resin composition is 1 to 300 mass ppm.
8. The resin composition according to any one of claims 1 to 7, wherein the resin contains a group represented by the formula (3).
   

   

   In formula (3), Q ³¹ represents an ethylenically unsaturated bond-containing group, L ³¹ represents a divalent linking group, R ³¹ represents a hydrogen atom or a substituent, and * represents a linking hand.
9. The resin composition according to any one of claims 1 to 8, wherein the resin contains a resin containing a repeating unit represented by the formula (3-1).
   

   

   In formula (3-1), Q ³¹ represents an ethylenically unsaturated bond-containing group, L ³¹ and L ³² each independently represent a divalent linking group, and R ³¹ represents a hydrogen atom or a substituent. R ³² represents a hydrogen atom or a methyl group.
10. The resin composition according to any one of claims 1 to 9, wherein the resin composition contains 0.3 to 2.0% by mass of water.
11. The resin composition according to any one of claims 1 to 10, further comprising a coloring material.
12. The resin composition according to any one of claims 1 to 11, further comprising a polyfunctional polymerizable monomer having two or more ethylenically unsaturated bond-containing groups and a photopolymerization initiator.
13. A film obtained by using the resin composition according to any one of claims 1 to 12.
14. An optical filter containing the film according to claim 13.
15. A solid-state image sensor including the film according to claim 13.
16. An image display device including the film according to claim 13.