Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
  • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • 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
• • 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
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

• the present invention relates to a photosensitive resin composition, an image display element, and a method for producing a photosensitive resin composition.
• photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in various fields such as coatings, printing, paints, and adhesives.
• the photosensitive resin composition is used as a solder resist, a resist for a color filter, and the like in the field of electronic materials such as printed wiring boards.
• the color filter generally includes a transparent substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on the transparent substrate, and a black matrix formed at the boundary between the pixels. It has a pixel and a protective film formed on a black matrix.
• the color filter is usually manufactured by sequentially forming a black matrix, each pixel, and a protective film on a transparent substrate.
• the photosensitive resin composition used in the photolithography method contains a resin, a reactive diluent, a photopolymerization initiator, a colorant and a solvent.
• the photosensitive resin composition used in the photolithography method needs to have developability.
• a resin used in a photosensitive resin composition an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, a radically polymerizable compound having an epoxy group, and a resin which is a copolymer of another radically polymerizable compound have been used. It has been proposed (see, for example, Patent Document 1). Further, a copolymer synthesized by using glycidyl (meth) acrylate as the resin used in the photosensitive resin composition, having no acid group, and having a polystyrene-equivalent weight average molecular weight of 1000 to 50,000, and an acid group. A resin composition containing a copolymer having a polystyrene-equivalent weight average molecular weight of 1000 to 50,000 has been proposed (see, for example, Patent Document 2).
• liquid crystal display elements and each member forming the liquid crystal display element are required to have stricter dimensional accuracy. Therefore, a photosensitive resin composition used as a material for a black matrix, a color filter, and a black column spacer is required to have better developability. Further, in order to improve the display characteristics of the liquid crystal display element, the cured film obtained by curing the photosensitive resin composition used for the above application needs to have good colorant dispersibility. Further, in order to prevent deterioration of the liquid crystal display element, the cured film obtained by curing the photosensitive resin composition used for the above-mentioned applications is required to have a high elastic recovery rate.
• the present invention has been made to solve the above problems, and an object of the present invention is to provide a photosensitive resin composition having excellent colorant dispersibility, developability and elastic recovery rate.
• the present invention includes the following aspects.
• the first aspect of the present invention provides the following photosensitive resin compositions.
• the resin (A) is A structural unit (a) having an aromatic ring skeleton and The structural unit (b) having a carboxy group and Constituent unit (c) and A structural unit (d) having a bridging alicyclic hydrocarbon group having 7 to 20 carbon atoms, and Have,
• the structural unit (c) is at least one selected from the group consisting of a structural unit (c-1) having a (meth) acryloyloxy group and a structural unit (c-2) having a functional group that reacts with a carboxy group.
• a photosensitive resin composition characterized in that the content of the structural unit (a) having an aromatic ring skeleton is 5 to 50 mol% with respect to the total amount of the structural units of the resin (A).
• the photosensitive resin composition according to the first aspect of the present invention preferably has the characteristics described in the following [2] to [9]. It is also preferable to arbitrarily combine two or more of the features described in the following [2] to [9]. [2]
• the structural unit (b) having a carboxy group is derived from an unsaturated carboxylic acid-derived structural unit (b-1), a polybasic acid-derived structural unit (b-2), and a polybasic acid anhydride.
• the structural unit (a) having an aromatic ring skeleton is one or more selected from the group consisting of a structural unit derived from styrene and a structural unit derived from benzyl (meth) acrylate.
• the resin (A) contains the resin (A-1) and the resin (A-2).
• the resin (A-1) has a content of the structural unit (a) having the aromatic ring skeleton of 5 to 30 mol% with respect to the total amount of the structural units of the resin (A-1).
• the content of the structural unit (a) having the aromatic ring skeleton of the resin (A-2) is 35 mol% to 50 mol% with respect to the total amount of the structural units of the resin (A-2) [1]. ]
• the photosensitive resin composition according to any one of. [6]
• the resin (A-1) is contained in an amount of 10 to 90% by mass and the resin (A-2) is contained in an amount of 10 to 90% by mass based on the total amount of the resin (A).
• the resin (A-1) has a carboxy group-containing (meth) acrylic compound added to the epoxy group of the resin (A-1) precursor having an epoxy group, and further to the hydroxy group generated by the ring opening of the epoxy group.
• a resin to which a polybasic acid or a polybasic acid anhydride is added is added,
• the resin (A-2) is a resin in which an epoxy group-containing (meth) acrylate or an isocyanato group-containing (meth) acrylate is added to a part of the carboxy group of the resin (A-2) precursor having a carboxy group.
• the epoxy group-containing resin (A-1) precursor is polymerizable having an aromatic ring-containing polymerizable monomer, an epoxy group-containing (meth) acrylate, and a bridging alicyclic hydrocarbon group having 7 to 20 carbon atoms. It is a polymer of monomers and
• the resin (A-2) precursor having a carboxy group is a polymerizable monomer having an aromatic ring-containing polymerizable monomer, a carboxy group-containing polymerizable monomer, and a bridging alicyclic hydrocarbon group having 7 to 20 carbon atoms.
• the photosensitive resin composition according to any one of [1] to [5], which is a polymer.
• the resin (A) is contained in an amount of 2 to 20% by mass.
• the reactive diluent (B) is contained in an amount of 3 to 20% by mass.
• a second aspect of the present invention provides the following black column spacers.
• a black column spacer made of a cured product of the photosensitive resin composition according to any one of [1] to [9].
• a third aspect of the present invention provides the following image display element. [11] An image display element comprising the black column spacer according to [10].
• a fourth aspect of the present invention provides the following method for producing a photosensitive resin composition. [12] Step I: A step of mixing the resin (A1), the solvent (C1), the colorant (E), and the dispersant (F) of an arbitrary component. Step II: A step of mixing the resin (A2), the reactive diluent (B), the solvent (C2), the photopolymerization initiator (D), and the mixture obtained in the step I in this order.
• a method for producing a photosensitive resin composition which is a method for producing a photosensitive resin composition.
• the resin (A1) and the resin (A2) are each A structural unit (a) having an aromatic ring skeleton and The structural unit (b) having a carboxy group and Constituent unit (c) and It has a structural unit (d) having a bridging alicyclic hydrocarbon group having 7 to 20 carbon atoms, and the structural unit (c) is a structural unit (c-1) having a (meth) acryloyloxy group. It is at least one selected from the group consisting of structural units (c-2) having a functional group that reacts with a carboxy group.
• Each of the resin (A1) and the resin (A2) is characterized in that the content of the structural unit (a) having the aromatic ring skeleton is 5 to 60 mol% with respect to the total amount of the structural units.
• the resin (A1) is either the resin (A-1) or the resin (A-2).
• the resin (A2) is the other of the resin (A-1) and the resin (A-2), which is different from the resin (A1).
• the resin (A-1) has a content of the structural unit (a) having the aromatic ring skeleton of 5 to 30 mol% with respect to the total amount of the structural units of the resin (A-1).
• the content of the structural unit (a) having the aromatic ring skeleton of the resin (A-2) is 35 mol% to 50 mol% with respect to the total amount of the structural units of the resin (A-2) [12]. ].
• the present invention it is possible to provide a photosensitive resin composition having excellent colorant dispersibility, developability and elastic recovery rate.
• the cured resin film obtained by curing the photosensitive resin composition of the present invention is excellent in colorant dispersibility and elastic recovery rate.
• the “constituent unit” is a monomer unit constituting the resin (A).
• the “content of the constituent unit” is the content (mol%) with respect to the total number of moles of the constituent monomers.
• the “monomer-derived structural unit” is a structural unit derived from a specific monomer among the monomers constituting the resin (A).
• the photosensitive resin composition of the present embodiment contains a resin (A), a reactive diluent (B), a solvent (C), a photopolymerization initiator (D), and a colorant (E).
• the photosensitive resin composition of the present embodiment may contain a dispersant (F), if necessary.
• the resin (A) of the present embodiment has a structural unit (a) having an aromatic ring skeleton (hereinafter, also simply referred to as “constituent unit (a)”) and a structural unit (b) having a carboxy group (hereinafter, simply “”. (Also also referred to as “constituent unit (b)”), the structural unit (c), and the structural unit (d) having a bridging alicyclic hydrocarbon group having 7 to 20 carbon atoms (hereinafter, simply “constituent unit (d)). Also called), and has at least.
• the structural unit (c) has a structural unit (c-1) having a (meth) acryloyloxy group (hereinafter, also simply referred to as “constituent unit (c-1)”) and a functional group that reacts with a carboxy group. It is at least one selected from the group consisting of units (c-2) (hereinafter, also simply referred to as “constituent units (c-2)”).
• the structural unit (a) has an aromatic ring skeleton. Since the resin (A) has the structural unit (a), a photosensitive resin composition having more excellent dispersibility of the colorant (E) can be obtained. In particular, when a pigment is used as the colorant (E), the effect of improving the dispersibility due to the resin (A) having the structural unit (a) can be remarkably obtained.
• the structural unit (a) is introduced by using the aromatic ring-containing polymerizable monomer (m-1) as the polymerizable monomer used when the resin (A) is produced by copolymerization (derived from the aromatic ring-containing polymerizable monomer). ).
• aromatic ring-containing polymerizable monomer (m-1) examples include styrene, ⁇ -methylstyrene, o-vinyltorene, m-vinyltoluene, p-vinyltorene, o-chlorostyrene, m-chlorostyrene, and p-.
• Aromatic vinyl compounds such as chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene; benzyl (meth) acrylate, phenoxyethyl (meth).
• phenoxy-styrene glycol (meth) acrylate (trade name: light acrylate P-200A, manufactured by Kyoei Kagaku Co., Ltd.), o-phenoxybenzyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, p-phenoxybenzyl ( Meta) acrylate and the like can be mentioned.
• styrene and benzyl (meth) acrylate are preferable from the viewpoint of improving the developability of availability.
• aromatic ring-containing polymerizable monomers (m-1) may be used alone or in combination of two or more.
• the structural unit (a) having an aromatic ring skeleton is one or more selected from the group consisting of a structural unit derived from styrene and a structural unit derived from benzyl (meth) acrylate.
• Constant unit (b) The structural unit (b) does not have an aromatic ring skeleton and has a carboxy group.
• the carboxy group may have as an anhydrate.
• the structural unit (b) having a carboxy group is a structural unit derived from unsaturated carboxylic acid (b-1), a structural unit derived from polybasic acid (b-2), and a structural unit derived from polybasic acid anhydride (b). It is preferably one or more selected from the group consisting of -3).
• the structural unit (b) can be generally introduced into the resin (A) by the following two methods.
• the first method is a method of introducing by using a carboxy group-containing polymerizable monomer (derived from the carboxy group-containing polymerizable monomer) as the polymerizable monomer used when the resin (A) is produced by copolymerization.
• a carboxy group-containing polymerizable monomer derived from the carboxy group-containing polymerizable monomer
• Examples of the carboxy group-containing polymerizable monomer (m-2) include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and ⁇ -bromo (meth).
• Acrylic acid ⁇ -frill (meth) acrylic acid, crotonic acid, propiole acid, katsura acid, ⁇ -cyanoceric acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconate, etc.
• examples include unsaturated carboxylic acid.
• These carboxy group-containing polymerizable monomers may be used alone or in combination of two or more.
• (meth) acrylic acid is preferable from the viewpoint of availability and reactivity.
• the second method uses an epoxy group-containing (meth) acrylate (m-3) as a polymerizable monomer used when producing a precursor of the resin (A) by copolymerization, and the epoxy group contains a carboxy group.
• An epoxy group is opened by subjecting the carboxy group of the compound to an addition reaction, and a polybasic acid (n-1) or a polybasic acid anhydride (n-2) is added to the hydroxyl group generated at that time to add a carboxy group. Is a method of introducing.
• Examples of the epoxy group-containing (meth) acrylate (m-3) include glycidyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate having an alicyclic epoxy.
• the lactone adduct eg, Cyclomer® A200, M100 manufactured by Daicel Chemical Industry Co., Ltd.
• Examples thereof include acid esters, epoxidates of dicyclopentenyl (meth) acrylate, and epoxidates of dicyclopentenyloxyethyl (meth) acrylate.
• These epoxy group-containing (meth) acrylates (m-3) may be used alone or in combination of two or more.
• glycidyl (meth) acrylate is preferable from the viewpoint of availability and reactivity.
• the carboxy group-containing compound the unsaturated carboxylic acid mentioned in the above-mentioned first method can be used.
• (meth) acrylic acid is preferable from the viewpoint of reactivity.
• polybasic acid (n-1) examples include tetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, succinic acid and the like.
• polybasic acid anhydride (n-2) examples include the above-mentioned polybasic acid anhydride. These polybasic acids and polybasic acid anhydrides may be used alone or in combination of two or more. Among these, tetrahydrophthalic acid anhydride is preferable from the viewpoint of improving developability.
• the carboxy group of the carboxy group-containing compound when added to the epoxy group contained in the precursor, a part of the epoxy group of the precursor is left unreacted to react with the carboxy group. It can be left as a structural unit (c-2) having a functional group. Further, a carboxy group-containing compound having a (meth) acryloyloxy group may be subjected to an addition reaction with the epoxy group of the precursor to introduce a structural unit (c-1) having a (meth) acryloyloxy group.
• Constant unit (c) "Constituent unit (c-1)”
• the structural unit (c-1) does not have an aromatic ring skeleton and a carboxy group, but has a (meth) acryloyloxy group.
• the structural unit (c-1) can be generally introduced into the resin (A) by the following two methods.
• the first method uses an epoxy group-containing (meth) acrylate (m-3) as a polymerizable monomer used when producing a precursor of the resin (A) by copolymerization, and the epoxy group contains a carboxy group.
• This is a method of introducing by adding a (meth) acrylic compound.
• the epoxy group-containing (meth) acrylate (m-3) the above-mentioned ones can be used.
• the carboxy group-containing (meth) acrylic compound (m-2) include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and ⁇ -bromo.
• Examples thereof include (meth) acrylic acid and ⁇ -frill (meth) acrylic acid.
• (meth) acrylic acid is preferable from the viewpoint of reactivity and availability when synthesizing the resin (A).
• carboxy group-containing (meth) acrylic compounds may be used alone or in combination of two or more.
• a carboxy group-containing monomer is used as the polymerizable monomer used when producing the precursor of the resin (A) by copolymerization, and the carboxy group contains an epoxy group (meth) acrylate (m-3).
• an isocyanato group-containing (meth) acrylate (m-4) As the carboxy group-containing monomer, an unsaturated carboxylic acid listed as the above-mentioned carboxy group-containing polymerizable monomer can be used.
• the epoxy group-containing (meth) acrylate (m-3) the above-mentioned ones can be used.
• the isocyanato group-containing (meth) acrylate (m-4) include 2-isocyanatoethyl (meth) acrylate.
• the structural unit (c-2) does not have an aromatic ring skeleton, a carboxy group, and a (meth) acryloyloxy group, and has a functional group that reacts with the carboxy group.
• the functional group that reacts with the carboxy group of the structural unit (c-2) is not particularly limited, but usually includes an epoxy group, an oxetanyl group, an isocyanato group and the like, and an epoxy group is particularly preferable.
• the structural unit (c-2) is introduced by using a functional group-containing polymerizable monomer that reacts with a carboxy group as the polymerizable monomer used when the resin (A) is produced by copolymerization (reaction with a carboxy group).
• a functional group-containing polymerizable monomer (Derived from a functional group-containing polymerizable monomer).
• the functional group-containing polymerizable monomer that reacts with the carboxy group include oxetanyl (meth) acrylate and (meth) acrylic acid (3-methyloxetan-3) in addition to the above-mentioned epoxy group-containing (meth) acrylate (m-3).
• the resin (A) comprises a structural unit (b) having a carboxy group, a structural unit (c-1) having a (meth) acryloyloxy group, and a structural unit (c-2) having a functional group that reacts with the carboxy group.
• a structural unit (b) having a carboxy group a structural unit having a carboxy group
• a structural unit (c-1) having a (meth) acryloyloxy group and a structural unit (c-2) having a functional group that reacts with the carboxy group.
• a structural unit (c-1) having a (meth) acryloyloxy group
• c-2 having a functional group that reacts with the carboxy group.
• a preferred method is to use an epoxy group-containing (meth) acrylate (m-3) as a polymerizable monomer used when producing a precursor of the resin (A) by copolymerization, and a carboxy group as a part of the epoxy group.
• the epoxy group may be opened by adding the contained (meth) acrylic compound, and the polybasic acid anhydride may be added to a part of the hydroxyl groups generated at that time. That is, as the structural unit introduced into the resin (A), a structural unit (b) having a carboxy group (a structural unit derived from a polybasic acid anhydride) and a structural unit having a (meth) acryloyloxy group (c-1).
• Epoxide group-containing (meth) acrylate or isocyanato group-containing (meth) acrylate may be added. That is, examples of the structural unit introduced into the resin (A) include a structural unit (b) having a carboxy group and a structural unit (c-1) having a (meth) acryloyloxy group.
• the structural unit (d) does not have an aromatic ring skeleton, a carboxy group, a (meth) acryloyloxy group, and a functional group that reacts with the carboxy group, and is a crosslinked alicyclic hydrocarbon group having 7 to 20 carbon atoms.
• the structural unit (d) is a polymerizable monomer (m-5) having a bridging alicyclic hydrocarbon group having 7 to 20 carbon atoms as a polymerizable monomer used for producing the resin (A) by copolymerization.
• a polymerizable monomer having a cross-linked alicyclic hydrocarbon group having 7 to 20 carbon atoms examples include dicyclopentadiene (meth) acrylate, tricyclodecanyl (meth) acrylate, and isobornyl (meth).
• the polymerizable monomer (m-5) having a bridging alicyclic hydrocarbon group having 7 to 20 carbon atoms include dicyclopentadiene (meth) acrylate, tricyclodecanyl (meth) acrylate, and isobornyl (meth).
• the resin (A) of the present embodiment has, if necessary, a structural unit (e) derived from a radically polymerizable monomer (m-6) having an ethylenic carbon-carbon double bond other than the above-mentioned structural unit. You may.
• Examples of the radically polymerizable monomer (m-6) having an ethylenic carbon-carbon double bond include diene compounds such as butadiene, isoprene and chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate and n-propyl ( Meta) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylic rate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylic rate, benzyl (meth) Acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate,
• the resin (A) used in the present embodiment contains 5 to 50 mol% of the constituent unit (a) having an aromatic ring skeleton with respect to the total amount of the constituent units (total number of moles of the constituent monomers).
• the content of the structural unit (a) is 5 mol% or more, the photosensitive resin composition has good colorant dispersibility and good developability.
• the contents of the structural unit (b), the structural unit (c), and the structural unit (d) can be sufficiently secured, so that the photosensitive resin composition can be sufficiently secured.
• a photosensitive resin composition having a good balance of necessary properties such as photocurability, developability, and elastic recovery rate as a cured product can be obtained.
• the content of the structural unit (a) is 5 to 10 mol%, 10 to 20 mol%, 20 to 30 mol%, 30 to 40 mol%, or 40 to 50 mol%. There may be.
• the resin (A) used in the present embodiment is obtained by using two kinds of resins (A-1) and resins (A-2) having different contents of the structural unit (a) having an aromatic ring skeleton in combination. It is possible to obtain a photosensitive resin composition which exerts a synergistic effect, gives a cured film having a further improved elastic recovery rate, and has a further improved colorant dispersibility and developability.
• the content of the structural unit (a) having the aromatic ring skeleton of the resin (A-1) is preferably 5 to 30 mol% with respect to the total amount of the structural units of the resin (A-1). It is preferably 5 to 25 mol%.
• the content is preferably 5 to 8 mol%, 5 to 10 mol%, 5 to 15 mol%, or 10 to 20 mol%, if necessary.
• the content of the structural unit (a) having the aromatic ring skeleton of the resin (A-2) is preferably 35 mol% to 50 mol% with respect to the total amount of the structural units of the resin (A-2). , More preferably 40 to 50 mol%.
• the content is preferably 38 to 50 mol% or 42 to 45 mol%, if necessary.
• the ratio of the resin (A-1) to the resin (A) is 10 to 90% by mass. Is more preferable, 30 to 70% by mass is more preferable, and 45 to 65% by mass is further preferable.
• the ratio may be 48 to 60% by mass, 50 to 58% by mass, or the like.
• the ratio of the resin (A-2) to the resin (A) is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and even more preferably 35 to 55% by mass.
• the ratio may be 38 to 53% by mass, 40 to 50% by mass, or the like.
• Preferred configurations of the resin (A-1) include an aromatic ring-containing polymerizable monomer (m-1), an epoxy group-containing (meth) acrylate (m-3), and a bridging alicyclic type having 7 to 20 carbon atoms.
• a carboxy group-containing (meth) acrylic compound (m-2) is added to the epoxy group of the resin (A) precursor, which is a polymer of the polymerizable monomer (m-5) having a hydrocarbon group, and the epoxy group is further added.
• This is a resin in which a polybasic acid (n-2) or a polybasic acid anhydride (n-3) is added to a hydroxy group generated by the ring opening of the above.
• the resin (A-1) By forming the resin (A-1) in such a configuration, it is possible to control the content of the structural unit (a) having the aromatic ring skeleton while balancing the contents of the other structural units. A photosensitive resin composition having excellent colorant dispersibility and developability can be obtained, and a cured film having an excellent elastic recovery rate can be obtained.
• Preferred configurations of the resin (A-2) include an aromatic ring-containing polymerizable monomer (m-1), a carboxy group-containing polymerizable monomer (m-2), and a bridging alicyclic hydrocarbon having 7 to 20 carbon atoms.
• Epoxide group-containing (meth) acrylate (m-3) or isocyanato group-containing (meth) acrylate is part of the carboxy group of the resin (A) precursor, which is a polymer of the polymerizable monomer (m-5) having a group. It is a resin to which (m-4) is added.
• the resin (A-2) By making the resin (A-2) have such a constitution, it is possible to control the content of the constituent unit (a) having the aromatic ring skeleton while balancing the contents of the other constituent units. , A photosensitive resin composition having excellent colorant dispersibility and developability can be obtained, and a cured film having an excellent elastic recovery rate can be obtained.
• the content of the structural unit (b) having a carboxy group is preferably 5 to 50 mol%, preferably 8 to 40 mol%, based on the total amount of the structural units (total number of moles of the constituent monomers). More preferably, it is more preferably 10 to 30 mol%, and particularly preferably 13 to 25 mol%. The amount is preferably 15 to 23 mol% or 18 to 20 mol%.
• the content of the structural unit (b) is 5 mol% or more, a photosensitive resin composition having good developability can be obtained.
• the content of the structural unit (b) is 50 mol% or less, it is possible to prevent the exposed portion from being washed away during development and the residual film ratio from decreasing.
• the content of the structural unit (c-1) having the (meth) acryloyloxy group is preferably 5 to 50 mol% with respect to the total amount of the structural unit (total number of moles of the constituent monomers), and is preferably 10 to 40. It is more preferably mol%, still more preferably 12-30 mol%. The amount is preferably 15 to 28 mol% or 18 to 25 mol%.
• a photosensitive resin composition having good photocurability, solvent resistance, and developability can be obtained.
• the content of the structural unit (c-1) is 50 mol% or less, the photocurability can be suppressed to an appropriate range, and it is possible to prevent the generation of residues in the unexposed portion during development.
• the content of the structural unit (c-1) is particularly preferably 20 to 30 mol% in the case of the resin (A-1), and 10 to 20 mol% in the case of the resin (A-2). It is particularly preferable to have.
• the content of the structural unit (c-2) having a functional group that reacts with the carboxy group is preferably 0 to 20 mol%, preferably 0 to 20 mol%, based on the total amount of the structural units (total number of moles of the constituent monomers). It is more preferably 15 mol%, further preferably 0 to 10 mol%, and particularly preferably 0 to 5 mol%.
• the content of the structural unit (c-1) is particularly preferably 0.1 to 5 mol% in the case of the resin (A-1), and 0 mol% in the case of the resin (A-2). It is particularly preferable to have.
• the content of the structural unit (d) having a bridging alicyclic hydrocarbon group having 7 to 20 carbon atoms is 1 to 40 mol% with respect to the total amount of the structural units (total number of moles of the constituent monomers). It is preferably 3 to 35 mol%, more preferably 5 to 30 mol%. The amount may be 8 to 25 mol%, 10 to 20 mol%, 15 to 18 mol%, or the like, if necessary.
• the content of the structural unit (d) is 1 mol% or more, a cured film having an excellent elastic recovery rate can be obtained.
• the content of the structural unit (d) is 40 mol% or less, a photosensitive resin composition having excellent curability can be obtained.
• the content of the structural unit (d) is particularly preferably 10 to 30 mol% in the case of the resin (A-1) and 5 to 10 mol% in the case of the resin (A-2). Is particularly preferable.
• a constituent unit (e) other than the constituent unit (a), the constituent unit (b), the constituent unit (c), and the constituent unit (d) can be introduced into the resin (A), if necessary.
• the total amount of the structural units is compared with respect to the total amount of the structural units (total number of moles of the constituent monomers). It is preferably more than 0 mol% to 60 mol%, more preferably more than 0 mol% to 50 mol%.
• the following introduction examples can be mentioned.
• a carboxy group-containing (meth) acrylic compound is added to the epoxy group of the resin (A) precursor, which is a polymer containing an epoxy group-containing (meth) acrylate.
• the structural unit derived from the epoxy group-containing (meth) acrylate in which the unreacted epoxy group remains is counted as the structural unit (c-2) having a functional group that reacts with the carboxy group.
• the structural unit derived from the epoxy group-containing (meth) acrylate to which the carboxy group-containing (meth) acrylic compound is added and the epoxy group disappears the structural unit (a), the structural unit (b), and the structural unit (c) are used. , It is counted as a structural unit (e) other than the structural unit (d).
• the reaction conditions in the copolymerization reaction for obtaining the resin (A) used in the present embodiment or the copolymerization reaction for obtaining the resin (A) precursor before the addition reaction may be appropriately set according to a conventional method. ..
• the copolymerization reaction is carried out, for example, at 50 to 150 ° C., more preferably 60 to 140 ° C. for about 1 to 12 hours while dropping a polymerizable monomer for copolymerization in a solvent and a polymerization initiator. You just have to react.
• a monomer for the addition reaction with the resin (A) precursor is added to the solvent, and an addition reaction catalyst is further added, preferably 50 to 150 ° C., more preferably.
• the reaction may be carried out at 80 to 130 ° C. for about 3 to 12 hours. In this addition reaction, there is no problem even if the solvent used in the copolymerization reaction for obtaining the resin (A) precursor is contained. Therefore, after the copolymerization reaction for obtaining the resin (A) precursor is completed, the addition reaction can be continuously carried out without removing the solvent.
• the solvent that can be used for the copolymerization reaction is not particularly limited, and known ones can be appropriately used.
• Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, and triethylene.
• Glycol monoethyl ether propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene (Poly) alkylene glycol monoalkyl ethers such as glycol monomethyl ether and tripropylene glycol monoethyl ether; (poly) such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.
• Alkylene glycol monoalkyl ether acetate Alkylene glycol monoalkyl ether acetate; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate , 2-Hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethoxypropionate , 3-ethoxypropionate ethyl, ethoxyacetate ethyl, hydroxyacetate ethyl, 2-hydroxy-3-methylbutyrate methyl, 3-methyl-3-meth
• (poly) alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether
• (poly) alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate, that is, glycol ether-based solvents are preferable.
• the amount of the solvent used for the copolymerization reaction is not particularly limited, but is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass when the total amount of the monomers charged is 100 parts by mass. ..
• the amount of the solvent used is 1000 parts by mass or less, the decrease in the molecular weight of the resin (A) due to the chain transfer action can be efficiently suppressed, and the viscosity of the resin (A) can be controlled within an appropriate range. preferable.
• the amount of the solvent used is 30 parts by mass or more, it is preferable because it is possible to prevent an abnormality from occurring in the copolymerization reaction and to stably carry out the copolymerization reaction. In addition, coloring and gelation of the resin (A) can be prevented.
• the polymerization initiator that can be used in the copolymerization reaction is not particularly limited, and known ones can be appropriately used.
• Specific examples of the polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and the like. These polymerization initiators may be used alone or in combination of two or more.
• the amount of the polymerization initiator used is not particularly limited, but is generally 0.5 to 20 parts by mass, preferably 0.7 to 15 parts by mass, when the total amount of the monomers charged is 100 parts by mass. It is more preferably 1 to 10 parts by mass.
• the type of the addition reaction catalyst used for the addition reaction of the monomer to the resin (A) precursor is not particularly limited, and is selected as necessary.
• the addition reaction catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelating compounds. These addition reaction catalysts may be used alone or in combination of two or more.
• the amount of the addition reaction catalyst used is not particularly limited, but is generally 0.01 to 5 parts by mass, preferably 0.1 to 5 parts by mass, when the amount of the resin (A) precursor is 100 parts by mass. It is 2 parts by mass, more preferably 0.2 to 1 part by mass.
• the type of the polymerization inhibitor is not particularly limited and is selected as needed.
• examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, butylhydroxytoluene and the like. These polymerization inhibitors may be used alone or in combination of two or more.
• the amount of the polymerization inhibitor used is not particularly limited, but is generally 0.01 to 5 parts by mass, preferably 0.1 to 5 parts by mass when the amount of the resin (A) precursor is 100 parts by mass. It is 2 parts by mass, more preferably 0.2 to 1 part by mass.
• the resin (A) used in the present invention preferably has a weight average molecular weight of 1000 to 50,000, more preferably 3000 to 40,000, obtained by gel permeation chromatography (GPC) in terms of polystyrene. It is more preferably 20000.
• GPC gel permeation chromatography
• the weight average molecular weight is 1000 or more, pattern chipping does not occur after alkaline development, which is preferable.
• the weight average molecular weight is 50,000 or less, the developing time is appropriate and it is practical for use, which is preferable.
• the acid value (JIS K6901 5.3) of the resin (A) used in the present invention is not limited as long as the desired effect of the present invention is obtained, but is usually 20 to 300 KOH mg / g, preferably 30 to 200 KOH mg / g. ..
• the acid value is 20 KOH mg / g or more, the developability is good, which is preferable.
• the acid value is 300 KOHmg / g or less, the exposed portion (photo-curing portion) is less likely to dissolve in the alkaline developer, which is preferable.
• the unsaturated group equivalent of the resin (A) used in the present invention is not limited as long as the desired effect of the present invention is obtained, but is usually 100 to 4000 g / mol, preferably 200 to 2000 g / mol, more preferably. Is 300-500 g / mol.
• the unsaturated group equivalent is 100 g / mol or more, it is preferable because it is effective in improving the physical characteristics of the coating film and the alkali developability.
• the unsaturated group equivalent is 4000 g / mol or less, it is preferable because it is effective in further increasing the sensitivity.
• the unsaturated group equivalent is the mass of the resin (A) per mol of the unsaturated bond (ethylenic carbon-carbon double bond) in the resin (A).
• the unsaturated group equivalent can be determined by dividing the mass of the resin (A) by the number of unsaturated groups in the resin (A) (g / mol).
• the unsaturated group equivalent is a theoretical value calculated from the amount of the raw material charged for introducing the unsaturated group.
• the epoxy equivalent of the resin (A) used in the present invention is not limited as long as the desired effect of the present invention is obtained, but is usually 100 to 4000 g / mol, preferably 200 to 2000 g / mol, and more preferably 300. ⁇ 500 g / mol.
• the epoxy equivalent is 100 g / mol or more, it is effective and preferable for improving the physical characteristics of the coating film and the storage stability.
• the epoxy equivalent is 4000 g / mol or less, it is effective in further improving the solvent resistance.
• the epoxy equivalent is the mass of the polymer per mole of the epoxy group of the polymer. This value can be determined by dividing the mass of the polymer by the amount of epoxy groups in the polymer (g / mol).
• the "epoxy equivalent" is a theoretical value calculated from the charged amount of the raw material used for introducing the epoxy group.
• the blending amount of the resin (A) is not particularly limited, but is preferably 5 to 40 parts by mass, preferably 10 to 30 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent (C). It is more preferable to have.
• the blending amount of the resin (A) is 5% by mass or more, it is preferable because it has good curability.
• the blending amount of the resin (A) is 40 parts by mass or less, it is preferable because it has good coatability.
• the reactive diluent (B) used in this embodiment is a compound having at least one ethylenically unsaturated group in the molecule. Of these, a compound having a plurality of ethylenically unsaturated groups is preferable. By using the reactive diluent (B), the strength of the cured film and the adhesion to the substrate can be improved.
• Examples of the monofunctional monomer used as the reactive diluent (B) include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, and propoxymethyl (meth) acrylamide.
• Examples of the polyfunctional monomer used as the reactive diluent (B) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate.
• Aromatic vinyl compounds such as diallylbenzenephosphonate; Dicarboxylic acid ester compounds such as divinyl adipate; Triallyl cyanurate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol (meth) acrylamide.
• These polyfunctional monomers may be used alone or in combination of two or more.
• dipentaerythritol hexa (meth) acrylate is preferable from the viewpoint of adhesion.
• the blending amount of the reactive diluent (B) is not particularly limited, but is preferably 10 to 50 parts by mass, preferably 20 to 40 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent (C). It is more preferably by mass.
• the blending amount of the reactive diluent (B) is 10 parts by mass or more, it is preferable because the photosensitive resin composition has good photocurability.
• the blending amount of the reactive diluent (B) is 40 parts by mass or less, it is preferable because the residue of the unexposed part is less likely to be generated after the coating film of the photosensitive resin composition is exposed and developed.
• the solvent (C) used in the present embodiment is not particularly limited as long as it is an inert solvent that can dissolve the resin (A) and does not react with the resin (A), and can be arbitrarily selected. Further, the solvent (C) is preferably compatible with the above-mentioned reactive diluent (B). As the solvent (C), the same solvent that can be used when producing the resin (A) can be used. As the solvent (C), (poly) alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate are preferable.
• the target resin (A) can be isolated from the solution of the resin (A) that has completed the copolymerization reaction, and can be appropriately added to the isolated resin (A). However, it is not always necessary to isolate the target resin (A) from the resin solution. It is also possible to use the solvent as it is as the solvent (C) without separating the solvent contained at the end of the copolymerization reaction from the resin (A) solution. If necessary, another solvent may be added to the resin (A) solution. Further, the solvent contained in the other components used when preparing the photosensitive resin composition may be used as it is as the solvent (C).
• the blending amount of the solvent (C) is not particularly limited, but is preferably 150 to 300 parts by mass, preferably 200 to 250 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent (C). It is more preferable to have.
• the blending amount of the solvent (C) is 150 parts by mass or more, the photosensitive resin composition has good coatability, which is preferable.
• the blending amount of the solvent (C) is 300 parts by mass or less, it is preferable because the coating film can have a sufficient film thickness.
• the photopolymerization initiator (D) used in the present embodiment is not particularly limited, and is, for example, a benzophenone compound such as benzophenone, benzoinmethyl ether, benzoin ethyl ether, benzoin butyl ether; acetophenone, 2,2-dimethoxy-2-phenyl.
• a benzophenone compound such as benzophenone, benzoinmethyl ether, benzoin ethyl ether, benzoin butyl ether; acetophenone, 2,2-dimethoxy-2-phenyl.
• Xantone compounds such as xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; quetal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy) Benzophenone compounds such as -1-methylethyl) benzophenone, 3,3', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone; acylphosphine oxide compounds and the like can be mentioned.
• These photopolymerization initiators may be used alone or in combination of two or more.
• the blending amount of the photopolymerization initiator (D) is not particularly limited, but is preferably 0.03 to 15 parts by mass, preferably 0.03 to 15 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent (C). .1 to 10 parts by mass is more preferable, and 0.3 to 6 parts by mass is further preferable.
• the amount may be 0.5 to 8 parts by mass, 1 to 5 parts by mass, or the like, if necessary.
• the blending amount of the photopolymerization initiator (D) is 0.03 part by mass or more, it is preferable because the photosensitive resin composition has sufficient photocurability.
• the blending amount of the photopolymerization initiator (D) is 15 parts by mass or less, a residue in the unexposed portion after development is unlikely to occur, which is preferable.
• the colorant (E) may be any as long as it dissolves or disperses in the solvent (C), and is not particularly limited.
• Examples of the colorant (E) include dyes and pigments.
• the colorant (E) only the dye may be used, only the pigment may be used, or the dye and the pigment may be used in combination.
• the above-mentioned colorant (E) is used for the purpose of a member formed of the cured resin film. Depending on the situation, it can be used alone or in combination of two or more.
• a black colorant (E) is used, the cured resin film of the photosensitive resin composition is suitable as a black matrix and a black column spacer.
• dyes include, for example, acidalizarin violet N; acidblack1, 2, 24, 48; acidblue1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92. , 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56.
• dyes it is preferable to use azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes. These dyes may be used alone or in combination of two or more.
• pigments include, for example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; I.
• pigments may be used alone or in combination of two or more.
• an organic black pigment is preferable, and a lactam-based organic black is more preferable, from the viewpoint of the optical density of the image display element provided with the resin cured film of the photosensitive resin composition of the present embodiment.
• the blending amount of the colorant (E) is not particularly limited, but is preferably 10 to 50 parts by mass, preferably 15 to 45 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent (C). Is more preferable, and 20 to 40 parts by mass is further preferable. The amount may be 25 to 45 parts by mass, 30 to 35 parts by mass, or the like, if necessary.
• the blending amount of the colorant (E) is 10 parts by mass or more, the cured film has sufficient color reproducibility, and when a black pigment is used as the colorant (E), it has sufficient light-shielding property. preferable.
• the blending amount of the colorant (E) is 50 parts by mass or less, the residue of the unexposed part is less likely to be generated after development, which is preferable.
• the photosensitive resin composition of the present embodiment may contain a dispersant (F).
• a dispersant a known dispersant can be used without particular limitation.
• the dispersant (F) the dispersibility of the colorant is improved, especially when the pigment is used as the colorant (E).
• the dispersant (F) it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time.
• the polymer dispersant can be arbitrarily selected, and for example, a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, etc. Examples thereof include an aliphatic modified ester-based dispersant. Examples of such polymer dispersants include EFKA (registered trademark, manufactured by BASF Japan), Disperbyk (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), and SOLSERSE (registered trademark, manufactured by Geneca). ) And other commercially available products may be used. The blending amount of the dispersant may be appropriately set according to the type of pigment or the like to be used.
• the blending amount of the dispersant (F) is not particularly limited, but is preferably 0.03 to 15 parts by mass, preferably 0.1 part by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent (C). It is more preferably to 10 parts by mass, and further preferably 0.3 to 6 parts by mass. The amount may be 1 to 8 parts by mass, 2 to 5 parts by mass, or the like, if necessary.
• the blending amount of the dispersant (F) is 0.03 parts by mass or more, it is preferable because the dispersibility is further enhanced.
• the blending amount of the dispersant (F) is 15 parts by mass or less, the residue of the unexposed part is less likely to be generated after development, which is preferable.
• the photosensitive resin composition of the present embodiment may contain known additives such as a coupling agent, a leveling agent, and a thermal polymerization inhibitor, as long as the effects of the present invention are not impaired.
• the blending amount of these additives is not particularly limited as long as the effect of the present invention is not impaired.
• the photosensitive resin composition of the present embodiment can be produced by mixing each of the above-mentioned components using a known mixing device.
• Examples of the method for producing the photosensitive resin composition in one embodiment include a production method having the following steps I and II in this order.
• Step I A step of mixing the resin (A1), the solvent (C1), the colorant (E), and the dispersant (F) of an arbitrary component.
• Step II A step of mixing the resin (A2), the reactive diluent (B), the solvent (C2), the photopolymerization initiator (D), and the mixture obtained in Step I.
• the solvent (C1) in step I and the solvent (C2) in step II mixed as the solvent (C) in the photosensitive resin composition may be the same type of solvent or different types of solvents. Further, as the solvent (C1) or the solvent (C2) used in each step, the above-mentioned solvent (C) may be used alone, or two or more kinds may be used.
• the resin (A1) in step I and the resin (A2) in step II which are mixed as the resin (A) in the photosensitive resin composition, may use the same type of resin but different types of resin. Is also good. Further, as the resin (A1) or the resin (A2) used in each step, the above-mentioned resin (A) may be used alone, or two or more kinds may be used.
• the resin (A1) of the step I and the resin (A2) of the step II have a viewpoint of further improving all the characteristics of the colorant dispersibility as the photosensitive resin composition, the development time, and the elastic recovery rate as the cured product in a well-balanced manner. Therefore, it is preferable to use different types of resin (A).
• the combination of the different types of resin (A) used for the resin (A1) and the resin (A2) is not particularly limited, but the colorant dispersibility as a photosensitive resin composition, the development time, and the elastic recovery rate as a cured product are not particularly limited.
• a synergistic effect is exhibited by using two types of resins (A-1) and resins (A-2) having different contents of the constituent unit (a) having the aromatic ring skeleton in combination from the viewpoint of improving the balance. do.
• the content of the structural unit (a) having the aromatic ring skeleton of the resin (A-1) is preferably 5 to 30 mol% with respect to the total amount of the structural units of the resin (A-1). It is more preferably 5 to 25 mol%.
• the content of the structural unit (a) having the aromatic ring skeleton of the resin (A-2) is preferably 35 mol% to 50 mol% with respect to the total amount of the structural units of the resin (A-2). , More preferably 40 to 50 mol%.
• the cured resin film of the present embodiment is a cured resin film obtained by photo-curing the photosensitive resin composition of the present embodiment. Since the resin cured film of the present embodiment has good colorant dispersibility, solvent resistance, and elastic recovery rate, it is suitable as a black matrix, a color filter, a black column spacer, and a BPDL, which are members of an image display element.
• the cured resin film of the present embodiment can be produced, for example, by the method shown below.
• the photosensitive resin composition is applied onto the surface to be formed of the cured resin film to form a resin layer (coating film).
• the resin layer is exposed through a mask having a predetermined pattern, and the exposed portion is photocured.
• the unexposed portion of the resin layer is developed with a developing solution to obtain a cured resin film having a predetermined pattern.
• post-baking heat treatment
• a halftone mask having a predetermined pattern may be used. In this case, the unexposed portion and the semi-exposed portion are developed with a developing solution to obtain a resin cured film having a predetermined pattern.
• the material of the substrate is not particularly limited, and examples thereof include a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamide-imide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, and an array substrate.
• the method for applying the photosensitive resin composition is not particularly limited, and examples thereof include a screen printing method, a roll coating method, a curtain coating method, a spray coating method, and a spin coating method.
• the solvent (C) contained in the resin layer is volatilized by heating using a heating means such as a circulating oven, an infrared heater, or a hot plate, if necessary. May be good.
• the heating conditions after coating are not particularly limited and may be appropriately set according to the composition of the photosensitive resin composition.
• the heating temperature after coating can be 50 ° C. to 120 ° C.
• the heating time can be 30 seconds to 30 minutes.
• the exposure method of the resin layer is not particularly limited, and examples thereof include irradiation with active energy rays such as ultraviolet rays and excimer laser light.
• the energy dose to be irradiated may be appropriately set according to the composition of the photosensitive resin composition. For example, it is preferably 30 to 2000 mJ / cm 2 , but is not limited to this range.
• the light source used for exposure is not particularly limited, but a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be arbitrarily selected and used.
• the alkaline developing solution used for development is not particularly limited, and is, for example, an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide or the like; an aqueous solution of an amine compound such as ethylamine, diethylamine or dimethylethanolamine.
• Tetramethylammonium 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N- Ethyl-N- ⁇ -methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and p-such as sulfates, hydrochlorides or p-toluenesulfonates thereof.
• Examples thereof include an aqueous solution of a phenylenediamine-based compound.
• a defoaming agent, a surfactant, or the like may be added to these alkaline developers. Further, it is preferable to wash with water and dry after developing with an alkaline developer.
• the post-baking conditions are not particularly limited and can be arbitrarily selected.
• the heat treatment may be performed by selecting preferable conditions according to the composition of the photosensitive resin composition. For example, heating may be performed at a temperature of 130 ° C. to 250 ° C., preferably for 10 minutes to 4 hours, more preferably for 20 minutes to 2 hours.
• the resin cured film produced in this way is excellent in colorant dispersibility and elastic recovery rate.
• Image display element Specific examples of the image display element include a liquid crystal display element, an organic EL display element, and the like. There are no restrictions on the manufacture of the image display element, and the image display element can be manufactured according to a conventional method.
• a monomer mixture consisting of 68.0 g (molar ratio 0.3) of tricyclodecanyl methacrylate, 11.0 g (molar ratio 0.1) of styrene and 88.0 g (molar ratio 0.6) of glycidyl methacrylate was added to t-.
• a separately prepared product supplemented with 18.4 g of butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nichiyu Co., Ltd., Perbutyl (registered trademark) O).
• the mixture of the monomer and the polymerization initiator was added dropwise to the flask over 2 hours from the dropping funnel.
• the copolymerization reaction was carried out by further stirring at 120 ° C. for 2 hours to generate a precursor of the resin (A-1). Then, the inside of the flask was replaced with air, and 43.4 g (molar ratio 0.58) of acrylic acid, 1.1 g of triphenylphosphine (catalyst), and 0.1 g of methylhydroquinone (polymerization inhibitor) were added to the above resin ( A-1) It was put into a precursor solution. Then, the reaction was continued at 110 ° C. for 10 hours. Next, 61.0 g (molar ratio 0.39) of tetrahydrophthalic anhydride was added to the flask, and the reaction was continued at 110 ° C.
• the acid value of the resin (A-1) contained in this resin solution was 79 KOHmg / g, the weight average molecular weight was 8300, and the unsaturated group equivalent was 480.
• Propylene glycol monomethyl ether acetate was further added to this resin solution to prepare a resin (A-1) solution (solid content concentration 44% by mass) of Synthesis Example 1.
• the solid content means a residual amount of heating when the resin solution is heated at 130 ° C. for 2 hours, and the resin (A-1) and the polymerization initiator are the main components.
• the acid value, unsaturated group equivalent and weight average molecular weight described in the synthetic example are values obtained by the methods described below.
• Acid value The acid value of the resin (A) measured using a mixed indicator of bromothymol blue and phenol let according to JIS K6901 5.3.2. It means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin (A).
• Unsaturated group equivalent The mass of the polymer per number of moles of the polymerizable unsaturated bond, which is a calculated value calculated based on the amount of the monomer used.
• Weight average molecular weight means the weight average molecular weight converted to standard polystyrene measured under the following conditions using gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• Developing solvent Tetrahydrofuran Detector: Differential refractometer (SHODEX (registered trademark) RI-71S) (manufactured by Showa Denko KK)
• Flow velocity 1 mL / min
• Examples of the photosensitive resin composition in which the resin (A2), the reactive diluent (B), the solvent (C2), the photopolymerization initiator (D), and the mill base of the above-mentioned preparation example are mixed are shown below.
• Example 1 As the resin (A2), the resin (A-1) (resin sample No. p1) of Synthesis Example 1 was 9.3 parts by mass in terms of solid content, and the reactive diluent (B) was dipentaerythritol hexaacrylate (DPHA, Product name: A-DPH, manufactured by Shin-Nakamura Kogyo Co., Ltd.) 37 parts by mass, propylene glycol monomethyl ether acetate 33 parts by mass as solvent (C2), etanone as photopolymerization initiator (D), 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime) (OXE 02, product name: IRGACURE OXE 02, manufactured by BASF) 3.7 parts by mass, and production example 1 mill base (mill base sample No.
• DPHA dipentaerythritol hexaacrylate
• resin (A-1) of Synthesis Example 1 (resin sample No. 1) is 10.7 parts by mass in terms of solid content
• PGMEA is 200 parts by mass
• IBS0100CF is 35.7 parts by mass
• Table 3 10.7 parts by mass of the resin (A1) contained in the mill base (in Table 3, "* 1" is added.
• "* 1" is the resin contained in the mill base.
• 9.3 parts by mass of the newly added resin (A2) (resin sample No. p1) are described as the resin (A) component in terms of solid content.
• the amount of the solvent contained in the resin (A-1) solution of Synthesis Example 1 is added up in the solvent (C) as a compounding component. Further, 200 parts by mass of the solvent (C1) contained in the mill base and 33 parts by mass of the newly added solvent (C2) are described in total as the solvent (C) component.
• Examples 2 to 17, Comparative Examples 1 to 8 The photosensitive resin compositions of Examples 2 to 17 and Comparative Examples 1 to 8 were prepared in the same manner as in Example 1 except that the formulations shown in Tables 3 to 5 were used.
• the colorant dispersibility of the photosensitive resin composition was evaluated by the method shown below. First, the photosensitive resin compositions of Examples 1 to 17 and Comparative Examples 1 to 8 were spin-coated on a 10 cm ⁇ 10 cm IZO substrate so that the thickness of the coating film was 1.5 ⁇ m. After that, the solvent was volatilized by heating at 90 ° C. for 3 minutes. Next, the entire surface of the coating film was exposed (exposure amount 50 mJ / cm 2 ) using a multi-light ML-251D / B manufactured by Ushio, Inc. and an irradiation optical unit PM25C-100, and photocured.
• the optical density (OD) of the cured coating film having a thickness of 1 ⁇ m was measured by using a transmission densitometer (361T, X-lite). The results are shown in Tables 6-8. It can be said that the higher the optical density, the better the dispersibility of the colorant.
• the elastic recovery rate means the ratio of the distance recovered after the lapse of 10 minutes recovery time to the distance compressed when a constant force is applied (compressive displacement), which is expressed by the following equation.
• Elastic recovery rate (%) [(recovery distance / compression displacement) x 100] The results are shown in 6-8.
• the developed form includes a peeled form in which the unexposed portion is washed away while being peeled off, and a dissolved form in which the unexposed portion is washed away while being melted.
• Powder dissolution refers to a form in which an unexposed portion is slightly dissolved as powder. The results are shown in 6-8.
• the photosensitive resin compositions of Examples 1 to 17 are excellent in colorant dispersibility, developability and elastic recovery rate.
• the photosensitive resin compositions of Comparative Examples 1 to 8 were inferior in evaluation of colorant dispersibility, developability and elastic recovery rate.
• the present invention provides a photosensitive resin composition having excellent colorant dispersibility, developability and elastic recovery rate. Since the photosensitive resin composition of the present invention is excellent in colorant dispersibility, developability and elastic recovery rate, the cured resin film obtained by curing the photosensitive resin composition of the present invention has colorant dispersibility and elastic recovery. Excellent rate.
• a resin cured film is suitable as a black matrix, a color filter, a black column spacer, and a BPDL, which are members of an image display element.

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