Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

• the present invention relates to a photosensitive resin composition, a cured product, and an image display device.
• This application claims priority based on Japanese Patent Application No. 2022-048750 filed in Japan on March 24, 2022, the contents of which are incorporated herein.
• Organic EL (Electro Luminescence) devices are self-luminous devices that utilize the principle that when an electric field is applied, fluorescent substances emit light due to the recombination energy of holes injected from the anode and electrons injected from the cathode. It is. Organic EL elements have been actively researched and developed in recent years for use in lighting devices, display devices, and the like.
• organic EL display devices have advantages over conventional CRTs and LCDs in terms of visibility and viewing angle, as well as excellent features such as lighter weight, thinner layers, and flexibility.
• the refractive index of the organic layer including the light emitting layer is 1.6 to 2.1, which is higher than that of air. Therefore, total reflection or interference of the emitted light at the interface is likely to occur, and the light extraction efficiency is less than 20%, resulting in a loss of most of the light.
• the basic structure of an organic EL device is a structure in which a transparent electrode, at least one organic layer including a light emitting layer, and a back electrode are sequentially laminated on a transparent substrate.
• a TFT substrate in which a plurality of pixel electrodes forming the back electrode and TFTs (thin film transistors) serving as switching elements thereof are formed in a matrix is laminated on the organic layer. .
• the light emitted from the organic layer is reflected directly or by a back electrode made of aluminum or the like, and is emitted from the light-transmitting substrate. At that time, it is preferable that the generated light be efficiently extracted to the light-transmitting substrate side.
• the light undergoes total reflection and becomes guided light that travels inside the element while being totally reflected in the plane direction, and is absorbed and attenuated inside the element before being taken out to the outside. The problem was that I could't do it.
• Patent Document 1 describes an organic electroluminescent element with improved light extraction efficiency by combining a high refractive index layer and a nanoporous layer.
• Patent Document 2 describes a photosensitive composition with high refraction and high adhesiveness using oxide fine particles such as titanium oxide and a specific fluorene skeleton-containing compound.
• Patent Document 3 describes a composition for optical materials using a specific compound.
• metal oxide particles with a high refractive index such as TiO 2 and ZrO 2 into a photosensitive resin composition
• a cured product with a high refractive index can be obtained.
• a flattening film made of a cured material or a microlens is placed between a TFT and a pixel electrode in order to improve light extraction efficiency, problems such as signal delay and heat loss due to dielectric loss may occur.
• the photosensitive composition containing the fluorene skeleton-containing compound described in Patent Document 2 had a low refractive index and insufficient hole resolution.
• the compound described in Patent Document 3 has a problem in refractive index when combined with a specific alkali-soluble resin, and also has insufficient hole resolution.
• the present inventors have found that the above problems can be solved by using a specific ethylenically unsaturated compound and an alkali-soluble resin, and have completed the present invention. That is, the gist of the present invention is as follows.
• a photosensitive resin composition containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin,
• the ethylenically unsaturated compound (A) contains an ethylenically unsaturated compound (A1) having 1 to 3 ethylenically unsaturated bonds and 1 to 3 sulfur-containing aromatic heterocycles in the molecule
• a photosensitive resin composition, wherein the alkali-soluble resin (C) contains an epoxy (meth)acrylate resin (C1) having an aromatic ring in its main chain.
• the photosensitive resin composition of [2], wherein the ethylenically unsaturated compound (A1) is a compound represented by the following general formula (A1-1).
• R 1 represents a hydrogen atom or a methyl group.
• Cy represents a sulfur-containing aromatic heterocycle.
• Q 1 and Q 2 each independently represent an alkylene group having 1 to 6 carbon atoms.
• Z 1 and Z 2 each independently represent a divalent hydrocarbon group which may have a substituent.
• m and n each independently represent an integer of 1 to 3.
• p and q each independently represent an integer of 0 to 3.
• R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• [3] The photosensitive resin composition according to [1] or [2], wherein the content of the ethylenically unsaturated compound (A1) is 20% by mass or more in the total solid content of the photosensitive resin composition.
• (C) The photosensitive resin composition according to any one of [1] to [3], wherein the content ratio of the ethylenically unsaturated compound (A1) to 100 parts by mass of the alkali-soluble resin is 120 parts by mass or less.
• [5] The photosensitive resin according to any one of [1] to [4], wherein the epoxy (meth)acrylate resin (C1) having an aromatic ring in the main chain has a partial structure represented by the following general formula (i) Composition.
• R a represents a hydrogen atom or a methyl group.
• R b represents a divalent hydrocarbon group which may have a substituent.
• k represents 1 or 2.
• Formula (i ) The benzene ring in ) may be further substituted with any substituent.
• Each * represents a bond.
• An image display device comprising the cured product of [7].
• the present invention it is possible to provide a photosensitive resin composition that can form a cured product with a high refractive index and has excellent hole resolution.
• (meth)acrylic means “one or both of acrylic and methacrylic.”
• Total solid content shall mean all components other than the solvent in the photosensitive resin composition. Even if components other than the solvent are liquid at room temperature, they are not included in the solvent but included in the total solid content.
• the numerical range expressed using " ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
• the term "(co)polymer” includes both a single polymer (homopolymer) and a copolymer (copolymer), and also includes “(acid)anhydride” and “(anhydride)”. )...
• the term “acid” is meant to include both acids and their anhydrides.
• the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
• the acid value refers to the acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.
• Photosensitive resin composition contains (A) an ethylenically unsaturated compound, (B) a photoinitiator, and (C) an alkali-soluble resin, and further contains, if necessary, It may also contain other ingredients. Examples of other components include metal oxides, colorants, and solvents.
• [1-1-1] Component (A); Ethylenically unsaturated compound The photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound. (A) Including the ethylenically unsaturated compound increases the curability of the coating film. In the photosensitive resin composition of the present invention, (A) the ethylenically unsaturated compound has 1 to 3 ethylenically unsaturated bonds and 1 to 3 sulfur-containing aromatic heterocycles in the molecule. Contains a saturated compound (A1) (hereinafter sometimes simply referred to as an ethylenically unsaturated compound (A1)).
• A1 saturated compound
• ⁇ Ethylenically unsaturated compound (A1)> The ethylenically unsaturated compound (A1) has 1 to 3 ethylenically unsaturated bonds and 1 to 3 sulfur-containing aromatic heterocycles in the molecule.
• a high refractive index can be imparted to the cured product due to an increase in the electron density and polarizability derived from the sulfur atom and the aromatic ring.
• the number of ethylenically unsaturated bonds that the ethylenically unsaturated compound (A1) has from 1 to 3 in the molecule is preferably 2 to 3 from the viewpoint of curability.
• the number of sulfur-containing aromatic heterocycles that the ethylenically unsaturated compound (A1) has from 1 to 3 in the molecule is preferably 2 from the viewpoint of increasing the refractive index and ensuring solubility. From the viewpoint of curability, high refractive index, and ensuring solubility, it is more preferable that the ethylenically unsaturated compound (A1) has two ethylenically unsaturated bonds and two sulfur-containing aromatic heterocycles.
• the sulfur-containing aromatic heterocycle has at least one sulfur atom as a heteroatom constituting the aromatic heterocycle.
• the heteroatom may include an oxygen atom, a nitrogen atom, or an oxygen atom and a nitrogen atom.
• the number of sulfur atoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1 from the viewpoint of avoiding coloration.
• the number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of avoiding coloring and ensuring solubility.
• the sulfur-containing aromatic heterocycle may be a single ring or a condensed ring. A condensed ring is preferred from the viewpoint of increasing the refractive index.
• the number of rings constituting the condensed ring is preferably 2 to 5, more preferably 2 to 4, and particularly preferably 2 to 3 in terms of facilitating raw material acquisition and synthesis.
• the sulfur-containing aromatic heterocycle include aromatic heterocycles containing one sulfur atom such as a thiophene ring, benzothiophene ring, dibenzothiophene ring, thiopyran ring, naphthothiophene ring, dinaphthothiophene ring, and dibenzothiopyran ring.
• Ring aromatic heterocycle containing two or more sulfur atoms such as thianthrene ring; thiazole ring, isothiazole ring, benzothiazole ring, naphthothiazole ring, phenothiazine ring, thiazoloimidazole ring, thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, dioxazolopyrazine ring, thiazolopyrazine ring, thiazolooxazole ring, dibenzobenzothiophene ring, thienoxazole ring, thienothiadiazole ring, thiazolothiadiazole ring, etc.
• Examples include aromatic heterocycles.
• a benzothiazole ring, a dibenzothiophene ring, and a benzothiophene ring are preferable from the viewpoint of high refractive index, low coloration, and solubility, and a benzothiazole ring is more preferable.
• the ethylenically unsaturated compound (A1) is preferably a compound represented by the following general formula (A1-1).
• R 1 represents a hydrogen atom or a methyl group.
• Cy represents a sulfur-containing aromatic heterocycle.
• Q 1 and Q 2 each independently represent an alkylene group having 1 to 6 carbon atoms.
• Z 1 and Z 2 each independently represent a divalent hydrocarbon group which may have a substituent.
• m and n each independently represent an integer of 1 to 3.
• p and q each independently represent an integer of 0 to 3.
• R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• Cy represents a sulfur-containing aromatic heterocycle which may have a substituent.
• Sulfur-containing aromatic heterocycles contribute to high refractive index.
• the sulfur-containing aromatic heterocycle has at least one sulfur atom as a heteroatom constituting the aromatic heterocycle.
• the heteroatom may include an oxygen atom, a nitrogen atom, or an oxygen atom and a nitrogen atom.
• the number of sulfur atoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1 from the viewpoint of avoiding coloring.
• the number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of avoiding coloring and ensuring solubility.
• the sulfur-containing aromatic heterocycle may be a single ring or a condensed ring.
• a condensed ring is preferred from the viewpoint of increasing the refractive index.
• the number of rings constituting the condensed ring is preferably 2 to 5, more preferably 2 to 4, and particularly preferably 2 to 3 in terms of facilitating raw material acquisition and synthesis.
• sulfur-containing aromatic heterocycle examples include aromatic heterocycles containing one sulfur atom such as a thiophene ring, benzothiophene ring, dibenzothiophene ring, thiopyran ring, naphthothiophene ring, dinaphthothiophene ring, and dibenzothiopyran ring.
• Ring aromatic heterocycle containing two or more sulfur atoms such as thianthrene ring; thiazole ring, isothiazole ring, benzothiazole ring, naphthothiazole ring, phenothiazine ring, thiazoloimidazole ring, thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, dioxazolopyrazine ring, thiazolopyrazine ring, thiazolooxazole ring, dibenzobenzothiophene ring, thienoxazole ring, thienothiadiazole ring, thiazolothiadiazole ring, etc.
• Examples include aromatic heterocycles.
• a benzothiazole ring, a dibenzothiophene ring, and a benzothiophene ring are preferable from the viewpoint of high refractive index, low coloration, and solubility, and a benzothiazole ring is more preferable.
• Q 1 and Q 2 independently represent an alkylene group having 1 to 6 carbon atoms.
• the alkylene group having 1 to 6 carbon atoms may be linear or branched.
• the alkylene group preferably has 1 to 4 carbon atoms.
• a methylene group, an ethylene group, a methylmethylene group, and an ethylmethylene group are more preferable, a methylene group and an ethylene group are even more preferable, and a methylene group is particularly preferable.
• Q 1 and Q 2 in one molecule may be the same or different.
• Q 1 and Q 2 are preferably the same from the viewpoint of easy availability of raw materials and easy control of the stereoisomer of the product.
• R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, and butyl group.
• X 1 and X 2 are preferably -O- or -S- from the viewpoint of facilitating synthesis and lowering viscosity. From the viewpoint of raw material availability, -O- is more preferable, and from the viewpoint of refractive index, -S- is more preferable.
• Z 1 and Z 2 independently represent a hydrocarbon group which may have a substituent.
• the number of carbon atoms in the hydrocarbon group (not including the number of carbon atoms in substituents) is preferably 1 to 8.
• the refractive index is difficult to decrease, and since the molecular weight is small, the viscosity is easy to decrease, and the processability is easy to improve.
• Specific examples include a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, and a butylene group.
• the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, and a fluoroalkyl group.
• m and n each independently represent an integer of 1 to 3. From the viewpoint of curability, m is preferably 2 to 3, more preferably 2. From the viewpoint of refractive index, n is preferably 2 to 3, more preferably 2. It is particularly preferred that m and n are each 2.
• p and q each independently represent an integer of 0 to 3.
• the ethylenically unsaturated compounds (A1) represented by formulas (a3), (a4), and (a5) are preferable, and the ethylenically unsaturated compounds (A1) represented by formula (a3) are more preferable. preferable.
• the amount of sulfur atoms contained in one molecule of the ethylenically unsaturated compound (A1) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more.
• the content is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less.
• By setting it as the above-mentioned lower limit or more there is a tendency for the refractive index to become high. Further, by setting the content to be below the upper limit value, there is a tendency for low coloring property.
• the above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 40% by weight, more preferably 10 to 40% by weight, even more preferably 15 to 30% by weight, particularly preferably 20 to 25% by weight.
• the double bond equivalent of the ethylenically unsaturated compound (A1) is preferably 200 g/mol or more, more preferably 250 g/mol or more, and preferably 900 g/mol or less, more preferably 700 g/mol or less, even more preferably It is 500 g/mol or less, particularly preferably 300 g/mol or less.
• it is preferably 200 to 900 g/mol, more preferably 200 to 700 g/mol, even more preferably 250 to 500 g/mol, particularly preferably 250 to 300 g/mol.
• Ethylenically unsaturated compound other than ethylenically unsaturated compound (A1) In the photosensitive resin composition of the present invention, as the ethylenically unsaturated compound (A), an ethylenically unsaturated compound other than the ethylenically unsaturated compound (A1) (hereinafter may simply be referred to as other ethylenically unsaturated compound) ) may also be included.
• the ethylenically unsaturated compound refers to a compound having one or more ethylenically unsaturated bonds in the molecule.
• ethylenically unsaturated compounds have two ethylenically unsaturated bonds in the molecule because of their polymerizability, crosslinkability, and the ability to expand the difference in developer solubility between exposed and non-exposed areas. Compounds having the above are preferred.
• the ethylenically unsaturated bond is preferably derived from a (meth)acryloyloxy group. That is, as other ethylenically unsaturated compounds, (meth)acrylate compounds are preferred.
• polyfunctional ethylenically unsaturated compounds it is particularly desirable to use polyfunctional ethylenically monomers having two or more ethylenically unsaturated bonds in one molecule.
• the number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and is preferably 15 or less, more preferably 8 or less, and even more preferably is 6 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 2 to 15, preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6.
• the value is equal to or more than the lower limit, the developability tends to be better, and when the value is equal to or less than the upper limit, the curability is improved, and the dielectric constant and volume resistance tend to be high.
• ethylenically unsaturated compounds include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds Examples include esters obtained by an esterification reaction between polyhydric hydroxy compounds such as esters, etc., and unsaturated carboxylic acids and polybasic carboxylic acids.
• esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
• acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and some or all of the acrylates of the above-mentioned exemplified compounds.
• Methacrylic acid esters in which methacrylate is replaced examples include maleic esters in which part or all of the acrylate in the exemplary compound is replaced with maleate.
• esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
• esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
• acid esters include acid esters.
• Esters obtained by the esterification reaction of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single products, but are typical examples. Specific examples include, for example, a condensate of acrylic acid, phthalic acid, and ethylene glycol, a condensate of acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid, and pentaerythritol, acrylic acid, adipine Mention may be made of condensates of acids, butanediol and glycerin.
• polyfunctional ethylenic monomers include, for example, urethane obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic ester.
• other ethylenically unsaturated compounds are preferably esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth)acrylates, such as dipentaerythritol. More preferred are hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate. These may be used alone or in combination of two or more.
• the content of the ethylenically unsaturated compound (A) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably at least 1% by mass, more preferably at least 10% by mass, and even more preferably at least 10% by mass based on the total solid content. is 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less. be.
• the above upper and lower limits can be arbitrarily combined.
• the total solid content is 1 to 80% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight, even more preferably 30 to 60% by weight, particularly preferably 40 to 60% by weight.
• the refractive index tends to be high
• the hole resolution tends to be good.
• the content of the ethylenically unsaturated compound (A1) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably at least 1% by mass, more preferably at least 10% by mass, and even more preferably at least 10% by mass based on the total solid content. is 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less. be.
• the above upper and lower limits can be arbitrarily combined.
• the total solid content is 1 to 80% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight, even more preferably 30 to 60% by weight, particularly preferably 40 to 60% by weight.
• the refractive index tends to improve
• the hole resolution tends to be improved.
• the content ratio of the ethylenically unsaturated compound (A1) to the total content of the ethylenically unsaturated compound (A) in the photosensitive resin composition of the present invention is not particularly limited,
• the total content is preferably 1% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, particularly preferably 90% by mass or more, and preferably 100% by mass or less.
• it is 1 to 100% by weight, preferably 70 to 100% by weight, and more preferably 90 to 100% by weight.
• the refractive index is a tendency for the refractive index to improve by making it more than the above-mentioned lower limit.
• the content ratio of the ethylenically unsaturated compound (A) to 100 parts by mass of the alkali-soluble resin is not particularly limited, but is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 40 parts by mass or more, It is even more preferably 60 parts by mass or more, particularly preferably 80 parts by mass or more, and preferably 200 parts by mass or less, more preferably 150 parts by mass or less, still more preferably 120 parts by mass or less.
• the above upper and lower limits can be arbitrarily combined.
• 10 to 200 parts by weight preferably 20 to 150 parts by weight, more preferably 40 to 150 parts by weight, even more preferably 60 to 150 parts by weight, even more preferably 60 to 120 parts by weight, particularly preferably 80 to 120 parts by weight.
• Part by mass Setting the amount above the lower limit value tends to improve the curability, and setting the amount below the upper limit value tends to improve the hole resolution.
• the content ratio of the ethylenically unsaturated compound (A1) to 100 parts by mass of the alkali-soluble resin is not particularly limited, but is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 40 parts by mass or more, Even more preferably 60 parts by mass or more, particularly preferably 80 parts by mass or more, and preferably 200 parts by mass or less, more preferably 150 parts by mass or less, still more preferably 130 parts by mass or less, even more preferably 120 parts by mass. below.
• 10 to 200 parts by weight preferably 20 to 150 parts by weight, more preferably 40 to 150 parts by weight, even more preferably 60 to 150 parts by weight, even more preferably 60 to 130 parts by weight, even more preferably 60 to 150 parts by weight.
• 120 parts by weight particularly preferably 80 to 120 parts by weight.
• Photopolymerization initiator The photosensitive resin composition of the present invention contains (B) a photopolymerization initiator.
• the photopolymerization initiator is particularly limited if it is a compound that polymerizes (A) the ethylenically unsaturated compound with actinic rays, for example, polymerizes the ethylenically unsaturated bond of the (A) ethylenically unsaturated compound. Not done.
• photopolymerization initiator (B) a photopolymerization initiator commonly used in this field can be used.
• photopolymerization initiators include, for example, metallocene compounds containing titanocene compounds described in Japanese Patent Application Laid-open Nos. 59-152396 and 61-151197; Japanese Patent Applications 2000-56118; N-aryl- ⁇ such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in Japanese Patent Publication No.
• - Radical activators such as amino acids, N-aryl- ⁇ -amino acid salts, N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives; Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. Examples include oxime ester compounds described in Publication No. 2006-36750 and the like.
• metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), Examples include di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl) and dicyclopentadienyltitanium [2,6-difluoropheny
• biimidazole derivatives examples 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, (4'-methoxyphenyl) )-4,5-diphenylimidazole dimer.
• halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, Examples include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
• halomethyl-s-triazine derivatives examples 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, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine is mentioned.
• Examples of ⁇ -aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 3,6-bis(2-methyl- Examples include 2-morpholinopropionyl)-9-octylcarbazole.
• oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties; for example, when using an alkali-soluble resin containing a phenolic hydroxyl group, it is disadvantageous in terms of sensitivity.
• oxime ester compounds with excellent sensitivity are useful.
• Oxime ester compounds have a high photoreaction quantum yield and a high activity of generated radicals, so they have high sensitivity and are stable against thermal reactions, making them highly sensitive photosensitive resin compositions in small amounts. It is possible to obtain
• oxime ester compounds include compounds represented by the following general 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.
• R 21b represents an arbitrary substituent containing an aromatic ring.
• R 22a represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.
• n represents an integer of 0 or 1.
• the number of carbon atoms in the alkyl group in R 21a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and Preferably it is 10 or less.
• the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.
• substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2- Examples include methylphenyl group, N-acetyl-N-acetoxyamino group, methyloxycarbonyl group, and ethyloxycarbonyl group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted. Further, from the viewpoint of sensitivity, solubility, and chemical resistance, methyloxycarbonyl group and ethyloxycarbonyl group are preferable.
• Examples of the aromatic ring group for R 21a include an aromatic hydrocarbon ring group and 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 photosensitive resin composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, the number is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 12.
• Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. From the viewpoint of developability, a phenyl group and a naphthyl group are preferred, and a phenyl group is more preferred.
• Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked.
• R 21a is preferably an alkyl group that may have a substituent.
• R21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted fluorenyl group, an optionally substituted fluorenyl group, or an optionally substituted fluorenyl group.
• Examples include indolyl group. From the viewpoint of hole resolution, an optionally substituted diphenyl sulfide group is preferred.
• the number of carbon atoms in the alkanoyl group in R22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 2 or more, more preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and more. More preferably, it is 5 or less.
• the alkanoyl group include an acetyl group, an ethyl group, a propanoyl group, and a butanoyl group.
• the substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, and amide groups.
• the alkanoyl group is preferably unsubstituted from the viewpoint of ease of synthesis.
• the number of carbon atoms in the aroyl group in R 22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 7 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
• Examples of the aroyl group include benzoyl group and naphthoyl group.
• Examples of substituents that the aroyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
• R 22a is preferably an alkanoyl group that may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
• the photopolymerization initiator may be used alone or in combination of two or more types.
• the photopolymerization initiator may contain a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary, for the purpose of increasing sensitivity.
• Examples of the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Publication No. 4-219756, Japanese Patent Application Publication No. 3-239703, and Japanese Patent Application Publication No. 5-289335.
• a sensitizing dye containing an amino group is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
• a sensitizing dye a sensitizing dye containing an amino group is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
• Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benz
• polymerization accelerator examples include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and n-butylamine. , N-methyldiethanolamine, 2-dimethylaminoethyl benzoate, and the like can be used.
• the polymerization accelerators may be used alone or in combination of two or more.
• the content ratio of the photopolymerization initiator (B) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.01% by mass or more in the total solid content of the photosensitive resin composition. 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less. , and even more preferably 5% by mass or less.
• the above upper and lower limits can be arbitrarily combined.
• it is preferably 0.01 to 15% by weight, more preferably 0.01 to 10% by weight, even more preferably 1 to 10% by weight, even more preferably 1 to 10% by weight, and particularly preferably 2 to 7% by weight. .
• sensitivity to improve by setting the value to be equal to or higher than the lower limit value. By setting it below the upper limit value, hole resolution tends to improve.
• the blending ratio of (B) photopolymerization initiator to (A) ethylenically unsaturated compound in the photosensitive resin composition of the present invention is 1 part by mass per 100 parts by mass of (A) ethylenically unsaturated compound.
• the above is preferable, more preferably 3 parts by weight or more, even more preferably 5 parts by weight or more, preferably 100 parts by weight or less, more preferably 50 parts by weight or less, even more preferably 20 parts by weight or less, and 10 parts by weight or less. Particularly preferred.
• the above upper and lower limits can be arbitrarily combined.
• it is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, even more preferably 1 to 20 parts by weight, even more preferably 2 to 20 parts by weight, and particularly preferably 2 to 10 parts by weight.
• sensitivity to improve by setting the value to be equal to or higher than the lower limit value. By setting it below the upper limit value, hole resolution tends to improve.
• a chain transfer agent may be used in combination with a photopolymerization initiator.
• the chain transfer agent include mercapto group-containing compounds and carbon tetrachloride, and it is more preferable to use mercapto group-containing compounds because they have a high chain transfer effect and tend to improve sensitivity and surface curability. This is thought to be because the bond cleavage is likely to occur due to the small S--H bond energy, and hydrogen abstraction reactions and chain transfer reactions are likely to occur.
• Examples of mercapto group-containing compounds include mercapto group-containing compounds having an aromatic ring such as 2-mercaptobenzothiazole and 2-mercaptobenzimidazole; trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3 -Mercaptopropionate), Pentaerythritol Tris (3-Mercaptopropionate), Trimethylolpropane Tris (3-Mercaptobutyrate), Pentaerythritol Tetrakis (3-Mercaptobutyrate), Pentaerythritol Tris (3-Mercaptobutyrate) aliphatic polyfunctional mercapto such as 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione Examples include group-containing compounds. These may be used alone or in combination of two or more.
• composition of the present invention contains (C) an alkali-soluble resin.
• alkali-soluble resin (C) include various resins having a carboxyl group or a hydroxyl group, and those having a carboxyl group are preferred from the viewpoint of excellent developability.
• an alkali-soluble resin having an ethylenically unsaturated group is preferable.
• the photosensitive resin composition of the present invention is an epoxy (meth)acrylate resin (C1) having an aromatic ring in the main chain (hereinafter abbreviated as epoxy (meth)acrylate resin (C1)) as (C) an alkali-soluble resin. ). Since it has an aromatic ring in its main chain, it tends to have a high refractive index. In addition, since the compatibility with the sulfur-containing aromatic heterocycle in the ethylenically unsaturated compound (A1) is good, the alkali-soluble resin can be uniformly coated without phase separation in the coating film of the photosensitive resin composition. Easy to distribute. Along with this, since the alkaline developer during development easily permeates, the hole resolution tends to be improved.
• Epoxy (meth)acrylate resin (C1) Epoxy (meth)acrylate resin (C1) having an aromatic ring in the main chain is obtained by adding an ethylenically unsaturated monocarboxylic acid or ester compound to an epoxy resin having an aromatic ring in the main chain, and optionally adding an isocyanate group-containing compound. This is a resin obtained by reacting a polybasic acid with a polybasic acid or an anhydride thereof.
• an ethylenically unsaturated bond is added to the epoxy compound via an ester bond (-COO-), and examples include those in which one carboxy group of a polybasic acid anhydride is added to the hydroxyl group generated at that time. Also included are those added by simultaneously adding a polyhydric alcohol when adding a polybasic acid anhydride.
• epoxy (meth)acrylate resin (C1) is a resin obtained by reacting a compound having a functional group that can further react with the carboxy group of the resin obtained by the above reaction.
• epoxy (meth)acrylate resin has virtually no epoxy groups due to its chemical structure, and is not limited to "(meth)acrylate", but it is made from an epoxy compound (epoxy resin) as a raw material.
• epoxy compound (epoxy resin) is a typical example, it is named this way according to common usage.
• the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used.
• the phenolic compound is preferably a compound having a divalent or more than divalent phenolic hydroxyl group, and may be a monomer or a polymer. 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, trisphenol epoxy resin, polymerization of phenol and dicyclopentadiene.
• bisphenol A epoxy resin bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, diglycidyl of 9,9-bis(4'-hydroxyphenyl)fluorene Etherification products are preferred, and bisphenol A epoxy resins are particularly preferred.
• the epoxy resin include bisphenol A epoxy resins (for example, "jER (registered trademark, hereinafter the same applies)" manufactured by Mitsubishi Chemical Corporation, "jER1001", “jER1002", “jER1004", manufactured by Nippon Kayaku Co., Ltd.).
• NER-1302 (epoxy equivalent: 323, softening point: 76°C), etc.), bisphenol F type resins (for example, “jER807”, “jER4004P”, “jER4005P”, “jER4007P” manufactured by Mitsubishi Chemical Corporation, Nippon Kayaku Co., Ltd.) "NER-7406” (epoxy equivalent: 350, softening point 66°C) manufactured by Mitsubishi Chemical Corporation), 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 Company, “DEN-438” manufactured by Dow Chemical Company), (o , m, p-) cresol novolac type epoxy resin (for example, "EOCN (registered trademark, hereinafter the same)-
• Examples of the epoxy resin represented by the following general formula (i-11) include “XD-1000” manufactured by Nippon Kayaku Co., Ltd.
• Examples of the epoxy resin represented by the following general formula (i-12) include “NC-3000” manufactured by Nippon Kayaku Co., Ltd.
• Examples of the epoxy resin represented by the following general formula (i-14) include "ESF-300” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
• n is an average value and represents a number from 0 to 10.
• Each R 111 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Note that a plurality of R 111s present in one molecule may be the same or different.
• n is an average value and represents a number from 0 to 10.
• Each R 121 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Note that the plurality of R 121s present in one molecule may be the same or different.
• X represents a linking group represented by the following general formula (i-13-1) or (i-13-2).
• the molecular structure contains one or more adamantane structures.
• c represents 2 or 3.
• R 131 to R 134 and R 135 to R 137 each independently represent an adamantyl group that may have a substituent, a hydrogen atom, Represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. * represents a bond.
• p and q each independently represent an integer of 0 to 4
• R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom
• R 143 and R 144 each independently represent an alkylene group having 1 to 4 carbon atoms
• x and y each independently represent an integer of 0 or more.
• epoxy resin epoxy resins represented by any of formulas (i-11) to (i-14) are preferred.
• ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, and pentaerythritol tri(meth)acrylate succinic anhydride adduct.
• Examples include phthalic anhydride adducts and reaction products of (meth)acrylic acid and ⁇ -caprolactone. From the viewpoint of sensitivity, (meth)acrylic acid is preferred.
• polybasic acids examples include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, -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.
• succinic anhydride succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred, and succinic anhydride and tetrahydrophthalic anhydride are more preferred.
• the molecular weight of the epoxy (meth)acrylate resin (C1) can be increased and branching can be introduced into the molecule, which tends to balance the molecular weight and viscosity. Furthermore, the rate of introduction of acid groups into the molecule can be increased, and sensitivity, adhesion, etc. tend to be more balanced.
• the polyhydric alcohol include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol.
• Examples of the epoxy (meth)acrylate resin (C1) include, in addition to those mentioned above, the resins described in Korean Patent Publication No. 10-2013-0022955.
• the acid value of the epoxy (meth)acrylate resin (C1) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 50 mgKOH/g or more, even more preferably 70 mgKOH/g or more, It is particularly preferably at least 80 mgKOH/g, preferably at most 200 mgKOH/g, more preferably at most 180 mgKOH/g, even more preferably at most 150 mgKOH/g, even more preferably at most 120 mgKOH/g, and particularly preferably at most 110 mgKOH/g.
• the above upper and lower limits can be arbitrarily combined.
• it is 10 to 200 mgKOH/g, preferably 30 to 180 mgKOH/g, more preferably 50 to 150 mgKOH/g, even more preferably 70 to 120 mgKOH/g, even more preferably 80 to 110 mgKOH/g.
• the amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved.
• the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (C1) is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, even more preferably 4,000 or more, and particularly preferably 5,000. or more, and is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, even more preferably 10,000 or less, particularly preferably 8,000 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1,000 to 30,000, preferably 2,000 to 20,000, more preferably 3,000 to 15,000, even more preferably 4,000 to 10,000, particularly preferably 5,000 to 8,000.
• the content ratio of the epoxy (meth)acrylate resin (C1) contained in the alkali-soluble resin is not particularly limited, but is preferably 10% by mass or more in the alkali-soluble resin (C), more preferably 20% by mass or more, More preferably 30% by mass or more, even more preferably 35% by mass or more, even more preferably 40% by mass or more, particularly preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less. , more preferably 60% by mass or less.
• the above upper and lower limits can be arbitrarily combined.
• 10 to 90% by mass preferably 20 to 90% by mass, more preferably 30 to 70% by mass, even more preferably 35 to 70% by mass, even more preferably 40 to 60% by mass, particularly preferably 50 to 60% by mass. Mass%.
• the amount is equal to or more than the lower limit, linearity tends to improve, and when it is equal to or less than the upper limit, a high-definition cured product with narrow line width tends to be formed.
• the epoxy (meth)acrylate resin (C1) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, the acid or ester compound having an ethylenically unsaturated bond is added thereto in the coexistence of a catalyst and a thermal polymerization inhibitor, and then the polybasic acid or its A method can be used in which the reaction is continued by adding an anhydride. Examples include methods described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422.
• Examples of the organic solvent used in the reaction include methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
• the organic solvents used in the reaction may be used alone or in combination of two or more.
• Examples of catalysts used in the reaction include tertiary amines such as triethylamine, benzyldimethylamine, tribenzylamine, tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride, etc.
• the catalysts used in the reaction may be used alone or in combination of two or more.
• the thermal polymerization inhibitor used in the reaction include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, and the like.
• the thermal polymerization inhibitor used in the reaction may be used alone or in combination of two or more.
• the amount of the acid or ester compound having an ethylenically unsaturated bond to be used is preferably 0.7 to 1.3 chemical equivalents, more preferably 0.9 to 1 chemical equivalent per 1 chemical equivalent of the epoxy group of the epoxy resin. .1 chemical equivalent.
• the temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C.
• the amount of polybasic acid (anhydride) used is preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, per 1 chemical equivalent of hydroxyl group generated in the addition reaction. It can be set to an equivalent amount.
• epoxy (meth)acrylate resins (C1) from the viewpoint of film strength and linearity, epoxy (meth)acrylate resins having a partial structure represented by the following general formula (i), and those having a partial structure represented by the following general formula (ii). It is preferable to contain one or more types of epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii).
• R a represents a hydrogen atom or a methyl group.
• R b represents a divalent hydrocarbon group which may have a substituent.
• k represents 1 or 2.
• the benzene ring in formula (i) may be further substituted with any substituent.
• Each * represents a bond.
• R c each independently represents a hydrogen atom or a methyl group.
• R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.
• R e represents a hydrogen atom or a methyl group
• ⁇ is a single bond, -CO-, an alkylene group that may have a substituent, or a divalent group that may have a substituent.
• the benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.
• epoxy (meth)acrylate resin having a partial structure represented by formula (i) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (C1-1)") will be described in detail.
• R a represents a hydrogen atom or a methyl group
• R b represents a divalent hydrocarbon group which may have a substituent.
• k represents 1 or 2.
• the benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.
• R b represents a divalent hydrocarbon group which may have a substituent.
• divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic ring groups, and groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected. Can be mentioned.
• divalent aliphatic groups examples include linear, branched, and cyclic aliphatic groups.
• linear aliphatic groups are preferred from the viewpoint of development solubility.
• a cyclic aliphatic group is preferred from the viewpoint of reducing permeation of the developer into the exposed area.
• the number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 20, preferably 3 to 15, more preferably 6 to 10.
• divalent linear aliphatic group examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group. From the viewpoints of refractive index, hole resolution, and manufacturing cost, methylene groups are preferred.
• the divalent branched aliphatic group includes, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples include structures in which isobutyl groups, sec-butyl groups, and tert-butyl groups are bonded.
• the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, and preferably 5 or less.
• the above upper and lower limits can be arbitrarily combined. For example, from 1 to 10, preferably from 2 to 5.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• divalent cyclic aliphatic groups include groups in which two hydrogen atoms have been removed from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, dicyclopentane ring, norbornane ring, isobornane ring, or adamantane ring.
• examples include groups. From the viewpoint of film strength and developability, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
• Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
• divalent aromatic ring group examples include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
• the number of carbon atoms is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 4-20, preferably 5-15, more preferably 6-10. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring.
• Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
• the aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a fused ring.
• Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
• benzene rings and naphthalene rings having two free valences are preferred, and benzene rings and naphthalene rings having two free valences are preferred, and benzene rings and naphthalene rings having two free valences are preferred, and benzene rings and naphthalene rings having two free valences are preferred, and benzene rings and naphthalene rings having two free valences are preferred, and benz
• Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of curability, no substitution is preferred.
• the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group. Examples include groups in which one or more are linked.
• the number of divalent aliphatic groups in the group connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups is not particularly limited, but is preferably one or more, preferably two or more, Further, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, more preferably 2 to 3.
• the number of divalent aromatic ring groups in the group connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups is not particularly limited, but is preferably one or more, and more preferably two or more. It is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, more preferably 2 to 3.
• Examples of groups that connect one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the following general formulas (i-A) to (i-F). Can be mentioned. From the viewpoint of refractive index and hole resolution, a group represented by the following general formula (iA) is preferable.
• the benzene ring in formula (i) may be further substituted with any substituent.
• Permissible substituents on the benzene ring in formula (i) include, for example, a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
• the number of substituents is not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferable that it is unsubstituted.
• (k) k represents 1 or 2. From the viewpoint of refractive index, k is preferably 1. From the viewpoint of developability and curability, k is preferably 2.
• the partial structure represented by formula (i) is preferably a partial structure represented by formula (i-1) below.
• R a and R b have the same meanings as in formula (i).
• R Y represents a hydrogen atom or a polybasic acid residue.
• k represents 1 or 2.
• * represents a bond.
• the benzene ring in formula (i-1) may be further substituted with any substituent.
• the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
• polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
• examples include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
• maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred; is more preferable.
• the repeating unit structure represented by formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (C1-1) may be one type or two or more types.
• the number of partial structures represented by formula (i) contained in one molecule of epoxy (meth)acrylate resin (C1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3 or more. More preferably, it is 10 or less, and even more preferably 8 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 10, more preferably 3 to 8. When the amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved.
• the number of partial structures represented by formula (i-1) contained in one molecule of epoxy (meth)acrylate resin (C1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3 or more.
• the above is more preferable, 10 or less is preferable, and 8 or less is even more preferable.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 10, more preferably 3 to 8.
• the amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved.
• epoxy (meth)acrylate resin (C1-1) Specific examples of the epoxy (meth)acrylate resin (C1-1) are listed below.
• epoxy (meth)acrylate resin (C1-2) having a partial structure represented by formula (ii) will be described in detail.
• R c each independently represents a hydrogen atom or a methyl group.
• R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.
• R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
• the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
• the number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, more preferably 2 to 3.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• the number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 4 to 30, more preferably 6 to 20, and even more preferably 8 to 15.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of film strength and developability, an adamantane ring is preferred.
• the number of rings that the aromatic ring group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less. .
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 5, more preferably 3 to 4.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• the aromatic ring group examples include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
• the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or more.
• 20 or less is more preferable, and 15 or less is particularly preferable.
• the above upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 6 to 40, more preferably 8 to 30, even more preferably 10 to 20, even more preferably 12 to 15.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
• a fluorene ring is preferred.
• the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but includes, for example, a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent hydrocarbon groups. Examples include groups in which a valent aliphatic group and one or more divalent aromatic ring groups are connected.
• divalent aliphatic groups examples include linear, branched, and cyclic aliphatic groups.
• linear aliphatic groups are preferred from the viewpoint of improving developability.
• a cyclic aliphatic group is preferred.
• the number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 25, preferably 3 to 20, more preferably 6 to 15.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• divalent linear aliphatic group examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group. From the viewpoint of refractive index and hole resolution, a methylene group is preferred.
• the divalent branched aliphatic group includes, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples include structures in which isobutyl groups, sec-butyl groups, and tert-butyl groups are bonded.
• the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, more preferably 2 to 3.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• divalent cyclic aliphatic groups include groups in which two hydrogen atoms have been removed from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, dicyclopentane ring, norbornane ring, isobornane ring, or adamantane ring.
• examples include groups. From the viewpoint of film strength, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
• Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
• divalent aromatic ring group examples include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
• the number of carbon atoms is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 4-30, preferably 5-20, more preferably 6-15. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring.
• Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
• the aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a fused ring.
• Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
• benzene rings and naphthalene rings having two free valences are preferred, and benzene rings and naphthalene rings having two free valences are preferred, and benzene rings and naphthalene rings having two free valences are preferred, and benzene rings and naphthalene rings having two free valences are preferred, and benzene rings and naphthalene rings having two free valences are preferred, and benz
• Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of curability, no substitution is preferred.
• the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group. Examples include groups in which one or more are linked.
• the number of divalent aliphatic groups in the group connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups is not particularly limited, but is preferably one or more, more preferably two or more. , and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, more preferably 2 to 3.
• the number of divalent aromatic ring groups in the group connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups is not particularly limited, but is preferably one or more, and more preferably two or more. It is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 1 to 5, more preferably 2 to 3.
• Examples of groups that connect one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the aforementioned formulas (i-A) to (i-F). Can be mentioned. From the viewpoint of film strength and high refractive index, a group represented by formula (iA) is preferable.
• the bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but for example, if one hydrogen atom of an aliphatic group or an aromatic ring group is Examples include an embodiment in which the aliphatic group is substituted with a hydrocarbon group, and an embodiment in which a cyclic hydrocarbon group that is a side chain includes one of the carbon atoms of the aliphatic group.
• the partial structure represented by formula (ii) is preferably a partial structure represented by the following general formula (ii-1) from the viewpoint of improving the refractive index.
• R c has the same meaning as in formula (ii).
• R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
• n is an integer of 1 or more. * represents a bond.
• the benzene ring in formula (ii-1) may be further substituted with any substituent.
• R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
• the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
• the number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 6, preferably 1 to 4, more preferably 2 to 3.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• the number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 4 to 30, more preferably 6 to 20, and even more preferably 8 to 15.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of film strength and developability, an adamantane ring is preferred.
• the number of rings that the aromatic ring group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and is preferably 10 or less, more preferably 5 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 10, more preferably 3 to 5.
• the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
• the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 4-30, preferably 5-20, more preferably 6-15.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of film strength and developability, a fluorene ring is preferred.
• substituents that the cyclic hydrocarbon group may have include hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as amyl group and isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; and carboxy group. From the viewpoint of ease of synthesis, no substitution is preferred.
• n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1 to 3, preferably 2 to 3.
• the amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved.
• R ⁇ is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group.
• the benzene ring in formula (ii-1) may be further substituted with any substituent.
• Permissible substituents on the benzene ring in formula (ii-1) include, for example, a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
• the number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of curability, it is preferable that it is unsubstituted.
• the partial structure represented by formula (ii) is preferably a partial structure represented by formula (ii-2) below.
• R c has the same meaning as in formula (ii).
• R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent. * represents a bond.
• the benzene ring in formula (ii-2) may be further substituted with any substituent.
• R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
• the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
• the number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less.
• the above upper and lower limits can be arbitrarily combined. For example, from 1 to 10, preferably from 2 to 5.
• the number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
• the above upper and lower limits can be arbitrarily combined.
• the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of film strength and developability, an adamantane ring is preferred.
• the number of rings that the aromatic ring group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and is preferably 10 or less, more preferably 5 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 10, more preferably 3 to 5.
• the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
• the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, particularly preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and still more preferably 20 or more. It is preferably 15 or less, particularly preferably 15 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 6 to 30, more preferably 8 to 20, and even more preferably 10 to 15. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of film strength and developability, a fluorene ring is preferred.
• substituents that the cyclic hydrocarbon group may have include hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as amyl group and isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; and carboxy group. From the viewpoint of ease of synthesis, no substitution is preferred.
• R ⁇ is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group. From the viewpoint of film strength and developability, R ⁇ is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
• the benzene ring in formula (ii-2) may be further substituted with any substituent.
• Permissible substituents on the benzene ring in formula (ii-2) include, for example, a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
• the number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of curability, it is preferable that it is unsubstituted.
• the partial structure represented by formula (ii) is preferably a partial structure represented by general formula (ii-3) below.
• R c and R d have the same meanings as in formula (ii).
• R Z represents a hydrogen atom or a polybasic acid residue.
• the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
• polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
• examples include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
• maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred; is more preferable.
• the partial structure represented by formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (C1-2) may be one type or two or more types.
• the number of partial structures represented by formula (ii) contained in one molecule of epoxy (meth)acrylate resin (C1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and 20 The following is preferable, 15 or less is more preferable, and 10 or less is still more preferable.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 20, preferably 1 to 15, more preferably 3 to 10.
• the number of partial structures represented by formula (ii-1) contained in one molecule of epoxy (meth)acrylate resin (C1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and , is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 20, preferably 1 to 15, more preferably 3 to 10.
• the amount is equal to or more than the lower limit, the film strength and refractive index tend to improve, and when the amount is less than the upper limit, the hole resolution tends to improve.
• the number of partial structures represented by formula (ii-2) contained in one molecule of epoxy (meth)acrylate resin (C1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and , is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 20, preferably 1 to 15, more preferably 3 to 10.
• the amount is equal to or more than the lower limit, the film strength and refractive index tend to improve, and when the amount is less than the upper limit, the hole resolution tends to improve.
• the number of partial structures represented by formula (ii-3) contained in one molecule of epoxy (meth)acrylate resin (C1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and , is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 20, preferably 1 to 15, more preferably 3 to 10.
• epoxy (meth)acrylate resin (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (C1-3)") having a partial structure represented by formula (iii) will be described in detail.
• R e represents a hydrogen atom or a methyl group
• ⁇ is a single bond, -CO-, an alkylene group that may have a substituent, or a divalent group that may have a substituent.
• the benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.
• ⁇ represents a single bond, -CO-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.
• the alkylene group may be linear or branched. From the viewpoint of solubility during development, it is preferable to have a straight chain. From the viewpoint of development adhesion, branched chains are preferred.
• the number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, and more preferably 4 or less.
• the above upper and lower limits can be arbitrarily combined. For example, from 1 to 6, preferably from 2 to 4. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• alkylene group examples include methylene group, ethylene group, propylene group, butylene group, hexylene group, and heptylene group. From the viewpoint of film strength and developability, ethylene group and propylene group are preferable, and propylene group is more preferable. preferable.
• Examples of the substituent that the alkylene group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
• divalent cyclic hydrocarbon group examples include a divalent aliphatic cyclic group and a divalent aromatic cyclic group.
• the number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less.
• the above upper and lower limits can be arbitrarily combined. For example, from 1 to 10, preferably from 2 to 5.
• the number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
• the above upper and lower limits can be arbitrarily combined.
• the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of film strength and developability, an adamantane ring is preferred.
• the number of rings that the aromatic ring group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and is preferably 10 or less, more preferably 5 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1 to 10, preferably 2 to 10, more preferably 3 to 5.
• the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
• the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, particularly preferably 10 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or more, 15 or less is particularly preferred.
• the above upper and lower limits can be arbitrarily combined. For example, it is 4 to 40, preferably 6 to 30, more preferably 8 to 20, and even more preferably 10 to 15.
• the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
• aromatic ring in the aromatic ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
• fluorene rings are preferred from the viewpoints of film strength and developability.
• substituents that the cyclic hydrocarbon group may have include hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as amyl group and isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; and carboxy group. From the viewpoint of ease of synthesis, no substitution is preferred.
• ⁇ is preferably an alkylene group which may have a substituent, and more preferably a dimethylmethylene group.
• the benzene ring in formula (iii) may be further substituted with any substituent.
• Permissible substituents on the benzene ring in formula (iii) include, for example, a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
• the number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of curability, it is preferable that it is unsubstituted.
• the partial structure represented by formula (iii) is preferably a partial structure represented by the following general formula (iii-1) from the viewpoint of development solubility.
• R e and ⁇ have the same meanings as in formula (iii) above.
• R W represents a hydrogen atom or a polybasic acid residue. * represents a bond.
• the benzene ring in formula (iii-1) may be further substituted with any substituent.
• the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
• polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
• examples include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
• maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred; is more preferable.
• the number of repeating unit structures represented by formula (iii) contained in one molecule of epoxy (meth)acrylate resin (C1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and 10 or more. is more preferable, 18 or less is preferable, and 15 or less is even more preferable.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1-18, preferably 5-18, more preferably 10-15.
• the number of repeating unit structures represented by formula (iii-1) contained in one molecule of epoxy (meth)acrylate resin (C1-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, It is more preferably 5 or more, more preferably 18 or less, and even more preferably 15 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 1-18, preferably 3-18, more preferably 5-15.
• epoxy (meth)acrylate resin (C1-3) Specific examples of the epoxy (meth)acrylate resin (C1-3) are listed below.
• alkali-soluble resin other than epoxy (meth)acrylate resin (C1) The alkali-soluble resin (C) contained in the photosensitive resin composition of the present invention is an alkali-soluble resin other than the epoxy (meth)acrylate resin (C1) (hereinafter sometimes referred to as "other alkali-soluble resin”). ) may be included.
• other alkali-soluble resins include acrylic copolymer resins, epoxy resins, urethane resins, novolak resins, polyimide resins, and polyvinylphenol resins.
• resins described in Japanese Patent Publication No. 8-297366, Japanese Patent Application Publication No. 2001-89533, and International Publication No. 2019/146685 can be mentioned. These may be used alone or in combination of two or more.
• the acid value of the alkali-soluble resin is not particularly limited, but is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, even more preferably 70 mgKOH/g or more, and preferably 200 mgKOH/g or less, 150 mgKOH/g.
• the following is more preferable, and 100 mgKOH/g or less is even more preferable.
• the above upper and lower limits can be arbitrarily combined. For example, it is 30 to 200 mgKOH/g, preferably 50 to 150 mgKOH/g, and more preferably 70 to 100 mgKOH/g.
• the acid value means a weighted average value according to their content ratios.
• the content ratio of the alkali-soluble resin (C) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more in the total solid content of the photosensitive resin composition. , more preferably 30% by mass or more, even more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and even more preferably 40 to 70% by weight.
• the total content of (A) ethylenically unsaturated compound and (C) alkali-soluble resin in the total solid content of the photosensitive resin composition is not particularly limited, but is preferably 30% by mass or more, and 60% by mass. % or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and preferably 100% or less, more preferably 95% by mass or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is preferably 30 to 100% by weight, more preferably 60 to 100% by weight, even more preferably 80 to 100% by weight, even more preferably 90 to 100% by weight, particularly preferably 90 to 95% by weight.
• the amount is at least the lower limit, the adhesion of the cured product to the substrate tends to improve, and when it is at most the upper limit, the curability tends to improve.
• the photosensitive resin composition of the present invention includes a surfactant, metal oxide particles, a coloring agent, a silane coupling agent, an adhesive An improver, a phosphoric acid compound, an ultraviolet absorber, a polymerization inhibitor, a thermal polymerization initiator, an amino compound, a solvent, etc. can be blended as appropriate.
• the photosensitive resin composition of the present invention may contain a surfactant.
• Surfactants can be used for the purpose of improving the coating properties of the photosensitive resin composition as a coating solution and the developability of the coating film, among others, silicone-based surfactants and fluorine-based surfactants are used. preferable.
• silicone surfactants are preferred because they have the effect of removing residues of the photosensitive resin composition from unexposed areas and also have the function of developing wettability, and polyether-modified silicone surfactants are preferable. More preferred are agents.
• fluorine-based surfactant a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain, and side chain is suitable.
• fluorosurfactants include, for example, "BM-1000” and “BM-1100” manufactured by BM Chemie, "Megafac F142D”, “Megafac F172”, and “Megafac F173” manufactured by DIC; Examples include “Megafac F183", “Megafac F470", “Megafac F475", “Megafac F554", “Megafac F559", “FC430” manufactured by 3M Japan, and “DFX-18” manufactured by Neos. can.
• silicone surfactants include, for example, “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, and “SH8400” manufactured by Dow Corning Toray Industries. , “BYK (registered trademark, hereinafter the same)” and “BYK330” manufactured by BYK Chemie.
• the surfactant may include things other than fluorine-based surfactants and silicone-based surfactants, and other surfactants include, for example, nonionic, anionic, cationic, and amphoteric surfactants. Can be mentioned.
• Surfactants may be used in combination of two or more types, for example, a combination of silicone surfactant/fluorine surfactant, a combination of silicone surfactant/special polymer surfactant, and fluorine surfactant. Combinations of active agents/special polymer surfactants may be mentioned, and combinations of silicone surfactants/fluorosurfactants are preferred. Examples of combinations of silicone surfactants/fluorosurfactants include BYK-300 or BYK-330 manufactured by BYK Chemie/DFX-18 manufactured by NEOS, and BYK-300 manufactured by BYK Chemie.
• the photosensitive resin composition of the present invention may contain metal oxide particles. Containing metal oxide particles tends to increase the refractive index.
• metal oxide particles include titanium oxide, zirconium oxide, hafnium oxide, aluminum oxide, iron oxide, copper oxide, zinc oxide, yttrium oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, tantalum oxide, and tungsten oxide. , lead oxide, bismuth oxide, cerium oxide, antimony oxide, and germanium oxide particles.
• Composite oxide particles composed of two or more metal elements, such as barium titanate, can also be used.
• the photosensitive resin composition of the present invention may contain a colorant.
• a colorant known colorants such as pigments and dyes and their derivatives can be used.
• a known dispersant or dispersion aid may be used in combination so that the pigment can stably exist in the photosensitive resin composition without agglomerating.
• the photosensitive resin composition of the present invention contains a colorant, the content of the colorant is preferably 1% by mass or more in the total solid content of the photosensitive resin composition from the viewpoint of curability.
• it is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less.
• it is preferably 1 to 30% by weight, more preferably 1 to 10% by weight, and even more preferably 1 to 5% by weight.
• the photosensitive resin composition of the present invention may contain a silane coupling agent in order to improve the adhesion to the substrate.
• examples of the silane coupling agent include epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are preferred.
• the photosensitive resin composition of the present invention contains a silane coupling agent, its content is preferably 1% by mass or more in the total solid content of the photosensitive resin composition from the viewpoint of adhesiveness, Moreover, it is preferably 10% by mass or less, more preferably 5% by mass or less. For example, it is preferably 1 to 10% by weight, more preferably 1 to 5% by weight.
• the photosensitive resin composition of the present invention may contain a phosphoric acid compound for the purpose of imparting adhesion to a substrate.
• phosphoric acid compounds include phosphoric acid ethylenic monomers.
• As the phosphoric acid-based ethylenic monomer (meth)acryloyloxy group-containing phosphates are preferred, and phosphoric acid-based ethylenic monomers represented by the following general formulas (g1), (g2), and (g3) Body is preferred.
• R 51 represents a hydrogen atom or a methyl group
• l and l' are integers of 1 to 10
• m is 1, 2, or 3.
• One type of phosphoric acid-based ethylenic monomer may be used alone, or two or more types may be used in combination.
• the photosensitive resin composition of the present invention may contain an ultraviolet absorber.
• the ultraviolet absorber is added for the purpose of controlling the photocuring distribution by causing the ultraviolet absorber to absorb a specific wavelength of the light source used for exposure. By adding an ultraviolet absorber, the effect of increasing the taper angle can be obtained.
• Examples of the ultraviolet absorber include compounds having an absorption maximum between wavelengths of 250 nm and 400 nm, from the viewpoint of inhibiting light absorption of the photopolymerization initiator (B).
• Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes.
• the ultraviolet absorber preferably contains one or both of a benzotriazole compound and a triazine compound.
• the photosensitive resin composition of the present invention may contain a polymerization inhibitor. Since the inclusion of a polymerization inhibitor inhibits radical polymerization, it tends to be possible to increase the taper angle of the resulting cured product.
• polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of taper angle control, hydroquinone or methoxyphenol is preferred, and methylhydroquinone is more preferred.
• polymerization inhibitor may be used alone, or two or more types may be used in combination.
• C When producing an alkali-soluble resin, a polymerization inhibitor may be contained in the resin. In that case, it may be used as it is, or in addition to the polymerization inhibitor contained in the resin, the same or different polymerization inhibitor may be added at the time of producing the photosensitive resin composition.
• Thermal polymerization initiator The photosensitive resin composition of the present invention may contain a thermal polymerization initiator. Containing a thermal polymerization initiator tends to increase the degree of crosslinking of the membrane. Examples of the thermal polymerization initiator include azo compounds, organic peroxides, and hydrogen peroxide. These may be used alone or in combination of two or more.
• the photosensitive resin composition of the present invention may contain an amino compound to promote thermosetting.
• the amino compound include amino compounds having a methylol group as a functional group and at least two alkoxymethyl groups obtained by condensing and modifying the same with an alcohol having 1 to 8 carbon atoms.
• melamine resin obtained by polycondensing melamine and formaldehyde
• benzoguanamine resin obtained by polycondensing benzoguanamine and formaldehyde
• glycoluril resin obtained by polycondensing glycoluril and formaldehyde
• examples include polycondensed urea resins; resins in which formaldehyde is copolycondensed with two or more of melamine, benzoguanamine, glycoluril, or urea; and modified resins in which the methylol groups of the above resins are modified by alcohol condensation. These may be used alone or in combination of two or more.
• the photosensitive resin composition of the present invention may contain a solvent. If a solvent is contained, each of the above-mentioned components can be used in a state dissolved or dispersed in the solvent. There are no particular restrictions on the solvent, but examples include the following organic solvents.
• 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-t-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, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, Glycol monoalkyl ethers such as triethylene glycol monoethyl ether and tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
• solvents include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, 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, diglyme (all trade names).
• the solvent only needs to be capable of dissolving or dispersing each component in the photosensitive resin composition, and is selected depending on the method of using the photosensitive resin composition of the present invention. From the viewpoint of coating properties, a solvent with a boiling point of 60 to 280°C under atmospheric pressure is preferable, and a solvent with a boiling point of 70 to 260°C is more preferable. Examples include propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate.
• the total solid content of the solvent in the photosensitive resin composition solution is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, Further, the content is preferably 90% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, particularly preferably 35% by mass or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is used in an amount of 10 to 90% by weight, preferably 15 to 50% by weight, more preferably 20 to 40% by weight, and even more preferably 25 to 35% by weight.
• the photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components using a stirrer.
• the photosensitive resin composition of the present invention contains a colorant
• the dispersion treatment is preferably carried out in a system that uses a colorant, a solvent, a dispersant, and part or all of (C) an alkali-soluble resin (hereinafter referred to as the mixture to be subjected to dispersion treatment and the mixture obtained by dispersion treatment).
• C an alkali-soluble resin
• the resulting composition is sometimes referred to as a "pigment dispersion.”
• a polymer dispersant as the dispersant because it suppresses the increase in viscosity over time of the obtained pigment dispersion liquid and photosensitive resin composition, that is, it has excellent dispersion stability.
• the photosensitive resin composition of the present invention contains a colorant
• a pigment dispersion containing at least a colorant, a solvent, and a dispersant can be produced as described above.
• the colorant, organic solvent, and dispersant that can be used in the pigment dispersion those described as those that can be used in the photosensitive resin composition can be preferably employed.
• the content ratio of each colorant in the pigment dispersion the content ratios described as the content ratios in the photosensitive resin composition can be preferably adopted.
• the dispersion treatment temperature is preferably from 0°C to 100°C, more preferably from room temperature to 80°C.
• the appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, etc., and is therefore adjusted as appropriate.
• a guideline for dispersion is to control the gloss so that the 20 degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.
• the dispersed particle size of the colorant dispersed in the pigment dispersion is preferably 0.01 to 1 ⁇ m, more preferably 0.02 to 0.5 ⁇ m, and still more preferably 0.03 to 0.3 ⁇ m.
• the dispersed particle diameter is measured as a number-based median diameter by, for example, a dynamic light scattering method.
• the pigment dispersion obtained by the dispersion treatment and the other components mentioned above contained in the photosensitive resin composition are mixed to form a uniform solution or dispersion. In the manufacturing process of a photosensitive resin composition, fine dust may be mixed into the liquid, so it is desirable to filter the obtained photosensitive resin composition using, for example, a filter.
• the cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention.
• the use of the cured product is not particularly limited, but it can be suitably used as an insulating film or a functional film for improving light extraction efficiency in organic electroluminescent devices.
• the method of forming a cured product using a photosensitive resin composition is not particularly limited, and conventionally known methods can be employed.
• a photolithography method includes a coating process of coating a photosensitive resin composition onto a substrate to form a photosensitive resin composition layer, an exposure process of exposing the photosensitive resin composition layer, and a developing process. Can be mentioned.
• the material of the substrate for forming the cured product is not particularly limited as long as it has appropriate strength. It can be selected as appropriate depending on the type of organic electroluminescent device manufactured using the substrate on which the cured product is formed.
• Materials for the substrate include, for example, polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; polycarbonate; thermoplastic resin sheets such as polymethyl methacrylate and polysulfone; epoxy resins; unsaturated polyester resins; Examples include thermosetting resin sheets such as meth)acrylic resin; various glasses; From the viewpoint of heat resistance, glass and heat-resistant resin are preferred.
• a transparent electrode such as ITO or IZO, or a metal electrode such as silver, gold, platinum, aluminum, or magnesium may be formed on the surface of the substrate.
• an organic film such as an insulating film may be further formed on top of the film.
• a cured product may be formed on a TFT array.
• a photosensitive resin composition is applied to substantially the entire surface of a substrate to form a photosensitive resin composition layer. After exposing the formed photosensitive resin composition layer according to a predetermined pattern, the exposed photosensitive resin composition layer is developed to form a cured product on the substrate.
• a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, a spinner (rotary coating device), a curtain flow coating device, etc. are applied to the substrate.
• the photosensitive resin composition is applied using a non-contact coating device such as a coater, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.
• the photosensitive resin composition layer is exposed to active energy rays such as ultraviolet rays and excimer laser light using a negative mask.
• active energy rays such as ultraviolet rays and excimer laser light using a negative mask.
• 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, can be used.
• the exposure amount varies depending on the composition of the photosensitive resin composition, it is preferably about 10 to 400 mJ/cm 2 , for example.
• a cured product is formed by developing the exposed photosensitive resin composition layer with a developer.
• the developing method is not particularly limited, and a dipping method, a spray method, etc. can be used.
• the developer include organic developers such as tetramethylammonium hydroxide (TMAH), dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, as well as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and Examples include aqueous solutions such as grade ammonium salts.
• TMAH tetramethylammonium hydroxide
• dimethylbenzylamine dimethylbenzylamine
• monoethanolamine diethanolamine
• diethanolamine diethanolamine
• triethanolamine sodium hydroxide
• potassium hydroxide sodium carbonate
• ammonia examples include aqueous solutions such as grade ammonium salts.
• An antifoaming agent and a surfactant may be added to the developer.
• a post-exposure step and a post-bake (firing) step may be performed after development.
• the post-bake temperature is preferably 150 to 250°C.
• the post-bake time is preferably 15 to 60 minutes.
• the film thickness of the cured product is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, even more preferably 0.8 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 5.0 ⁇ m or less, and even more preferably is 3.0 ⁇ m or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is 0.1 ⁇ m to 10 ⁇ m, preferably 0.5 to 5 ⁇ m, and more preferably 0.8 to 3.0 ⁇ m.
• the amount is at least the lower limit, the refractive index of the cured product tends to improve, and when it is at most the upper limit, the hole resolution tends to improve.
• the film thickness of the cured product is measured using a step/surface roughness/fine shape measuring device, a scanning white interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, and an electron microscope.
• a cured product made from the photosensitive composition of the present invention has a high refractive index.
• the refractive index of the cured product is preferably 1.620 or more, more preferably 1.630 or more, still more preferably 1.640 or more. Further, it is preferably 1.680 or less, more preferably 1.660 or less.
• the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1.620 to 1.680, more preferably 1.630 to 1.680, even more preferably 1.640 to 1.660.
• the light extraction efficiency tends to improve when it is equal to or more than the lower limit value.
• An example of a method for measuring the refractive index of the cured product is a method using a prism coupler.
• a refractive index measurement substrate with a cured product formed on a glass substrate was prepared, and a He-Ne laser was used as a light source and a prism coupler was used to measure the refractive index at 20°C.
• the value measured at a wavelength of 633 nm can be taken as the refractive index of the cured product.
• Image display device The image display device of the present invention includes the cured product of the present invention.
• Examples of the image display device include a liquid crystal display device and an image display device including an organic electroluminescent element.
• 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 the gist thereof is exceeded.
• the constituent components of the photosensitive resin compositions used in the following Examples and Comparative Examples are as follows.
• Ethylenically unsaturated compound-I A compound with the following structure.
• Ethylenically unsaturated compound-I can be produced, for example, by the method described in Japanese Patent Application Publication No. 2021-024842.
• Ethylenically unsaturated compound-I corresponds to ethylenically unsaturated compound (A1).
• Ethylenically unsaturated compound-II > Ogsol EA-0200 manufactured by Osaka Gas Chemical Co., Ltd. A compound with the following structure. Ethylenically unsaturated compound-II does not correspond to ethylenically unsaturated compound (A1).
• An epoxy (meth)acrylate resin having the following partial structure, where each * represents a bond.
• Alkali-soluble resin-I corresponds to epoxy (meth)acrylate resin (C1-1).
• Alkali-soluble resin-II corresponds to epoxy (meth)acrylate resin (C1-1).
• the weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 10,000, and the solid content acid value was 68.8 mgKOH/g.
• a copolymer resin whose constituent monomers are dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.02/0.05/0.93) is subjected to an addition reaction of an equal amount of acrylic acid with glycidyl methacrylate, and then anhydrous
• the weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 8900, and the solid content acid value was 26.9 mgKOH/g.
• Photopolymerization initiator-I> It is a compound having the following chemical structure, and can be produced by the synthesis method described in International Publication No. 2019/131189.
• a photosensitive resin composition was coated onto a glass substrate using a spinner so that it had a thickness of 2 ⁇ m after being heated and cured.
• the obtained substrate was vacuum dried for 1 minute, and further heated and dried on a hot plate at 100° C. for 100 seconds to obtain a coated substrate.
• a manual exposure machine MA-1100 manufactured by Dainippon Kaken Co., Ltd.
• the entire surface of the coated substrate was exposed to light at an exposure dose of 100 mJ/cm 2 using a high-pressure mercury lamp that cuts wavelengths of 330 nm or less. At this time, the light intensity at a wavelength of 365 nm was 45 mW/cm 2 .
• the entire surface of the exposed substrate was heated and cured in an oven at 230° C. for 30 minutes to obtain a substrate for refractive index measurement.
• the refractive index of the cured product was measured using a refractive index measurement substrate. Specifically, the measurement was performed at 20° C. using a prism coupler Model 2010 manufactured by Metricon, using a He--Ne laser with a wavelength of 633 nm as incident light. If the refractive index was 1.630 or more, it was evaluated as "A,” if it was 1.600 or more and less than 1.630, it was evaluated as "B,” and if it was less than 1.600, it was evaluated as "C.”
• ⁇ Preparation of hole resolution evaluation board> The photosensitive resin compositions obtained in each of the Examples and Comparative Examples were applied onto a glass substrate using a spinner so as to have a thickness of 2 ⁇ m after heat curing.
• the obtained substrate was vacuum dried for 1 minute, and further heated and dried at 100° C. for 100 seconds on a hot plate.
• the obtained coating film was exposed to light using a photomask. Exposure was performed using a mirror projection type exposure machine manufactured by Canon Inc. (MPA-600FA) so that the exposure amount was 40 mJ/cm 2 .
• the illuminance was 500 mW/cm 2 and the slit width was 1.6 mm.
• a photomask having a covering area of 10 ⁇ m ⁇ 10 ⁇ m was used.
• ⁇ Preparation of glass substrate with organic base film> An ethylenically unsaturated compound, an alkali-soluble resin, a photopolymerization initiator, an additive, and a solvent are prepared in the following composition, and an organic base film is formed using the obtained photosensitive resin composition for forming an organic base film in the following manner. was fabricated on a glass substrate. First, each component was added so that the solid content of the ethylenically unsaturated compound, alkali-soluble resin, photopolymerization initiator, and additive was as follows, and the total solid content was 30% by mass. Solvent-I was added as a solvent, stirred, and dissolved to prepare a photosensitive resin composition for forming an organic base film.
• the composition of the photosensitive resin composition for forming an organic base film is as follows, and parts by mass represent the amount of solid content in each component excluding the solvent.
• composition of photosensitive resin composition for organic base film formation The following compounds were mixed, diluted to 30% by mass with PGMEA, stirred and dissolved to prepare a photosensitive resin composition for forming an organic base film.
• ⁇ Ethylenically unsaturated compound Dipentaerythritol hexaacrylate manufactured by Toagosei Co., Ltd. 49.2 parts by mass
• ⁇ Alkali-soluble resin Alkali-soluble resin-IV 49.2 parts by mass
• Photopolymerization initiator Photopolymerization initiator-I 3 mass Part/Additive: 0.1 part by mass of BYK-330 manufactured by BYK, 0.5 part by mass of PM-21 manufactured by Nippon Kayaku Co., Ltd.
• a photosensitive resin composition for forming an organic base film was coated onto the glass substrate using a spinner so that the composition would have a thickness of 1.5 ⁇ m after being heated and cured.
• the obtained substrate was vacuum dried for 1 minute, and further heated and dried at 90° C. for 90 seconds on a hot plate.
• the entire surface of the obtained coated substrate was exposed to light using a high-pressure mercury lamp, cutting off wavelengths of 330 nm or less, at an exposure dose of 40 mJ/cm 2 . At this time, the light intensity at a wavelength of 365 nm was 45 mW/cm 2 .
• this substrate was heated and cured in an oven at 230°C for 30 minutes, and then dry-cleaned using a UV dry processor VUM-3073-F02-00 manufactured by Oak Seisakusho, with the lamp turned on for 1 minute. A glass substrate was obtained.
• a photomask having a covering area of 10 ⁇ m ⁇ 10 ⁇ m was used.
• development was performed using a 2.38% TMAH aqueous solution in a shower at a pressure of 0.05 MPa for a development time of 40 seconds, followed by washing with pure water for 30 seconds. Finally, it was heated and cured in an oven at 230° C. for 30 minutes to produce a hole resolution evaluation substrate with an organic base film.
• Examples 1 and 2 show that when ethylenically unsaturated compound-I is used in combination with alkali-soluble resin-I or II, the resulting cured product has a high refractive index. This is because the ethylenically unsaturated compound-I has a sulfur-containing aromatic heterocycle, and the alkali-soluble resins-I and II are epoxy (meth)acrylate resins each having an aromatic ring in the main chain. caused by.
• the refractive index it is necessary to reduce the speed of light when it passes through molecules compared to the speed of light in vacuum. That is, it is effective to locally increase the electron density within the molecule and introduce a structure with high polarizability.
• Examples 1 and 2 are able to achieve not only a high refractive index but also good hole resolution.
• ethylenically unsaturated compound-I having a sulfur-containing aromatic heterocycle when developing a coating film of a photosensitive resin composition with an alkaline developer, it is possible to reduce the molecular volume while giving a high refractive index.
• the alkali-soluble resins-I and II are epoxy (meth)acrylate resins having an aromatic ring in the main chain, and have good compatibility with the ethylenically unsaturated compound-I having a sulfur-containing aromatic heterocycle. Therefore, the alkali-soluble resin can be uniformly distributed in the coating film of the photosensitive resin composition without phase separation, and as a result, the alkaline developer can penetrate easily during development, resulting in good hole resolution. It is thought that it was.
• Comparative Example 1 the ethylenically unsaturated compound-II is not a compound having a sulfur-containing aromatic heterocycle, and in Comparative Examples 2 and 3, the alkali-soluble resin-III and the alkali-soluble resin-IV have an aromatic group in the main chain. It can be seen that the refractive index and hole resolution are poor because the acrylic ester copolymer has no
• a photosensitive resin composition was coated onto a glass substrate using a spinner so that it had a thickness of 1.5 ⁇ m after being heated and cured.
• the obtained substrate was vacuum dried for 1 minute, and further heated and dried on a hot plate at 100° C. for 100 seconds to obtain a coated substrate.
• a manual exposure machine MA-1100 manufactured by Dainippon Kaken Co., Ltd.
• the entire surface of the coated substrate was exposed to light at an exposure dose of 100 mJ/cm 2 using a high-pressure mercury lamp that cuts wavelengths of 330 nm or less. At this time, the light intensity at a wavelength of 365 nm was 45 mW/cm 2 .
• the entire surface of the exposed substrate was heated and cured in an oven at 230° C. for 30 minutes to obtain a substrate for refractive index measurement.
• the refractive index of the cured product was measured using a refractive index measurement substrate. Specifically, the measurement was performed at 20° C. using a prism coupler Model 2010 manufactured by Metricon, using a He--Ne laser with a wavelength of 633 nm as incident light. If the refractive index is 1.640 or more, it is “AA”, if it is 1.630 or more, it is “A”, if it is 1.600 or more and less than 1.630, it is “B”, and if it is less than 1.600, it is " It was evaluated as "C”.
• a spinner was used on a substrate with an indium tin oxide (ITO) film formed on the surface of a glass substrate, and the photosensitizers obtained in each example and comparative example were heated and cured (baked) to a thickness of 1.5 ⁇ m.
• a synthetic resin composition was applied.
• the obtained substrate was vacuum dried for 1 minute, and further heated and dried at 100° C. for 100 seconds on a hot plate.
• the obtained coating film was exposed to light using a photomask. Exposure was performed using a mirror projection type exposure machine manufactured by Canon Inc. (MPA-600FA) so that the exposure amount was 60 mJ/cm 2 .
• the illuminance was 500 mW/cm 2 and the slit width was 1.6 mm.
• a photomask having a covering area of 10 ⁇ m ⁇ 10 ⁇ m was used.
• development was performed using a 2.38% TMAH aqueous solution in a shower at a temperature of 24° C. and a pressure of 0.05 MPa for a development time of 40 seconds, followed by washing with pure water for 30 seconds. Finally, it was heated and cured in an oven at 230° C. for 30 minutes to produce a hole resolution evaluation board.
• Examples 3 to 7 show that when ethylenically unsaturated compound-I is used in combination with alkali-soluble resin-I, the obtained cured product has a high refractive index. This is because the ethylenically unsaturated compound-I has a sulfur-containing aromatic heterocycle, and the alkali-soluble resin-I is an epoxy (meth)acrylate resin each having an aromatic ring in its main chain. do.
• the refractive index it is necessary to reduce the speed of light when it passes through molecules compared to the speed of light in vacuum. That is, it is effective to locally increase the electron density within the molecule and introduce a structure with high polarizability.
• the resulting cured product has a high refractive index.
• the resulting cured product has an extremely high refractive index exceeding 1.640. It turns out that it has.
• the hole resolution becomes good. In particular, it can be seen that the hole resolution becomes extremely good when the content ratio of the ethylenically unsaturated compound-I to 100 parts by mass of the alkali-soluble resin-I is from 67 parts by mass to 100 parts by mass.
• Comparative Example 4 the ethylenically unsaturated compound-II was not a compound containing a sulfur-containing aromatic heterocycle, and in Comparative Example 5, the alkali-soluble resin-IV was an acrylic ester copolymer having no aromatic ring in the main chain. Therefore, it can be seen that the refractive index and hole resolution are inferior.

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