Photosensitive resin composition, cured product, color filter, and image display device

Abstract

Provided is a photosensitive resin composition which has both high light scattering properties and high light transmittance, is developable, and has high heat resistance. This photosensitive resin composition contains (a) resin particles, (b) an alkali-soluble resin, and (c) a photopolymerization initiator, the resin particles (a) containing resin particles (a1) having a refractive index of 1.56-2.00 and an average primary particle diameter of 0.8 [mu] m or more, the alkali-soluble resin (b) containing an alkali-soluble resin (b1) having an olefinic double bond, and the photopolymerization initiator (c) containing a photopolymerization initiator. The photosensitive resin composition further contains at least one of (e) a polymerization inhibitor and (f) an ultraviolet absorber, and a cured film obtained by curing the photosensitive resin composition and having a thickness of 5 [mu] m has an average transmittance of 70% or more in a wavelength range of 400-700 nm.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, and further to a cured product obtained by curing the photosensitive resin composition, and a color filter and an image display device composed of the cured product.

[0002] This application claims priority based on Japanese Patent Application No. 2022-127368 filed in Japan on August 9, 2022, and the contents are incorporated herein by reference. Background Art

[0003] Conventional displays often use color filters that form red, green, and blue pixels using organic pigments. When light from a light source passes through the color filter, the pigments absorb the light, which reduces luminous efficiency.

[0004] In recent years, for the wide color range of display, low power consumption, the formation of pixel, color filter of luminescent nanocrystal particles such as quantum dots is being studied.Specifically, the structure of the blue pixel of the blue light from the light source is known to have the red pixel of the nanocrystal particles that comprises red luminescence, the green pixel of the nanocrystal particles that comprises green luminescence.Utilize the nanocrystal particles of luminescence, the light of red pixel and green pixel is scattered, but if the light of blue pixel is advanced in a straight line, then can become unclear image, therefore studied to import the scattering particles that are purpose with scattering in blue pixel.

[0005] In Patent Documents 1 and 2, metal oxides are used as scattering particles.

[0006] In order to improve the luminous efficiency of an organic electroluminescent device, Patent Documents 3 and 4 use melamine resin fine particles as scattering particles in a resin composition for a light scattering layer.

[0007] In Patent Documents 5 and 6, melamine resin fine particles are used as scattering particles of the composition containing quantum dots.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application No. 2020-508497

[0011] Patent Document 2: Japanese Patent Application Publication No. 2021-89433

[0012] Patent Document 3: Japanese Patent Application Publication No. 2015-114588

[0013] Patent Document 4: International Publication No. 2020 / 262271

[0014] Patent Document 5: Japanese Patent Application Publication No. 2021-39310

[0015] Patent Document 6: Japanese Patent Application Publication No. 2009-110930 Summary of the invention

[0016] Problem that the invention aims to solve

[0017] The inventors of the present invention studied compositions for pixels and found that the compositions described in Patent Documents 1 and 2 use metal oxides (titanium oxide) with a high refractive index as scattering particles. Therefore, although the light scattering property is improved, the light transmittance is reduced, resulting in a problem of reduced luminous efficiency.

[0018] The composition described in Patent Document 3 uses melamine resin fine particles having an average primary particle size of 200 to 800 nm as scattering particles. Therefore, although the composition has high light transmittance, it is found that the light scattering property is reduced.

[0019] The composition described in Patent Document 4 uses titanium oxide as high refractive particles having a refractive index of 2.0 or more and melamine resin fine particles having a refractive index of 2.0 or less as scattering particles. Therefore, although the light scattering property is high, there is a problem that the light transmittance is reduced.

[0020] The composition described in Patent Document 5 is a composition in which a non-alkali-soluble resin having no alkali-soluble components such as carboxylic acid is mixed with melamine resin particles as a dispersing resin. Since no alkali-soluble resin is contained in the photosensitive resin composition, it is found that residues are easily left when pattern exposure is performed and the developability is low. In addition, in a composition containing an alkali-soluble resin having no olefinic double bonds in the side chain as a dispersant, it is found that the heat resistance after exposure is reduced.

[0021] The composition described in Patent Document 6 contains an acrylic resin having an acid value, but since the acrylic resin does not have an ethylenic double bond in the side chain, there is a problem that the heat resistance is reduced.

[0022] Therefore, the present invention provides a photosensitive resin composition which has both high light scattering property and high light transmittance, is developable, and has high heat resistance.

[0023] The present invention also provides a cured product obtained by curing a photosensitive resin composition that has both high light scattering properties and high light transmittance and is developable and highly heat resistant, and an organic electroluminescent element, a semiconductor light emitting element, a color filter, a light scattering film, and an image display device having the cured product.

[0024] Solutions for solving problems

[0025] The present inventors have conducted intensive studies and have found that the above-mentioned problems can be solved by using specific resin particles and an alkali-soluble resin in a photosensitive resin composition, thereby completing the present invention.

[0026] That is, the gist of the present invention is as follows.

[0027] [1] A photosensitive resin composition comprising (a) resin particles, (b) an alkali-soluble resin, and (c) a photopolymerization initiator.

[0028] The resin particles (a) contain resin particles (a1) having a refractive index of 1.56 or more and 2.00 or less and an average primary particle size of 0.8 μm or more,

[0029] The (b) alkali-soluble resin includes an alkali-soluble resin (b1) having an olefinic double bond,

[0030] The photosensitive resin composition further comprises at least one of (e) a polymerization inhibitor and (f) an ultraviolet absorber,

[0031] A cured film having a thickness of 5 μm obtained by curing the photosensitive resin composition has an average transmittance of 70% or more in a wavelength range of 400 to 700 nm.

[0032] [2] The photosensitive resin composition according to [1], wherein the resin particles (a1) contain at least one of a benzoguanamine resin, a melamine resin, and a styrene resin.

[0033] [3] The photosensitive resin composition according to [1] or [2], wherein the (c) photopolymerization initiator comprises an alkylphenone-based photopolymerization initiator.

[0034] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of the alkali-soluble resin (b1) in the alkali-soluble resin (b) is 20% by mass or more.

[0035] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the content of the resin particles (a1) is 5% by mass or more relative to the total solid content of the photosensitive resin composition.

[0036] [6] The photosensitive resin composition according to any one of [1] to [5], further comprising (d) a photopolymerizable compound.

[0037] [7] The photosensitive resin composition according to any one of [1] to [6], further comprising (e) a polymerization inhibitor.

[0038] [8] The photosensitive resin composition according to any one of [1] to [7], further comprising (f) an ultraviolet absorber.

[0039] [9] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [8].

[0040]

[10] A color filter comprising the cured product described in [9] and light-emitting nanocrystal particles.

[0041]

[11] An image display device comprising the cured product according to [9].

[0042] Effects of the Invention

[0043] According to the present invention, it is possible to provide a photosensitive resin composition which has both high light scattering properties and high light transmittance, is developable, and has high heat resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 It is a schematic cross-sectional view of an example of a color filter including the cured product of the present invention. DETAILED DESCRIPTION

[0045] Hereinafter, the present invention will be described in detail. It should be noted that the following description is an example of the embodiment of the present invention, and the present invention is not limited to these as long as it does not exceed the gist of the invention.

[0046] In the present invention, “(meth)acrylic acid” means “either or both of acrylic acid and methacrylic acid”.

[0047] The “total solid content” refers to all components other than the solvent in the photosensitive resin composition. Even if a component other than the solvent is liquid at room temperature, the component is not included in the solvent but is included in the total solid content.

[0048] A numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0049] The term "(co)polymer" means both homopolymers and copolymers, and the terms "(acid) anhydride" and "(anhydrous) acid" mean both acids and their anhydrides.

[0050] The weight average molecular weight refers to a polystyrene-equivalent weight average molecular weight (Mw) based on GPC (gel permeation chromatography).

[0051] Unless otherwise specified, the acid value refers to the acid value converted into the effective solid content and is calculated by neutralization titration.

[0052] [1] Photosensitive resin composition

[0053] The photosensitive resin composition of the present invention contains (a) resin particles, (b) alkali-soluble resin and (c) photopolymerization initiator, and further contains at least one of (e) polymerization inhibitor and (f) ultraviolet absorber. Other components may be contained as needed, for example, (d) photopolymerizable compound, (g) dispersant, solvent, chain transfer agent, etc.

[0054] [1-1] Components and composition of photosensitive resin composition

[0055] The components and compositions constituting the photosensitive resin composition of the present invention will be described in order.

[0056] [1-1-1] (a) Resin Pellets

[0057] The photosensitive resin composition of the present invention contains (a) resin particles, and the (a) resin particles include resin particles (a1) having a refractive index of 1.56 to 2.00 and an average primary particle size of 0.8 μm or more. By making the (a) resin particles include the resin particles (a1), the light transmittance of the cured product formed from the photosensitive resin composition can be maintained at a high state and the light scattering property can be improved.

[0058] Resin particles are particles containing resin as a main component.

[0059] The main component refers to the component that accounts for the largest proportion on a mass basis among the components constituting the particle, for example, a component that accounts for 50% or more of the mass of the particle, preferably a component that accounts for 80% or more of the mass of the particle, or 90% or more of the mass of the particle, and is usually 100% or less.

[0060] The resin particles (a) and the resin particles (a1) may each be in a particle shape or a non-particle shape. From the viewpoint of improving dispersion stability and light transmittance, the resin particles (a) and the resin particles (a1) are each preferably in a particle shape. Examples of the particle shape include spherical, hollow, porous, rod-like, plate-like, fibrous, or indefinite shapes, preferably spherical.

[0061] Examples of the components constituting the resin particles (a1) include polystyrene (styrene resin), polyvinylidene chloride, polyimide, polyethylene terephthalate, polysulfone, phenolic resin, melamine resin, benzoguanamine resin, and polycarbonate. From the perspective of high heat resistance and ease of producing the resin particles, benzoguanamine resin, melamine resin, and styrene resin are preferred.

[0062] The resin particles (a1) preferably contain at least one of a benzoguanamine resin, a melamine resin, and a styrene resin.

[0063] From the viewpoint of improving light scattering properties, melamine resins and benzoguanamine resins are particularly preferred.

[0064] From the viewpoint of improving light transmittance, styrene resin is particularly preferred.

[0065] The benzoguanamine resin is preferably a benzoguanamine-formaldehyde condensate.

[0066] As the melamine resin, a melamine-formaldehyde condensate is preferred.

[0067] As the styrene resin, a resin containing styrene or substituted styrene as a repeating unit is preferred. As the styrene with a substituent, for example, styrene with an alkyl substituent having 1 to 6 carbon atoms such as methyl styrene, ethyl styrene, and vinyl toluene can be cited. It can also be a copolymer of a resin containing styrene or substituted styrene as a repeating unit and a repeating unit other than styrene or substituted styrene. As the repeating unit other than styrene or substituted styrene, for example, (meth) acrylic acid, butadiene, maleic anhydride, and acrylonitrile can be cited. From the viewpoint of improving transparency, a styrene-(meth) acrylic acid copolymer is particularly preferred.

[0068] The average particle size of the primary particles of the resin particles (a1) is preferably 0.8 μm or more, more preferably 0.9 μm or more, further preferably 1.0 μm or more, and particularly preferably 1.1 μm or more. In addition, it is preferably 5.0 μm or less, more preferably 4.0 μm or less, further preferably 3.0 μm or less, further preferably 2.0 μm or less, and particularly preferably 1.8 μm or less. When the average particle size of the primary particles is below the upper limit value, there is a tendency for light transmittance and sedimentation stability to become higher. If it is above the lower limit value, there is a tendency for light scattering to become higher.

[0069] The upper and lower limits mentioned above may be arbitrarily combined. For example, it is preferably 0.8 to 5.0 μm, more preferably 0.9 to 4.0 μm, further preferably 1.0 to 3.0 μm, further preferably 1.1 to 2.0 μm, and particularly preferably 1.1 to 1.8 μm.

[0070] The average particle size of the primary particles of the resin particles (a1) is measured by directly measuring the size of the primary particles from the electron microscope photograph using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). Specifically, the primary particle size of each particle is calculated in the form of an equivalent circle diameter. An image is taken of a range of 10 μm to 100 μm square, and all particles within the range are measured. Different ranges are imaged several times, and the particle sizes of 50 to 1000 primary particles in total are measured, and the number average is taken to obtain the average particle size. The measurement of the primary particle size can be carried out, for example, on a resin particle monomer, its dispersion, or a cured film of a photosensitive resin composition. When preparing a measurement sample, the resin particles (a1) must be uniformly present in the sample. In the case of a dispersion, the dispersion just after dispersion is used, and the measurement is carried out after the solvent is volatilized. In addition, in the case of a cured film, a cured film is prepared using a photosensitive resin composition in which particles are uniformly dispersed, and the film is cut in the thickness direction, and its cross section is observed to thereby carry out the measurement.

[0071] The average particle size of the dispersed particles of the resin particles (a1) can be determined using a dynamic light scattering method, a laser diffraction method, and then a method of measuring the particle size using an SEM after making a coating of the dispersion and drying. It is not particularly limited, preferably 0.8 μm or more, more preferably 0.9 μm or more, further preferably 1.0 μm or more, and particularly preferably 1.1 μm or more. In addition, it is preferably 5.0 μm or less, more preferably 4.0 μm or less, further preferably 3.0 μm or less, particularly preferably 2.0 μm or less, and particularly preferably 1.8 μm or less. When the average particle size of the primary particles is below the aforementioned upper limit, there is a tendency for dispersion stability to increase. If it is above the aforementioned lower limit, there is a tendency for light scattering to increase.

[0072] The upper and lower limits mentioned above may be arbitrarily combined. For example, it is preferably 0.8 to 5.0 μm, more preferably 0.9 to 4.0 μm, further preferably 1.0 to 3.0 μm, further preferably 1.1 to 2.0 μm, and particularly preferably 1.1 to 1.8 μm.

[0073] The refractive index of the resin particles (a1) is usually 1.56 or more, preferably 1.58 or more, more preferably 1.60 or more, further preferably 1.61 or more, further preferably 1.62 or more, particularly preferably 1.63 or more, further particularly preferably 1.64 or more, and most preferably 1.65 or more. In addition, it is preferably 2.00 or less, more preferably 1.90 or less, further preferably 1.80 or less, and further preferably 1.70 or less. When the refractive index of the resin particles (a1) is below the above upper limit, there is a tendency for light transmittance to increase. If it is above the above lower limit, there is a tendency for light scattering to increase.

[0074] The upper and lower limits mentioned above may be combined arbitrarily. For example, it is usually 1.56 to 2.00, preferably 1.58 to 2.00, more preferably 1.60 to 2.00, further preferably 1.61 to 1.90, further preferably 1.62 to 1.80, particularly preferably 1.63 to 1.80, further particularly preferably 1.64 to 1.70, and most preferably 1.65 to 1.70.

[0075] (a) The refractive index of the resin particles is measured by attenuation spectroscopy, extrapolation, Becke line method, immersion method, etc. (a) The refractive index value of the resin particles is evaluated for light having a wavelength of 400 to 650 nm.

[0076] As the (a) resin particles, other resin particles may be used in combination in addition to the resin particles (a1).

[0077] Examples of the components constituting the other resin particles include (meth)acrylic resins, polycarbonates, polyethylene, polyesters, phenolic resins, urethane resins, epoxy resins, polyvinyl chloride, polyamides, and silicone resins.

[0078] The average particle size of the primary particles of the other resin particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, further preferably 0.05 μm or more, and particularly preferably 0.1 μm or more. In addition, it is preferably 5.0 μm or less, more preferably 4.0 μm or less, further preferably 3.0 μm or less, further preferably 2.0 μm or less, and particularly preferably 1.8 μm or less. When the average particle size of the primary particles is below the upper limit value, there is a tendency for light transmittance and sedimentation stability to become higher. If it is above the lower limit value, there is a tendency for light scattering to become higher.

[0079] The upper and lower limits mentioned above may be arbitrarily combined. For example, it is preferably 0.005 to 5.0 μm, more preferably 0.01 to 4.0 μm, further preferably 0.05 to 3.0 μm, further preferably 0.1 to 2.0 μm, and particularly preferably 0.1 to 1.8 μm.

[0080] As other resin particles, particles having the same constituent components as the resin particles (a1) but outside the preferred range of the average particle size of the primary particles of the resin particles (a1) may also be used in combination as other resin particles. Preferably, it is 0.005 μm or more, more preferably 0.01 μm or more, further preferably 0.05 μm or more, and particularly preferably 0.1 μm or more. In addition, it is preferably 0.7 μm or less, more preferably 0.6 μm or less, and further preferably 0.4 μm or less. When the average particle size of the primary particles is below the aforementioned upper limit, there is a tendency for light transmittance to increase. If it is above the aforementioned lower limit, there is a tendency for light scattering to increase.

[0081] The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.005 to 0.7 μm, more preferably 0.01 to 0.6 μm, further preferably 0.05 to 0.4 μm, and further preferably 0.1 to 0.4 μm. When it is below the above upper limit, there is a tendency for dispersion stability to increase. If it is above the above lower limit, there is a tendency for light scattering to increase.

[0082] The photosensitive resin composition used in the present invention may be used in combination with the resin particles (a) and other particles other than the resin particles (a). The type of other particles is not particularly limited, and particles mainly composed of organic pigments other than resins, inorganic particles, and luminescent nanocrystalline particles may be used in combination.

[0083] The organic pigment is not particularly limited, and examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments.

[0084] Examples of the inorganic particles include particles containing inorganic pigments and metal oxides as main components. Examples of the inorganic pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, and the like.

[0085] Examples of the metal oxide include silicon dioxide, titanium oxide, zirconium oxide, aluminum oxide, and hafnium oxide. Titanium oxide is particularly preferred from the viewpoint of improving light scattering properties.

[0086] When using particles other than the (a) resin particles, particles mainly composed of inorganic pigments or metal oxides are preferably used from the viewpoint of durability. In particular, particles mainly composed of metal oxides are preferred because of their high light transmittance.

[0087] From the viewpoint of controlling the transmission wavelength of the photosensitive resin composition and curing it efficiently, it is preferred to use particles containing an organic pigment as a main component.

[0088] In the photosensitive resin composition of the present invention, the content ratio of the (a) resin particles is 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less, with respect to the total solid content of the photosensitive resin composition. In addition, it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 14% by mass or more.

[0089] The above upper and lower limits can be combined arbitrarily. For example, preferably 1 to 80 mass %, more preferably 5 to 70 mass %, further preferably 10 to 60 mass %, further preferably 14 to 50 mass %, particularly preferably 14 to 40 mass %. By setting it above the above lower limit, there is a tendency for light scattering to become higher. By setting it below the above upper limit, there is a tendency for light transmittance to become higher.

[0090] In the photosensitive resin composition of the present invention, the content ratio of the resin particles (a1) is 80 mass % or less, preferably 70 mass % or less, more preferably 60 mass % or less, further preferably 50 mass % or less, and particularly preferably 40 mass % or less, relative to the total solid content of the photosensitive resin composition.

[0091] Moreover, it is preferably 1 mass % or more, more preferably 5 mass % or more, further preferably 10 mass % or more, and particularly preferably 14 mass % or more.

[0092] The above upper and lower limits can be combined arbitrarily. For example, preferably 1 to 80 mass %, more preferably 5 to 70 mass %, further preferably 10 to 60 mass %, further preferably 14 to 50 mass %, particularly preferably 14 to 40 mass %. By setting it above the above lower limit, there is a tendency for light scattering to become higher. By setting it below the above upper limit, there is a tendency for light transmittance to become higher.

[0093] When the resin particles (a1) contain at least one of benzoguanamine resin, melamine resin, and styrene resin as a constituent component, in the photosensitive resin composition of the present invention, the content ratio of benzoguanamine resin, melamine resin, and styrene resin relative to the total solid content of the photosensitive resin composition is 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and further preferably 40% by mass or less. In addition, it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 14% by mass or more. When two or more of benzoguanamine resin, melamine resin, and styrene resin are contained as constituent components of the resin particles (a1), the content ratio of benzoguanamine resin, melamine resin, and styrene resin adopts the value obtained by adding the two resins.

[0094] The above upper and lower limits can be combined arbitrarily. For example, preferably 1 to 80 mass %, more preferably 5 to 70 mass %, further preferably 10 to 60 mass %, further preferably 14 to 50 mass %, particularly preferably 14 to 40 mass %. By setting it above the above lower limit, there is a tendency for light scattering to become higher. By setting it below the above upper limit, there is a tendency for light transmittance to become higher.

[0095] The content ratio of the resin particles (a1) in the resin particles (a) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and is 100% by mass or less, relative to the total mass of the resin particles (a). When the content ratio is equal to or more than the above lower limit, the light scattering property tends to be higher.

[0096] [1-1-2] (b) Alkali-soluble resin

[0097] The photosensitive resin composition of the present invention contains (b) an alkali-soluble resin, and the alkali-soluble resin (b) contains an alkali-soluble resin (b1) having an ethylenic double bond (hereinafter also referred to as alkali-soluble resin (b1). The inclusion of the alkali-soluble resin (b1) tends to improve heat resistance.

[0098] In the present invention, the (b) alkali-soluble resin is not particularly limited as long as it is a resin that can be developed with an alkali developer.

[0099] (b) The alkali-soluble resin includes various resins having a carboxyl group or a hydroxyl group. From the viewpoint of excellent developability, a resin having a carboxyl group is preferred.

[0100] The alkali-soluble resin (b1) having an olefinic double bond preferably has an olefinic double bond in a side chain. Examples of the alkali-soluble resin (b1) having an olefinic double bond in a side chain include: an acrylic copolymer resin (b11) having an olefinic double bond in a side chain (hereinafter also referred to as an acrylic copolymer resin (b11)), an epoxy (meth)acrylate resin (b12) having an olefinic double bond in a side chain (hereinafter also referred to as an epoxy (meth)acrylate resin (b12)), and the following alkali-soluble resin (b13) having an olefinic double bond in a side chain (hereinafter also referred to as an alkali-soluble resin (b13)).

[0101] The alkali-soluble resin (b13) is a resin having a repeating unit represented by the following general formula (V) (hereinafter sometimes referred to as “repeating unit (V)”).

[0102]

[0103] In formula (V), R 1 ~R 4 Each independently represents a hydrogen atom or a hydrocarbon group. n represents an integer of 0 to 2. * represents a connecting bond.

[0104] From the viewpoint of developability, acrylic copolymer resin (b11) is preferred.

[0105] From the viewpoint of outgassing resistance and heat resistance, epoxy (meth)acrylate resin (b12) is preferred.

[0106] From the viewpoint of adhesion, chemical resistance and dispersion stability, an alkali-soluble resin (b13) is preferred.

[0107] From the viewpoint of achieving both transparency and outgassing resistance, the alkali-soluble resin (b1) preferably contains both an acrylic copolymer resin (b11) and an epoxy (meth)acrylate resin (b12).

[0108] [Acrylic copolymer resin (b11)]

[0109] The acrylic copolymer resin (b11) is an acrylic copolymer resin having an ethylenic double bond in the side chain. It is considered that the presence of an ethylenic double bond in the side chain allows photocuring by exposure to light, resulting in a stronger film and higher heat resistance.

[0110] (Partial structure represented by general formula (I))

[0111] The partial structure having a side chain having an ethylenic double bond of the acrylic copolymer resin (b11) is not particularly limited, but preferably has a partial structure represented by the following general formula (I) from the viewpoint of ease of radical emission accompanying film flexibility.

[0112]

[0113] In formula (I), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group. * represents a connecting bond.

[0114] Among the partial structures represented by the formula (I), the partial structures represented by the following general formula (I′) are preferred from the viewpoints of sensitivity and alkali developability.

[0115]

[0116] In formula (I'), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group. X represents a hydrogen atom or a polyacid residue.

[0117] The polyacid residue in formula (I') refers to a monovalent or divalent or higher group obtained by removing one OH group from a polyacid. Examples of the polyacid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0118] From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

[0119] The content ratio of the partial structure represented by formula (I) contained in the acrylic copolymer resin (b11) is not particularly limited, but is preferably 10 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, further preferably 60 mol% or more, further preferably 70 mol% or more, particularly preferably 80 mol% or more, and is preferably 99 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, relative to the total molar number of the structural units of the acrylic copolymer resin (b11).

[0120] The upper and lower limits can be combined arbitrarily. For example, it is preferably 10 to 99 mol%, more preferably 30 to 95 mol%, further preferably 50 to 95 mol%, further preferably 60 to 95 mol%, further preferably 70 to 95 mol%, and particularly preferably 80 to 90 mol%. By setting it above the lower limit, there is a tendency for heat resistance to be improved. By setting it below the upper limit, there is a tendency for developability to be improved.

[0121] When the acrylic copolymer resin (b11) has a partial structure represented by formula (I'), the content ratio thereof is not particularly limited, but is preferably 10 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, further preferably 60 mol% or more, further preferably 70 mol% or more, particularly preferably 80 mol% or more, and is preferably 99 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, relative to the total molar number of the structural units of the acrylic copolymer resin (b11).

[0122] The upper and lower limits can be combined arbitrarily. For example, it is preferably 10 to 99 mol%, more preferably 30 to 95 mol%, further preferably 50 to 95 mol%, further preferably 60 to 95 mol%, further preferably 70 to 95 mol%, and particularly preferably 80 to 90 mol%. By setting it above the lower limit, there is a tendency for heat resistance to be improved. By setting it below the upper limit, there is a tendency for developability to be improved.

[0123] (Partial structure represented by general formula (II))

[0124] As a partial structure which an acrylic copolymer resin (b11) has, from a viewpoint of image development adhesiveness, it can have the partial structure represented by following general formula (II), for example.

[0125]

[0126] In formula (II), R 3 represents a hydrogen atom or a methyl group, R 4 It represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.

[0127] (R 4 )

[0128] In formula (II), R 4 It represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.

[0129] As R 4 The alkyl group in the group may be a linear, branched, or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and particularly preferably 8 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less.

[0130] The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, further preferably 5 to 14, and particularly preferably 8 to 12. By setting it above the above lower limit, there is a tendency that the film strength becomes higher and the development adhesion is improved. By setting it below the above upper limit, there is a tendency that the residue is reduced.

[0131] Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group. From the viewpoint of developability, a dicyclopentyl group and a dodecyl group are preferred, and a dicyclopentyl group is more preferred.

[0132] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0133] As R 4 The aromatic ring group in the formula (a) may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group. The carbon number is preferably 6 or more, and preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less.

[0134] The upper and lower limits may be combined arbitrarily. For example, it is preferably 6 to 24, more preferably 6 to 22, further preferably 6 to 20, and particularly preferably 6 to 18. By setting it above the lower limit, the developing adhesion tends to be improved. By setting it below the upper limit, the residue tends to be reduced.

[0135] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0136] The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. From the viewpoint of developability, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.

[0137] Examples of the substituent which the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0138] As R 4 The alkenyl in , can be a linear, branched or cyclic alkenyl. Its carbon number is 2 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less.

[0139] The upper and lower limits may be combined arbitrarily. For example, it is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and further preferably 2 to 14. By setting it to be above the lower limit, there is a tendency for the development adhesion to be improved. By setting it to be below the upper limit, there is a tendency for the residue to be reduced.

[0140] Examples of the substituent which the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0141] As R 4 From the viewpoint of developability and film strength, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred.

[0142] When the acrylic copolymer resin (b11) has a partial structure represented by formula (II), the content ratio thereof is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, further preferably 10 mol% or more, particularly preferably 20 mol% or more, and is preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and further preferably 40 mol% or less, relative to the total molar number of the structural units of the acrylic copolymer resin (b11).

[0143] The upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 70 mol%, more preferably 2 to 70 mol%, further preferably 5 to 60 mol%, further preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%. By setting it above the lower limit, there is a tendency for the development adhesion to be improved. By setting it below the upper limit, there is a tendency for the heat resistance to be improved.

[0144] (Partial structure represented by general formula (III))

[0145] The partial structure of the acrylic copolymer resin (b11) may be a partial structure represented by the following general formula (III) from the viewpoint of heat resistance and film strength.

[0146]

[0147] In formula (III), R 5 represents a hydrogen atom or a methyl group, R 6 represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group or an alkylthioether group optionally having a substituent. t represents an integer of 0 to 5.

[0148] (R 6 )

[0149] As R 6 The alkyl group in may be a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, and further preferably 5 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less.

[0150] The upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 20, more preferably 1 to 18, further preferably 3 to 16, and further preferably 5 to 14. By setting it to be above the lower limit, the developing adhesion tends to be improved. By setting it to be below the upper limit, the residue tends to be reduced.

[0151] Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group. From the viewpoint of developability and film strength, a dicyclopentyl group or a dodecyl group is preferred, and a dicyclopentyl group is more preferred.

[0152] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0153] As R 6 The alkenyl in , can be a linear, branched or cyclic alkenyl. Its carbon number is 2 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less.

[0154] The upper and lower limits may be combined arbitrarily. For example, it is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and further preferably 2 to 14. By setting it to be above the lower limit, there is a tendency for the development adhesion to be improved. By setting it to be below the upper limit, there is a tendency for the residue to be reduced.

[0155] Examples of the substituent which the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0156] As R 6 The alkynyl in alkynyl may be a straight chain, branched chain or cyclic alkynyl. The carbon number is 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less.

[0157] The upper and lower limits may be combined arbitrarily. For example, it is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and further preferably 2 to 14. By setting it to be above the lower limit, there is a tendency for the development adhesion to be improved. By setting it to be below the upper limit, there is a tendency for the residue to be reduced.

[0158] Examples of the substituent which the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0159] As R 6 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0160] As R 6 The alkoxy group in the alkoxy group may be a linear, branched or cyclic alkoxy group. The carbon number is 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less.

[0161] The upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 20, more preferably 1 to 18, further preferably 1 to 16, further preferably 1 to 14, and further preferably 1 to 12. By setting it to be above the lower limit, there is a tendency for the development adhesion to be improved. By setting it to be below the upper limit, there is a tendency for the residue to be reduced.

[0162] Examples of the substituent which the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0163] As R 6 The alkyl sulfide group in the alkyl sulfide group may be a linear, branched or cyclic alkyl sulfide group. The carbon number is preferably 1 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less.

[0164] The upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 20, more preferably 1 to 18, further preferably 1 to 16, further preferably 1 to 14, and further preferably 1 to 12. By setting it to be above the lower limit, there is a tendency for the development adhesion to be improved. By setting it to be below the upper limit, there is a tendency for the residue to be reduced.

[0165] Examples of the substituent which the alkyl group in the alkyl thioether group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0166] As R 6From the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

[0167] In formula (III), t represents an integer of 0 to 5. From the viewpoint of ease of production, t is preferably 0.

[0168] When the acrylic copolymer resin (b11) has a partial structure represented by formula (III), the content ratio thereof is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, further preferably 2 mol% or more, and particularly preferably 4 mol% or more relative to the total molar number of the structural units of the acrylic copolymer resin (b11). In addition, it is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, further preferably 10 mol% or less, and particularly preferably 6 mol% or less.

[0169] The above upper and lower limits can be combined arbitrarily. For example, preferably 0.5 to 50 mol%, more preferably 1 to 30 mol%, further preferably 1 to 20 mol%, further preferably 2 to 10 mol%, and further preferably 4 to 6 mol%. By setting it above the above lower limit, there is a tendency for the uniformity of the film to be improved. By setting it below the above upper limit, there is a tendency for the residue to be reduced.

[0170] (Partial structure represented by general formula (IV))

[0171] As the partial structure that the acrylic copolymer resin (b11) has, from the viewpoint of developability, the partial structure represented by the following general formula (IV) may be included.

[0172]

[0173] In formula (IV), R 7 represents a hydrogen atom or a methyl group.

[0174] When the acrylic copolymer resin (b11) has a partial structure represented by formula (IV), the content ratio thereof is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more, relative to the total molar number of the structural units of the acrylic copolymer resin (b11). In addition, it is preferably 80 mol% or less, more preferably 70 mol% or less, and further preferably 60 mol% or less.

[0175] The upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and further preferably 20 to 60 mol%. By setting it above the lower limit, there is a tendency to reduce residue. By setting it below the upper limit, there is a tendency to improve heat resistance.

[0176] The double bond equivalent of the acrylic copolymer resin (b11) is preferably 700 g / mol or less, more preferably 600 g / mol or less, and further preferably 500 g / mol or less. In addition, it is preferably 100 g / mol or more, more preferably 200 g / mol or more, further preferably 300 g / mol or more, and particularly preferably 400 g / mol or more.

[0177] The upper and lower limits may be combined arbitrarily. For example, it is preferably 100 to 700 g / mol, more preferably 200 to 600 g / mol, further preferably 300 to 500 g / mol, and particularly preferably 400 to 500 g / mol. By setting it below the upper limit, there is a tendency for the developability to be improved. By setting it above the lower limit, there is a tendency for the heat resistance to be improved.

[0178] The double bond equivalent of the acrylic copolymer resin (b11) can be calculated according to the following formula.

[0179] (Double bond equivalent of acrylic copolymer resin (b11)) = (weight average molecular weight of acrylic copolymer resin (b11)) / (number of ethylenic double bonds per molecule of acrylic copolymer resin (b11))

[0180] The acid value of the acrylic copolymer resin (b11) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 30 mgKOH / g or more, further preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. It is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, further preferably 100 mgKOH / g or less, and further preferably 90 mgKOH / g or less.

[0181] The upper and lower limits may be combined arbitrarily. For example, it is preferably 10 to 150 mgKOH / g, more preferably 20 to 120 mgKOH / g, further preferably 30 to 100 mgKOH / g, further preferably 40 to 90 mgKOH / g, and particularly preferably 50 to 90 mgKOH / g. By setting it above the lower limit, there is a tendency for the developability to be improved. In addition, by setting it below the upper limit, there is a tendency for the developability to be improved.

[0182] The weight average molecular weight (Mw) of the acrylic copolymer resin (b11) is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, further preferably 4,000 or more, further preferably 6,000 or more, and particularly preferably 7,000 or more. It is preferably 30,000 or less, more preferably 20,000 or less, further preferably 15,000 or less, and particularly preferably 10,000 or less.

[0183] The upper and lower limits may be combined arbitrarily. For example, it is preferably 1000 to 30000, more preferably 2000 to 20000, further preferably 4000 to 20000, further preferably 6000 to 15000, further preferably 7000 to 15000, and particularly preferably 7000 to 10000. By setting it to be above the lower limit, there is a tendency for the development adhesion to be improved. By setting it to be below the upper limit, there is a tendency for the residue to be reduced.

[0184] When the (b) alkali-soluble resin contains an acrylic copolymer resin (b11), the content ratio thereof is not particularly limited. The content ratio of the acrylic copolymer resin (b11) contained in the (b) alkali-soluble resin is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 50% by mass or more, relative to the total mass of the (b) alkali-soluble resin. In addition, it is preferably 100% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0185] The above upper and lower limits may be combined arbitrarily. For example, it is preferably 10 to 100% by mass, more preferably 20 to 95% by mass, further preferably 30 to 90% by mass, further preferably 40 to 85% by mass, and particularly preferably 50 to 85% by mass. By setting it above the above lower limit, there is a tendency for the developability to be improved. By setting it below the above upper limit, there is a tendency for the heat resistance and outgassing resistance to be improved.

[0186] Specific examples of the acrylic copolymer resin (b11) include resins described in Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.

[0187] [Epoxy (meth)acrylate resin (b12)]

[0188] Epoxy (meth) acrylate resin (b12) is a resin obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin and optionally reacting a compound containing an isocyanate group, and then further reacting a polybasic acid or its anhydride. For example, the following resins can be cited: a resin obtained by adding an ethylenically unsaturated bond to an epoxy compound via an ester bond (-COO-) by ring-opening addition of a carboxyl group of an unsaturated carboxylic acid to the epoxy group of an epoxy resin, and then adding a carboxyl group of a polybasic acid anhydride to the hydroxyl group generated at this time. In addition, a resin obtained by simultaneously adding a polyol and adding the polybasic acid anhydride when adding the polybasic acid anhydride can also be cited.

[0189] Furthermore, a resin obtained by reacting a compound having a functional group that can further react with the carboxyl group of the resin obtained by the above reaction is also included in the above epoxy (meth)acrylate resin (b12).

[0190] As such, epoxy (meth) acrylate resins do not substantially have epoxy groups in their chemical structure and are not limited to "(meth) acrylates", but are named as such according to convention because epoxy compounds (epoxy resins) are raw materials and "(meth) acrylates" are representative examples. As epoxy (meth) acrylate-based resins (b12), resins having an aromatic ring in the main chain can be more preferably used from the viewpoint of heat resistance.

[0191] Here, epoxy resin refers to also forming the raw material compound before the resin by thermosetting, and as this epoxy resin, can suitably select to use from known epoxy resin.In addition, epoxy resin can use the compound that makes phenolic compound and epihalohydrin react and obtain.As phenolic compound, preferably have the compound of binary or more than binary phenolic hydroxyl group, can be monomer and can also be polymer.

[0192] Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, triglycidyl isocyanurate resin, phenol and dicyclopentadiene polymerized epoxy resin, dihydroxyfluorene type epoxy resin, dihydroxyalkyleneoxyfluorene type epoxy resin, diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene, diglycidyl ether of 1,1-bis(4'-hydroxyphenyl)adamantane, and adamantyl group-containing phenol epoxy resin can be mentioned. Such substances having an aromatic ring in the main chain can be preferably used.

[0193] Examples of the epoxy resin include bisphenol A type epoxy resins (e.g., "jER (registered trademark, hereinafter the same) 828", "jER1001", "jER1002", "jER1004" manufactured by Mitsubishi Chemical Corporation, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76° C.)), bisphenol F type resins (e.g., "jER 807", "jER4004P", "jER4005P", "jER4007P", "NER-7406" (epoxy equivalent 350, softening point 66°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "jERYX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, "EPPN (registered trademark, hereinafter the same)-201" manufactured by Nippon Kayaku Co., Ltd., "jER152", "jER154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Company), (o-, m-, p-) cresol novolac type epoxy resin (for example, EOCN (registered trademark, the same below)-102S, EOCN-1020, EOCN-104S), biphenyl novolac epoxy resin (e.g., Nippon Kayaku Co., Ltd.'s "NC-3000", "NC-3500"), triglycidyl isocyanurate (e.g., Nissan Chemical Co., Ltd.'s "TEPIC (registered trademark)"), trisphenol methane type epoxy resin (e.g., Nippon Kayaku Co., Ltd.'s "EPPN-501", "EPPN-502", "EPPN-503"), alicyclic epoxy resin (Daicel Corporation's "CELLOXIDE (registered trademark, the same below) 2021P", "CELLOXIDE EHPE"), epoxy resins obtained by glycidylating a phenolic resin obtained by the reaction of dicyclopentadiene and phenol (e.g., "EXA-7200" manufactured by DIC Corporation, "NC-7300" and "XD-1000" manufactured by Nippon Kayaku Co., Ltd.), and adamantyl-containing phenol epoxy resins (e.g., "ADAMANTATE E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd.).

[0194] Among the above-mentioned epoxy resins, biphenyl glycidyl ether and adamantyl group-containing phenol epoxy resins are preferred from the viewpoint of heat resistance.

[0195] Examples of the ethylenically unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, as well as succinic anhydride adducts of pentaerythritol tri(meth)acrylate, tetrahydrophthalic anhydride adducts of pentaerythritol tri(meth)acrylate, succinic anhydride adducts of dipentaerythritol penta(meth)acrylate, phthalic anhydride adducts of dipentaerythritol penta(meth)acrylate, tetrahydrophthalic anhydride adducts of dipentaerythritol penta(meth)acrylate, and reaction products of (meth)acrylic acid and ε-caprolactone. (Meth)acrylic acid is preferred from the viewpoint of sensitivity.

[0196] Examples of the polyacid (anhydride) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof. From the viewpoint of exhaust, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred, and succinic anhydride and tetrahydrophthalic anhydride are more preferred.

[0197] By using a polyol, there is a tendency to increase the molecular weight of the epoxy (meth) acrylate resin (b12), introduce a branched chain into the molecule, and achieve a balance between the molecular weight and the viscosity. In addition, there is a tendency to increase the introduction rate of the acid group into the molecule, making it easier to achieve a balance between sensitivity and adhesion.

[0198] As the polyol, for example, one or more polyols selected from the group consisting of trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol are preferred.

[0199] Examples of the epoxy (meth)acrylate resin (b12) include, in addition to the above-described ones, those described in Korean Patent Publication No. 10-2013-0022955.

[0200] The acid value of the epoxy (meth) acrylate resin (b12) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 50 mgKOH / g or more, further preferably 70 mgKOH / g or more, and particularly preferably 80 mgKOH / g or more. It is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, further preferably 150 mgKOH / g or less, further preferably 120 mgKOH / g or less, and particularly preferably 110 mgKOH / g or less.

[0201] The upper and lower limits may be combined arbitrarily. For example, it is preferably 10 to 200 mgKOH / g, more preferably 30 to 180 mgKOH / g, further preferably 50 to 150 mgKOH / g, further preferably 70 to 120 mgKOH / g, and particularly preferably 80 to 110 mgKOH / g. By setting it above the lower limit, there is a tendency for the developability to be improved. By setting it below the upper limit, there is a tendency for the film strength to be improved.

[0202] The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b12) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more. It is preferably 30000 or less, more preferably 20000 or less, further preferably 15000 or less, further preferably 10000 or less, and particularly preferably 8000 or less.

[0203] The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1000 to 30000, more preferably 2000 to 20000, further preferably 3000 to 15000, further preferably 4000 to 10000, and particularly preferably 5000 to 8000. By setting it above the above lower limit, there is a tendency for the film strength to be improved. By setting it below the above upper limit, there is a tendency for the residue to be reduced.

[0204] The double bond equivalent of the epoxy (meth) acrylate resin (b12) is not particularly limited, but is preferably 700 g / mol or less, more preferably 600 g / mol or less, further preferably 500 g / mol or less, and particularly preferably 400 g / mol or less. In addition, it is preferably 100 g / mol or more, more preferably 200 g / mol or more, further preferably 250 g / mol or more, and particularly preferably 300 g / mol or more.

[0205] The upper limit and the lower limit may be combined arbitrarily. For example, it is preferably 100 to 700 g / mol, more preferably 200 to 600 g / mol, further preferably 250 to 500 g / mol, and particularly preferably 300 to 400 g / mol. By setting it below the upper limit, there is a tendency for heat resistance to be improved. By setting it above the lower limit, there is a tendency for developability to be improved.

[0206] The double bond equivalent of the epoxy (meth)acrylate resin (b12) can be calculated by the same method as the double bond equivalent of the acrylic copolymer resin (b11).

[0207] When the (b) alkali-soluble resin contains an epoxy (meth)acrylate resin (b12), the content ratio thereof is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, further preferably 35% by mass or more, particularly preferably 40% by mass or more, and most preferably 50% by mass or more, and is preferably 90% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less, relative to the total mass of the (b) alkali-soluble resin.

[0208] The above upper and lower limits can be combined arbitrarily. For example, preferably 10 to 90 mass %, more preferably 20 to 90 mass %, further preferably 30 to 70 mass %, further preferably 35 to 70 mass %, further preferably 40 to 60 mass %, particularly preferably 50 to 60 mass %. By setting it above the above lower limit, there is a tendency for outgassing resistance to improve. By setting it below the above upper limit, there is a tendency for transparency to improve.

[0209] Epoxy (meth) acrylate resin (b12) can be synthesized by a conventionally known method. Specifically, the following method can be used: dissolving the aforementioned epoxy resin in an organic solvent, adding the aforementioned acid or ester compound having an ethylenically unsaturated bond in the presence of a catalyst and a thermal inhibitor to cause an addition reaction, and further adding a polyacid or its anhydride to continue the reaction. For example, the method described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422 can be cited.

[0210] Examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.

[0211] Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine; quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride; phosphorus compounds such as triphenylphosphine; and one or more antimonides such as triphenylstibine.

[0212] Examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone.

[0213] The amount of the acid or ester compound having an ethylenically unsaturated bond used is preferably 0.7 to 1.3 chemical equivalents, more preferably 0.9 to 1.1 chemical equivalents, relative to 1 chemical equivalent of epoxy groups in the epoxy resin.

[0214] The temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C.

[0215] The amount of the polybasic acid (anhydride) used is preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the hydroxyl group generated in the addition reaction.

[0216] [Alkali soluble resin (b13)]

[0217] The alkali-soluble resin (b13) is a resin having a repeating unit represented by the following general formula (V) (hereinafter sometimes referred to as “repeating unit (V)”).

[0218]

[0219] In formula (V), R 1 ~R 4 Each independently represents a hydrogen atom or a hydrocarbon group. n represents an integer of 0 to 2. * represents a connecting bond.

[0220] The alkali-soluble resin (b13) has a repeating unit represented by the general formula (V) (hereinafter sometimes referred to as "repeating unit (V)"). It is believed that although it is not as rigid as aromatic hydrocarbons, it is a bulky structure in three dimensions. Due to a certain degree of flexibility, the reaction points are close to each other during light and / or heat curing reactions, and the curing reaction will not be excessively hindered. Furthermore, after curing, the heat resistance is improved due to the bulky structure.

[0221] In the above formula (V), R 1 ~R 4 Each independently represents a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aromatic ring group, and an aralkyl group.

[0222] The alkyl group may be any of a linear, branched, or cyclic group. The number of carbon atoms in the alkyl group is not particularly limited, but is generally 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 15 or less, more preferably 8 or less. When the number is greater than the lower limit, the adhesion tends to be improved, and when the number is less than the upper limit, the developability tends to be improved.

[0223] Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, adamantyl, cyclopentyl, cyclohexyl and cyclooctyl.

[0224] The number of carbon atoms in the alkenyl group is not particularly limited, but is usually 2 or more, preferably 3 or more, preferably 10 or less, and more preferably 8 or less. The upper and lower limits may be arbitrarily combined. For example, the number may be 2 to 10, or 3 to 8. When the number is greater than the lower limit, the adhesion tends to be improved, and when the number is less than the upper limit, the developability tends to be improved.

[0225] Specific examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a pentenyl group.

[0226] The number of carbon atoms in the alkynyl group is not particularly limited, but is usually 2 or more, preferably 3 or more, preferably 10 or less, and more preferably 8 or less. The upper and lower limits may be arbitrarily combined. For example, the number may be 2 to 10, or 3 to 8. When the number is greater than the lower limit, the adhesion tends to be improved, and when the number is less than the upper limit, the developability tends to be improved.

[0227] Specific examples of the alkynyl group include an ethynyl group.

[0228] Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but is generally 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, it may be 4 to 20, 5 to 15, or 6 to 10. By setting it to be above the aforementioned lower limit, there is a tendency for improved adhesion, and by setting it to be below the aforementioned upper limit, there is a tendency for improved developability.

[0229] Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, an anthracenyl group, a tolyl group, and a xylyl group.

[0230] The carbon number of the aralkyl group is not particularly limited, but is usually 5 or more, preferably 6 or more, more preferably 7 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, it may be 5 to 20, 6 to 15, or 7 to 10. By setting it to be above the above lower limit, there is a tendency for the adhesion to be improved, and by setting it to be below the above upper limit, there is a tendency for the developability to be improved.

[0231] Examples of the aralkyl group include groups in which one hydrogen atom of the above-mentioned alkyl group is substituted with the above-mentioned aromatic ring group.

[0232] Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

[0233] R 1 ~R 4 Each independently represents a hydrogen atom or a hydrocarbon group, but R 1 With R 4 can also be connected to form a ring structure. Similarly, R 2 With R 3 They can also be linked to form a ring structure.

[0234] Among these, R is preferred from the viewpoint of ease of synthesis. 1 ~R 4 Any one of is a hydrogen atom, and more preferably R 1 ~R 4 All are hydrogen atoms.

[0235] Moreover, n represents the integer of 0-2, and n is preferably 0 from the viewpoint of developability.

[0236] Specific examples of the repeating unit (V) include structures represented by the following general formulae (V-1) to (V-3). Among these, the repeating unit represented by the following general formula (V-1) is more preferred from the viewpoint of adhesion.

[0237]

[0238] The alkali-soluble resin (b13) preferably contains a repeating unit (VI) having a carboxyl group (hereinafter sometimes referred to as “repeating unit (VI)”).

[0239] The structure of the repeating unit (VI) having a carboxyl group of the alkali-soluble resin (b13) is not particularly limited, and examples thereof include repeating units derived from an unsaturated group-containing carboxylic acid and an unsaturated group-containing carboxylic acid anhydride.

[0240] Among them, from the viewpoint of improving developability and adhesion, the alkali-soluble resin (b13) preferably has a repeating unit represented by the following general formula (VI-1) (hereinafter sometimes referred to as "repeating unit (VI-1)").

[0241]

[0242] In formula (VI-1), R 5 Indicates a hydrogen atom or an organic group. *Indicates a connecting bond.

[0243] Examples of the organic group include an alkyl group which may have a substituent and an aryl group which may have a substituent, and the organic group preferably has 1 to 18 carbon atoms.

[0244] R 5 In the case of an alkyl group, the carbon number is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and is preferably 9 or less, more preferably 7 or less.

[0245] Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, adamantyl, cyclopentyl, cyclohexyl and cyclooctyl.

[0246] R 5 In the case of an aryl group, the carbon number is not particularly limited, but is more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less.

[0247] Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a tolyl group, and a xylyl group.

[0248] Examples of the substituent that the alkyl group and the aryl group may have include a hydroxyl group and a (meth)acryloyl group.

[0249] Among these, from the viewpoint of adhesion, R 5 More preferably, the repeating unit is represented by the following general formula (VI-2).

[0250]

[0251] In formula (VI-2), R 6 represents a hydrogen atom or a methyl group. e represents an integer of 1 to 5. * represents a connecting bond.

[0252] In formula (VI-2), e represents an integer of 1 to 5, and from the viewpoint of adhesion, e is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

[0253] The repeating unit (VI-1) is more preferably any of the repeating units represented by the following general formulae (VI-3) to (VI-6), and particularly preferably a repeating unit represented by the following general formula (VI-3) or formula (VI-4).

[0254]

[0255] In formulae (VI-3) to (VI-6), * represents a connecting bond.

[0256] <Other repeating units>

[0257] The alkali-soluble resin (b13) may have a repeating unit other than the repeating unit (V) and the repeating unit (VI).

[0258] Examples of other repeating units include repeating units represented by the following general formulae (VII-1) to (VII-5) (hereinafter sometimes referred to as "repeating units (VII-1) to (VII-5)"), but are not limited thereto.

[0259]

[0260] In formula (VII-1), R 5 Same as in formula (VI-1), in formula (VII-1) and formula (VII-2), R 7 Each independently represents a hydrogen atom or a methyl group. * represents a connecting bond.

[0261]

[0262] In formula (VII-5), R 8 represents an alkyl group which may have a substituent. * represents a connecting bond.

[0263] By having the repeating unit represented by the formula (VII-5), the heat resistance of the alkali-soluble resin (b13) tends to be improved.

[0264] As R 8 Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group and a benzyl group.

[0265] From the viewpoint of surface smoothness and adhesion, the alkali-soluble resin (b13) preferably has a repeating unit (V), a repeating unit (VI-1) and a repeating unit (VII-1), and more preferably has a repeating unit (V), a repeating unit (VI-1), a repeating unit (VII-1) and a repeating unit (VII-4).

[0266] [Method for producing alkali-soluble resin (b13)]

[0267] The method for producing the alkali-soluble resin (b13) is not particularly limited, and a conventionally known method can be used. For example, it can be produced by the following (step i) to (step iii). It should be noted that the following ring-opening precursor polymer obtained by (step ii) can also be used as the alkali-soluble resin (b13).

[0268] (Step i) A step of preparing a precursor polymer including a repeating unit represented by the above formula (V) and a repeating unit represented by formula (VII-4).

[0269] (Step ii) A step of allowing an alcohol or water to act on the precursor polymer to ring-open the acid anhydride skeleton in formula (VII-4) to generate a carboxyl group or an ester thereof in the precursor polymer to obtain a ring-opened precursor polymer.

[0270] As the alcohol, from the viewpoint of adhesion, it is more preferable to use a compound represented by the following general formula (VI-2-1).

[0271]

[0272] In formula (VI-2-1), R 6 , e have the same meanings as in formula (VI-2).

[0273] (Step iii) A step of optionally reacting the ring-opening precursor polymer with a compound having an epoxy group and an ethylenic double bond.

[0274] As a compound which has an epoxy group and an ethylenic double bond, glycidyl methacrylate is mentioned, for example.

[0275] In addition, as a specific production method of the alkali-soluble resin (b13), for example, the method described in International Publication No. 2016 / 194619 and International Publication No. 2017 / 154439 can be mentioned.

[0276] The content ratio of the repeating unit (V) in the alkali-soluble resin (b13) is not particularly limited. In the alkali-soluble resin (b13), it is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more. In addition, it is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 10 to 50% by mass, 20 to 40% by mass, or 25 to 30% by mass. By setting it to above the aforementioned lower limit, there is a tendency for improved adhesion. In addition, by setting it to below the aforementioned upper limit, there is a tendency for improved developability.

[0277] The content ratio of the repeating unit (V) in the alkali-soluble resin (b13) is not particularly limited. In all the repeating units of the alkali-soluble resin (b13), it is preferably 20 mol% or more, more preferably 30 mol% or more, and further preferably 40 mol% or more. In addition, it is preferably 80 mol% or less, more preferably 70 mol% or less, and further preferably 60 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 20 to 80 mol%, 30 to 70 mol%, or 40 to 60 mol%. By setting it to above the aforementioned lower limit, there is a tendency for improved adhesion. In addition, by setting it to below the aforementioned upper limit, there is a tendency for improved developability.

[0278] When the alkali-soluble resin (b13) has a repeating unit (VI-1), the content ratio thereof is not particularly limited. In all repeating units of the alkali-soluble resin (b13), it is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more. In addition, it is preferably 40 mol% or less, more preferably 30 mol% or less, and further preferably 20 mol% or less. The above upper and lower limits may be combined arbitrarily. For example, it may be 5 to 40 mol%, 10 to 30 mol%, or 15 to 20 mol%. By setting it to above the aforementioned lower limit, there is a tendency for the developability to be improved. In addition, by setting it to below the aforementioned upper limit, there is a tendency for the adhesion to be improved.

[0279] When the alkali-soluble resin (b13) has a repeating unit (VII-1), the content ratio thereof is not particularly limited. In all repeating units of the alkali-soluble resin (b13), it is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more. In addition, it is preferably 40 mol% or less, more preferably 30 mol% or less, and further preferably 20 mol% or less. The above upper and lower limits may be combined arbitrarily. For example, it may be 5 to 40 mol%, 10 to 30 mol%, or 15 to 20 mol%. By setting it to above the aforementioned lower limit, there is a tendency for improved adhesion. In addition, by setting it to below the aforementioned upper limit, there is a tendency for improved developability.

[0280] When the alkali-soluble resin (b13) has a repeating unit (VII-4), the proportion thereof is not particularly limited. In all repeating units of the alkali-soluble resin (b13), it is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more. In addition, it is preferably 40 mol% or less, more preferably 30 mol% or less, and further preferably 20 mol% or less. The above upper and lower limits may be combined arbitrarily. For example, it may be 5 to 40 mol%, 10 to 30 mol%, or 15 to 20 mol%. By setting it to above the aforementioned lower limit, there is a tendency for synthesis to become easier. In addition, by setting it to below the aforementioned upper limit, there is a tendency for adhesion and developability to improve.

[0281] When the alkali-soluble resin (b13) has a repeating unit (VI-1), a repeating unit (VII-1) and a repeating unit (VII-4), the content ratio of the repeating unit (VI-1) relative to the total content ratio of the repeating unit (VI-1), the repeating unit (VII-1) and the repeating unit (VII-4) in the alkali-soluble resin (b13) is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more. In addition, it is preferably 90 mol% or less, more preferably 70 mol% or less, and further preferably 50 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 10 to 90 mol%, 20 to 70 mol%, or 30 to 50 mol%. By setting it to above the aforementioned lower limit, there is a tendency to improve the developability, and by setting it to below the aforementioned upper limit, there is a tendency to improve the adhesion.

[0282] The acid value of the alkali-soluble resin (b13) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, and further preferably 50 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 100 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. For example, it may be 10 to 200 mgKOH / g, 10 to 150 mgKOH / g, 30 to 100 mgKOH / g, or 50 to 80 mgKOH / g. By setting it to be above the aforementioned lower limit, there is a tendency for the developability to be improved, and by setting it to be below the aforementioned upper limit, there is a tendency for the developability to be improved.

[0283] The weight average molecular weight (Mw) of the alkali-soluble resin (b13) is not particularly limited, but is preferably 2000 or more, more preferably 3000 or more, further preferably 4000 or more, further preferably 5000 or more, and particularly preferably 6000 or more. In addition, it is preferably 35000 or less, more preferably 20000 or less, and further preferably 15000 or less. The above upper and lower limits may be combined arbitrarily. For example, it may be 2000 to 35000, 3000 to 35000, 4000 to 20000, 5000 to 20000, or 6000 to 15000. By setting it to the above lower limit value or more, there is a tendency for the developing adhesion to be improved, and by setting it to the above upper limit value or less, there is a tendency for the developing property to be improved.

[0284] The double bond equivalent of the alkali-soluble resin (b13) is not particularly limited, but is preferably 200 g / mol or more, more preferably 300 g / mol or more, further preferably 400 g / mol or more, further preferably 500 g / mol or more, and particularly preferably 600 g / mol or more. In addition, it is preferably 800 g / mol or less, more preferably 700 g / mol or less, and further preferably 600 g / mol or less. The above upper and lower limits may be combined arbitrarily. For example, it may be 200 to 800 g / mol, 300 to 800 g / mol, 400 to 700 g / mol, 500 to 700 g / mol, 600 to 700 g / mol, or 500 to 600 g / mol. By setting it to above the aforementioned lower limit, there is a tendency for the developability to be improved, and by setting it to below the aforementioned upper limit, there is a tendency for the adhesion to be improved.

[0285] The double bond equivalent of the alkali-soluble resin (b13) can be calculated by the same method as the double bond equivalent of the acrylic copolymer resin (b11).

[0286] When (b) the alkali-soluble resin includes the alkali-soluble resin (b13), the content ratio of the alkali-soluble resin (b13) is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 50% by mass or more, and is preferably 100% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less, relative to the total mass of the alkali-soluble resin (b).

[0287] The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10 to 100 mass %, more preferably 20 to 95 mass %, further preferably 30 to 90 mass %, further preferably 40 to 85 mass %, and particularly preferably 50 to 85 mass %. By setting it above the above lower limit, there is a tendency for the developability to be improved. In addition, by setting it below the above upper limit, there is a tendency for the adhesion to be improved.

[0288] The (b) alkali-soluble resin in the present invention may contain other alkali-soluble resins other than the alkali-soluble resin (b1).

[0289] (b) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and further preferably 25 mgKOH / g or more. It is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 100 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less.

[0290] The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, further preferably 25 to 100 mgKOH / g, and particularly preferably 25 to 80 mgKOH / g. By setting it above the above lower limit, there is a tendency for the developability to be improved. In addition, by setting it below the above upper limit, there is a tendency for the developability to be improved. It should be noted that when (b) the alkali-soluble resin is a mixture of two or more, the acid value refers to the weighted average value corresponding to the content ratio thereof.

[0291] The acid value of the alkali-soluble resin (b1) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and further preferably 25 mgKOH / g or more. It is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 100 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less.

[0292] The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, further more preferably 25 to 100 mgKOH / g, and particularly preferably 25 to 80 mgKOH / g. By setting it above the above lower limit, there is a tendency for the developability to be improved. In addition, by setting it below the above upper limit, there is a tendency for the developability to be improved. It should be noted that when the alkali-soluble resin (b1) is a mixture of two or more, the acid value refers to the weighted average value corresponding to the content ratio thereof.

[0293] (b) The double bond equivalent of the alkali-soluble resin is 700 g / mol or less, preferably 600 g / mol or less, more preferably 500 g / mol or less, and preferably 100 g / mol or more, more preferably 200 g / mol or more, and further preferably 300 g / mol or more.

[0294] The upper limit and lower limit may be combined arbitrarily. For example, it is preferably 100 to 700 g / mol, more preferably 200 to 600 g / mol, and further preferably 300 to 500 g / mol. By setting it below the upper limit, there is a tendency for the developability to be improved. By setting it above the lower limit, there is a tendency for the heat resistance to be improved.

[0295] The double bond equivalent of the alkali-soluble resin (b) can be calculated in the same manner as for the acrylic copolymer resin (b11). When the alkali-soluble resin (b) is a mixture of two or more kinds of resins, the double bond equivalent refers to a weighted average value according to the content ratios thereof.

[0296] The double bond equivalent of the alkali-soluble resin (b1) is 700 g / mol or less, preferably 600 g / mol or less, more preferably 500 g / mol or less, and preferably 100 g / mol or more, more preferably 200 g / mol or more, and further preferably 300 g / mol or more.

[0297] The upper limit and lower limit may be combined arbitrarily. For example, it is preferably 100 to 700 g / mol, more preferably 200 to 600 g / mol, and further preferably 300 to 500 g / mol. By setting it below the upper limit, there is a tendency for the developability to be improved. By setting it above the lower limit, there is a tendency for the heat resistance to be improved.

[0298] The double bond equivalent of the alkali-soluble resin (b1) can be calculated in the same manner as the double bond equivalent of the acrylic copolymer resin (b11). When the alkali-soluble resin (b1) is a mixture of two or more kinds of the alkali-soluble resin (b1), the double bond equivalent refers to a weighted average value according to the content ratios thereof.

[0299] The content ratio of the (b) alkali-soluble resin in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and further preferably 40% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and further preferably 60% by mass or less, relative to the total solid content.

[0300] The above upper and lower limits can be combined arbitrarily. For example, preferably 5 to 90% by mass, more preferably 10 to 90% by mass, further preferably 20 to 90% by mass, further preferably 30 to 80% by mass, further preferably 40 to 70% by mass, and particularly preferably 40 to 60% by mass. By setting it above the above lower limit, there is a tendency for the residue to decrease.

[0301] When the content is equal to or less than the above upper limit, heat resistance tends to improve.

[0302] The content ratio of the alkali-soluble resin (b1) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and further preferably 40% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and further preferably 60% by mass or less, relative to the total solid content.

[0303] The above upper and lower limits can be combined arbitrarily. For example, preferably 5 to 90% by mass, more preferably 10 to 90% by mass, further preferably 20 to 90% by mass, further preferably 30 to 80% by mass, further preferably 40 to 70% by mass, and particularly preferably 40 to 60% by mass. By setting it above the above lower limit, there is a tendency for the residue to be reduced. By setting it below the above upper limit, there is a tendency for the heat resistance to be improved.

[0304] The content ratio of the alkali-soluble resin (b1) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, further preferably 70% by mass or more, and further preferably 90% by mass or more, relative to the alkali-soluble resin (b). In addition, it is preferably 100% by mass or less, and more preferably 95% by mass or less.

[0305] The upper and lower limits may be combined arbitrarily. For example, it is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, further preferably 50 to 100% by mass, further preferably 70 to 100% by mass, and further preferably 90 to 95% by mass. By setting it above the lower limit, there is a tendency for heat resistance to be improved. By setting it below the upper limit, there is a tendency for developability to be improved.

[0306] The content ratio of the alkali-soluble resin (b11) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and further preferably 40% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and further preferably 60% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0307] The above upper and lower limits can be combined arbitrarily. For example, preferably 5 to 90% by mass, more preferably 10 to 90% by mass, further preferably 20 to 90% by mass, further preferably 30 to 80% by mass, further preferably 40 to 70% by mass, and particularly preferably 40 to 60% by mass. By setting it above the above lower limit, there is a tendency for heat resistance to be improved. By setting it below the above upper limit, there is a tendency for developability to be improved.

[0308] The content ratio of the alkali-soluble resin (b12) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and further preferably 40% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and further preferably 60% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0309] The above upper and lower limits can be combined arbitrarily. For example, preferably 5 to 90% by mass, more preferably 10 to 90% by mass, further preferably 20 to 90% by mass, further preferably 30 to 80% by mass, further preferably 40 to 70% by mass, and particularly preferably 40 to 60% by mass. By setting it above the above lower limit, there is a tendency for heat resistance to be improved. By setting it below the above upper limit, there is a tendency for developability to be improved.

[0310] The content ratio of the alkali-soluble resin (b13) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and further preferably 40% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and further preferably 60% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0311] The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 90% by mass, more preferably 10 to 90% by mass, further preferably 20 to 90% by mass, further preferably 30 to 80% by mass, further preferably 40 to 70% by mass, and particularly preferably 40 to 60% by mass. By setting it above the above lower limit, there is a tendency for dispersion stability and heat resistance to be improved. By setting it below the above upper limit, there is a tendency for developability to be improved.

[0312] The sum of the content ratio of (d) the photopolymerizable compound and the content ratio of (b) the alkali-soluble resin relative to the total solid content of the photosensitive resin composition is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more, and is preferably 98% by mass or less, more preferably 95% by mass or less, and further preferably 92% by mass or less.

[0313] The above upper and lower limits can be combined arbitrarily. For example, preferably 10 to 98 mass %, more preferably 30 to 95 mass %, further preferably 60 to 92 mass %, and further preferably 70 to 92 mass %. By setting it above the above lower limit, there is a tendency to improve the adhesion to the substrate. By setting it below the above upper limit, there is a tendency for the heat resistance to become higher.

[0314] [1-1-3] (c) Photopolymerization initiator

[0315] The photosensitive resin composition of the present invention contains (c) a photopolymerization initiator. The (c) photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes the (d) photopolymerizable compound by active light.

[0316] The photosensitive resin composition of the present invention can use substances commonly used in the technical field of the present invention as (c) photopolymerization initiators. For example, metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197; hexaarylbiimidazole derivatives described in Japanese Patent Application Laid-Open No. 2000-56118; halogenated methylated oxadiazole derivatives, halogenated methyl s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other free radical activators, and alkylphenone derivatives (alkylphenone-based initiators) described in Japanese Patent Application Laid-Open No. 10-39503.

[0317] Specifically, examples of the metallocene compound include dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl)titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorophenyl)titanium, dicyclopentadienyl bis(2,4,6-trifluorophenyl)titanium, dicyclopentadienyl bis(2,6-difluorophenyl)titanium, dicyclopentadienyl bis(2,4-difluorophenyl)titanium, di(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, di(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, and dicyclopentadienyl [2,6-difluoro-3-(pyrrol-1-yl)-phenyl]titanium.

[0318] Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0319] Examples of the halogenated methylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuranyl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

[0320] Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0321] Examples of the alkylphenone-based initiator include benzyl ketal-based initiators such as 2,2-dimethoxy-2-phenylacetophenone; hydroxyalkylphenone-based initiators such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and 2,2'-dihydroxy-2,2'-dimethyl-1,1'-[methylenebis(4,1-phenylene)]bis(propan-1-one); and α-aminoalkylphenone-based initiators such as 2-methyl-1〔4-(methylthio)phenyl〕-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butane-1-one.

[0322] From the viewpoint of improving the developability, the (c) photopolymerization initiator preferably contains an alkylphenone-based photopolymerization initiator. Among the alkylphenone-based photopolymerization initiators, from the viewpoint of achieving both adhesion and developability, α-aminoalkylphenone-based photopolymerization initiators are preferred, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butane-1-one are more preferred.

[0323] As the (c) photopolymerization initiator, an oxime ester-based photopolymerization initiator is effective from the perspectives of sensitivity and platemaking properties. When an alkali-soluble resin containing a phenolic hydroxyl group is used, the sensitivity is disadvantageous, and therefore an oxime ester-based photopolymerization initiator having excellent sensitivity is particularly useful.

[0324] Oxime ester photopolymerization initiators have high quantum yields in photoreactions and highly active free radicals, so they have high sensitivity. They are also stable to thermal reactions, and a highly sensitive photosensitive resin composition can be obtained with a small amount.

[0325] Oxime ester photopolymerization initiators have structures that absorb ultraviolet rays, transmit light energy, and generate radicals. Therefore, they are highly sensitive even in small amounts and are stable to thermal reactions. Thus, a highly sensitive photosensitive resin composition can be obtained in small amounts.

[0326] Examples of the oxime ester-based photopolymerization initiator include compounds represented by the following general formula (IV).

[0327]

[0328] In formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0329] R 21b represents an arbitrary substituent including an aromatic ring.

[0330] R 22a It represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.

[0331] n represents an integer of 0 or 1.

[0332] R 21a The carbon number of the alkyl group in is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less from the viewpoint of solubility in a solvent and sensitivity. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl.

[0333] Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl, and N-acetyl-N-acetoxyamino. From the viewpoint of ease of synthesis, the alkyl group is preferably unsubstituted.

[0334] As R 21a The aromatic ring group in the photosensitive resin composition may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored photosensitive resin composition. In addition, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less.

[0335] The above upper and lower limits may be arbitrarily combined. For example, 5 to 30 are preferred, 5 to 20 are more preferred, and 5 to 12 are further preferred.

[0336] Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, a phenyl group and a naphthyl group are preferred, and a phenyl group is more preferred from the viewpoint of developability.

[0337] Examples of the substituent that the aromatic ring group may optionally have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group obtained by connecting these substituents. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group obtained by connecting these substituents are preferred, and a connected alkoxy group is more preferred.

[0338] From the perspective of sensitivity, R 21a An alkyl group which may have a substituent or an aromatic ring group which may have a substituent is preferred.

[0339] As R 21b , preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthone group, an optionally substituted diphenyl sulfide group, an optionally substituted fluorenyl group or an optionally substituted indolyl group. From the viewpoint of sensitivity, an optionally substituted carbazolyl group is preferred.

[0340] R 22a The carbon number of the alkanoyl group in is not particularly limited, but is preferably 2 or more, and is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and particularly preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity.

[0341] Examples of the alkanoyl group include acetyl, ethyl, propionyl, and butyryl.

[0342] Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the alkanoyl group is preferably unsubstituted.

[0343] R 22a The carbon number of the aromatic acyl group in is not particularly limited, but is preferably 7 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity.

[0344] Examples of the aroyl group include a benzoyl group and a naphthoyl group.

[0345] Examples of the substituent that the aroyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group, and the aroyl group is preferably unsubstituted from the viewpoint of ease of synthesis.

[0346] From the perspective of sensitivity, R 22aAn alkanoyl group which may have a substituent is preferred, an unsubstituted alkanoyl group is more preferred, and an acetyl group is further preferred.

[0347] For example, photopolymerization initiators described in Japanese Patent No. 4454067, International Publication No. 2002 / 100903, International Publication No. 2012 / 45736, International Publication No. 2015 / 36910, International Publication No. 2006 / 18973, Japanese Patent No. 4818458, International Publication No. 2005 / 80338, International Publication No. 2008 / 75564, International Publication No. 2009 / 131189, International Publication No. 2010 / 133077, International Publication No. 2010 / 102502, and International Publication No. 2012 / 68879 can be used.

[0348] (c) The photopolymerization initiator may be used alone or in combination of two or more.

[0349] If necessary, in order to improve the sensitivity, a sensitizing dye or a polymerization accelerator that matches the wavelength of the image exposure light source may be mixed into the (c) photopolymerization initiator. Examples of sensitizing dyes include xanthene dyes described in Japanese Patent Laid-Open Nos. 4-221958 and 4-219756; coumarin dyes having a heterocyclic ring described in Japanese Patent Laid-Open Nos. 3-239703 and 5-289335; 3-ketocoumarin compounds described in Japanese Patent Laid-Open Nos. 3-239703 and 5-289335; pyrromethene dyes described in Japanese Patent Laid-Open No. 6-19240; and pyrrolemethine dyes described in Japanese Patent Laid-Open Nos. 47-2528 and 54-155292. The pigment having a dialkylaminobenzene skeleton described in Japanese Patent Publication No. 45-37377, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168088, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Application Laid-Open No. 4-288818.

[0350] As the sensitizing dye, an amino group-containing sensitizing dye is preferred, and a compound having an amino group and a phenyl group in the same molecule is more preferred. Further preferred are benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)benzoxazole, Compounds containing a p-dialkylaminophenyl group include 4,4'-dialkylaminophenyl and 4'-dialkylaminophenyl groups. The compounds are preferably 4,4'-dialkylaminophenyl groups. Among these, 4,4'-dialkylaminophenyl groups are particularly preferred.

[0351] The sensitizing dye may be used alone or in combination of two or more.

[0352] As the polymerization accelerator, for example, aromatic amines such as 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone; and aliphatic amines such as n-butylamine, N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate can be used.

[0353] The polymerization accelerator may be used alone or in combination of two or more.

[0354] The content ratio of the (c) photopolymerization initiator in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 1% by mass or more, relative to the total solid content of the photosensitive resin composition, and is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 7% by mass or less, further further preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 2% by mass or less.

[0355] The above upper and lower limits can be combined arbitrarily. For example, preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, further preferably 0.1 to 15% by mass, further preferably 1 to 10% by mass, further preferably 1 to 7% by mass, further preferably 1 to 5% by mass, particularly preferably 1 to 3% by mass, and most preferably 1 to 2% by mass. By setting it above the above lower limit, there is a tendency for improved adhesion. By setting it below the above upper limit, there is a tendency for improved developability.

[0356] When the photosensitive resin composition of the present invention contains an alkylphenone-based photopolymerization initiator, the content ratio is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 1% by mass or more, relative to the total solid content of the photosensitive resin composition, and is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 7% by mass or less, further further preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 2% by mass or less.

[0357] The above upper and lower limits can be combined arbitrarily. For example, preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, further preferably 0.1 to 15% by mass, further preferably 1 to 10% by mass, further preferably 1 to 7% by mass, further preferably 1 to 5% by mass, particularly preferably 1 to 3% by mass, and most preferably 1 to 2% by mass. By setting it above the above lower limit, there is a tendency for improved adhesion. By setting it below the above upper limit, there is a tendency for improved developability.

[0358] When the photosensitive resin composition of the present invention contains an α-aminoalkylphenone-based photopolymerization initiator, the content ratio is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 1% by mass or more, relative to the total solid content of the photosensitive resin composition, and is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 7% by mass or less, further further preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 2% by mass or less.

[0359] The above upper and lower limits can be combined arbitrarily. For example, preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, further preferably 0.1 to 15% by mass, further preferably 1 to 10% by mass, further preferably 1 to 7% by mass, further preferably 1 to 5% by mass, particularly preferably 1 to 3% by mass, and most preferably 1 to 2% by mass. By setting it above the above lower limit, there is a tendency for improved adhesion. By setting it below the above upper limit, there is a tendency for improved developability.

[0360] When the photosensitive resin composition of the present invention contains an alkylphenone photopolymerization initiator, the content ratio of the alkylphenone photopolymerization initiator in the (c) photopolymerization initiator is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the (c) photopolymerization initiator. In addition, it is 100% by mass or less.

[0361] The upper and lower limits can be combined arbitrarily. For example, it is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, further preferably 70 to 100% by mass, and particularly preferably 90 to 100% by mass. By setting it above the lower limit, there is a tendency for improved adhesion. By setting it below the upper limit, there is a tendency for improved developability.

[0362] When the photosensitive resin composition of the present invention contains an α-aminoalkylphenone-based photopolymerization initiator, the content ratio of the α-aminoalkylphenone-based photopolymerization initiator in the (c) photopolymerization initiator is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the (c) photopolymerization initiator. In addition, it is 100% by mass or less.

[0363] The upper and lower limits can be combined arbitrarily. For example, it is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, further preferably 70 to 100% by mass, and particularly preferably 90 to 100% by mass. By setting it above the lower limit, there is a tendency for improved adhesion. By setting it below the upper limit, there is a tendency for improved developability.

[0364] The mixing ratio of the (c) photopolymerization initiator to the (d) photopolymerizable compound in the photosensitive resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and further preferably 3 parts by mass or more, and is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, relative to 100 parts by mass of the (d) photopolymerizable compound.

[0365] The above upper and lower limits may be combined arbitrarily. For example, it is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, further preferably 2 to 50 parts by mass, further preferably 3 to 30 parts by mass, and particularly preferably 3 to 20 parts by mass. By setting it to be above the above lower limit, there is a tendency for improved adhesion. By setting it to be below the above upper limit, there is a tendency for improved developability.

[0366] When the photosensitive resin composition of the present invention contains an alkylphenone photopolymerization initiator, the compounding ratio of the alkylphenone photopolymerization initiator to the (d) photopolymerizable compound in the photosensitive resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and further preferably 3 parts by mass or more, and is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, based on 100 parts by mass of the (d) photopolymerizable compound.

[0367] The above upper and lower limits may be combined arbitrarily. For example, it is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, further preferably 2 to 50 parts by mass, further preferably 3 to 30 parts by mass, and particularly preferably 3 to 20 parts by mass. By setting it to be above the above lower limit, there is a tendency for improved adhesion. By setting it to be below the above upper limit, there is a tendency for improved developability.

[0368] When the photosensitive resin composition of the present invention contains an α-aminoalkylphenone photopolymerization initiator, the compounding ratio of the α-aminoalkylphenone photopolymerization initiator to the (d) photopolymerizable compound in the photosensitive resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and further preferably 3 parts by mass or more, and is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, based on 100 parts by mass of the (d) photopolymerizable compound.

[0369] The above upper and lower limits may be combined arbitrarily. For example, it is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, further preferably 2 to 50 parts by mass, further preferably 3 to 30 parts by mass, and particularly preferably 3 to 20 parts by mass. By setting it to be above the above lower limit, there is a tendency for improved adhesion. By setting it to be below the above upper limit, there is a tendency for improved developability.

[0370] A chain transfer agent can also be used in combination with (c) a photopolymerization initiator. As a chain transfer agent, for example, a thiol-containing compound and carbon tetrachloride can be cited. Among these, thiol-containing compounds are more preferred because they have a high tendency for chain transfer effect. It is believed that this is because bond cleavage is likely to occur due to the small SH bond energy, and hydrogen abstraction reaction and chain transfer reaction are likely to occur. The use of a chain transfer agent is effective for improving sensitivity and surface curability.

[0371] The mercapto group-containing compound may have a plurality of mercapto groups in the molecule, and examples thereof include mercapto group-containing compounds having an aromatic ring, such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene.

[0372] Aliphatic mercapto group-containing compounds such as hexanediol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trihydroxyethyl trithiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0373] Among the mercapto-containing compounds having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and among the aliphatic mercapto-containing compounds, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.

[0374] From the viewpoint of sensitivity, aliphatic mercapto-containing compounds are preferred, and specifically, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred, and pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred.

[0375] These may be used alone or in combination of two or more.

[0376] Among these, from the viewpoint of improving the cone angle, it is suitable to use one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole in combination with a photopolymerization initiator as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole can be used, 2-mercaptobenzimidazole can be used, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole can also be used in combination.

[0377] From the viewpoint of sensitivity, it is preferred to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate). Furthermore, from the viewpoint of sensitivity, it is preferred to use one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole, one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate), and a photopolymerization initiator in combination.

[0378] When the photosensitive resin composition of the present invention contains a chain transfer agent, the content ratio of the chain transfer agent is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and further preferably 0.8% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, and further preferably 2% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0379] The upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, further preferably 0.5 to 3% by mass, and particularly preferably 0.8 to 2% by mass. By setting it above the lower limit, there is a tendency for improved adhesion. By setting it below the upper limit, there is a tendency for improved developability.

[0380] [1-1-4] (d) Photopolymerizable compound

[0381] The photosensitive resin composition of the present invention may contain (d) a photopolymerizable compound. It is considered that the inclusion of the (d) photopolymerizable compound increases the curability of the coating film and improves the adhesiveness.

[0382] As the (d) photopolymerizable compound used herein, there can be mentioned compounds having one or more ethylenic double bonds in the molecule (hereinafter also referred to as ethylenically unsaturated compounds). From the perspectives of polymerizability, crosslinking, and the ability to increase the difference in developer solubility between the exposed portion and the non-exposed portion, compounds having two or more ethylenic double bonds in the molecule are preferred, and further preferably, the unsaturated bond is derived from a (meth)acryloyloxy group, that is, a (meth)acrylate compound is further preferred.

[0383] In the present invention, it is particularly desirable to use a polyfunctional olefinic monomer having two or more olefinic double bonds in one molecule. The number of olefinic double bonds possessed by the polyfunctional olefinic monomer is not particularly limited, but is preferably two or more, more preferably three or more, and further preferably five or more, and is preferably 15 or less, more preferably 10 or less, further preferably 8 or less, and particularly preferably 7 or less.

[0384] The above upper and lower limits may be combined arbitrarily. For example, 2 to 15 are preferred, 2 to 10 are more preferred, 3 to 8 are further preferred, and 5 to 7 are particularly preferred.

[0385] When the content is at least the above lower limit, the polymerizability tends to be improved and the adhesiveness tends to be high, while when the content is at most the above upper limit, the developability tends to be further improved.

[0386] Examples of the ethylenically unsaturated compound include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids.

[0387] Examples of the esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylates of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylates obtained by replacing the acrylates of these exemplified compounds with methacrylates, itaconates obtained by similarly replacing the acrylates with itaconates, crotonates obtained by replacing the acrylates with crotonates, or maleates obtained by replacing the acrylates with maleates.

[0388] Examples of the esters of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylates and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0389] The esters obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids are not necessarily a single substance. Representative specific examples include condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol and glycerol.

[0390] In addition, useful examples of the multifunctional olefinic monomer used in the present invention include: urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylate or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylate; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound with a hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl-containing compounds such as divinyl phthalate.

[0391] Examples of the urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, and UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, and UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), and UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).

[0392] Among these, from the viewpoint of adhesion, as the (d) photopolymerizable compound, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, or urethane (meth)acrylates are preferably used, and dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2,2,2-tri(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate dibasic acid anhydride adducts, and dipentaerythritol tri(meth)acrylate dibasic acid anhydride adducts are more preferably used.

[0393] These may be used alone or in combination of two or more.

[0394] In the present invention, the molecular weight of the photopolymerizable compound (d) is not particularly limited, but is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, further preferably 300 or more, particularly preferably 400 or more, and most preferably 500 or more, and is preferably 1000 or less, and more preferably 700 or less. When the molecular weight is equal to or greater than the lower limit, the adhesiveness tends to be improved. When the molecular weight is equal to or less than the upper limit, the developability tends to be improved.

[0395] The upper and lower limits may be arbitrarily combined. For example, it is preferably 100 to 1000, more preferably 150 to 1000, further preferably 200 to 1000, further preferably 300 to 700, further preferably 400 to 700, and particularly preferably 500 to 700.

[0396] (d) The carbon number of the photopolymerizable compound is not particularly limited, but from the viewpoint of adhesion and suppression of residue, it is preferably 7 or more, more preferably 10 or more, further preferably 15 or more, further preferably 20 or more, and particularly preferably 25 or more, and is preferably 50 or less, more preferably 40 or less, further preferably 35 or less, and particularly preferably 30 or less.

[0397] The above upper and lower limits may be arbitrarily combined. For example, 7 to 50 are preferred, 10 to 50 are more preferred, 15 to 40 are further preferred, 20 to 35 are further preferred, and 25 to 30 are particularly preferred.

[0398] From the viewpoint of both adhesion and developability, ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferred, among which trifunctional or higher ester (meth)acrylates such as pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred; and adducts of trifunctional or higher ester (meth)acrylates with acid anhydrides added thereto such as 2,2,2-tri(meth)acryloyloxymethylethylphthalate and dipentaerythritol penta(meth)acrylate dibasic acid anhydride adducts.

[0399] The content ratio of the photopolymerizable compound (d) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 40% by mass or less, and further preferably 30% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0400] The upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 80% by mass, more preferably 5 to 80% by mass, further preferably 10 to 60% by mass, further preferably 15 to 40% by mass, and particularly preferably 20 to 30% by mass. By setting it above the lower limit, there is a tendency for improved adhesion. By setting it below the upper limit, there is a tendency for improved developability.

[0401] The content ratio of the (d) photopolymerizable compound relative to 100 parts by mass of the (b) alkali-soluble resin is not particularly limited, but is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 15 parts by mass or more, further preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and most preferably 40 parts by mass or more. In addition, it is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, further preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less.

[0402] The upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 150 parts by mass, more preferably 5 to 150 parts by mass, further preferably 10 to 100 parts by mass, further preferably 15 to 100 parts by mass, further preferably 20 to 70 parts by mass, particularly preferably 30 to 60 parts by mass, and most preferably 40 to 50 parts by mass. By setting it to be above the lower limit, there is a tendency for the adhesion to be improved. By setting it to be below the upper limit, there is a tendency for the developability to be improved.

[0403] [1-1-5] (e) Inhibitor

[0404] The photosensitive resin composition of the present invention may contain (e) a polymerization inhibitor from the viewpoint of suppressing residue after development. When the photosensitive resin composition of the present invention does not contain the (f) ultraviolet absorber described later, the photosensitive resin composition of the present invention contains at least one (e) polymerization inhibitor.

[0405] (e) The polymerization inhibitor includes, for example, hydroquinone, 2,6-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 4-methoxyphenol, 2-methylhydroquinone, hydroquinone, benzoquinone, tert-butylcatechol, and phenoxazine. From the viewpoint of developability and storage stability, 4-methoxyphenol and 2-methylhydroquinone are preferred, and 2-methylhydroquinone is more preferred.

[0406] When the photosensitive resin composition of the present invention contains (e) a polymerization inhibitor, the content ratio of the (e) polymerization inhibitor in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.08% by mass or more, particularly preferably 0.1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, and further preferably 1% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0407] The upper and lower limits may be combined arbitrarily. For example, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, further preferably 0.08 to 3% by mass, further preferably 0.1 to 2% by mass, and further preferably 0.1 to 1% by mass. By setting it above the lower limit, there is a tendency for the developability to be improved. By setting it below the upper limit, there is a tendency for the adhesion to be improved.

[0408] When the photosensitive resin composition of the present invention contains (e) a polymerization inhibitor, the content ratio of the (e) polymerization inhibitor relative to 100 parts by mass of the (c) photopolymerization initiator is not particularly limited, but is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and further preferably 5 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, further preferably 20 parts by mass or less, and further preferably 10 parts by mass or less.

[0409] The above upper and lower limits may be combined arbitrarily. For example, it is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, further preferably 2 to 30 parts by mass, further preferably 5 to 20 parts by mass, and further preferably 5 to 10 parts by mass. By setting it to be above the above lower limit, there is a tendency for the developability to be improved. By setting it to be below the above upper limit, there is a tendency for the adhesion to be improved.

[0410] The polymerization inhibitor may be used alone or in combination of two or more.

[0411] The alkali-soluble resin produced by the method for producing an alkali-soluble resin (b) may contain a polymerization inhibitor. In this case, the alkali-soluble resin may be used as it contains the polymerization inhibitor, or a polymerization inhibitor that is the same as or different from the polymerization inhibitor contained in the resin may be added during the production of the photosensitive resin composition.

[0412] [1-1-6] (f) Ultraviolet light absorber

[0413] The photosensitive resin composition of the present invention may contain (f) an ultraviolet absorber. When the photosensitive resin composition of the present invention does not contain (e) a polymerization inhibitor, the photosensitive resin composition of the present invention contains at least one (f) ultraviolet absorber.

[0414] (f) As examples of the ultraviolet absorber, there may be mentioned benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, triazine ultraviolet absorbers, and benzoxazine ultraviolet absorbers.

[0415] Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0416] Examples of the benzotriazole ultraviolet absorber include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, and 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole. 2-Hydroxy-4-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-(2H-benzotriazol-2-yl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(2-hydroxyethyl)phenol], 2-[2-hydroxy-3-(4,5,6,7-tetrahydro-1,3-dioxo-1H-isoindol-2-yl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propanoate, octyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propanoate, nonyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propanoate.

[0417] Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, hexadecyl-2-cyano-3-(4-methylphenyl)acrylate, 2-cyano-3-(4-methylphenyl)acrylate, and 1,3-bis(2'-cyano-3,3'-diphenylacryloyl)oxy)-2,2-bis(((2'-cyano-3,3'-diphenylacryloyl)oxy)methyl)propane.

[0418] Examples of the triazine-based ultraviolet absorber include 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-ethoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-propoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-butoxyphenyl)-4,6-diphenyl-1,3,5-triazine, and 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine. Phenyl-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-benzyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3-5-triazine, 2,4,6-tris(2-hydroxy-4-hexyloxyphenyl)- 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-acryloyloxyethoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxynaphthyl)-1,3,5-triazine, and 2,4,6-tris(2-hydroxynaphthyl)-1,3,5-triazine.

[0419] Examples of the benzoxazine ultraviolet absorber include 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, and 2-phenyl-3,1-benzoxazin-4-one.

[0420] From the viewpoint of heat resistance, triazine-based, benzotriazole-based, and benzoxazine-based ultraviolet absorbers are preferred, and benzotriazole-based ultraviolet absorbers are more preferred.

[0421] The ultraviolet absorber may be used alone or in combination of two or more.

[0422] When the photosensitive resin composition of the present invention contains (f) an ultraviolet absorber, the content ratio of the (f) ultraviolet absorber in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and further preferably 1% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and further preferably 2% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0423] The upper and lower limits may be combined arbitrarily. For example, it is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, further preferably 0.5 to 3% by mass, and further preferably 1 to 2% by mass. By setting it above the lower limit, there is a tendency for the developability and adhesion to be improved. By setting it below the upper limit, there is a tendency for the adhesion to be improved.

[0424] When the photosensitive resin composition of the present invention contains (f) an ultraviolet absorber, the content ratio of the (f) ultraviolet absorber relative to 100 parts by mass of the (c) photopolymerization initiator is not particularly limited, but is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, and further preferably 2 parts by mass or more, and is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, further preferably 30 parts by mass or less, further preferably 20 parts by mass or less, and further preferably 10 parts by mass or less.

[0425] The above upper and lower limits may be combined arbitrarily. For example, it is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, further preferably 1 to 30 parts by mass, further preferably 2 to 20 parts by mass, and further preferably 2 to 10 parts by mass. By setting it to be above the above lower limit, there is a tendency for the developability to be improved. By setting it to be below the above upper limit, there is a tendency for the adhesion to be improved.

[0426] The photosensitive resin composition of the present invention may contain a surfactant. The surfactant may be used, for example, to improve the coating properties of the photosensitive resin composition as a coating solution and the developability of the coating film, and among these, silicone-based and fluorine-based surfactants are preferred.

[0427] In particular, from the perspective of having the function of removing the residue of the photosensitive resin composition from the unexposed portion during development and having the function of exhibiting wettability, a silicone-based surfactant is preferred, and a polyether-modified silicone-based surfactant is more preferred. From the perspective of improving the flatness of the cured product, a fluorine-based surfactant is preferred.

[0428] As the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group at least at any position among a terminal, a main chain, and a side chain is suitable.

[0429] Examples of commercially available products thereof include "BM-1000" and "BM-1100" manufactured by BM Chemie; "Megafac F142D", "Megafac F172", "Megafac F173", "Megafac F183", "Megafac F470", "Megafac F475", "Megafac F554", and "Megafac F559" manufactured by DIC Corporation; "FC430" manufactured by 3M JAPAN; and "DFX-18" manufactured by NEOS Corporation.

[0430] Examples of the silicone-based surfactants include “DC3PA,” “SH7PA,” “DC11PA,” “SH21PA,” “SH28PA,” “SH29PA,” “8032 Additive,” and “SH8400” manufactured by Dow Corning Toray Co., Ltd.; and commercially available products such as “BYK (registered trademark, hereinafter the same) 323” and “BYK330” manufactured by BYK-Chemie.

[0431] As the surfactant, a surfactant other than a fluorine-based surfactant and a silicone-based surfactant may be contained. Examples of the surfactant include nonionic, anionic, cationic, and amphoteric surfactants.

[0432] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

[0433] Examples of commercially available products thereof include polyoxyethylene surfactants such as "EMULGEN (registered trademark, hereinafter the same) 104P" and "EMULGEN A60" manufactured by Kao Corporation.

[0434] Examples of the anionic surfactant include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts, aliphatic alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and special polymer surfactants. Among them, special polymer surfactants are preferred, and special polycarboxylic acid-type polymer surfactants are more preferred.

[0435] As their commercial products, for example, for alkyl sulfate ester salts, there can be mentioned "EMAL (registered trademark, hereinafter the same) 10" manufactured by Kao Corporation; for alkyl naphthalene sulfonates, there can be mentioned "PELEX (registered trademark) NB-L" manufactured by Kao Corporation; for special polymer surfactants, there can be mentioned "HOMOGENOL (registered trademark, hereinafter the same) L-18" and "HOMOGENOL L-100" manufactured by Kao Corporation.

[0436] Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts, and examples of the amphoteric surfactant include betaine compounds, imidazolium salts, imidazolines, and amino acids.

[0437] As the cationic surfactant, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred.

[0438] Examples of commercially available products thereof include "ACETAMIN (registered trademark) 24" manufactured by Kao Corporation for alkylamine salts, and "QUARTAMIN (registered trademark, hereinafter the same) 24P" and "QUARTAMIN 86W" manufactured by Kao Corporation for quaternary ammonium salts.

[0439] The surfactant may be used alone or in combination of two or more. For example, a combination of a silicone surfactant and a fluorine surfactant, a combination of a silicone surfactant and a special polymer surfactant, and a combination of a fluorine surfactant and a special polymer surfactant may be cited. Among them, a combination of a silicone surfactant and a fluorine surfactant is preferred.

[0440] Examples of the combination of a silicone surfactant and a fluorine-based surfactant include a combination of "DFX-18" manufactured by NEOS, "BYK-300" or "BYK-330" manufactured by BYK-Chemie, and "S-393" manufactured by AGC SEIMI CHEMICAL; a combination of "KP340" manufactured by Shin-Etsu Silicone Co., Ltd. and "F-554" or "F-559" manufactured by DIC; a combination of "SH7PA" manufactured by Dow Corning Toray and "DS-401" manufactured by DAIKIN; and a combination of "L-77" manufactured by NUC and "FC4430" manufactured by 3M JAPAN.

[0441] In the photosensitive resin composition of the present invention, a liquid repellent can also be used. By adding a liquid repellent, ink repellency can be imparted to the surface of the photosensitive resin composition. Therefore, when other compositions are formed after the photosensitive resin composition is cured, mixing of the compositions can be prevented. The liquid repellent contains a compound having a fluorine atom and / or a siloxane chain, and may also have a crosslinking group. From the viewpoint of improving ink repellency, it is preferred to have a crosslinking group. Specifically, the liquid repellent described in Japanese Patent Application No. 2022-020652 can be used.

[0442] [1-1-7] (g) Dispersant

[0443] The photosensitive resin composition of the present invention preferably contains (g) a dispersant in order to finely disperse the (a) resin particles and stabilize the dispersion state. The photosensitive resin composition of the present invention may contain a dispersant in addition to the alkali-soluble resin (b1).

[0444] As the (g) dispersant, a polymer dispersant having a functional group is preferred, and further, from the viewpoint of dispersion stability, a polymer dispersant having functional groups such as a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a salt thereof; a primary, secondary or tertiary amino group; a quaternary ammonium salt group; or a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, or pyrazine is preferred. In particular, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium salt group; or a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, or pyrazine is particularly preferred from the viewpoint that a small amount of dispersant is required when dispersing the pigment.

[0445] Examples of the polymer dispersant include urethane dispersants, acrylic acid dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants containing monomers and macromonomers having an amino group, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0446] Specific examples of the polymer dispersant include, for example, EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by Ajinomoto Co., Ltd.).

[0447] The polymer dispersants may be used alone or in combination of two or more.

[0448] The weight average molecular weight (Mw) of the polymer dispersant is preferably 700 or more, more preferably 1000 or more, and preferably 100,000 or less, more preferably 50,000 or less.

[0449] The above upper and lower limits may be arbitrarily combined. For example, the weight average molecular weight (Mw) of the polymer dispersant is preferably 700 to 100,000, more preferably 1,000 to 50,000.

[0450] From the viewpoint of dispersion stability of the resin particles, the (g) dispersant preferably contains an acrylic polymer dispersant having a functional group.

[0451] From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having either or both of a polyester bond and a polyether bond is preferred.

[0452] As the acrylic polymer dispersant, it is preferred to use a random copolymer, a graft copolymer, or a block copolymer of an unsaturated group-containing monomer having a functional group (the functional group referred to herein is the functional group described above as the functional group contained in the polymer dispersant) and an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.

[0453] The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer comprising a block having a functional group and a B block having no functional group. In this case, the A block may contain, in addition to the partial structure derived from the above-mentioned unsaturated group-containing monomer having a functional group, a partial structure derived from the above-mentioned unsaturated group-containing monomer having no functional group, and these may be contained in the A block in any form of random copolymerization or block copolymerization.

[0454] The content of the partial structure not including a functional group in the A block is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0455] The B block contains a partial structure derived from the unsaturated group-containing monomer having no functional group. One B block may contain partial structures derived from two or more monomers. These may be contained in the B block in any form of random copolymerization or block copolymerization.

[0456] The AB or BAB block copolymer can be prepared, for example, by the living polymerization method shown below.

[0457] The living polymerization methods include anionic living polymerization, cationic living polymerization, and free radical living polymerization.

[0458] The amount of the quaternary ammonium salt group in 1 g of the AB block copolymer or BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. By setting the amount within the above range, good dispersibility tends to be ensured.

[0459] When the block copolymer contains amino groups generated during the production process, the amine value is preferably 1 to 100 mgKOH / g. From the viewpoint of dispersibility, it is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, and even more preferably 50 mgKOH / g or more. It is preferably 90 mgKOH / g or less, more preferably 80 mgKOH / g or less, and even more preferably 75 mgKOH / g or less.

[0460] The above upper and lower limits may be arbitrarily combined. For example, it is preferably 1 to 100 mgKOH / g, more preferably 10 to 90 mgKOH / g, further preferably 30 to 80 mgKOH / g, and particularly preferably 50 to 75 mgKOH / g.

[0461] The amine value is represented by the mass of KOH corresponding to the amount of alkali per 1 g of solid content after removing the solvent in the dispersant sample, and is measured by the following method.

[0462] In a 100mL beaker, accurately weigh 0.5-1.5g of the dispersant sample and dissolve it in 50mL of acetic acid. Use an automatic titrator equipped with a pH electrode to neutralize and titrate the solution with 0.1mol / L HClO4 acetic acid solution. The inflection point of the titration pH curve is taken as the titration endpoint, and the amine value is calculated using the following formula.

[0463] Amine value [mgKOH / g] = (561×V) / (W×S) [W]: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the titration endpoint [mL], S: represents the solid content concentration of the dispersant sample [mass %].

[0464] The acid value of the block copolymer depends on the presence or absence and type of the acidic group serving as the basis of the acid value, but is preferably lower, preferably 10 mgKOH / g or less.

[0465] The weight average molecular weight (Mw) of the block copolymer is preferably in the range of 1000 to 100000. By setting it in the above range, there is a tendency that good dispersibility can be ensured.

[0466] When the photosensitive resin composition of the present invention contains (g) a dispersant, the content ratio thereof is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and is preferably 8% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 2% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0467] The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 8 mass %, more preferably 0.1 to 5 mass %, further preferably 0.5 to 3 mass %, and particularly preferably 0.5 to 2 mass %. By setting it above the above lower limit, there is a tendency to suppress aggregation and form a uniform coating film. By setting it below the above upper limit, there is a tendency to improve heat resistance and developability.

[0468] When the photosensitive resin composition of the present invention contains (g) a dispersant, the content ratio of the (g) dispersant is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more, relative to 100 parts by mass of the resin particles (a1), and is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, further preferably 25 parts by mass or less, further preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, and further preferably 12 parts by mass or less.

[0469] The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, further preferably 1 to 25 parts by mass, further preferably 3 to 20 parts by mass, particularly preferably 5 to 15 parts by mass, and further preferably 5 to 12 parts by mass. By setting it to be above the above lower limit, there is a tendency to suppress the generation of residues due to aggregates. By setting it to be below the above upper limit, there is a tendency to improve heat resistance and developability.

[0470] [1-1-8] Thermal polymerization initiator

[0471] The photosensitive resin composition of the present invention may contain a thermal polymerization initiator. By containing a thermal polymerization initiator, there is a tendency to increase the degree of crosslinking of the film. Specific examples of such thermal polymerization initiators include azo compounds, organic peroxides, and hydrogen peroxide.

[0472] The thermal polymerization initiator may be used alone or in combination of two or more.

[0473] When a thermal polymerization initiator is used in combination with a photopolymerization initiator in order to improve film strength and heat resistance and increase the crosslinking density of the film, it is preferred that the total of their content ratios be the content ratio of the aforementioned photopolymerization initiator relative to the total solid content of the photosensitive resin composition. In addition, when a thermal polymerization initiator is used in combination with a photopolymerization initiator, the combined use ratio of the photopolymerization initiator and the thermal polymerization initiator is preferably 5 to 300 parts by mass of the thermal polymerization initiator relative to 100 parts by mass of the photopolymerization initiator from the viewpoint of heat resistance.

[0474] [1-1-9] Silane coupling agent

[0475] The photosensitive resin composition of the present invention may contain a silane coupling agent in order to improve adhesion to a substrate.

[0476] As the silane coupling agent, for example, epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents can be used. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferred.

[0477] When the photosensitive resin composition of the present invention contains a silane coupling agent, from the viewpoint of adhesion, the content thereof is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 2% by mass or less, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more, relative to the total solid content of the photosensitive resin composition.

[0478] The above-mentioned upper and lower limits can be combined arbitrarily. For example, it can be more than 0.1 mass % and less than 20 mass %, it can be more than 0.1 mass % and less than 15 mass %, it can be more than 0.5 mass % and less than 10 mass %, it can be more than 0.5 mass % and less than 5 mass %, it can also be more than 1 mass % and less than 2 mass %. By being set to more than the above-mentioned lower limit, there is a tendency to improve the adhesion with the substrate. By being set to below the above-mentioned upper limit, there is a tendency to improve the storage stability of the coating liquid.

[0479] [1-1-10] Inorganic fillers

[0480] The photosensitive resin composition of the present invention may contain an inorganic filler other than the above-mentioned inorganic particles for the purpose of improving the strength of the cured product and improving the excellent perpendicularity and taper angle of the coating film due to the appropriate interaction with the alkali-soluble resin (formation of a matrix structure).

[0481] Examples of the inorganic filler include talc, barium sulfate, and those obtained by surface-treating these with various silane coupling agents.

[0482] The average particle size of the inorganic filler is preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm. The average particle size is a value measured using a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter, Inc., etc. Among inorganic fillers, silica sol and modified silica sol are preferred because they tend to have excellent dispersion stability and cone angle improvement effects.

[0483] When the photosensitive resin composition of the present invention contains an inorganic filler, the content thereof is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, relative to the total solid content of the photosensitive resin composition, from the viewpoint of crack resistance of the cured product.

[0484] The above upper and lower limits may be arbitrarily combined. For example, it is preferably 5 to 80% by mass, and more preferably 10 to 70% by mass.

[0485] [1-1-11] Adhesion enhancer

[0486] The photosensitive colored resin composition of the present invention may contain an adhesion improver in order to impart adhesion to a substrate. Examples of the adhesion improver include phosphoric acid-based ethylenic monomers.

[0487] As the phosphoric acid-based ethylenic monomer, a phosphoric acid ester containing a (meth)acryloyloxy group is preferred, and substances represented by the following general formulas (g1), (g2), and (g3) are preferred.

[0488]

[0489] (In the above general formulas (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2 or 3. )

[0490] These phosphoric acid-based ethylenic monomers may be used alone or in combination of two or more.

[0491] When the photosensitive resin composition of the present invention contains a phosphoric acid-based olefinic monomer as an adhesion improver, the content ratio thereof is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and is preferably 4% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, particularly preferably 1% by mass or less, relative to the total solid content of the photosensitive resin composition.

[0492] The above upper and lower limits can be combined arbitrarily. For example, preferably 0.02 to 4 mass%, more preferably 0.05 to 3 mass%, further preferably 0.1 to 2 mass%, and particularly preferably 0.2 to 1 mass%. By setting it above the above lower limit, there is a tendency that the improvement effect of the adhesion with the substrate becomes sufficient. By setting it below the above upper limit, there is a tendency that the adhesion with the substrate is easily suppressed.

[0493] [1-1-12] Solvents

[0494] The photosensitive resin composition of the present invention generally contains a solvent in addition to the above-mentioned components, and is used in a state where the components contained in the photosensitive resin composition are dissolved or dispersed in the solvent. The solvent is not particularly limited, and examples thereof include the organic solvents described below.

[0495] Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0496] Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether;

[0497] Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, 3-methoxy-1-butyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0498] Glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butylene glycol diacetate, and 1,6-hexanol diacetate;

[0499] Alkyl acetates such as cyclohexanol acetate;

[0500] Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

[0501] Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;

[0502] Monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0503] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0504] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexyl;

[0505] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0506] Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone;

[0507] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0508] Halogenated hydrocarbons such as butyl chloride and amyl chloride;

[0509] Ether ketones such as methoxymethylpentyl ketone;

[0510] Nitriles such as acetonitrile and benzonitrile;

[0511] Tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran and dimethoxytetrahydrofuran.

[0512] Examples of commercially available solvents include mineral spirits, VALSOL #2, APCO #18 solvent, Apcothinner, Socal solvent No. 1 and No. 2, SOLVESSO #150, SHELL TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diethylene glycol dimethyl ether (all trade names).

[0513] The solvent can dissolve or disperse the components contained in the photosensitive resin composition, and is selected according to the method of using the photosensitive resin composition of the present invention. From the viewpoint of coating properties, the boiling point of the solvent at atmospheric pressure is preferably 60 to 280° C., more preferably 70 to 260° C. Among them, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred.

[0514] The solvent may be used alone or in combination of two or more.

[0515] The solvent is preferably used in a manner such that the content ratio of all solid components in the photosensitive resin composition solution is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more, and further preferably 90% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 35% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably used in a manner such that it is preferably 10 to 90% by mass, more preferably 15 to 50% by mass, further preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass. By setting it to above the aforementioned lower limit, there is a tendency to suppress the generation of uneven coating. By setting it to below the aforementioned upper limit, there is a tendency to suppress the generation of shrinkage cavities, etc.

[0516] The photosensitive resin composition of the present invention has an average transmittance of 70% or more in a wavelength range of 400 to 700 nm in a cured film having a thickness of 5 μm obtained by curing the photosensitive resin composition.

[0517] When the average transmittance in the wavelength range of 400 to 700 nm is 70% or more, the light transmittance mainly in the visible light region is improved, and when the photosensitive resin composition of the present invention is used to form pixels or a light scattering film, the light emission efficiency tends to be maintained.

[0518] The average transmittance of a cured film having a thickness of 5 μm obtained by curing the photosensitive resin composition in the wavelength range of 400 to 700 nm is 70% or more, preferably 80% or more, more preferably 90% or more, and further preferably 95% or more, and is usually 100% or less.

[0519] The average transmittance in the wavelength range of 400 to 700 nm can be measured using a spectrophotometer. For example, the transmittance can be measured at intervals of 1 nm in the wavelength range of 400 to 700 nm, and the arithmetic mean value thereof can be taken as the average transmittance.

[0520] [1-2] Preparation method of photosensitive resin composition

[0521] The photosensitive resin composition of the present invention is prepared by mixing the components contained in the above-mentioned photosensitive resin composition with a stirrer.

[0522] For example, when a solvent-insoluble component such as (a) resin particles is contained, it is preferably dispersed in advance using a stirrer, a three-one motor, a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc. The dispersion treatment can micronize the (a) resin particles, the organic pigment, and the inorganic particles, thereby improving the coating properties of the photosensitive resin composition.

[0523] The dispersion treatment is usually preferably performed in a system using (a) resin particles, organic pigments, inorganic particles, a solvent and (g) a dispersant in combination, or in a system using part or all of (b) an alkali-soluble resin in combination (hereinafter, the mixture subjected to the dispersion treatment and the composition obtained by the dispersion treatment may be referred to as "ink" or "resin particle dispersion"). In particular, when a polymer dispersant is used as the (g) dispersant, the obtained ink and photosensitive resin composition have excellent dispersion stability and thickening over time is suppressed, which is preferred.

[0524] In this way, in the step of producing the photosensitive resin composition, it is preferred to produce a particle dispersion containing at least (a) resin particles, an organic pigment, inorganic particles, a solvent, and (g) a dispersant.

[0525] As the (a) resin particles, organic pigments, inorganic particles, organic solvents and (g) dispersants that can be used in the particle dispersion, the examples described as the substances that can be used in the photosensitive resin composition can be preferably used. In addition, as the content ratio of the (a) resin particles in the resin particle dispersion, the content ratio described as the content ratio in the photosensitive composition can also be preferably used.

[0526] When the (a) resin particles, organic pigments, and inorganic particles are dispersed using a sand mill, it is preferred to use glass beads or zirconia beads having a particle size of about 0.1 to 8 mm.

[0527] The temperature of the dispersion treatment condition is preferably in the range of 0°C to 100°C, more preferably in the range of room temperature to 80°C. As for the dispersion time, since the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment device, it is appropriately adjusted. The standard of dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.

[0528] The dispersed particle size of the (a) resin particles dispersed in the ink is preferably 0.8 to 5 μm. The dispersed particle size of the organic pigment and inorganic particles dispersed in the ink is preferably 0.01 to 5 μm, more preferably 0.03 to 5 μm. The dispersed particle size of the (a) resin particles, organic pigments, and inorganic particles in the ink is measured by a dynamic light scattering method or the like.

[0529] Next, the ink obtained by the dispersion treatment is mixed with other components contained in the photosensitive resin composition to prepare a uniform solution or dispersion. In the manufacturing process of the photosensitive resin composition, sometimes fine garbage is mixed into the liquid, so it is ideal to filter the obtained photosensitive resin composition using a filter or the like.

[0530] [2] Solidified product and method for forming the same

[0531] The cured product of the present invention can be obtained by curing the photosensitive color resin composition of the present invention.

[0532] The photosensitive resin composition of the present invention can be used as a cured product in partition walls. For example, the cured product of the present invention can be suitably used as a material for scattering light from an organic electroluminescent element or a semiconductor light-emitting element.

[0533] The method for forming a cured product using the photosensitive resin composition of the present invention is not particularly limited, and a conventionally known method can be used. As a method for forming a cured product, for example, a method including the following steps can be cited: a coating step of coating the photosensitive resin composition on a substrate to form a photosensitive resin composition layer; and an exposure step of exposing the photosensitive resin composition layer. As specific examples of such a method for forming a cured product, an inkjet method and a photolithography method can be cited.

[0534] In the inkjet method, a photosensitive resin composition whose viscosity is adjusted by dilution with a solvent is used as ink, and ink droplets are ejected onto a substrate along a predetermined pattern by the inkjet method, thereby coating the photosensitive resin composition on the substrate to form an uncured pattern. Next, the uncured pattern is exposed to form a cured product on the substrate. The exposure of the uncured pattern is performed in the same manner as the exposure step in the photolithography method described later, except that a mask is not used.

[0535] In the photolithography method, a photosensitive resin composition is applied to the entire surface of a region of a substrate where a pattern is to be formed to form a photosensitive resin composition layer. The formed photosensitive resin composition layer is exposed according to a predetermined pattern, and then the exposed photosensitive resin composition layer is developed to form a cured product on the substrate.

[0536] In the coating step of coating a photosensitive resin composition on a substrate in the photolithography method, a contact transfer coating device such as a roll coater, a reverse coater, a bar coater, a die coater, a screen printer, or a non-contact coating device such as a spin coater (rotary coating device) or a curtain coater is used to coat the photosensitive resin composition on the substrate on which a cured product is to be formed, and the solvent is removed by drying as needed to form a photosensitive resin composition layer.

[0537] Next, in the exposure step, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays or excimer lasers using a negative mask, and the photosensitive resin composition layer is partially exposed corresponding to the pattern. The exposure can be performed using a light source that emits ultraviolet rays, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp. The exposure dose also varies depending on the composition of the photosensitive resin composition, and is preferably 10 to 3000 mJ / cm 2 about.

[0538] Next, in the development step, the photosensitive resin composition layer exposed in accordance with the pattern is developed with a developer to form a cured product. The development method is not particularly limited, and an immersion method, a spray method, etc. can be used. Specific examples of the developer include organic developers such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine; and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. In addition, a defoaming agent or a surfactant may be added to the developer.

[0539] Thereafter, the cured product after development is post-baked (baked) to heat and cure. As the condition for post-baking, it is preferably 80°C or more, more preferably 90°C or more, further preferably 100°C or more, and further preferably 120°C or more. In addition, it is preferably 250°C or less, more preferably 200°C or less, further preferably 180°C or less, and further preferably 160°C or less. It is preferably 80-250°C, more preferably 90-200°C, further preferably 100-180°C, and further preferably 120-160°C. When it is above the lower limit, there is a tendency that heat resistance and solvent resistance become good, and by setting it below the upper limit, there is a tendency that the manufacturing cost, and the influence corresponding to substrates and components with limited heat resistance such as plastic substrates, etc., become less.

[0540] As the post-baking time, it is preferably more than 5 minutes, more preferably more than 10 minutes, more preferably more than 20 minutes, and particularly preferably more than 30 minutes. In addition, it is preferably less than 180 minutes, more preferably less than 150 minutes, more preferably less than 120 minutes, particularly preferably less than 100 minutes, and further preferably less than 60 minutes. It is preferably 15 to 180 minutes, more preferably 10 to 150 minutes, more preferably 20 to 120 minutes, particularly preferably 30 to 100 minutes, and particularly preferably 30 to 60 minutes. When it is above the lower limit, there is a tendency that heat resistance and solvent resistance become good. By setting it below the upper limit, there is a tendency that the manufacturing cost, the influence corresponding to the substrate and the element with limited heat resistance such as the plastic substrate, etc., are reduced.

[0541] The substrate used to form the cured product is not particularly limited and can be appropriately selected according to the type of organic electroluminescent element or semiconductor light-emitting element manufactured using the substrate on which the cured product is formed. Glass and various resin materials can be listed as suitable materials for the substrate. Specific examples of resin materials include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)acrylic resins; polysulfone; and polyimide. Among the materials of these substrates, glass and polyimide are preferred from the perspective of excellent heat resistance. In addition, a transparent electrode layer such as ITO or ZnO can be pre-set on the surface of the substrate to form the cured product, depending on the type of the organic electroluminescent element or semiconductor light-emitting element to be manufactured.

[0542] The film thickness of the cured product of the present invention is preferably 0.1 μm or more, preferably 1 μm or more, more preferably 2 μm or more, further preferably 3 μm or more, particularly preferably 5 μm or more, and preferably 1 mm or less, more preferably 100 μm or less, further preferably 50 μm or less, further preferably 30 μm or less, particularly preferably 20 μm or less, and further preferably 10 μm or less. By setting it to above the aforementioned lower limit, there is a tendency for light scattering to be improved. In addition, by setting it to below the aforementioned upper limit, there is a tendency for transparency to be improved. The film thickness of the cured product is measured by a height difference / surface roughness / fine shape measuring device, a scanning white interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, and an electron microscope.

[0543] [3] Color filter containing luminescent nanocrystal particles

[0544] The color filter containing the light-emitting nanocrystal particles of the present invention is not particularly limited as long as it includes the cured product of the present invention, and examples thereof include a color filter in which pixels are formed in regions partitioned by partition walls.

[0545] Figure 1FIG. 1 is a schematic cross-sectional view of an example of a color filter having a cured product of the present invention. Figure 1 As shown in FIG. 1 , the color filter 100 includes a substrate 10, a partition wall 20 provided on the substrate, a red pixel 30, a green pixel 40, and a blue pixel 50. The red pixel 30, the green pixel 40, and the blue pixel 50 are arranged in a lattice shape in a repeated manner in this order. The partition wall 20 is provided between these mutually adjacent pixels. In other words, these mutually adjacent pixels are divided by the partition wall 20.

[0546] The red pixel 30 includes red luminescent nanocrystal particles 1, and the green pixel 40 includes green luminescent nanocrystal particles 2. The blue pixel 50 is a pixel that can transmit blue light from a light source. It includes particles 3 that scatter light from the light source. The photosensitive resin composition of the present invention can be preferably used for the formation of a blue pixel portion, and the cured product of the present invention can be preferably used for the blue pixel portion.

[0547] The red-light-emitting and green-light-emitting nanocrystal particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and have a maximum particle size of 100 nm or less as measured by, for example, a transmission electron microscope or a scanning electron microscope.

[0548] Luminescent nanocrystal particles can emit light of a wavelength different from the absorption wavelength by absorbing light of a specified wavelength (fluorescence or phosphorescence). For example, red luminescent nanocrystal particles 1 emit light with a peak luminescence wavelength in the range of 605 to 665 nm (red light), and green luminescent nanocrystal particles 2 emit light with a peak luminescence wavelength in the range of 500 to 560 nm (green light).

[0549] According to the solution of the Schrodinger wave equation of the trap potential model, the wavelength (luminescent color) of the light emitted by the luminescent nanocrystal particle depends on the size (for example particle diameter) of the luminescent nanocrystal particle, and also depends on the energy gap possessed by the luminescent nanocrystal particle.Therefore, by changing the constituent material and the size of the luminescent nanocrystal particle used, luminescent color can be selected.As the luminescent nanocrystal particle, quantum dot etc. can be listed.

[0550] The method for manufacturing the color filter containing luminescent nanocrystal particles is not particularly limited, and examples thereof include: preparing a substrate with partition walls, and forming a layer containing luminescent nanocrystal particles in the region divided by the partition walls, and forming a layer containing the photosensitive resin composition of the present invention in the blue pixel. The method for forming the layer containing luminescent nanocrystal particles and the layer containing the photosensitive resin composition of the present invention is not particularly limited, and for example, the method of selectively attaching them by inkjet method, and curing them by irradiation or heating with active energy rays, or photolithography can be used to manufacture.

[0551] [4] Light scattering film

[0552] The cured product of the present invention can be used as a light-scattering film. When used as a light-scattering film of an image display device including an organic electroluminescent element, a semiconductor light-emitting element, etc., the light-emitting efficiency tends to be improved.

[0553] Since the refractive index of the light-emitting layer of an organic electroluminescent element or a semiconductor light-emitting element is high, the light emitted is easily totally reflected at the interface, and the efficiency of light extraction to the outside is easily reduced. Therefore, the light scattering film of the present invention can be used in applications of changing the traveling direction of light generated by the light scattering film, suppressing light reflection at the interface, and improving light extraction efficiency, and in applications of forming concavities and convexities on the surface of the scattering film by adding particles, suppressing light reflection at the interface, and thus improving light extraction efficiency.

[0554] In addition, the present invention can be preferably used as a light scattering film for image display devices including organic electroluminescent elements, semiconductor light emitting elements, etc. to suppress unevenness caused by external light reflection. By changing the traveling direction of light reflected from the outside by the light scattering film, unevenness caused by external light reflection can be suppressed.

[0555] Furthermore, the present invention can be preferably used as a light scattering film of an image display device including an organic electroluminescent element, a semiconductor light emitting element, or the like in order to improve a viewing angle.

[0556] [5] Image display device

[0557] The image display device of the present invention comprises a color filter including the cured product of the present invention in a pixel region, and a light scattering film using the cured product of the present invention.

[0558] There is no particular limitation on the type and structure of the image display device, and the light source may be an organic electroluminescent element or a semiconductor light emitting element.

[0559] In addition, examples of the image display device of the present invention include an image display device including the color filter containing the light-emitting nanocrystal particles of the present invention.

[0560] As types of image display devices, there are liquid crystal display devices, image display devices including organic electroluminescent elements, semiconductor light-emitting elements, etc. In the case of liquid crystal display devices, there are devices including a light source including a blue LED and a liquid crystal layer including electrodes, and the electrodes control the blue light emitted by the light source in each pixel portion.

[0561] In addition, a device in which a blue-emitting organic electroluminescent element or a semiconductor light-emitting element is arranged at a position corresponding to each pixel portion of the color filter can be listed. Specifically, for example, the methods described in Japanese Patent Publication No. 2019-87746 and Japanese Patent Publication No. 2021-089433 can be listed.

[0562] Example

[0563] Hereinafter, the photosensitive resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

[0564] The constituent components of the photosensitive resin composition used in the following Examples and Comparative Examples are as follows.

[0565] <Alkali Soluble Resin-I>

[0566] For a copolymer resin having dicyclopentyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.30 / 0.10 / 0.60) as a constituent monomer, acrylic acid and the aforementioned glycidyl methacrylate are subjected to an addition reaction in equal amounts, and then an addition reaction is carried out in such a manner that tetrahydrophthalic anhydride becomes 0.39 moles relative to 1 mole of the above copolymer resin, thereby obtaining an alkali-soluble acrylic copolymer resin. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene is 9000, the solid content acid value is 80 mgKOH / g, and the double bond equivalent is 470 g / mol. It belongs to an alkali-soluble resin (b1) having an olefinic double bond.

[0567] <Alkali-soluble resin-II>

[0568] Alkali-soluble acrylic copolymer resin with benzyl methacrylate / methacrylic acid (molar ratio: 0.73 / 0.27) as monomers. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene is 12300, and the solid content acid value is 98 mgKOH / g. It does not belong to the alkali-soluble resin (b1) having an olefinic double bond.

[0569] <Solvent-I>

[0570] PGMEA: propylene glycol monomethyl ether acetate.

[0571] <Solvent-II>

[0572] PGMEA: propylene glycol monomethyl ether.

[0573] <Photopolymerizable compound-I>

[0574] DPHA: manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

[0575] <Photopolymerizable compound-II>

[0576] M-933: manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.

[0577] <Photopolymerization Initiator-I>

[0578] 2-(N,N-dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one.

[0579] <Photopolymerization Initiator-II>

[0580] A compound having the following chemical structure was used.

[0581]

[0582] <Photopolymerization Initiator-III>

[0583] A compound having the following chemical structure is used. This compound can be prepared by the synthesis method described in International Publication No. 2019 / 131189.

[0584]

[0585] <Surfactant-I>

[0586] DIC Corporation, MEGAFAC F-559 (fluorine-based surfactant).

[0587] <Inhibitor-I>

[0588] 2-Methylhydroquinone.

[0589] <Ultraviolet Absorber-I>

[0590] Manufactured by BASF JAPAN, TINUVIN384-2.

[0591] <Additive-I>

[0592] Made by Nippon Kayaku Co., Ltd., KAYAMER PM-21 (methacryloyl group-containing phosphate ester).

[0593] <Resin Pellets-I>

[0594] EPOSTAR MS (benzoguanamine-formaldehyde condensate (benzoguanamine resin), average particle size 1.6 μm, refractive index 1.66) manufactured by Nippon Shokubai Co., Ltd. This belongs to resin particles (a1) having a refractive index of 1.56 to 2.00 and an average primary particle size of 0.8 μm or more.

[0595] <Resin Particles-II>

[0596] EPOSTAR S12 (melamine-formaldehyde condensate (melamine resin), average particle size 1.4 μm, refractive index 1.66) manufactured by Nippon Shokubai Co., Ltd. This belongs to the resin particles (a1) having a refractive index of 1.56 to 2.00 and an average primary particle size of 0.8 μm or more.

[0597] <Resin Particles-III>

[0598] EPOSTAR S6 (melamine-formaldehyde condensate (melamine resin), average particle size 0.4 μm, refractive index 1.66, manufactured by Nippon Shokubai) does not belong to the resin particles (a1) having a refractive index of 1.56 to 2.00 and an average primary particle size of 0.8 μm or more.

[0599] <Resin Particles-IV>

[0600] MX-150 (acrylic resin, average particle size 1.5 μm, refractive index 1.49) manufactured by Soken Chemical Co., Ltd. It does not belong to the resin particles (a1) having a refractive index of 1.56 to 2.00 and an average primary particle size of 0.8 μm or more.

[0601] <Resin Pellets-V>

[0602] SX-130H (styrene resin, average particle size 1.3 μm, refractive index 1.59) manufactured by Soken Chemical Co., Ltd. This belongs to the resin particles (a1) having a refractive index of 1.56 to 2.00 and an average primary particle size of 0.8 μm or more.

[0603] <Pigment-I>

[0604] PT501R (titanium oxide, average primary particle size 0.18 μm, refractive index 2.7) manufactured by Ishihara Sangyo Co., Ltd.

[0605] <Pigment-II>

[0606] Ishihara Sangyo Co., Ltd., TTO-51(A) (titanium oxide, average primary particle size 0.01 to 0.03 μm, refractive index 2.7).

[0607] <Pigment Dispersion-I>

[0608] Pigment-I, amine basic polymer acrylic dispersant (dispersant-I) and solvent were mixed in a mass ratio as shown in Table 1. The mixture was dispersed in a paint shaker at 25 to 45°C for 6 hours. Zirconia beads of 2.5 times the mass of the mixed solution were added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare pigment dispersion 1.

[0609] The blending ratio of the dispersant in Table 1 is expressed as a solid content conversion value, and the blending ratio of the solvent also includes the amount of the solvent derived from the dispersant.

[0610] <Pigment Dispersion-II>

[0611] The pigment-II, the alkali-soluble resin-I, and the solvent were mixed so as to have the mass ratio described in Table 1. The same operation as that of the pigment dispersion-I was carried out except that the dispersion time was changed to 8 hours to prepare a pigment dispersion-II.

[0612] <Resin Particle Dispersion-I>

[0613] The resin particles-V, the dispersant-I and the solvent were mixed in a mass ratio as shown in Table 1. The dispersion time was set to 2 hours, and the Resin particle dispersion-I was prepared by carrying out the same operation as that of pigment dispersion-I except that zirconia beads were added.

[0614] [Table 1]

[0615]

[0616] [Examples 1 to 5 and Comparative Examples 1 to 3]

[0617] Each component was added so that the ratio of the solid content of each component in the total solid content became the blending ratio of Tables 2 to 4, and a solvent was further added so that the content ratio of the total solid content was 31% by mass and the solvent-I / solvent-II in the total solvent was 80 / 20 (mass ratio), and the mixture was stirred and dissolved to prepare photosensitive resin compositions 1 to 14 (compositions 1 to 14) shown in Tables 2 to 4. The obtained photosensitive resin compositions were evaluated by the method described below.

[0618] The mixing ratios of the pigment dispersion and the alkali-soluble resin in Table 2 are expressed in terms of solid content.

[0619] [Table 2]

[0620]

[0621] [Table 3]

[0622]

[0623] [Table 4]

[0624]

[0625] The evaluation method is described below.

[0626] <Measurement of transmittance of cured film with a film thickness of 5 μm>

[0627] The photosensitive resin composition was applied on a glass substrate using a spin coater so that the thickness of the cured film after heating and curing was 5 μm. The coated substrate was vacuum dried for 1 minute and then heated and dried on a hot plate at 100°C for 120 seconds to obtain a coated substrate. Next, a high-pressure mercury lamp was used with a wavelength of 330 nm or less cut off and a luminometer was used at 50 mJ / cm 2 The entire surface was exposed. The light intensity at a wavelength of 365 nm was 45 mW / cm 2 Next, an aqueous solution containing 0.03% by mass of KOH and 0.07% by mass of Emulgen A-60 (surfactant manufactured by Kao Corporation) was used as a developer, and the substrate was spray-developed at 24°C for 70 seconds, and then washed with pure water for 10 seconds. Finally, the substrate was heat-cured at 150°C in an oven for 30 minutes to obtain a substrate for transmittance measurement having a cured film having a film thickness of 5 μm.

[0628] The transmittance of the substrate for transmittance measurement was measured with reference to the glass substrate using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.), and the transmittance was measured at a wavelength range of 400 to 700 nm with a pitch of 1 nm, and the arithmetic mean was calculated. The results of evaluating the average transmittance in the wavelength range of 400 to 700 nm according to the following criteria are shown in Tables 2 to 4.

[0629] (Evaluation criteria for average transmittance in the wavelength range of 400 to 700 nm)

[0630] A: More than 70%

[0631] B: less than 70%

[0632] <Haze measurement>

[0633] A substrate for haze measurement was obtained by the same operation procedure as for the substrate for transmittance measurement, except that the photosensitive resin composition was applied on the glass substrate using a spin coater so that the thickness of the cured film after heat curing became a predetermined film thickness.

[0634] The haze of the substrate for haze measurement was measured using a haze meter (NDH5000 SP manufactured by Nippon Denshoku Industries Co., Ltd.). D65 was used as a light source. The measurement results and the results of evaluation based on the following criteria are shown in Tables 2 to 4. The higher the haze, the higher the light scattering property.

[0635] (Evaluation criteria for haze)

[0636] A: More than 80%

[0637] B: less than 80%

[0638] Tables 2 to 4 show the results of measuring the film thickness of the cured film of the substrate for haze measurement using a stylus-type height difference film thickness meter (Alpha-Step IQ manufactured by KLA-Tencor Corporation).

[0639] <Developability Evaluation>

[0640] During exposure, a photomask with linear openings of various widths having an opening width of 5 to 50 μm (5 to 20 μm: every 1 μm, 25 to 50 μm: every 5 μm) and an opening length of 2 mm was used. The exposure gap was set to 100 μm. Otherwise, a linear pattern substrate was prepared by the same operating steps as for preparing a substrate for haze measurement.

[0641] The entire line (2 mm) on the line pattern substrate was observed with an optical microscope to confirm the presence of the line that was closely attached to the substrate without chipping or peeling and whether there was any residue on the substrate other than the line. The evaluation criteria for the presence of the line and the evaluation criteria for the residue are as follows.

[0642] In addition, the film thickness of the line pattern substrate was measured using a stylus-type height difference film thickness meter (Alpha-Step IQ manufactured by KLA-Tencor Corporation).

[0643] (Evaluation criteria for the presence or absence of lines)

[0644] A: There are wires on the substrate.

[0645] B: Wireless on the substrate.

[0646] C: After development, the unexposed portion remains as a residue and no line is formed.

[0647] (Evaluation criteria for residue)

[0648] A: There are residues other than the wires on the substrate.

[0649] B: There is no residue other than the wire on the substrate.

[0650] <Heat resistance evaluation>

[0651] A heat resistance evaluation substrate was prepared using a 5 cm square glass substrate in the same manner as the haze measurement substrate. The heat resistance evaluation substrate was placed upright at an angle of 80° to the bottom of an oven and heated in an oven at 150° C. for 30 minutes.

[0652] The film thickness at a position moved 1.5 cm from the center of the upper end (the end farthest from the bottom of the oven) of the substrate for heat resistance evaluation in a vertically heated state in an oven was set as film thickness 1, and the film thickness at a position moved 1.5 cm from the center of the lower end (the end closest to the bottom of the oven) to the center of the substrate was set as film thickness 2. The film thickness was measured using a stylus height difference film thickness meter (Alpha-Step IQ manufactured by KLA-Tencor).

[0653] The in-plane distribution of the film thickness of the upper and lower parts of the film was calculated as the film thickness change according to the following formula. The evaluation criteria for the film thickness change are as follows. The smaller the film thickness change, the higher the heat resistance.

[0654] Film thickness change (%)=|Film thickness 2-Film thickness 1|×100 / {(Film thickness 1+Film thickness 2) / 2}

[0655] (Evaluation criteria for film thickness change)

[0656] A: Less than 10%

[0657] B: 10% or more

[0658] From the comparison of Examples 1 to 11 and Comparative Example 1, it can be seen that by containing an alkali-soluble resin (b1) having a double bond, the change in film thickness after heat resistance evaluation can be reduced and the heat resistance can be improved. It is believed that by containing an acrylic copolymer resin (b1) having a double bond, the crosslinking density in the coating film becomes higher and the heat resistance becomes higher. In addition, by containing an alkali-soluble resin (b1) having a double bond, a line can be formed without residue after development, and the developability can be improved. It is believed that since the alkali-soluble resin (b1) having a double bond has high solubility in the developer, the unexposed part is easily dissolved in the developer. On the other hand, the curing degree of the exposed part becomes higher, so the solubility in the developer is reduced, and a line can be formed, showing high developability.

[0659] From the comparison between Examples 1 to 11 and Comparative Example 2, it can be seen that the average transmittance in the wavelength range of 400 to 700 nm can be increased by containing the resin particles (a1) having a refractive index of 1.56 or more and 2.00 or less, and the light transmittance can be improved. This is considered to be because the interface reflection between the resin in the coating film and the resin particles is suppressed by using the resin particles (a1) having a refractive index of 2.00 or less, and the average transmittance can be increased.

[0660] It can be seen from the comparison between Examples 1 to 11 and Comparative Example 3 that the haze can be improved by containing the resin particles (a1) having a refractive index of 1.56 or more and 2.00 or less. This is considered to be because the use of the resin particles (a1) having a refractive index of 1.56 or more increases the scattering intensity at the interface between the resin in the coating film and the resin particles, thereby increasing the haze.

[0661] From the comparison of Examples 1 to 11 and Comparative Example 4, it can be seen that the haze can be improved by containing resin particles (a1) with an average particle size of 0.8 μm or more. It is believed that this is because, when the average particle size of the resin particles is 0.8 μm or more, the scattering intensity becomes larger for the D65 light source during haze measurement, and the haze becomes higher. In addition, by containing resin particles (a1) with an average particle size of 0.8 μm or more, lines can be formed without residue after development, and the developability can be improved. It is believed that when containing resin particles (a1) with an average particle size of 0.8 μm or more, the isotropic scattering when irradiated with light is suppressed compared to resin particles with a small average particle size, so that the unexposed part is easily dissolved in the developer, showing high developability.

[0662] From the comparison between Examples 1 to 11 and Comparative Example 5, it can be seen that by containing (e) a polymerization inhibitor and / or (f) an ultraviolet absorber, a line can be formed without residue after development, and the developability can be improved. Since the light after exposure is scattered by the unexposed part, the photosensitive resin composition containing resin particles tends to leave residue in the unexposed part after development. It is believed that by making the photosensitive resin composition contain (e) a polymerization inhibitor and / or (f) an ultraviolet absorber, the photocuring of the unexposed part caused by the scattered light is suppressed, thereby suppressing the residue of the unexposed part and showing high developability.

[0663] Description of Reference Numerals

[0664] 1Red luminescent nanocrystal particles

[0665] 2Green luminescent nanocrystal particles

[0666] 3Particles that scatter light from a light source

[0667] 10 substrate

[0668] 20 Next door

[0669] 30 red pixels

[0670] 40 green pixels

[0671] 50 blue pixels

[0672] 100 color filters

Claims

1. A photosensitive resin composition comprising (a) resin particles, (b) an alkali-soluble resin, and (c) a photopolymerization initiator. The (a) resin particles contain resin particles (a1) having a refractive index of 1.56 or more and 2.00 or less and an average primary particle size of 0.8 μm or more, The (b) alkali-soluble resin comprises an alkali-soluble resin (b1) having an olefinic double bond, The photosensitive resin composition further comprises at least one of (e) a polymerization inhibitor and (f) an ultraviolet absorber, A cured film having a thickness of 5 μm obtained by curing the photosensitive resin composition has an average transmittance of 70% or more in a wavelength range of 400 to 700 nm.

2. The photosensitive resin composition according to claim 1, wherein The resin particles (a1) include at least one of a benzoguanamine resin, a melamine resin, and a styrene resin.

3. The photosensitive resin composition according to claim 1, wherein The (c) photopolymerization initiator includes an alkylphenone-based photopolymerization initiator.

4. The photosensitive resin composition according to claim 1, wherein The content of the alkali-soluble resin (b1) in the alkali-soluble resin (b) is 20% by mass or more.

5. The photosensitive resin composition according to claim 1, wherein The content of the resin particles (a1) is 5% by mass or more based on the total solid content of the photosensitive resin composition. The photosensitive resin composition according to claim 1 , further comprising (d) a photopolymerizable compound. The photosensitive resin composition according to claim 1 , further comprising (e) a polymerization inhibitor. The photosensitive resin composition according to claim 1 , further comprising (f) an ultraviolet absorber. 9 . A cured product obtained by curing the photosensitive resin composition according to claim 1 . 10 . A color filter comprising the cured product according to claim 9 and light-emitting nanocrystal particles. 11 . An image display device comprising the cured product according to claim 9 .

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