JP7403662B2 - Resin compositions, films, optical filters, solid-state imaging devices, and image display devices - Google Patents

Description

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 sensor, and an image display device.

Solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors) are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. Further, the solid-state image sensor is equipped with an optical filter such as a color filter. Optical filters are manufactured using, for example, resin compositions (see Patent Document 1).

JP2020-086222A

In recent years, the pattern size of optical filters used in solid-state imaging devices 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 studied the composition described in Patent Document 1, it was found that there is room for improvement in the adhesion of the resulting membrane to the support.

Therefore, an object of the present invention is to provide a resin composition, a film, an optical filter, a solid-state imaging device, and an image display device that can form a film with excellent adhesion to a support.

According to the studies of the present inventors, it has been found that the above object can be achieved by the resin composition described below, and the present invention has been completed. Accordingly, 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 formula (1), and an organic solvent;
In 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 ppm by mass.
<3> The compound A is a compound represented by formula (1-1), a compound represented by formula (1-2), a compound represented by formula (1-3), or a compound represented by 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 formula (2) and having a molecular weight of 300 or less in the total solid content of the resin composition. The resin composition described in;
In 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 formula (2-1), a compound represented by formula (2-2), a compound represented by formula (2-3), or a compound represented by formula (2- The resin composition according to <1> or <2>, which is a compound represented by 4).
<6> The resin composition according to <4> or <5>, containing 0.1 to 120 parts by mass of the compound B based on 100 parts by mass of the compound A.
<7> According to any one of <4> to <6>, the total content of the compound A and the compound B in the total solid content of the resin composition is 1 to 300 ppm by mass. Resin composition.
<8> The resin composition according to any one of <1> to <7>, wherein the resin contains a group represented by 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 includes a resin containing a repeating unit represented by 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, 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 using the resin composition according to any one of <1> to <12>.
<14> An optical filter comprising the film according to <13>.
<15> A solid-state imaging device comprising 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 imaging device, and an image display device that can form a film with excellent adhesion to a support.

The content of the present invention will be explained in detail below.
In this specification, "~" is used to include the numerical values described before and after it as a lower limit and an upper limit.
In the description of a group (atomic group) in this specification, the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "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 actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents acrylate and/or methacrylate, "(meth)acrylic" represents both acrylic and/or methacrylic, and "(meth)acrylate" represents acrylic and/or methacrylate. ) "Acryloyl" refers to either or both of acryloyl and methacryloyl.
In this 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 this specification, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
In this specification, near-infrared rays refer to light with a wavelength of 700 to 2500 nm.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent.
In this specification, the term "process" is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process 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 represented by formula (1) with a molecular weight of 300 or less, and an organic solvent.

According to the resin composition of the present invention, a film having excellent adhesion to a support can be formed. Although the detailed reason why such an effect is obtained is unknown, by including the above-mentioned compound A in the resin composition, the hydroxyl groups of compound A and the silanol groups (SiOH) etc. present on the surface of the support are formed during film formation. It is presumed that a dehydration condensation reaction occurs to form a chemical bond, and the ethylenically unsaturated bond-containing group of compound A reacts with a component in the film, such as a resin, to form a chemical bond. It is therefore presumed that a film with excellent adhesion to the support can be formed.

Furthermore, when the resin composition of the present invention further contains the above-mentioned compound B, the adhesion of the resulting membrane 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 resulting membrane to the support can be further improved. Although the detailed reason for obtaining such an effect is unknown, it is presumed as follows. That is, it is presumed that the water contained in the resin composition is not completely volatilized immediately after being applied with a spin coater or the like and remains in the film. During prebaking, the water remaining in this film is mixed with the hydroxy group of compound A (if compound B is further included, the hydroxy group of compound A or the epoxy group of compound B) and the silanol group present on the surface of the support ( It is estimated that it functions as a catalyst when a chemical bond is formed 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 coating also increases. If the amount of water remaining in the film is too large, the hydroxyl group of compound A (if compound B is further included, the hydroxyl group of compound A or the epoxy group of compound B) will be present on the surface of the support during prebaking. The reverse reaction of the dehydration condensation reaction that forms chemical bonds with the silanol groups (SiOH), etc. that are present, that is, the hydrolysis reaction, becomes dominant, and the chemical bonds formed between the support surface and compound A, etc., dissociate. , it is estimated that it becomes difficult to obtain sufficient adhesion. For these reasons, it is presumed that better adhesion was obtained by containing water within 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 this specification, the water content of the resin composition is a value measured by Karl Fischer measurement method.

The resin composition of the present invention is preferably used as a resin composition for optical filters. Examples of the optical filter include color filters, near-infrared transmission filters, near-infrared cut filters, etc., and color filters are preferred. Furthermore, the resin composition of the present invention is preferably used for solid-state imaging devices. More specifically, it is preferably used as a resin composition for an optical filter used in a solid-state imaging device, and more preferably used as a resin composition for forming colored pixels in a color filter used in a solid-state imaging device.

Examples of color filters include filters having colored pixels that transmit light of a specific wavelength. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. The colored pixels of the color filter can be formed using a resin composition containing a chromatic coloring material.

The maximum absorption wavelength of the near-infrared cut filter preferably exists in a wavelength range of 700 to 1800 nm, more preferably exists in a wavelength range of 700 to 1300 nm, and even more preferably exists in a wavelength range of 700 to 1000 nm. . Further, the transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even 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. Further, 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. , more preferably from 70 to 450, particularly preferably from 100 to 400. The near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing coloring material.

A near-infrared transmission filter is a filter that transmits at least a portion of near-infrared rays. The near-infrared transmission filter may be a filter (transparent film) that transmits both visible light and near-infrared rays, or may be a filter that blocks at least part of visible light and transmits at least part of near-infrared rays. Good too. The near-infrared transmission filter has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and a transmittance in the wavelength range of 1100 to 1300 nm. Preferred examples include filters that satisfy spectral characteristics with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). 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 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 transmittance in the wavelength range of 800 to 1500 nm is 20% or less (preferably 15% or less, more preferably 10% or less). 70% or more (preferably 75% or more, more preferably 80% or more).
(2): The maximum value of 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 transmittance in the wavelength range of 900 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
(3): The maximum value of 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 transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
(4): The maximum value of 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 transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
(5): The maximum value of 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 transmittance in the wavelength range of 1200 to 1500 nm is 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 transparent films, light-shielding films, and the like.

Each component used in the resin composition of the present invention will be explained below.

<<Resin>>
The resin composition of the present invention contains a resin. The resin is blended, for example, for use in dispersing pigments in a resin composition or for use as a binder. Note that a resin used mainly for dispersing pigments is also referred to as a dispersant. However, this use of the resin is just an example, and the resin can also be used for purposes other than this use.

The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

Examples of resins include (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamideimide resin. , polyimine resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One type of these resins may be used alone, or two or more types may be used in combination. Further, resins described in paragraph numbers 0041 to 0060 of JP2017-206689A and resins described in paragraphs 0022 to 0071 of JP2018-010856A can also be used.

The resin composition of the present invention preferably contains a resin containing a group represented by formula (3) (hereinafter also referred to as resin (3)). According to this aspect, a film having excellent adhesion to the support can be formed.
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 in formula (3) include a vinyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, etc. (meth)allyl group, (meth)acryloyl group and (meth)acryloyloxy group are preferable, and (meth)acryloyloxy group is more preferable.

The divalent linking group represented by L ³¹ in formula (3) includes an alkylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and two or more thereof. Combination groups are mentioned. 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. 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 connects the above alkylene groups include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.

R ³¹ in 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. R ³¹ in formula (3) is preferably a hydrogen atom. According to this aspect, a film having excellent adhesion to the support can be formed.

The resin (3) is preferably a resin containing a repeating unit represented by 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, 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 in formula (3-1) have the same meanings as Q ³¹ , L ³¹ and R ³¹ in formula (3), respectively.

The divalent linking group represented by L ³² in formula (3-1) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species. 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 in the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5. The aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or cyclic. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 10 carbon atoms. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group. 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 connects the above hydrocarbon groups include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.

It is preferable that the resin composition of the present invention 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 a carboxyl group is preferred. A 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 its side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group in its side chain based on the total repeating units of the resin. The upper limit of the content of repeating units having acid groups in their side chains is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units having acid groups in their side chains 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 components.

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED2), the description in JP-A No. 2010-168539 can be referred to, the contents of which are incorporated herein.

As a specific example of the ether dimer, for example, the description in paragraph number 0317 of JP-A-2013-029760 can be referred to, the contents of which are incorporated herein.

It is also preferable that the resin used in the present invention contains a repeating unit derived from a compound represented by the following formula (X).
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 an alkylene group having 1 to 20 carbon atoms that may contain a benzene ring. represents an alkyl group. n represents an integer from 1 to 15.

Regarding resins having acid groups, the descriptions in paragraph numbers 0558 to 0571 of JP 2012-208494 (corresponding paragraph numbers 0685 to 0700 of US Patent Application Publication No. 2012/0235099), JP 2012-198408 The descriptions in paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated into the present specification. Furthermore, commercially available resins having acid groups can also be used.

The acid value of the resin having acid groups 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 acid groups is preferably 3,000 to 35,000. 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 4,000 or more, more preferably 6,000 or more, and even more preferably 7,000 or more.

For 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 its side chain, and a resin having a repeating unit having a basic group in its 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 its side chain and a repeating unit not containing a basic group is even more 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, more preferably 20 mgKOH/g or more. The upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less. Examples of the resin having a basic group include block copolymers (B) described in paragraph numbers 0063 to 0112 of JP-A No. 2014-219665, and block copolymers (B) described in paragraph numbers 0046 to 0076 of JP-A No. 2018-156021. and block copolymer A1.

The resin composition of the present invention preferably contains a graft resin having an acid group (hereinafter also referred to as acidic graft resin). 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. Furthermore, the term "graft chain" refers to 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; More preferably, it is a polymer chain containing at least one type of 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, and an amino group. Among these, from the viewpoint of improving the dispersibility of pigments, groups having a steric repulsion effect are preferred, and alkyl groups or alkoxy groups having 5 to 24 carbon atoms are preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.

The weight average molecular weight of the graft chain is preferably 500 to 10,000. The upper limit is preferably 5,000 or less, more preferably 3,000 or less. The lower limit is preferably 800 or more, more preferably 1000 or more. In this 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 polymerization of the repeating unit having the graft chain. For example, a repeating unit having a graft chain can be formed by polymerizing a macromonomer. Here, the macromonomer refers to 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, a polystyrene equivalent value measured by GPC (gel permeation chromatography) method is used.

Examples of the acid group that the acidic graft resin has include a carboxyl group, a sulfo group, and a phosphoric acid group, with a carboxyl group being preferred. 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 3,000 to 35,000. 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 4,000 or more, more preferably 6,000 or more, and even more preferably 7,000 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 polymerizable groups. Examples of the polymerizable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.

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

Next, the repeating unit represented by formula (Ac-2) will be explained.
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.

In formula (Ac-2), the group containing an aromatic carboxyl group represented by Ar ¹⁰ includes 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 anhydride and aromatic tetracarboxylic anhydride include compounds having the following structures.

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

The aromatic carboxyl group-containing 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 formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). Examples include groups such as

In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
In 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 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 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- Represents a group represented by 1) or a group represented by the above formula (Q-2).
In 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 formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in 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 aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group. The trivalent linking group represented by L ¹² is preferably a group represented by formula (L12-1), more preferably a group represented by formula (L12-2).

In formula (L12-1), L ^12b represents a trivalent linking group, X ¹ represents S, *1 represents the bonding position with L ¹¹ of formula (Ac-2), and *2 represents the bonding position of 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 kind selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-. A hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferable.

In formula (L12-2), L ^12c represents a trivalent linking group, X ¹ represents S, *1 represents the bonding position with L ¹¹ of formula (Ac-2), and *2 represents formula ( 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 kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. A hydrocarbon group is preferable.

The polymer chain represented by P ¹⁰ in formula (Ac-2) includes 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 preferably a polymer chain containing at least one type of 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 10,000. The upper limit is preferably 5,000 or less, more preferably 3,000 or less. The lower limit is preferably 800 or more, more preferably 1000 or more.

It is also preferable that the polymer chain represented by P ¹⁰ includes a repeating unit containing an ethylenically unsaturated bond-containing group in the side chain. Furthermore, the proportion of repeating units containing ethylenically unsaturated bond-containing groups in their side chains in all repeating units constituting ^P10 is preferably 5% by mass or more, more preferably 10% by mass or more. , more preferably 20% by mass or more. 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 includes a repeating unit containing an acid group. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. The proportion of repeating units containing acid groups in all 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. More preferably.

Specific examples of the acidic graft resin include resins B-1 to B-7 described in Examples below. Furthermore, as the acidic graft resin, resins described in paragraph numbers 0025 to 0094 of JP2012-255128A and polyimine resins described in paragraphs 0102 to 0166 of JP2012-255128A can also be used. can.

The resin composition of the present invention preferably contains a resin as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. More preferred is a resin consisting only of groups. The acid group that the acidic dispersant (acidic resin) has 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. Moreover, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater 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 acid groups and basic groups is 100 mol%. The basic group that the basic dispersant has is preferably an amino group.

It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.

Further, resins such as the above-mentioned acidic graft resins can also be used as dispersants.

Dispersants are also available as commercial products, and specific examples include the DISPERBYK series (for example, DISPERBYK-111, 161, etc.) manufactured by BYK Chemie, and the Solsperse series (manufactured by Japan Lubrizol Co., Ltd.). For example, Solsparse 76500, etc.). Further, pigment dispersants described in paragraph numbers 0041 to 0130 of JP 2014-130338 A can also be used, the contents of which are incorporated herein. In addition, the resin explained as the said dispersant can also be used for uses other than a 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 compound A represented by formula (1) and having a molecular weight of 300 or less (hereinafter also referred to as compound A).
In 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 in formula ( ¹ ) include a vinyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, etc. (meth)allyl group, (meth)acryloyl group and (meth)acryloyloxy group are preferable, and (meth)acryloyloxy group is more preferable.

The divalent linking group represented by L ¹ in formula (1) includes an alkylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and two or more thereof. Combination groups are mentioned. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or cyclic. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group. The divalent linking group represented by ^L1 includes a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a linking group, preferably a hydrocarbon group, and an aliphatic hydrocarbon group. It is more preferable that Examples of the linking group that connects the above hydrocarbon groups include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.

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

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

The content of compound A in the total solid content of the resin composition is preferably 0.1 to 2000 ppm by mass. 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 even more preferably 50 mass ppm or more.

<<Compound B>>
The resin composition of the present invention preferably contains a compound B represented by formula (2) and having a molecular weight of 300 or less (hereinafter also referred to as compound B). By using Compound A and Compound B in combination, a film having better adhesion can be formed.
In 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 Q ² in formula (2) include a vinyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, etc. (meth)allyl group, (meth)acryloyl group and (meth)acryloyloxy group are preferable, and (meth)acryloyloxy group is more preferable.

The divalent linking group represented by L ² in formula (2) includes an alkylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and two or more thereof. Combination groups are mentioned. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or cyclic. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group. The divalent linking group represented by ^L2 includes a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a linking group, preferably a hydrocarbon group, and an aliphatic hydrocarbon group. It is more preferable that Examples of the linking group that connects the above hydrocarbon groups include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.

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

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

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

Further, it is preferable that 0.1 to 120 parts by mass of compound B be contained per 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, even more 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, more preferably 0.5 parts by mass or more. According to this aspect, a film having better adhesion can be formed. Furthermore, generation of development residues can be more effectively suppressed.

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

<<Polyfunctional polymerizable monomer>>
The resin composition of the present invention can contain a polyfunctional polymerizable monomer (hereinafter also referred to as a polyfunctional polymerizable monomer) having two or more ethylenically unsaturated bond-containing groups. Examples of the ethylenically unsaturated bond-containing group possessed by the polyfunctional polymerizable monomer include a vinyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, and the like. A (meth)allyl group, a (meth)acryloyl group and a (meth)acryloyloxy group are preferred, and a (meth)acryloyloxy group is more preferred. 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 3,000. 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; More preferably, it is a compound containing 3 to 6 saturated bond-containing groups. Further, the polyfunctional polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples of the polyfunctional polymerizable monomer include paragraph numbers 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, paragraph 0254 to 0257 of JP 2008-292970, Paragraph numbers 0034 to 0038 of JP 2013-253224, paragraph 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807, JP 2017- Examples include compounds described in Japanese Patent No. 194662, the contents of which are incorporated herein.

Examples of polyfunctional polymerizable monomers include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D) -320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercial product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercial product) Examples include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.; NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth)acryloyl groups contain ethylene glycol and/or propylene glycol residues. Compounds having a structure in which they are bonded through (for example, SR454 and SR499, commercially available from Sartomer) are preferred. In addition, as polymerizable monomers, diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), NK ester A-TMMT), 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (Nippon Kayaku Co., Ltd.), Aronix TO-2349 (Toagosei Co., Ltd.) ), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. You can also use

Examples of polyfunctional polymerizable monomers include trimethylolpropane tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, trimethylolpropaneethylene oxide-modified tri(meth)acrylate, isocyanuric acid ethylene oxide-modified tri(meth)acrylate, It is also preferable to use trifunctional (meth)acrylate compounds 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 Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Examples include.

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 unexposed areas 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 a carboxyl group is preferred. Commercially available polymerizable monomers having acid groups include Aronix M-305, M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like. The acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g.

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

As the polyfunctional polymerizable monomer, a polymerizable monomer having an alkyleneoxy group can also be used. The polymerizable monomer having an alkyleneoxy group is preferably a polymerizable monomer having an ethyleneoxy group and/or a propyleneoxy group, more preferably a polymerizable monomer having an ethyleneoxy group, and a polymerizable monomer having 4 to 20 ethyleneoxy groups. More preferred are hexafunctional (meth)acrylate compounds. Commercially available polymerizable monomers having alkyleneoxy groups include SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups, manufactured by Sartomer, and trifunctional (meth)acrylate having three isobutyleneoxy groups. ) KAYARAD TPA-330, which is an acrylate.

As the polyfunctional polymerizable monomer, a polymerizable monomer having a fluorene skeleton can also be used. Examples of commercially available polymerizable monomers having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).

As the polyfunctional polymerizable monomer, it is also preferable to use a compound substantially free of environmentally controlled substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

Examples of polyfunctional polymerizable monomers include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-open No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. Also suitable are urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. It is also preferable to use polymerizable monomers having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238. In addition, the polyfunctional polymerizable monomers include 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, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

The polyfunctional polymerizable monomer used in the resin composition of the present invention is a trifunctional or less polymerizable monomer C1 containing two or three ethylenically unsaturated bond-containing groups, and a trifunctional or less polymerizable monomer C1 containing four ethylenically unsaturated bond-containing groups. It is preferable to include the above-mentioned tetrafunctional or higher functional polymerizable monomer C2. According to this embodiment, the curing shrinkage of the film is appropriately suppressed and the adhesion to the support is improved, so that the effects of the present invention are more significantly exhibited. When using the polymerizable monomer C1 and the polymerizable monomer C2 together, the ratio of the two is preferably 10 to 1000 parts by mass, and 30 to 300 parts by mass, relative to 100 parts by mass of the polymerizable monomer C1. The amount is more preferably 50 to 200 parts by mass, 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 can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the ultraviolet to visible light range is preferred. The photopolymerization initiator is preferably a radical photopolymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (for example, compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, 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, photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triarylimidazole. Dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds are preferred, and oxime compounds and α-hydroxyketone compounds , α-aminoketone compounds, and acylphosphine compounds, and even more preferably oxime compounds. In addition, as photopolymerization initiators, compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173 and Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A No. 2019-044030, the peroxide-based initiator described in JP-A No. 2019-167313, the photopolymerization initiator described in JP-A No. 2020-055992 Examples include the aminoacetophenone-based initiator having an oxazolidine group as described above, the oxime-based photopolymerization initiator described in JP-A No. 2013-190459, and the contents thereof are incorporated herein.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (and above, BASF (manufactured by a company). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF) (manufactured by). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.

Examples of oxime compounds include the compounds described in JP-A No. 2001-233842, the compounds described in JP-A No. 2000-080068, the compounds described in JP-A No. 2006-342166, and the compounds described in JP-A No. 2006-342166. C. S. Perkin II (1979, pp. 1653-1660); C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP-A No. 2000-066385 things, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2006-342166, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, International Publication No. 2015 /152153, the compound described in International Publication No. 2017/051680, the compound described in JP 2017-198865, the compound described in paragraph numbers 0025 to 0038 of International Publication No. 2017/164127, Examples include compounds described in International Publication No. 2013/167515. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy Examples include imino-1-phenylpropan-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), and Adeka Optomer N-1919 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.). Photopolymerization initiator 2) manufactured by ADEKA and described in JP-A-2012-014052 can be mentioned. Further, as the oxime compound, it is also preferable to use a compound without coloring property or a compound with high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Co., Ltd.).

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

As the photopolymerization initiator, it is also possible to use an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring. Specific examples of such oxime compounds include 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 oxime compounds having a fluorine atom include compounds described in JP-A No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and compounds described in JP-A No. 2013-164471. Examples include compound (C-3).

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is in the form of a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466, Examples include compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles 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, it is also possible to use an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055.

As the photopolymerization initiator, it is also possible to use an oxime compound having an aromatic ring group Ar ^OX1 (hereinafter also referred to as oxime compound OX) in which an electron-withdrawing group is introduced into the aromatic ring. Examples of the electron-withdrawing group possessed by 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 preferred, an acyl group is more preferred because a film with excellent light resistance can be easily formed, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, and more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group. More preferably, it is a sulfanyl group or an amino group.

The oxime compound OX is preferably at least one selected from a compound represented by formula (OX1) and a compound represented by formula (OX2), and more preferably a compound represented by formula (OX2). preferable.
In the formula, ^R group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group or sulfamoyl group,
^R Represents a sulfonyl group, acyloxy group or amino group,
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.

In the above formula, R ^X12 is preferably an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 , and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include compounds described in paragraph numbers 0083 to 0105 of Japanese Patent No. 4,600,600.

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

As the photopolymerization initiator, a difunctional, trifunctional or more functional photoradical polymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in organic solvents improves, making it difficult to precipitate over time and improving the stability of the resin composition over time. can. Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Application Publication No. 2016-532675. Dimers of oxime compounds described in paragraph numbers 0407 to 0412, paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compound ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of Japanese Patent Publication No. 2017-523465, Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP2017-151342A, and photoinitiators (A) 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 their total amount falls within the above range.

＜＜Color material＞＞
It is preferable that the resin composition of the present invention contains a coloring material. Examples of coloring materials include white coloring materials, black coloring materials, chromatic coloring materials, and near-infrared absorbing coloring materials. Note that, in the present invention, the white coloring material includes not only pure white but also a light gray coloring 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 coloring material, a black coloring material, and a near-infrared absorbing coloring material, and more preferably a chromatic coloring material. Further, the content of the chromatic coloring material in the coloring 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. A pigment and a dye may be used together. Further, the pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, an inorganic pigment or an organic-inorganic pigment partially substituted with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.

The average primary particle diameter 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, and even more preferably 100 nm or less. When the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the photosensitive composition is good. In the present invention, the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment using a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles. Moreover, the primary particles of pigment refer to independent particles without agglomeration.

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

(Chromatic color materials)
Examples of chromatic coloring materials include coloring materials having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples include yellow coloring material, orange coloring material, red coloring material, green coloring material, purple coloring material, blue coloring material, and the like. Specific examples of chromatic color materials include those shown below.

Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232 (methine type), 233 (quinoline type), 234 ( Yellow pigments such as aminoketone-based), 235 (aminoketone-based), and 236 (aminoketone-based).
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, Organo Ultramarine, Bluish 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 type), Blue pigments such as 88 (methine type).

In addition, as a green coloring material, halogenated zinc phthalocyanine has an average number of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule. Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green coloring material, the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound having a phosphoric acid ester as a ligand described in International Publication No. 2012/102395, and the phthalocyanine compound described in JP-A No. 2019-008014 The phthalocyanine compounds described in JP-A No. 2018-180023, the compounds described in JP-A No. 2019-038958, and the like can also be used.

Moreover, an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue coloring material. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.

Moreover, as a yellow coloring material, an azobarbituric acid nickel complex having the following structure can also be used.

In addition, as yellow coloring materials, compounds described in JP 2017-201003, JP 2017-197719, and paragraph numbers 0011 to 0062 and 0137 to 0276 of JP 2017-171912 are also used. Compounds described in paragraph numbers 0010 to 0062 and 0138 to 0295 of JP 2017-171913, compounds described in paragraph numbers 0011 to 0062 and 0139 to 0190 of JP 2017-171914, JP 2017 - Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A No. 2013-054339, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP-A-2013-054339, and paragraph numbers 0013 to 0013 of JP-A-2014-026228. Quinophthalone compound described in JP 2018-062644, isoindoline compound described in JP 2018-062644, quinophthalone compound described in JP 2018-203798, quinophthalone compound described in JP 2018-062578, Japanese Patent No. 6432076. Quinophthalone compounds described in Japanese Patent Publication No. 2018-155881, Quinophthalone compounds described in Japanese Patent Application Publication No. 2018-111757, Quinophthalone compounds described in Japanese Patent Application Publication No. 2018-040835, Japanese Patent Publication No. 2018-040835, Quinophthalone compounds described in -197640, quinophthalone compounds described in JP2016-145282, quinophthalone compounds described in JP2014-085565, quinophthalone compounds described in JP2014-021139, Quinophthalone compounds described in JP-A No. 2013-209614, quinophthalone compounds described in JP-A No. 2013-209435, quinophthalone compounds described in JP-A No. 2013-181015, quinophthalone compounds described in JP-A No. 2013-061622 , quinophthalone compounds described in JP2013-032486A, quinophthalone compounds described in JP2012-226110A, quinophthalone compounds described in JP2008-074987A, quinophthalone compounds described in JP2008-081565A Quinophthalone compounds, quinophthalone compounds described in JP2008-074986A, quinophthalone compounds described in JP2008-074985A, quinophthalone compounds described in JP2008-050420A, quinophthalone compounds described in JP2008-031281A The quinophthalone compounds described in Japanese Patent Publication No. 48-032765, the quinophthalone compounds described in Japanese Patent Publication No. 2019-008014, the quinophthalone compounds described in Japanese Patent No. 6607427, the quinophthalone compounds described in Japanese Patent Publication No. 2019-073695 Methine dyes described in JP 2019-073696, methine dyes described in JP 2019-073697, methine dyes described in JP 2019-073698, Korean Published Patent No. 10- Compounds described in JP 2014-0034963, JP 2017-095706, Taiwan Patent Application Publication No. 201920495, Compounds described in JP 6607427, JP 2020-033521 The quinophthalone dimer described in the publication can also be used. Furthermore, polymerized versions of these compounds are also preferably used from the viewpoint of improving 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 formula (QP1), X ¹ to X ¹⁶ each 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 formula (QP1) include the compound described in paragraph number 0016 of Japanese Patent No. 6443711.

In formula (QP2), Y ¹ to Y ³ each independently represent a halogen atom. 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 formula (QP2) include compounds described in paragraph numbers 0047 to 0048 of Japanese Patent No. 6432077.

As a red coloring material, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP 2017-201384, and a diketopyrrolopyrrole compound described in paragraph numbers 0016 to 0022 of Patent No. 6248838. , diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No. 2012/117965, naphthol azo compounds described in JP 2012-229344, Patent No. 6516119 It is also possible to use the red coloring material described in Japanese Patent No. 6525101, and the like. Further, as a red pigment, a compound having a structure in which an aromatic ring group into which a group to which an oxygen atom, sulfur atom, or nitrogen atom is bonded is bonded to a diketopyrrolopyrrole skeleton may also be used. can.

Furthermore, a diarylmethane compound described in Japanese Patent Publication No. 2020-504758 can also be used as a coloring material.

Regarding the diffraction angles that various pigments preferably have, the descriptions in 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.

Furthermore, dyes can also be used as the chromatic coloring material. There are no particular restrictions on the dye, and known dyes can be used. For example, pyrazole azo compounds, anilinoazo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, xanthene compounds, Examples include phthalocyanine compounds, benzopyran compounds, indigo compounds, and pyrromethene 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 be the same dye structure or may be different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. The dye multimers are disclosed in JP 2011-213925, JP 2013-041097, JP 2015-028144, JP 2015-030742, JP 2016-102191, International Publication No. 2016/ Compounds described in No. 031442 and the like can also be used.

Two or more chromatic color materials may be used in combination. For example, C. I. Pigment Green7 and C. I. Pigment Green36 and C. I. Pigment Yellow139 and C. I. Pigment Yellow 185 may form a green color, and C. I. Pigment Green58 and C. I. Pigment Yellow150 and C. I. Pigment Yellow 185 may be used in combination to form a green color.

Moreover, when using a combination of two or more types of chromatic color materials, black may be formed by a combination of two or more types of chromatic color materials. Examples of such combinations include the following embodiments (1) to (7). In cases where the resin composition contains two or more chromatic coloring materials and exhibits black color by a combination of two or more chromatic coloring materials, by using such a resin composition, a near-infrared transmission filter can be obtained. can be formed.
(1) Embodiment containing a red coloring material and a blue coloring material.
(2) An embodiment containing a red coloring material, a blue coloring material, and a yellow coloring material.
(3) An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, and a purple coloring material.
(4) An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, a purple coloring material, and a green coloring material.
(5) An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, and a green coloring material.
(6) An embodiment containing a red coloring material, a blue coloring material, and a green coloring material.
(7) An embodiment containing a yellow coloring material and a purple coloring material.

(white coloring 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 include hollow resin particles and inorganic pigments (white pigments) such as zinc sulfide. The white pigment is preferably particles containing titanium atoms, and more preferably titanium oxide. Moreover, it is preferable that the white pigment is a particle having a refractive index of 2.10 or more with respect to light with a wavelength of 589 nm. The above-mentioned refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.

Further, as the white pigment, titanium oxide described in "Titanium oxide physical properties and applied technology, Manabu Seino, pages 13 to 45, published June 25, 1991, published by Gihodo Publishing" can also be used.

The white pigment may be not only made of a single inorganic substance, but also particles made of a composite with other materials. For example, particles with pores or other materials inside, particles with a core particle attached to a large number of inorganic particles, and core/shell composite particles with a core particle made of polymer particles and a shell layer made of inorganic nanoparticles are used. It is preferable. For the core and shell composite particles consisting of a core particle consisting of a polymer particle and a shell layer consisting of an inorganic nanoparticle, for example, the description in paragraphs 0012 to 0042 of JP 2015-047520A can be referred to, This content is incorporated herein.

Hollow inorganic particles can also be used as the white pigment. A hollow inorganic particle is an inorganic particle having a structure that has a cavity inside, and is an inorganic particle having a cavity surrounded by an outer shell. Examples of hollow inorganic particles include hollow inorganic particles described in JP2011-075786A, WO2013/061621A, JP2015-164881A, etc., the contents of which are not incorporated herein. It will be done.

(black color material)
The black coloring material is not particularly limited, and any known material can be used. For example, examples of the inorganic black coloring material include carbon black, titanium black, graphite, etc., carbon black and titanium black are preferred, and titanium black is more preferred. Titanium black is black particles containing titanium atoms, and lower titanium oxide and titanium oxynitride are preferable. The surface of titanium black can be modified as necessary for the purpose of improving dispersibility, suppressing agglomeration, and the like. 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. Furthermore, treatment with a water-repellent substance as disclosed in JP-A No. 2007-302836 is also possible. Examples of the black coloring material include Color Index (C.I.) Pigment Black 1, 7, and the like. It is preferable that the titanium black has a small primary particle size and an average primary particle size of each particle. Specifically, it is preferable that the average primary particle diameter is 10 to 45 nm. Titanium black can also be used as a dispersion. For example, there may be mentioned a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50. Regarding the above-mentioned dispersion, the descriptions in paragraphs 0020 to 0105 of JP-A-2012-169556 can be referred to, the contents of which are incorporated herein. Examples of commercially available titanium blacks include Titanium Black 10S, 12S, 13R, 13M, 13MC, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D ( Product name: Ako Kasei Co., Ltd.). Examples of the organic black coloring material include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. Examples of bisbenzofuranone compounds include those described in Japanese Translated Patent Publication No. 2010-534726, Japanese Translated Patent Publication No. 2012-515233, Japanese Translated Patent Publication No. 2012-515234, International Publication No. 2014/208348, Japanese Translated Patent Publication No. 2015-525260, etc. For example, it is available as "Irgaphor Black" manufactured by BASF. As perylene compounds, C. I. Pigment Black 31, 32, etc. Examples of the azomethine compound include compounds described in JP-A-01-170601 and JP-A-02-034664, and are available as "Chromofine Black A1103" manufactured by Dainichiseika Kaisha, Ltd., for example. Further, as the organic black coloring material, perylene black (Lumogen Black FK4280, etc.) described in paragraphs 0016 to 0020 of JP 2017-226821A may be used.

(Near infrared absorbing coloring material)
The near-infrared absorbing coloring material is preferably a pigment, and more preferably an organic pigment. Further, the near-infrared absorbing coloring material is preferably a compound having a maximum absorption wavelength in a range of more than 700 nm and 1400 nm or less. Further, the maximum absorption wavelength of the near-infrared absorbing coloring material is preferably 1200 nm or less, more preferably 1000 nm or less, and even more preferably 950 nm or less. Further, in the near-infrared absorbing coloring material, A 550 /A max, which is the ratio of the absorbance A ₅₅₀ at a wavelength of ₅₅₀ nm to the absorbance A _max at the maximum absorption wavelength, is preferably 0.1 or less, and preferably 0.05 or less _. It is more preferable that it is 0.03 or less, and it is particularly preferable that it is 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 within the above range, a near-infrared absorbing coloring material with excellent visible transparency and near-infrared shielding properties can be obtained. Note that the maximum absorption wavelength of the near-infrared absorbing coloring material and the absorbance value at each wavelength are values determined from the absorption spectrum of a film formed using a photosensitive composition containing the near-infrared absorbing coloring material.

Near-infrared absorbing coloring materials are not particularly limited, but include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, and thiol compounds. Examples include lylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, and dithiolene metal complexes. Examples of pyrrolopyrrole compounds include compounds described in paragraph numbers 0016 to 0058 of JP2009-263614A, compounds described in paragraphs 0037 to 0052 of JP2011-068731A, and compounds described in WO2015/166873A. Examples include compounds described in paragraph numbers 0010 to 0033. Examples of squarylium compounds include compounds described in paragraph numbers 0044 to 0049 of JP-A No. 2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of International Publication No. 2016/181987. Compounds described in JP 2015-176046, Compounds described in paragraph number 0072 of WO 2016/190162, Compounds described in paragraph numbers 0196 to 0228 of JP 2016-074649 , the compound described in paragraph number 0124 of JP 2017-067963, the compound described in WO 2017/135359, the compound described in JP 2017-114956, the compound described in JP 6197940, Examples include compounds described in International Publication No. 2016/120166. Examples of cyanine compounds include compounds described in paragraph numbers 0044 to 0045 of JP 2009-108267, compounds described in paragraph 0026 to 0030 of JP 2002-194040, and compounds described in JP 2015-172004. Compounds described in JP 2015-172102, compounds described in JP 2008-088426, compounds described in paragraph number 0090 of WO 2016/190162, JP 2017-031394 Examples include the compounds described in . Examples of the croconium compound include compounds described in JP-A No. 2017-082029. Examples of iminium compounds include compounds described in Japanese Patent Publication No. 2008-528706, compounds described in Japanese Patent Application Publication No. 2012-012399, compounds described in Japanese Patent Application Publication No. 2007-092060, and International Publication No. 2018/043564. Examples include the compounds described in paragraph numbers 0048 to 0063 of . Examples of phthalocyanine compounds include compounds described in paragraph number 0093 of JP-A No. 2012-077153, oxytitanium phthalocyanine described in JP-A 2006-343631, and paragraphs 0013 to 0029 of JP-A 2013-195480. , the vanadium phthalocyanine compound described in Patent No. 6081771, and the compound described in International Publication No. 2020/071470. Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A No. 2012-077153. Examples of the dithiolene metal complex include compounds described in Japanese Patent No. 5733804.

Near-infrared absorbing coloring materials include squarylium compounds described in JP2017-197437A, squarylium compounds described in JP2017-025311A, squarylium compounds described in International Publication No. 2016/154782, and Japanese Patent No. 5884953. Squarylium compounds described in Japanese Patent No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraphs 0090 to 0107 of International Publication No. 2017/213047, Pyrrole ring-containing compounds described in paragraph numbers 0019 to 0075 of JP-A No. 2018-054760, pyrrole ring-containing compounds described in paragraph numbers 0078 to 0082 of JP-A No. 2018-040955, paragraphs of JP-A No. 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 paragraph numbers 0024 to 0086 of JP 2018-041047, and amides described in JP 2017-179131. Linked squarylium compounds, compounds having a pyrrole bis-type squarylium skeleton or croconium skeleton described in JP 2017-141215, dihydrocarbazole bis-type squarylium compounds described in JP 2017-082029, JP 2017-068120 Asymmetric compounds described in paragraph numbers 0027 to 0114 of the publication, pyrrole ring-containing compounds (carbazole type) described in JP2017-067963A, phthalocyanine compounds described in Patent No. 6251530, International Publication The vanadium phthalocyanine compound described in No. 2020/071486, the phthalocyanine compound described in International Publication No. 2020/071470, etc. 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 even more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
Further, the pigment content 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 even more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
Further, the content of the dye in the coloring material is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

<<Pigment derivative>>
The resin composition of the present invention preferably contains a pigment derivative. Examples of pigment derivatives 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, benzimidazolone pigment skeleton, benzisoindole pigment skeleton, benzothiazole pigment skeleton, iminium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, and pyrrolopyrrole pigment. Skeleton, diketopyrrolopyrrole dye skeleton, azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton , thiazine indigo dye skeleton, thioindigo dye skeleton, isoindoline dye skeleton, isoindolinone dye skeleton, quinophthalone dye skeleton, iminium dye skeleton, dithiol dye skeleton, triarylmethane dye skeleton, pyrromethene dye skeleton, etc. Phthalocyanine dyes skeleton, diketopyrrolopyrrole dye skeleton, pyrrolopyrrole dye skeleton, benzisoindole dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, thiazine indigo dye skeleton, azo dye skeleton, quinophthalone dye skeleton or quinacridone dye skeleton. preferable. Examples of acid groups include sulfo groups, carboxyl groups, phosphoric acid groups, and salts thereof. Atoms or atomic groups constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ^{+ ,} etc.), alkaline earth metal ions (Ca ²⁺ , Mg ^{2+ ,} etc.), ammonium ions, imidazolium ions, pyridinium ions, Examples include phosphonium ions. Basic groups include amino groups, pyridinyl groups and their salts, ammonium group salts, and phthalimidomethyl groups. Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

The pigment derivative may also contain a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative). The maximum molar extinction coefficient (εmax) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is preferably 3000 L·mol ⁻¹ ·cm ⁻¹ or less, and preferably 1000 L·mol ⁻¹ ·cm ⁻¹ or less. is more preferable, and even more preferably 100 L·mol ⁻¹ ·cm ⁻¹ or less. 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 pigment derivatives include compounds described in the Examples below, JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, and JP-A-03-009961. , JP 03-026767, JP 03-153780, JP 03-045662, JP 04-285669, JP 06-145546, JP 06-212088, JP-A-06-240158, JP-A-10-030063, JP-A-10-195326, paragraph numbers 0086 to 0098 of International Publication No. 2011/024896, paragraph numbers 0063 to 0094 of International Publication No. 2012/102399 , paragraph number 0082 of International Publication No. 2017/038252, paragraph number 0171 of JP 2015-151530, paragraph number 0162 to 0183 of JP 2011-252065, JP 2003-081972, Patent No. 5299151 No. 2015-172732, 2014-199308, 2014-085562, 2014-035351, and 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, 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 even more preferably 10% by mass or less. Further, the content of the pigment derivative is preferably 1 to 30 parts by mass based on 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, 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 even more preferably 15 parts by mass or less. In the resin composition of the present invention, only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types are used in combination, it is preferable that the total amount is within the above range.

<<Specific amine compound>>
The resin composition of the present invention must contain 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 do it.

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, even more preferably 10,000 or less, and particularly preferably 2,000 or less. Regarding the value of the molecular weight of the specific amine compound, if the molecular weight 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, if the molecular weight of a 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. In addition, if 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 the viscosity method cannot be used or it is difficult to measure, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) 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 even more 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 even more preferably 10 or more.

The basic group that the specific amine compound has 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, and a primary amino group and a secondary amino group. More preferably, it is a compound containing a group and a tertiary amino group, respectively.

Moreover, the amino group that the specific amine compound has 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 structure or a 6-membered ring structure, more preferably a cyclic amino group having a 6-membered ring structure, and an aliphatic cyclic amino group having a 6-membered ring structure. More preferably, it is a group. The cyclic amino group preferably has a hindered amine structure, particularly preferably a 6-membered ring hindered amine structure. The hindered amine structure preferably has substituents such as alkyl groups on two carbon atoms in the ring structure adjacent to the nitrogen atom of the cyclic amino 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. 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 include pentamethylpyrrolidyl group and 2,2,5,5-tetramethylpyrrolidyl group. Among them, 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 a polyalkylene imine because it can further improve the storage stability of the resin composition. Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine, and has a branched structure each containing a primary amino group, a secondary amino group, and a tertiary amino group. The alkylene imine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms. Specific examples of alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, etc. Ethyleneimine or propyleneimine is preferable, and ethyleneimine is more preferable. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. Further, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more of primary amino groups based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. , more preferably 30 mol% or more. Commercial products of polyethyleneimine 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 even more 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 even more preferably 3% by mass or less.

Further, the content of the specific amine compound is preferably 0.5 to 10 parts by weight per 100 parts by weight of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more 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 even more preferably 5 parts by mass or less.

Further, the content of the specific amine compound is preferably 0.5 to 50 parts by mass based on 100 parts by mass of the graft resin having acid groups. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more 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 even more preferably 30 parts by mass or less.

<<Compound having a 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 epoxy compounds include those described in paragraph numbers 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0085 to 0092 of JP2014-089408. Compounds described in JP-A No. 2017-179172 can also be used. Their contents are incorporated herein.

The epoxy compound may be a low-molecular compound (for example, molecular weight less than 2000, or even less than 1000), or a macromolecule (for example, molecular weight 1000 or more; in the case of a polymer, the weight average molecular weight is 1000 or more). But that's fine. 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 5,000 or less, and even more preferably 3,000 or less.

As the epoxy compound, epoxy resin can be preferably used. Examples of epoxy resins include epoxy resins that are glycidyl ethers of phenolic compounds, epoxy resins that are glycidyl ethers of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, and glycidyl esters. Epoxy resins, glycidylamine-based epoxy resins, epoxy resins made by glycidylating halogenated phenols, condensates of silicon compounds with epoxy groups and other silicon compounds, polymerizable unsaturated compounds with epoxy groups and other Examples include copolymers with other polymerizable unsaturated compounds. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g/eq, more preferably 310 to 1700 g/eq, even more preferably 310 to 1000 g/eq.

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

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, more preferably 1% by mass or more. The upper limit is, for example, preferably 15% by mass or less, more preferably 10% by mass or less. The number of compounds having a cyclic ether group may be one, or two or more. In the case of two or more types, it is preferable that their total amount falls within the above range.

<<Organic solvent>>
The resin composition of the present invention contains an organic solvent. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For these details, paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein. Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents 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, ethyl carbitol acetate, butyl carbyl 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, methyl ethyl ketone, Examples include gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol, and the like. However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).

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

Examples of methods for removing impurities such as metals from organic solvents 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 material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

The organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.

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, from the viewpoint of environmental regulations, it is preferable that the resin composition of the present invention does not substantially contain environmentally regulated substances. In the present invention, "not substantially containing environmentally controlled substances" means that the content of environmentally controlled substances in the resin composition is 50 mass ppm or less, preferably 30 mass ppm or less. , more preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less. Examples of environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are REACH (Registration Evaluation Authorization and Restriction of Chemicals) rules, PRTR (Pollutant Release and Transfer Register) ) Act, VOC (Volatile Organic Compounds) regulations, etc., it is registered as an environmentally regulated substance, and the amount used and handling The method is strictly regulated. These compounds are sometimes used as solvents when producing each component used in the resin composition, and may be mixed into the resin composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is preferable to reduce the amount of these substances as much as possible. Examples of methods for reducing environmentally controlled substances include a method of heating or reducing pressure in the system to raise the temperature above the boiling point of the environmentally controlled substance to distill off the environmentally controlled substances from the system. Furthermore, when distilling off a small amount of environmentally regulated substances, it is also useful to carry out azeotropy with a solvent having the same boiling point as the relevant solvent in order to increase efficiency. In addition, if a compound that has radical polymerizability is contained, a polymerization inhibitor or the like may be added to prevent the radical polymerization reaction from proceeding during vacuum distillation and crosslinking between molecules. You can. These distillation methods include the stage of raw materials, the stage of products made by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or the stage of resin compositions prepared by mixing these compounds. It is possible at any stage.

<<Curing accelerator>>
The resin composition of the present invention may also contain a curing accelerator. Examples of the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds, and the like. Specific examples of the curing accelerator include compounds described in paragraph numbers 0094 to 0097 of International Publication No. 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, and JP 2013-041165. Compounds described in paragraph numbers 0186 to 0251 of JP-A No. 2014-055114, compounds described in paragraph numbers 0071 to 0080 of JP-A-2012-150180, JP-A-2011-253054 Examples include alkoxysilane compounds having an epoxy group described in Japanese Patent Publication No. 5765059, compounds described in paragraph numbers 0085 to 0092 of Japanese Patent No. 5765059, and carboxyl group-containing epoxy curing agents described in JP 2017-036379. When containing a curing accelerator, 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.

<<Ultraviolet 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, etc. can be used. These details are described in paragraph numbers 0052 to 0072 of JP2012-208374A, paragraphs 0317 to 0334 of JP2013-068814A, and paragraphs 0061 to 0080 of JP2016-162946A. The contents of these compounds are incorporated herein. Commercially available UV absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Furthermore, examples of the benzotriazole compound include the MYUA series manufactured by Miyoshi Yushi (Kagaku Kogyo Nippo, February 1, 2016). Further, as the ultraviolet absorber, compounds described in paragraph numbers 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 type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.

<<Antioxidant>>
The resin composition of the present invention can contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenol compounds include hindered phenol compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. The above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Further, as the antioxidant, a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable. Further, as the antioxidant, phosphorus-based antioxidants can also be suitably used. Further, as the antioxidant, a 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 type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.

<<Polymerization inhibitor>>
The resin composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. When containing a polymerization inhibitor, the content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass. The number of polymerization inhibitors may be one, or two or more. In the case of two or more types, it is preferable that the total amount falls 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. Furthermore, the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through 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 an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferable. Specific examples of silane coupling agents 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 Examples include 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 compounds described in paragraph numbers 0018 to 0036 of JP-A No. 2009-288703 and compounds described in paragraph numbers 0056 to 0066 of JP-A-2009-242604. , the contents of which are incorporated herein. When containing a silane coupling agent, 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. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, it is preferable that the total amount falls within the above range.

<<Surfactant>>
The resin composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. Examples of the surfactant include the surfactants described in paragraph numbers 0238 to 0245 of International Publication No. 2015/166779, the contents of which are incorporated herein.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By incorporating the fluorine-based surfactant into the resin composition, liquid properties (especially fluidity) are further improved, and liquid saving properties are further improved. It can be improved. Furthermore, it is also possible to form a film with small thickness unevenness.

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

Examples of fluorine-based surfactants include surfactants described in paragraph numbers 0060 to 0064 of JP 2014-041318 (corresponding paragraph numbers 0060 to 0064 of WO 2014/017669), and the like; Examples include the surfactants described in paragraph numbers 0117 to 0132 of Publication No. 132503 and the surfactants described in JP-A-2020-008634, the contents of which are incorporated herein. Commercially available fluorosurfactants include Megafac 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 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo Corporation) 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by 3M Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Ftergent 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (manufactured by NEOS), etc. Can be mentioned.

In addition, fluorine-based surfactants are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing a fluorine atom is severed and the fluorine atom volatizes. It can be used suitably. Examples of such fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), An example is DS-21.

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. Regarding such a fluorine-based surfactant, the description in JP-A No. 2016-216602 can be referred to, and the contents thereof are incorporated herein.

A block polymer can also be used as the fluorosurfactant. Examples include compounds described in JP-A No. 2011-089090. The fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) (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 No. 2010-032698 and the following compounds are also exemplified as the fluorine-containing surfactant used in the present invention.
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. In the above compounds, % indicating the proportion of repeating units is mol%.

Further, as the fluorine-containing surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A No. 2010-164965, such as Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation. , RS-72-K, etc. Further, as the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa (manufactured by Hikari Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), etc. can be mentioned.

Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (manufactured by Momentive Performance Materials), (manufactured by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (manufactured by BYK-Chemie Co., Ltd.), 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 their total amount falls within the above range.

<<Other ingredients>>
The resin composition of the present invention may contain sensitizers, curing accelerators, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, fillers, antifoaming agents, flame retardants), as necessary. , a leveling agent, a peeling accelerator, a fragrance, a surface tension regulator, a chain transfer agent, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. These components are described, for example, in paragraphs 0183 and after of JP-A-2012-003225 (corresponding paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812), and in paragraphs of JP-A-2008-250074. The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated into the present specification. Furthermore, the resin composition of the present invention may contain a latent antioxidant, if necessary. A latent antioxidant is a compound whose moiety that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst. Examples include compounds that function as antioxidants by removing protective groups. Examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Co., Ltd.).

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

In the resin composition of the present invention, the content of free metal that is not bonded or coordinated with pigments is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less. , it is particularly preferable that it does not substantially contain it. According to this aspect, stabilization of pigment dispersibility (inhibition of agglomeration), improvement of spectral characteristics due to improved dispersibility, stabilization of curable components, suppression of conductivity fluctuations due to elution of metal atoms and metal ions, Effects such as improved display characteristics can be expected. In addition, JP 2012-153796, JP 2000-345085, JP 2005-200560, JP 08-043620, JP 2004-145078, JP 2014-119487, Described in JP 2010-083997, JP 2017-090930, JP 2018-025612, JP 2018-025797, JP 2017-155228, JP 2018-036521, etc. You can also get the same effect. The types of free metals mentioned above include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Examples include Cs, Ni, Cd, Pb, Bi, and the like. Further, in the resin composition of the present invention, the content of free halogen that is not bonded or coordinated with pigments etc. is preferably 100 ppm or less, more preferably 50 ppm or less, and preferably 10 ppm or less. It is more preferable, and it is particularly preferable that it is substantially not contained. Halogens include F, Cl, Br, I and their anions. Examples of methods for reducing free metals and halogens in the resin composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchange resins.

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

From the perspective of environmental regulations, the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts may be regulated. In the resin composition of the present invention, when reducing the content of the above-mentioned compounds, perfluoroalkylsulfonic acids (particularly perfluoroalkylsulfonic acids whose perfluoroalkyl group has 6 to 8 carbon atoms), salts thereof, and perfluoroalkylsulfonic acids, The content of fluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid whose perfluoroalkyl group has 6 to 8 carbon atoms) and its salt is 0.01 ppb to 1,000 ppb based on the total solid content of the resin composition. It is preferably in the range of , more preferably in the range of 0.05 ppb to 500 ppb, 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 perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt. For example, by using a compound that can be substituted for perfluoroalkylsulfonic acid and its salt, and a compound that can be substituted for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid You may also select a resin composition that is substantially free of and salts thereof. Compounds that can be substituted for regulated compounds include, for example, compounds that are excluded from regulated targets due to differences in the number of carbon atoms in perfluoroalkyl groups. However, the above content does not preclude the use of perfluoroalkylsulfonic acids and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof. The resin composition of the present invention may contain perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof, within the maximum allowable range.

<<Storage container>>
The container for storing the resin composition is not particularly limited, and any known container can be used. In addition, for the purpose of suppressing impurities from entering raw materials and resin compositions, we also use multilayer bottles with container inner walls made of 6 types and 6 layers of resin, and bottles with 7 layers of 6 types of resin as storage containers. It is also preferable to use Examples of such a container include the container described in JP-A No. 2015-123351. Further, the inner wall of the container is preferably made of glass, stainless steel, or the like for the purpose of preventing metal elution from the inner wall of the container, increasing the storage stability of the resin composition, and suppressing component deterioration.

<Method for preparing resin composition>
The resin composition of the present invention can be prepared by mixing the above-mentioned components. When preparing a resin composition, the resin composition may be prepared by simultaneously dissolving and/or dispersing all components in an organic solvent, or, if necessary, each component may be suitably mixed into two or more solutions or dispersions. The resin composition may be prepared by mixing these at the time of use (at the time of application).

Further, it is preferable to include a process of dispersing an organic pigment in preparing the resin composition. In the process of dispersing organic pigments, mechanical forces used for dispersing organic pigments include 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. Furthermore, when grinding organic pigments in a sand mill (bead mill), it is preferable to use small-diameter beads or increase the filling rate of the beads, thereby increasing the grinding efficiency. Further, it is preferable to remove coarse particles by filtration, centrifugation, etc. after the pulverization treatment. In addition, the process and dispersion machine for dispersing organic pigments are described in ``Complete collection of dispersion techniques, published by Information Technology Co., Ltd., July 15, 2005'' and ``Dispersion technology centered on suspensions (solid/liquid dispersion systems) and industrial The process and dispersion machine described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be suitably used. In addition, in the process of dispersing the organic pigment, particle refinement treatment may be performed in a salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in JP-A No. 2015-194521 and JP-A No. 2012-046629 can be referred to, for example.

In 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 and the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (for example, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP). Examples include filters using materials such as (including high-density, ultra-high molecular weight polyolefin resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

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. Regarding the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Microfilter Co., Ltd., etc. can be used. .

Moreover, it is also preferable to use a fibrous filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include the SBP type series (SBP008, etc.), the TPR type series (TPR002, TPR005, etc.), and the SHPX type series (SHPX003, etc.) manufactured by Loki Techno.

When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed two or more times. Further, filters having different pore diameters within the above-mentioned range may be combined. Alternatively, only the dispersion liquid may be filtered with the first filter, and then filtered with the second filter after other components are mixed.

<Membrane>
The film of the present invention is a film obtained from the resin composition of the present invention described above. The film thickness of the film of the present invention can be adjusted as appropriate depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

The film of the present invention can be used for color filters, near-infrared transmission filters, near-infrared cut filters, black matrices, light-shielding films, and the like. The film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

<Membrane manufacturing method>
Next, a method for manufacturing the membrane of the present invention will be explained. The film of the present invention can be manufactured 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 methods for forming patterns (pixels) include photolithography and dry etching, with photolithography being preferred.

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 to light in a pattern, and a step of exposing the resin composition layer to light. 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-bake step) and a step of baking the developed pattern (pixel) (post-bake step) may be provided.

In the step of forming a resin composition layer, a resin composition layer is formed on a support using the resin composition of the present invention. The support is not particularly limited and can be appropriately selected depending on the application. For example, a glass substrate, a silicon substrate, etc. may be mentioned, and a silicon substrate is preferable. Further, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate. Further, a black matrix that isolates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with a base layer for improving adhesion with the upper layer, preventing substance diffusion, or flattening the substrate surface. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30 to 80° when measured with water. When the surface contact angle of the underlayer is within the above range, the resin composition has good wettability. The surface contact angle of the underlayer can be adjusted, for example, by adding a surfactant.

As a method for applying the resin composition, a known method can be used. For example, dropping method (drop casting); slit coating method; spray method; roll coating method; spin coating method; casting coating method; slit and spin method; (methods described in publications); inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Examples include various printing methods; transfer methods using molds, etc.; nanoimprint methods. The application method for inkjet is not particularly limited, and for example, the method shown in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents," Published February 2005, Sumibe Techno Research (especially from page 115). 133 pages), and methods described in JP-A No. 2003-262716, JP-A No. 2003-185831, JP-A No. 2003-261827, JP-A No. 2012-126830, JP-A No. 2006-169325, etc. Can be mentioned. Furthermore, regarding the method of applying the resin composition, the descriptions in International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and the contents of these are incorporated herein.

The resin composition layer formed on the support may be dried (prebaked). If the film is manufactured by a low-temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even 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, even more preferably 80 to 220 seconds. Prebaking can be performed on a hot plate, 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 to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.

Examples of radiation (light) that can be used for exposure include g-line and i-line. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used.

Moreover, upon exposure, exposure may be performed by continuously irradiating light, or may be performed by irradiating light in a pulsed manner (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the 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 during exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially The exposure may be carried out in an oxygen-free environment (without oxygen), or in a high oxygen atmosphere with an oxygen concentration of more than 21 vol% (for example, 22 vol%, 30 vol%, or 50 vol%). Further, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000W/m ² to 100000W/m ² (for example, 5000W/m ² , 15000W/m ² , or 35000W/m ² ). Can be done. The oxygen concentration and the exposure illuminance may be appropriately combined. For example, the illumination intensity may be 10,000 W/m ² at an oxygen concentration of 10% by volume, or 20,000 W/m ² at an oxygen concentration of 35% by volume.

Next, the unexposed portions of the resin composition layer are developed and removed to form a pattern (pixel). The unexposed areas of the resin composition layer can be removed by development using a developer. As a result, the unexposed portions of the resin composition layer in the exposure step are eluted into the developer, leaving only the photocured portions. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) prepared by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents 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 include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. As for the alkali agent, compounds with a large molecular weight are preferable from the environmental and safety standpoints. 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. Moreover, the developer may further contain a surfactant. For convenience in transportation and storage, the developing solution may be manufactured as a concentrated solution and then diluted to a required concentration before use. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, rinsing is preferably performed by supplying a 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 that discharges the rinsing liquid from the center of the support to the periphery of the support. At this time, when moving the nozzle from the center of the support to the peripheral edge, the nozzle may be moved while gradually decreasing its moving speed. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. The same effect can also be obtained by gradually reducing the rotational speed of the support while moving the nozzle from the center of the support to the peripheral edge.

After development, it is preferable to perform additional exposure treatment or heat treatment (post-bake) after drying. Additional exposure processing and post-bake are post-development curing processing to complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C. Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions. . When performing additional exposure processing, the light used for exposure is preferably light with 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.

Pattern formation by the dry etching method includes the steps 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 this cured material layer, a step of exposing the photoresist layer in a pattern and then developing it to form a resist pattern, and etching the cured material layer using this resist pattern as a mask. It is preferable to include a step of dry etching using gas. In forming the photoresist layer, it is preferable to further perform a prebaking process. In particular, as a process for forming the photoresist layer, it is desirable to perform a heat treatment after exposure and a heat treatment after development (post-bake treatment). Regarding pattern formation by the dry etching method, the descriptions in paragraphs 0010 to 0067 of JP-A No. 2013-064993 can be referred to, and the contents thereof are incorporated into the present specification.

<Optical filter>
The optical filter of the present invention has the film of the present invention described above. Types of optical filters include color filters, near-infrared cut filters, near-infrared transmission filters, etc., and color filters are preferred. The color filter preferably has the film of the invention as its pixels, more preferably the film of the invention as colored pixels, and even more preferably the film of the invention as green pixels.

Optical filters can be used in solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), image display devices, and the like.

In the optical filter, the film thickness of the film of the present invention can be adjusted as appropriate depending on the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

The width of 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 even more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, even more preferably 1.0 μm or less, and even more preferably 0.8 μm or less. Furthermore, 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 even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example. The surface roughness of a pixel can be measured using, for example, an AFM (atomic force microscope) Dimension 3100 manufactured by Veeco. Further, the contact angle of water on the pixel can be set to a suitable 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 10 ⁹ Ω·cm or more, more preferably 10 ¹¹ Ω·cm or more. Although the upper limit is not specified, it is preferably 10 ¹⁴ Ω·cm or less, for example. The volume resistance value of a 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 a protective layer, various functions such as oxygen blocking, low reflection, hydrophilic and hydrophobic properties, 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 the protective layer, a chemical vapor deposition method, and a method of pasting a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide. Resin, 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 include resin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, 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 intended for oxygen blocking, the protective layer preferably contains a polyol resin, SiO ₂ and Si ₂ N ₄ . Furthermore, in the case of a protective layer intended for low reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

The protective layer may contain organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, and other additives, as necessary. It may contain. Examples of organic/inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like. As the absorber for light of a specific wavelength, a known absorber can be used. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, based on the total weight of the protective layer.

Further, as the protective layer, the protective layers described in paragraph numbers 0073 to 0092 of JP-A No. 2017-151176 can also be used.

The optical filter may have a base layer. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30 to 80° when measured with water. The surface contact angle of the underlayer can be adjusted, for example, by adding a surfactant.

The optical filter may have a structure in which each pixel is embedded in a space partitioned into, for example, a grid pattern by partition walls.

<Solid-state imaging device>
The solid-state imaging device of the present invention has the film of the present invention described above. The structure of the solid-state image sensor 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 sensor, and examples thereof include the following structures.

The substrate has a plurality of photodiodes that constitute the light receiving area of a solid-state image sensor (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 is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a configuration in which a color filter is provided on the device protective film. Furthermore, a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film and below the color filter (on the side closer to the substrate), or a configuration in which the condensing means is provided on the color filter, etc. There may be. Further, the color filter may have a structure in which each pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition wall preferably has a low refractive index for each pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No. 2018/043654. Further, as shown in Japanese Patent Application Laid-open No. 2019-211559, an ultraviolet absorbing layer may be provided within the structure of the solid-state image sensor to improve light resistance. An imaging device equipped with the solid-state imaging device of the present invention can be used not only as a digital camera or an electronic device having an imaging function (such as a mobile phone), but also as a vehicle-mounted camera or a surveillance camera.

<Image display device>
The image display device of the present invention has the film of the present invention described above. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of an image display device and details of each image display device, see, for example, “Electronic Display Devices (written by Akio Sasaki, Kogyo Chosenkai Co., Ltd., published in 1990)” and “Display Devices (written by Junaki Ibuki, published by Sangyo Tosho)”. Co., Ltd., issued in 1989). Further, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994)". There is no particular restriction on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to 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, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit 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)
Precolumn: TSKGUARDCOLUMN MP (XL) 6mm x 40mm (manufactured by Tosoh Corporation)
Sample side column: Directly connect the following 4 columns [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℃
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 volume: 100μL
Data collection time: 16-46 minutes after sample injection Sampling pitch: 300ms (milliseconds)

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

<Method for measuring C=C value (ethylenic unsaturated bond-containing group value)>
The C=C value (ethylenic unsaturated bond-containing group value) of the resin was calculated from the raw materials used to synthesize the resin.

<Production 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 was prepared as a reaction tank, and the other , as a monomer dropping tank, 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"), and t-butylperoxy-2-ethylhexane. Prepare a mixture of 4 parts by mass of Noate ("Perbutyl O" manufactured by NOF Corporation; hereinafter referred to as "PBO") and 60 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") by stirring, A chain transfer agent dropping tank was prepared in which 8 parts by mass of n-dodecanethiol (hereinafter referred to as "n-DM") and 32 parts by mass of PGMEA were thoroughly stirred and mixed. After charging 375 parts by mass of PGMEA into a reaction tank and purging with nitrogen, the reaction tank was heated in an oil bath while stirring to raise the temperature of the reaction tank to 90°C. After the temperature of the reaction tank stabilized at 90°C, dropping into the reaction tank was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropwise addition took 135 minutes while maintaining the temperature at 90°C. Sixty minutes after the dropwise addition was completed, the temperature was started to rise to 110° C. in the reaction tank. After maintaining the temperature at 110° C. for 3 hours, the reaction solution was cooled to room temperature. Add 1000 parts by mass of water to the cooled reaction solution, collect the precipitated solid (polymer) by filtration, and wash the filtered solid twice with 100 parts by mass of ethanol and once with 500 parts by mass of water. 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, a PGMEA solution of glycerin monomethacrylate (compound (1-1) having the following structure, hereinafter referred to as "GLA") and glycidyl methacrylate ( A PGMEA solution of compound (2-1) with 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 is Resin solutions (B-1-1) to (B-1-6) were produced so that the contents were 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) does not contain any GLA or GMA components.

In the table below, the contents of GLA and GMA in each resin solution are the results of quantitative determination by high performance liquid chromatography (HPLC). In addition, since the lower limit of detection of each component by HPLC method was 0.1 mass ppm, when it was below the lower limit of detection, it was written as "<0.1" in the table below. Moreover, among the components corresponding to Compound A contained in each resin solution, components other than GLA were below the lower detection limit. Therefore, the content of GLA corresponds to the content of compound A. Moreover, among the components corresponding to Compound B contained in each resin composition, components other than GMA were below the lower detection limit. 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 was prepared as a reaction tank, and on the other hand, dimethyl-2,2'-[oxybis( 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 stirring mixture of 4 parts by mass of PBO and 60 parts by mass of diethylene glycol dimethyl ether (hereinafter referred to as "DMDG"), and add 8 parts by mass of n-DM and 32 parts by mass of DMDG as a chain transfer agent dropping tank. A stirred mixture was prepared. After charging 375 parts by mass of DMDG into a reaction tank and purging with nitrogen, the temperature of the reaction tank was raised to 90° C. by heating in an oil bath while stirring. After the temperature of the reaction tank stabilized at 90°C, dropping into the reaction tank was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropwise addition took 135 minutes while maintaining the temperature at 90°C. Sixty minutes after the dropwise addition was completed, the temperature was started to rise to 110° C. in the reaction tank. After maintaining the temperature at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of an oxygen/nitrogen=5/95 (v/v) mixed gas was started. Next, in a reaction tank, 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. 0.8 parts by mass of (referred to as ")" was added, and the mixture was reacted as it was at 110° C. for 3 hours. 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. Add 1000 parts by mass of water to the cooled reaction solution, collect the precipitated solid (polymer) by filtration, and wash the filtered solid 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, a PGMEA solution of GLA and a PGMEA solution of GMA are further added, and the resin concentration (solid content) of the final resin solution is A resin solution (B-2-1) was produced so that the resin solution (concentration) was 30% and the content of each component was as shown in the table below.
Note that among the components corresponding to compound A contained in the resin solution (B-2-1), components other than GLA were below the detection limit. Therefore, the content of GLA corresponds to the content of compound A. Furthermore, among the components corresponding to compound B contained in the resin solution (B-2-1), components other than GMA were below the detection limit. 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) and ω-carboxy-polycaprolactone monoacrylate (Toa) were added. 51 parts by mass of PGMEA (Aronix M-5300, manufactured by Seimei Co., Ltd.) were introduced to obtain a mixture. The mixture was stirred while bubbling nitrogen.
Next, the mixture was heated to 75° C. while flowing nitrogen gas into the flask. Next, 0.82 parts by mass of n-DM was added to the mixture, followed by 0.43 parts by mass of methyl 2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-601). was added to start the polymerization reaction. 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 reacting for an additional 2 hours, the mixture was heated to 90°C and stirred for 3 hours. The polymerization reaction was completed by the above operation. After the polymerization reaction was completed, 9.6 parts by mass of dimethyldodecylamine as an amine compound and 0.3 parts by mass of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a polymerization inhibitor were added under air. Then, 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 the dropwise addition was completed, the reaction was continued for 24 hours at 90° C. in air, the completion of the reaction was confirmed by acid value measurement, and the reaction solution was cooled to room temperature. Add 1000 parts by mass of water to the cooled reaction solution, collect the precipitated solid (polymer) by filtration, and wash the filtered solid twice with 100 parts by mass of ethanol and once with 500 parts by mass of water. 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, 4-(2,3-dihydroxypropoxy)butyl acrylate (compound (1-4) with the following structure, A PGMEA solution of 4HBAGE (referred to as "4HBAGE-O") and a PGMEA solution of 4HBAGE are added, and the resin concentration (solid content concentration) of the final resin solution is 30%, and the content of each component is A resin solution (B-3-1) was prepared so that the amount was as shown in the table below.
Note that among the components corresponding to compound A contained in the resin solution (B-3-1), components other than 4HBAGE-O were below the detection limit. Therefore, the content of 4HBAGE-O corresponds to the content of compound A. Furthermore, among the components corresponding to compound B contained in the resin solution (B-3-1), components other than 4HBAGE were below the detection limit. 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 was placed in a reaction vessel equipped with a gas introduction tube, thermometer, condenser, and 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, and after purging with nitrogen gas, the reaction was carried out at 120°C for 5 hours (first step ). It was confirmed by measuring the acid value 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 were added. 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 mixture was reacted for 12 hours (second step). It was confirmed by solid content measurement that 95% had reacted. Next, the inside of the flask was purged with air, and 35.0 parts by mass of 2-methacryloyloxyethyl isocyanate and 0.1 parts by mass of hydroquinone were charged and reacted at 70° C. for 4 hours (third step). After confirming by infrared absorption spectroscopy that the peak at 2270 cm ^-1 based on isocyanate groups had disappeared, the reaction solution was cooled to obtain Resin B-4 having the following structure. The resulting resin B-4 had an acid value of 40 mgKOH/g, a weight average molecular weight of 12,000, and a double bond equivalent of 692 g/mol.
In formula (B-4), one of *1 and *2 is combined with *5 or *6 to form a polyester main chain, and the other is combined with *3 or *4 to form a polyester main chain. is forming. One of *3 and *4 is combined with *1 or *2 to form a polyester main chain, and the other is combined with an OH group to form a carboxylic acid. One of *5 and *6 is combined with *1 or *2 to form a polyester main chain, and the other is combined with an OH group to form a carboxylic acid.

<Production of finely divided pigment>
[Production example 2-1]
(Manufacture of finely divided 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 into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and Kneaded for hours. The obtained kneaded composition was poured into 3000 parts by mass of warm water, stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C overnight to form a finely divided pigment. (PR254M) was obtained.

[Production Examples 2-2 to 2-23]
Each finely divided pigment was obtained by performing the same treatment as in Production Example 2-1 above, except that the pigment used in Production Example 2-1 was changed from Pigment Red 254 to the pigment shown in the table below.

<Production of pigment dispersion>
[Manufacture example 3-1]
(Manufacture of pigment dispersion (GB-1))
The raw materials shown below were mixed in the parts by mass shown below, and then dispersed for 3 hours in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm. Thereafter, the resulting mixture was filtered through a filter with a pore size of 5.0 μm to produce a pigment dispersion (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, derivative 1 is a compound represented by the following structural formula. Further, resin solution B-5-1 is a 30% by mass PGMEA solution of resin B-5 having the following structure (weight average molecular weight: 23,000, acid value: 50 mgKOH/g).

[Production Examples 3-2 to 3-45]
Each dispersion was prepared in the same manner as in Production Example 3-1 above, except that the types and amounts (parts by mass) of the finely divided pigment, derivative, resin solution, and solvent used were changed as shown in the table below. Manufactured.

In the above table, TiB is titanium oxynitride particles (manufactured by Mitsubishi Materials Electronic Chemicals), CB is carbon black particles (manufactured by Cabot, average primary particle diameter 15 nm), and _ZrO2 is zirconium oxide particles (manufactured by Nippon Denko Corporation, average primary particle diameter 15 nm). TiO ₂ is titanium oxide particles (manufactured by Ishihara Sangyo Co., Ltd., TTO-51 (C), average primary particle size 10 to 30 nm, surface treated with alumina and stearic acid). Further, derivatives 2 to 7 are compounds represented by the following structural formulas.

<Manufacture of resin composition>
[Manufacture example 4-1]
(Manufacture of resin composition (GR-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a filter with 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 Photoinitiator (I-1): 0.6 parts by mass Ultraviolet absorber (U-1): 0.4 parts by mass Surfactant (S-1): 4.2 parts by mass Polymerization inhibitor (IN-1): 0.005 parts by mass PGMEA: 6.3 parts by mass

Here, the abbreviations of various materials represent the following.
Polymerizable monomer (M-1): 7:3 mixture of dipentaerythritol hexaacrylate (DPHA) and dipentaerythritol pentaacrylate (Nippon Kayaku, KAYARAD DPHA)
Photopolymerization initiator (I-1): Irgacure OXE-01 (manufactured by BASF)
Ultraviolet absorber (U-1): Triazine-based ultraviolet absorber "Tinuvin477" (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 proportion of repeating units is mol%).
Polymerization inhibitor (IN-1): p-methoxyphenol

[Production Examples 4-2 to 4-48]
(Manufacture of polymerizable composition)
A resin composition was produced in the same manner as in Production Example 4-1 above, except that the materials used were changed to those shown in the table below.

[Manufacture 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 table above, the abbreviations for various materials represent the following.
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): Compound with the following structure
Photoinitiator (I-4): Omnirad 369 (manufactured by IGM Resins B.V.)
Photopolymerization initiator (I-5): Compound with the following structure
Additive (AD-1): Pionin D6112W (Takemoto Yushi Co., Ltd., arylphenyl ether type nonionic surfactant)
Additive (AD-2): Ultrapure water

<Evaluation of resin composition>
(Measurement of content and moisture content of GLA, GMA, 4HBAGE-O and 4HBAGE)
The contents of GLA, GMA, 4HBAGE-O, and 4HBAGE contained in each of the prepared resin compositions were determined using high performance liquid chromatography (HPLC). The quantitative results are summarized in the table below. In addition, since the lower limit of detection of each component by HPLC method was 0.1 mass ppm, when it was below the lower limit of detection, it was written as "<0.1" in the table below.
Further, the amount of water contained in each resin composition was determined by Karl Fischer measurement method. The measurement results of moisture content are also recorded in the table below.

(Evaluation of adhesion)
Each resin composition was prebaked onto a silicon wafer with a diameter of 8 inches (203.2 mm) on which a thermal oxide film (SiO ₂ film) with a thickness of 400 nm was formed using a spin coater so that the thickness after prebaking was 4 μm. The coating was applied using a hot plate at 110° C. for 120 seconds (prebaking).
Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm is exposed (exposure amount 50 to 1700 mJ/cm ² ).
Next, the exposed composition layer was developed using a developing device (Act8 manufactured by Tokyo Electron). Shower development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as the developer. Thereafter, rinsing was performed using a spin shower using pure water, followed by spin drying, and then heat treatment (post-bake) was performed for 5 minutes using a 200° C. hot plate to obtain a pattern.
Find the difference ΔE (E2-E1) between the minimum exposure amount E1 required to form a pattern of width 100 μm x length 1000 μm and the minimum exposure amount E2 required for all of the aforementioned patterns to be in close contact, and calculate the following: Adhesion was evaluated using standards. It means that the smaller ΔE is, the better the adhesion is. The adhesion of the patterns 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 less than 100 mJ/cm ² .
3: ΔE exceeds 100 mJ/cm ² .
At an exposure dose of 2:50 to 1700 mJ/ ^cm2 , at least one line pattern with a width of 100 μm and a length of 1000 μm could be formed, but all 25 lines could not be formed.
With an exposure dose of 1:50 to 1700 mJ/cm ² , a pattern with 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 was applied onto a silicon wafer with a diameter of 8 inches (203.2 mm) on which a thermal oxide film (SiO ₂ film) with a thickness of 400 nm was formed on the surface so that the film thickness after post-baking was 0.6 μm. It was applied using a spin coating method. Then, using a hot plate, post-baking was performed at 100° C. for 2 minutes. Next, using a KrF scanner exposure machine, pulse exposure was performed under the following conditions by irradiating light through a mask having a Bayer pattern with a pixel (pattern) size of 1.1 μm square. Next, paddle development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, it was rinsed with a spin shower and further washed with pure water. Next, pixels (patterns) were formed by heating at 200° C. for 5 minutes using a hot plate. The pulse exposure conditions using the KrF scanner exposure machine are as follows.

-Pulse exposure conditions-
Exposure light: KrF line (wavelength 248nm)
Maximum instantaneous illuminance: 250000000W/m ² (Average illuminance: 30000W/m ² )
Pulse width: 30 nanoseconds Frequency: 4kHz

Among the pixel patterns obtained above, the area where no hardened pixel pattern remains was observed using a length measurement SEM (scanning electron microscope, product name: S-9260, manufactured by Hitachi High-Technologies), and the degree of residue in this area was measured. was evaluated on the following five scales.

-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 with a size of 0.05 μm or less are observed. 2: More than 10 residues with a size (width of the longest axis) of 0.05 μm or less are observed, and the size is 0.05 μm or less. 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 using the above procedure are shown in the table below.

As shown in the table above, the examples had good adhesion evaluations.

Instead of the surfactant (S-1) in the resin compositions of Production Examples 4-1 to 4-47, 1.0% by mass of the surfactants (S-2) to (S-32) shown in the table below Even when a resin composition was used in place of the PGMEA solution, effects similar to those described above were obtained.
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: Ftergent 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: Megafac F-556 (manufactured by DIC Corporation)
S-10: Megafac F-557 (manufactured by DIC Corporation)
S-11: Megafac F-563 (manufactured by DIC Corporation)
S-12: Megafac F-560 (manufactured by DIC Corporation)
S-13: Megafac F-575 (manufactured by DIC Corporation)
S-14: Megafac R-41 (manufactured by DIC Corporation)
S-15: Megafac R-41-LM (manufactured by DIC Corporation)
S-16: Megafac R-01 (manufactured by DIC Corporation)
S-17: Megafac R-40 (manufactured by DIC Corporation)
S-18: Megafac R-40-LM (manufactured by DIC Corporation)
S-19: Megafac RS-43 (manufactured by DIC Corporation)
S-20: Megafac TF-1956 (manufactured by DIC Corporation)
S-21: Megafac R-94 (manufactured by DIC Corporation)
S-22: Megafac F-558 (manufactured by DIC Corporation)
S-23: Megafac F-561 (manufactured by DIC Corporation)
S-24: Megafac F-477 (manufactured by DIC Corporation)
S-25: Megafac F-554 (manufactured by DIC Corporation)
S-26: Megafac F-565 (manufactured by DIC Corporation)
S-27: Megafac F-568 (manufactured by DIC Corporation)
S-28: Megafac F-559 (manufactured by DIC Corporation)
S-29: Megafac F-555-A (manufactured by DIC Corporation)
S-30: Megafac RS-90 (manufactured by DIC Corporation)
S-31: Megafac RS-72-K (manufactured by DIC Corporation)
S-32: Megafac DS-21 (manufactured by DIC Corporation)

A non-photosensitive resin composition was prepared by replacing the entire amount of the polymerizable monomer and photopolymerization initiator with an epoxy compound (manufactured by Daicel Corporation, EHPE-3150) in resin composition G-9. Using this resin composition, a green pattern (green pixels) was formed in the same manner as described in paragraphs 0460 to 0468 of JP-A No. 2013-064999, and the adhesion of the pixel pattern was evaluated. However, it was confirmed that good adhesion was obtained.

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

(Example 1001)
A green colored composition was applied onto a silicon wafer by spin coating 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 device FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at an exposure dose of 1000 mJ/cm ² through a mask with a 2 μm square dot pattern. Next, paddle development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, it was rinsed with a spin shower and further washed with pure water. Next, the green colored composition was patterned by heating at 200° C. for 5 minutes using a hot plate to form green pixels. Similarly, a red colored composition and a blue colored composition were patterned using the same process to sequentially form red pixels and blue pixels, thereby forming a color filter having green pixels, red pixels, and blue pixels. In this color filter, green pixels are formed in a Bayer pattern, and in adjacent areas, red pixels and blue pixels are formed in an island pattern. 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. Note that a resin composition (GR-21) was used as the green colored composition. A resin composition (RR-1) was used as the red colored composition. A resin composition (BR-1) was used as the blue colored composition.

Claims (14)

A resin composition comprising a resin, a compound A having a molecular weight of 300 or less represented by formula (1), a compound B having a molecular weight of 300 or less represented by formula (2), and an organic solvent,
The content of the compound A in the total solid content of the resin composition is 0.1 to 2000 ppm by mass,
A resin composition in which the content of the compound B in the total solid content of the resin composition is 0.1 to 300 ppm by mass ;
In formula (1), Q ¹ represents an ethylenically unsaturated bond-containing group, and L ¹ represents a divalent linking group ;
In formula (2), Q ² represents an ethylenically unsaturated bond-containing group, and L ² represents a divalent linking group. The compound A is a compound represented by formula (1-1), a compound represented by formula (1-2), a compound represented by formula (1-3), or a compound represented by formula (1-4). The resin composition according to claim 1 , which is a compound represented by the following formula.
The compound B is a compound represented by formula (2-1), a compound represented by formula (2-2), a compound represented by formula (2-3), or a compound represented by formula (2-4). The resin composition according to claim 1 or 2, which is a compound represented by the formula:
The resin composition according to any one of claims 1 to 3 , comprising 0.1 to 120 parts by mass of the compound B per 100 parts by mass of the compound A. The resin composition according to any one of claims 1 to 4 , 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 ppm by mass. The resin composition according to any one of claims 1 to 5 , wherein the resin contains a group represented by 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. The resin composition according to any one of claims 1 to 6 , wherein the resin includes a resin containing a repeating unit represented by 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, R ³¹ represents a hydrogen atom or a substituent, R ³² represents a hydrogen atom or a methyl group. The resin composition according to any one of claims 1 to 7 , wherein the resin composition contains 0.3 to 2.0% by mass of water. The resin composition according to any one of claims 1 to 8 , further comprising a coloring material. The resin composition according to any one of claims 1 to 9 , further comprising a polyfunctional polymerizable monomer having two or more ethylenically unsaturated bond-containing groups and a photopolymerization initiator. A film obtained using the resin composition according to any one of claims 1 to 10 . An optical filter comprising the film according to claim 11 . A solid-state imaging device comprising the film according to claim 11 . An image display device comprising the film according to claim 11 .