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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification

Definitions

• the present invention provides an active energy ray-curable composition which, when irradiated with an active energy ray, gives a cured product with excellent breaking strength and excellent adhesion to a substrate after alkali development, and which has excellent alkali solubility in unexposed areas. and a vinyl polymer that gives the composition.
• active energy ray-curable compositions using active energy rays such as ultraviolet rays, visible rays, electron beams, and X-rays have excellent workability such as coating and have properties such as high curing speed.
• active energy rays such as ultraviolet rays, visible rays, electron beams, and X-rays
• photoresists such as ultraviolet rays, visible rays, electron beams, and X-rays
• Acrylic polymers are widely used as the main component of active energy ray-curable compositions for such applications.
• Active energy ray-curable compositions containing acrylic polymers are described, for example, in Patent Documents 1 to 6 below.
• Patent Document 1 discloses a main chain containing (A-1) an ethylenically unsaturated group and a carboxyl group for use in a photosensitive film, a photosensitive film with a support, a printed wiring board, and a semiconductor device.
• Patent Document 2 for example, for forming a colored pattern in a color filter substrate for a liquid crystal display device, a sensor substrate for a touch panel, or the like, at least a coloring material, an acrylic copolymer and an organic solvent are contained, and the acrylic copolymer is , at least a structure having an ethylenically unsaturated group in the side chain, a structure having a tertiary amino group in the side chain and/or a structure having a quaternary ammonium salt in the side chain, and a structure having a carboxyl group in the side chain , having a structure having an aromatic ring, a base value of 5 to 70 mmol / 100 g, an acid value of 50 to 120 mg KOH / g, and a weight average molecular weight in terms of polystyrene by gel permeation chromatography of 5,000 to 30,000.
• a colorant dispersion characterized by:
• Patent Document 4 discloses, for example, (1) an alkali-soluble acrylic polymer and/or methacrylic polymer having a carboxyl group, and (2) a C ⁇ C unsaturated (3) a crosslinked elastic polymer in the form of fine particles having an average particle size of 5 ⁇ m or less;
• a resin composition for insulating material which contains a polymerization initiator capable of initiating polymerization of double bonds.
• Patent Document 5 discloses (A) component for forming an optical film used as a polarizer protective film or the like: a (meth)acrylate polymer having a functional group in a side chain capable of reacting with a carboxyl group or a hydroxyl group ( a1) [hereinafter referred to as "polymer (a1)”] and compound (a2) which is a compound having a carboxyl group or hydroxyl group and (meth)acryloyl group and has a number average molecular weight of 180 or more [hereinafter referred to as "compound (a2) A (meth)acrylate polymer having a (meth)acryloyl group in the side chain, which is a reactant with "", and / or (B) component: compound (a2) and a monomer copolymerizable therewith A (meth)acrylate polymer (b1) having a carboxyl group or a hydroxyl group in a side chain obtained by copolymerizing a compound (b2) having
• an unsaturated double bond-containing oligomer (a2 ) (hereinafter referred to as “unsaturated oligomer (a2)”)-modified (meth)acrylate polymer (A) (hereinafter referred to as “component (A)”).
• component (A) a reaction of a structural unit derived from a (meth)acrylate-based monomer (a1-1) having no reactive group, an epoxy group, a carboxyl group, a hydroxyl group, an isocyanate group, etc.
• a copolymer (a1) (hereinafter referred to as "copolymer (a1)") containing a structural unit derived from a (meth)acrylate monomer (a1-2) having a reactive group, the reactive group It is described that it can be a reaction product of an unsaturated oligomer (a2) having a group that reacts with the reactive group and an ethylenically unsaturated group.
• a light emitting element and a sealing layer are sequentially laminated on a substrate, and a contact hole is formed in the sealing layer via a wiring base layer if necessary. is provided.
• the patterning of contact holes is usually performed by photolithography including exposure using ultraviolet rays or the like and alkali development. In such photolithography, it is desired to form a cured resin pattern that has excellent adhesiveness to the base of the sealing layer or wiring underlayer, and that has excellent breaking strength and film retention properties.
• the object of the present invention is to provide a cured product (
• An object of the present invention is to provide an active energy ray-curable composition which gives a cured film) and has excellent alkali solubility in unexposed areas, and a vinyl polymer which gives the composition.
• the present inventors have found that (a1) a structural unit derived from at least one selected from styrene and ⁇ -methylstyrene, and (a2) an alkyl acrylate derived from an alkyl acrylate having 2 or more carbon atoms in the alkyl group of the ester moiety. (a3) a structural unit derived from a vinyl compound having a carboxy group, and (a4) a structural unit having a (meth)acryloyl group in a side chain as essential structural units. It has now been found that the above problems are solved using the composition.
• a vinyl polymer containing the following structural units (a1), (a2), (a3), (a4) and (a5) and having a (meth)acryloyl group in a side chain The content ratios of the structural units (a1), (a2), (a3), (a4) and (a5) are 20 to 82% by mass and 10 to 72%, respectively, when the total of these units is 100% by mass. % by mass, 5 to 67% by mass, 3 to 65% by mass, and 0 to 30% by mass.
• the vinyl polymer according to item 1 which has a number average molecular weight of 1,000 to 10,000 as determined by gel permeation chromatography. 3.
• the vinyl polymer according to item 1 or 2 wherein the structural unit (a2) contains a structural unit derived from an alkyl acrylate having an alkyl group in the ester moiety with 4 to 18 carbon atoms. 4.
• the vinyl-based polymer according to the item. 5 An active energy ray-curable composition containing the vinyl polymer according to any one of items 1 to 4 above. 6. 6.
• (meth)acrylate means acrylate and/or methacrylate.
• (meth)acryloyl means acryloyl and/or methacryloyl.
• (meth)acrylic means acrylic and/or methacrylic.
• weight average molecular weight (Mw)” and “number average molecular weight (Mn)” are standard polystyrene conversion values by gel permeation chromatography (GPC).
• the vinyl polymer of the present invention contains the structural unit (a3), it has excellent alkali solubility.
• a film (uncured film) formed using the active energy ray-curable composition containing the vinyl polymer of the present invention is irradiated with an active energy ray, it has excellent breaking strength and can be applied to the base material after alkali development. It is possible to obtain a cured film excellent in adhesion and film retention.
• the unexposed portion of the film (uncured film) contains the vinyl polymer as it is, it is efficiently removed by alkali development. Therefore, it is possible to suitably perform pattern formation using active energy rays.
• the active energy ray-curable composition of the present invention can be used in interlayer insulating films, planarizing films, surface protective films, spacers, and colored layers of color filters in liquid crystal, organic EL, and other display devices.
• Color resist used pixel forming materials such as black matrix, materials for forming a patterned cured resin layer having contact holes arranged around the electrodes of the touch panel; materials for insulating between wirings of flexible printed circuit boards in semiconductors, It is suitable as a pattern forming material such as an interlayer insulating film forming material, a planarizing film, a photoresist, a solder resist, an etching resist, and the like.
• the present invention includes the following structural units (a1), (a2), (a3), (a4) and (a5) in a specific ratio, and by including the structural unit (a4), (meta) A vinyl polymer having an acryloyl group and an active energy ray-curable composition containing the vinyl polymer.
• the structural unit (a1) is a structural unit derived from at least one selected from styrene and ⁇ -methylstyrene.
• the structural unit (a1) contained in the vinyl polymer of the present invention can be of one type or two types.
• the content ratio of the structural unit (a1) is the structural unit contained in the vinyl polymer of the present invention, since water resistance and alkali resistance of the cured product can be obtained when the active energy ray-curable composition is cured.
• the total content of (a1), (a2), (a3), (a4) and (a5) is 100% by mass, it is 20 to 82% by mass, preferably 25 to 75% by mass, and further It is preferably 35 to 70% by mass.
• the structural unit (a2) is a structural unit derived from an alkyl acrylate in which the alkyl group in the ester moiety has 2 or more carbon atoms.
• the structural unit (a2) contained in the vinyl-based polymer of the present invention can be of one kind or two or more kinds.
• alkyl acrylates in which the number of carbon atoms in the alkyl group of the ester moiety is 2 or more include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, decyl acrylate, undecyl acrylate, lauryl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate
• structural unit (a2) contains a structural unit derived from an alkyl acrylate having an alkyl group in the ester moiety with 4 to 18 carbon atoms (hereinafter referred to as “structural unit (a2-1)”)
• structural unit (a2-1) a structural unit derived from an alkyl acrylate having an alkyl group in the ester moiety with 4 to 18 carbon atoms
• the lower limit of the content of the structural unit (a2-1) is preferably 25% by mass, more preferably 55% by mass, based on the total amount of the structural unit (a2).
• the content ratio of the structural unit (a2) is such that the active energy ray-curable composition has excellent adhesion to substrates, wiring, etc., and furthermore, when the composition is cured, the cured product has breaking strength (especially, flexibility)
• the total content of the structural units (a1), (a2), (a3), (a4) and (a5) contained in the vinyl polymer of the present invention is 100% by mass, In addition, it is 10 to 72% by mass, preferably 12 to 60% by mass, more preferably 15 to 40% by mass.
• the structural unit (a3) is a structural unit derived from a vinyl compound having a carboxy group.
• the structural unit (a3) contained in the vinyl-based polymer of the present invention may be of one kind or two or more kinds.
• Vinyl compounds having a carboxyl group include (meth)acrylic acid, ethacrylic acid, crotonic acid, cinnamic acid, maleic acid monoester, fumaric acid monoester, itaconic acid monoester, maleic acid, fumaric acid, itaconic acid, (meth) ) acrylic acid, monohydroxyethyl phthalate acrylate, ⁇ -carboxy-polycaprolactone monoacrylate, (meth) acryloyloxyethyl succinate, (meth) acryloyloxyethyl hexahydrophthalate, (meth) acryloyloxyethyl phthalate, (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, ⁇ -carboxyethyl acrylate, phthalic anhydride adduct of pentaerythritol triacrylate, succinic anhydride adduct of pentaeryth
• the content of the structural unit (a3) gives a vinyl polymer with excellent alkali solubility, and when the active energy ray-curable composition containing this vinyl polymer is cured, the cured product has water resistance.
• the structural units (a1), (a2), (a3), (a4) and (a5) contained in the vinyl polymer of the present invention, since they provide alkali resistance and facilitate pattern formation by photolithography. is 5 to 67% by mass, preferably 6 to 40% by mass, more preferably 6 to 25% by mass, when the total content of 100% by mass.
• the structural unit (a4) is at least one structural unit selected from structural units represented by the general formula (1) and structural units represented by the general formula (2).
• the structural unit (a4) contained in the vinyl-based polymer of the present invention may be of one type or two or more types.
• R 1 is a hydrogen atom or a methyl group
• R 2 is a hydrogen atom or a methyl group
• R 3 is a hydrogen atom or a methyl group
• R 4 is a hydrocarbon group having 2 to 4 carbon atoms
• R 5 is a hydrogen atom or a methyl group. be.
• R 4 is preferably an ethylene group.
• the content ratio of the structural unit (a4) is included in the vinyl polymer of the present invention because the active energy ray-curable composition has excellent adhesion to substrates, wiring, etc., and excellent curability with active energy rays.
• the total content of the structural units (a1), (a2), (a3), (a4) and (a5) is 100% by mass, it is 3 to 65% by mass, preferably 5 to 50% by mass %, more preferably 10 to 45% by mass.
• the vinyl-based polymer of the present invention comprises the structural units (a1), (a2), (a3) and (a4), or the structural units (a1), (a2), (a3) and (a4). ) and (a5).
• the structural unit (a5) is a structural unit other than the structural units (a1), (a2), (a3) and (a4), and is not particularly limited, but is preferably a structural unit derived from a vinyl compound.
• monomers forming the structural unit (a5) include alkyl methacrylate and methyl acrylate having an ester moiety containing an aliphatic hydrocarbon group, and (meth)acryl having an ester moiety containing an alicyclic hydrocarbon group.
• Alkyl acids (meth)acrylic acid aromatic esters having ester moieties containing aromatic hydrocarbon groups, hydroxyl group-containing vinyl compounds, amino group-containing vinyl compounds, vinyl cyanide compounds (acrylonitrile, methacrylonitrile, etc.), unsaturated Acid anhydrides, maleimide compounds, alkyl (meth)acrylates having ester moieties containing alkoxyalkyl groups, halogen-containing vinyl compounds (vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, etc.), vinylsilane compounds (trimethoxy vinylsilane, triethoxyvinylsilane, methyldimethoxyvinylsilane, methyldiethoxyvinylsilane, dimethylmethoxysilane, etc.), vinyl ester compounds (vinyl acetate, vinyl propionate, etc.), vinyl ether compounds (methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexy
• the upper limit of the content of the structural unit (a5) is the structural units (a1), (a2), (a3), (a4) and
• the total content of (a5) is 100% by mass, it is preferably 30% by mass, more preferably 15% by mass.
• the number of (meth)acryloyl groups per molecule of the vinyl polymer of the present invention is such that when the active energy ray-curable composition is cured, the flexibility of the cured product, the adhesion to the substrate, the tensile physical properties and the residual properties. It is preferably from 1 to 20, more preferably from 2 to 10, since film properties can be obtained.
• the average number of (meth)acryloyl groups per molecule of the vinyl polymer of the present invention is preferably 1.0-20, more preferably 2.0-10. If the average number of the (meth)acryloyl groups is too small, the curability will be poor and the residual film property during alkali development will be poor, making it impossible to obtain a desired pattern.
• the number average molecular weight (Mn) of the vinyl polymer of the present invention is preferably 1,000 to 10,000, more preferably 2,000 to 8,500, because pattern formation by photolithography is easy. , particularly preferably 2,500 to 6,000.
• Mn number average molecular weight
• the number average molecular weight of the vinyl polymer is 1,000 or more, outgassing due to uncured components in the cured product after exposure can be reduced, and undercuts are less likely to occur in the formed pattern shape.
• the number average molecular weight exceeds 10,000, the compatibility with polyfunctional (meth)acrylates and photopolymerization initiators tends to decrease.
• the weight average molecular weight (Mw) of the vinyl polymer of the present invention is not particularly limited, but is preferably 3,000 to 100,000, more preferably 4,000 to 20,000.
• Mw weight average molecular weight
• the weight-average molecular weight of the vinyl-based polymer is 4,000 or more, the linearity of the formed pattern is improved.
• the weight-average molecular weight of the vinyl-based polymer exceeds 20,000, development residues tend to occur during alkali development.
• the (meth)acryloyl equivalent of the vinyl polymer of the present invention provides flexibility, adhesion to substrates, tensile physical properties and film retention properties of the cured product when the active energy ray-curable composition is cured. Therefore, it is preferably 300 to 4,000 g/eq, more preferably 600 to 2,000 g/eq.
• the glass transition point of the vinyl-based polymer of the present invention is preferably 0° C. because the flexibility of the cured product and the adhesion to the substrate can be obtained when the active energy ray-curable composition is cured. ⁇ 100°C, more preferably 0°C to 70°C, still more preferably 20°C to 60°C.
• the acid value of the vinyl polymer of the present invention is preferably 25-300 mgKOH/g, more preferably 40-150 mgKOH/g, in order to facilitate pattern formation by photolithography.
• the acid value is preferably 25-300 mgKOH/g, more preferably 40-150 mgKOH/g, in order to facilitate pattern formation by photolithography.
• the method for producing the vinyl-based polymer of the present invention is not particularly limited, and a method such as suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization of a monomer that provides a predetermined structural unit can be applied. can.
• a method such as suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization of a monomer that provides a predetermined structural unit can be applied.
• bulk polymerization and solution polymerization are preferred because they are easy to produce and do not contain impurities such as emulsifiers in the polymer solution.
• a vinyl polymer (hereinafter referred to as "vinyl polymer (P1)") containing a structural unit represented by the general formula (1) (hereinafter referred to as “structural unit (a4-1)”)
• structural unit (a4-1) a monomer that gives the structural unit (a1) (styrene or ⁇ -methylstyrene), a monomer that gives the structural unit (a2) (alkyl acrylate), and a unit that gives the structural unit (a3)
• a monomer mixture containing a monomer (vinyl compound having a carboxyl group) and, if necessary, a monomer giving the structural unit (a5) is polymerized to obtain a copolymer (hereinafter referred to as "precursor polymer X” ), and then react this precursor polymer X with a (meth)acrylate containing an epoxy group (hereinafter referred to as “epoxy group-containing (meth)acrylate”), that is, a part of the structure in the precursor
• the vinyl polymer (P1) is prepared by applying the bulk polymerization method described in, for example, JP-A-57-502171, JP-A-59-6207, JP-A-60-215007, etc. It can be produced by producing a polymer X and then reacting this precursor polymer X with an epoxy group-containing (meth)acrylate in the presence of a catalyst.
• bulk polymerization for the precursor polymer X is performed by filling a pressurizable reactor with a solvent, setting it to a predetermined temperature under pressure, and then adding each monomer, or, if necessary, a polymerization solvent or A monomer mixture consisting of a polymerization initiator is supplied to a reactor at a constant supply rate, and an amount of polymer solution corresponding to the supply amount of the monomer mixture is withdrawn.
• Precursor polymer X is preferably 20 to 82 % by weight, 10 to 72% by weight, 8 to 70% by weight and 0 to 30% by weight, more preferably 25 to 75% by weight, 12 to 60% by weight, 13 to 63% by weight and 0 to 15% by weight It is a copolymer containing
• the reaction of the precursor polymer X and the epoxy group-containing (meth)acrylate can be carried out in the presence of a catalyst in an organic solvent such as ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, etc. If the acrylate is liquid, the reaction can be carried out without solvent.
• the reaction temperature is usually selected from the range of 60°C to 120°C.
• Epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate and the like.
• the ratio of the amounts of the precursor polymer X and the epoxy group-containing (meth)acrylate to be used is preferably 0.1 to 1 mol of the epoxy group-containing (meth)acrylate per 1 mol of the carboxy group of the precursor polymer X. It is set to 0.9 mol, more preferably 0.4 to 0.75 mol.
• Catalysts include tetrabutylammonium bromide, tetrabutylammonium chloride, tetramethylammonium bromide, tetramethylammonium chloride, triphenylphosphine, tributylphosphine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1, 4-diazabicyclo[2,2,2]octane and the like.
• the amount of the catalyst used is usually about 0.5 to 5% by mass with respect to the total amount thereof.
• a vinyl polymer (hereinafter referred to as "vinyl polymer (P2)") containing a structural unit represented by the general formula (2) (hereinafter referred to as “structural unit (a4-2)")
• structural unit (a4-2) a structural unit represented by the general formula (2)
• a monomer that gives the structural unit (a1) styrene or ⁇ -methylstyrene
• structural unit (a2) alkyl acrylate
• a unit that gives the structural unit (a3) Polymerizing a monomer mixture containing a monomer (a vinyl compound having a carboxyl group), a hydroxy group-containing vinyl compound, and optionally a monomer giving the structural unit (a5) to obtain a copolymer (hereinafter referred to as (referred to as "precursor polymer Y”), and then reacting this precursor polymer Y with a (meth)acrylate containing an isocyanate group (hereinafter referred to as "isocyanate group-containing (meth
• the vinyl polymer (P2) is obtained by producing a precursor polymer Y in the same manner as the precursor polymer X, and optionally in the presence of a catalyst for forming a urethane bond, by combining the precursor polymer Y with an isocyanate group. It can be produced by reacting the contained (meth)acrylate.
• the reaction temperature is usually selected from the range of 60°C to 100°C.
• Examples of the hydroxy group-containing vinyl compound used for forming the precursor polymer Y include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, polyethylene glycol-polypropylene glycol mono(meth)acrylate, poly(ethylene) glycol-tetramethylene glycol) mono(meth)acrylate, polyethylene glycol-polytetramethylene glycol mono(meth)acrylate and the like.
• the total of the structural unit (a1), the structural unit (a2), the structural unit (a3), the structural unit derived from the hydroxy group-containing vinyl compound, and the structural unit (a5) is 100% by mass.
• reaction between the precursor polymer Y and the isocyanate group-containing (meth)acrylate can be carried out in an organic solvent such as hydrocarbon, ketone, ester, ether, etc. in the presence of a catalyst.
• isocyanate group-containing (meth)acrylates examples include 2-(meth)acryloyloxyethyl isocyanate, (meth)acryloylisocyanate, 1,1-bis(acryloyloxymethyl)ethylisocyanate, and the like.
• the ratio of the amount of the precursor polymer Y and the isocyanate group-containing (meth)acrylate used is preferably 0.9 to 0.9 to 1 mol of the isocyanate group of the isocyanate group-containing (meth)acrylate. It is set to be 1.1 mol.
• Catalysts for forming urethane bonds include organic tin compounds such as dibutyltin dichloride; Fatty acid salts of tin compounds; organic tin compounds such as dimethyltin bis(isooctylthioglycolic acid ester) salts, dimethyltin bis(isooctylthioglycolic acid ester) salts, dioctyltin bis(isooctylthioglycolic acid ester) salts Thioglycolic acid ester salts; tin carboxylates such as tin octoate and tin decanoate; bismuth carboxylates; titanium complexes; From the viewpoint of the reactivity of the precursor polymer Y and the isocyanate group-containing (meth)acrylate, the amount of the catalyst used is usually about 0.01 to 0.1% by mass with respect to the total amount thereof.
• the vinyl polymer of the present invention can be cured with active energy rays such as ultraviolet rays, visible rays, electron beams and X-rays.
• active energy rays such as ultraviolet rays, visible rays, electron beams and X-rays.
• the vinyl polymer of the present invention is an active energy ray-curable composition containing it together with a photopolymerization initiator used according to the type of active energy ray, other polyfunctional polymer, etc.
• the alkali dissolution rate when a film (uncured film) made of the vinyl polymer of the present invention is brought into contact with a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23° C. is preferably 40 nm/sec or more, and more Preferably, it can be 60 nm/sec or more.
• the alkali dissolution rate By setting the alkali dissolution rate to 40 nm/sec or more, it can be used as an active energy ray-curable composition without any problem, and a desired pattern can be obtained after alkali development.
• the active energy ray-curable composition of the present invention is a composition containing the vinyl polymer of the present invention (hereinafter referred to as "vinyl polymer (A)").
• vinyl polymer (A) the vinyl polymer of the present invention
• photopolymerization initiators, other polyfunctional polymers, surfactants, polymerization inhibitors, light resistance improvers, fine particles, and liquid media from the viewpoint of coatability on substrates, wiring, etc. be able to.
• the photopolymerization initiator is not particularly limited as long as it is excited by energy such as ultraviolet rays, visible rays, and near-infrared rays to generate radicals and at least promote radical polymerization of the vinyl polymer of the present invention.
• Photopolymerization initiators include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one.
• Benzophenone compounds bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, Acylphosphine oxide compounds such as bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4 -thioxanthone compounds such as propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthon-2-yl]oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothioxanthone ; acridone
• the content of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 1 to 6 parts by mass, when the content of the vinyl polymer (A) is 100 parts by mass.
• polyfunctional polymer examples include polyfunctional (meth)acrylates, aromatic polyvinyl compounds, diallyl compounds, allyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. Among these, polyfunctional (meth)acrylates are preferred.
• Polyfunctional (meth)acrylates include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tri- or tetra-(meth)acrylate of pentaerythritol, tri- or tetra-(meth)acrylate of ditrimethylolpropane, and diglycerin.
• Polyol poly (meth) acrylates such as tri or tetra (meth) acrylate of dipentaerythritol, tri, tetra, penta or hexa (meth) acrylate of dipentaerythritol; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polybutylene glycol di(meth)acrylate
• Poly(meth)acrylates of polyol alkylene oxide adducts di(meth)acrylates having a bisphenol skeleton such as ethylene oxide-modified di(meth)acrylates of bisphenol A and di(meth)acrylates of bisphenol A; tricyclodecanedimethylol di Di (meth) acrylate having an alicyclic skeleton such as (meth) acrylate; Ethylene oxide-modified diacrylate of isocyanuric acid, ⁇ -caprolactone modified tris ((meth) acryloxyethyl) isocyanurate skeleton such as isocyanurate ( meth) acrylate; urethane (meth) acrylate having a polyester skeleton; urethane (meth) acrylate having a polycarbonate skeleton; epoxy (meth) acrylate; polyether (meth) acrylate; Acrylates; polybasic acid-modified tetra-, penta- or he
• the content ratio thereof is preferably 10 to 200 when the content of the vinyl polymer (A) is 100 parts by mass. parts by mass, more preferably 50 to 150 parts by mass.
• surfactant various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used to improve the coating properties. Fluorosurfactants are preferred for the reason that they can be improved.
• fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, R41, R40LM, F437, F475, F479, F482, F554, F-557, F568, F780 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M), Surflon S-382, S-386, S-242, S-243, S-420 , S-431, S-611, S-47, S-651, S-656 (manufactured by AGC Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002, PF-151N (manufactured by OMNOVA) , Unidyne DSN-403N, DS-101, DS-202, DS-401, DS-403, DSN-403N, NS-1602, NS-1602
• the active energy ray-curable composition of the present invention contains a surfactant
• its content is preferably 0.001 to 0.2% by mass, preferably 0.0015 to 0.0015% by mass, based on the total solid content of the composition. 0.1% by mass is more preferable, and 0.002 to 0.05% by mass is even more preferable.
• the content of the surfactant is within the above range, the application properties of the active energy ray-curable composition are good, and the occurrence of coating unevenness and striations can be more effectively suppressed.
• polymerization inhibitor examples include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-t-butylphenol). , 2,2′-methylenebis(4-methyl-6-t-butylphenol), phenothiazine, 2-mercaptobenzimidazole and the like.
• UV absorbers include 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2 '-Hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole compounds such as benzotriazole; 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso- Triazine compounds such as octyloxyphenyl)-s-triazine; 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'- dihydroxy-4-methoxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,
• fine particles fine particles having a particle diameter of about 1 to 100 ⁇ m made of metal, inorganic compound, rubber or resin can be used.
• inorganic compounds include oxides of silicon, aluminum, zirconium, titanium, zinc, lead, germanium, indium, tin, antimony, cerium, lithium and the like, composite oxides thereof, calcium carbonate, bentonite and the like.
• the rubber or resin may consist of a crosslinked polymer.
• the above liquid medium is usually an organic solvent, for example, hydrocarbons such as n-hexane, benzene, toluene, xylene, ethylbenzene, cyclohexane; butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol , 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl Alcoholic solvents such as ether; tetrahydrofuran, dioxane, ethylene glycol dimethyl ether,
• organic solvents can be used alone or in combination of two or more.
• the active energy ray-curable composition of the present invention contains a liquid medium, its content is appropriately selected depending on the application and is not particularly limited.
• 100 parts by mass of the vinyl polymer (A), or the vinyl polymer (A) and the polyfunctional polymer When the total amount is 100 parts by mass, it is preferably 20 to 400 parts by mass, more preferably 40 to 200 parts by mass.
• the active energy ray-curable composition of the present invention can be produced by mixing the raw material components such as the vinyl polymer (A) using various mixers and dispersers.
• the active energy ray-curable composition of the present invention is particularly suitable for producing electronic components having a patterned cured resin layer on a substrate, wiring, or the like.
• Substrates for electronic parts include plate substrates made of soda glass, alkali-free glass, Pyrex (registered trademark) glass, quartz glass, etc. used in liquid crystal display elements, etc., and (transparent) conductive films on the surfaces of these substrates. , photoelectric conversion element substrates (silicon substrates, etc.) used in solid-state imaging devices and the like, color filter substrates, and the like.
• a step of forming a film (uncured film) on the surface of a substrate using an active energy ray-curable composition (hereinafter referred to as “film formation step"), a step of irradiating an active energy ray through a mask or scanning exposure without using a mask (hereinafter referred to as "exposure step”), using an alkaline aqueous solution (hereinafter also referred to as "developer”), A method of sequentially providing a step of developing the exposed film (hereinafter referred to as a “development step”) can be applied.
• an active energy ray-curable composition containing no photopolymerization initiator can be used in the film formation step.
• the active-energy-ray-curable composition containing a photoinitiator is used in a film formation process.
• a conventionally known coating method using a bar coater, applicator, doctor blade, knife coater, comma coater, reverse roll coater, die coater, lip coater, gravure coater, micro gravure coater, etc.
• drying under reduced pressure or heating is performed to remove the organic solvent in the composition to form a film (uncured film).
• the film thickness is appropriately selected depending on the application.
• the cured resin is a crosslinked resin formed based on a (meth)acryloyl group in the side chain of the structural unit (a4) of the vinyl polymer (A) contained in the active energy ray-curable composition.
• the active energy rays used in the exposure step are ultraviolet rays, visible rays, electron beams, or X-rays.
• Ultraviolet rays can be applied using an irradiation device having a light source such as a high-pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, a light emitting diode (LED), an ultraviolet laser, or the like.
• the electron beam can be applied using an electron curtain type, broad beam linear filament type, or scanning electron beam accelerator.
• the active energy ray ultraviolet rays are preferable because a cured resin can be formed in a short time and with low energy irradiation.
• the dose, irradiation amount, irradiation intensity, etc. of the ultraviolet rays are appropriately selected according to the application.
• a developer alkaline aqueous solution
• the unexposed areas are dissolved and removed, leaving the exposed areas (cured resin insoluble in the alkaline aqueous solution).
• the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, monoethanolamine, diethanolamine, and triethanolamine.
• aqueous solution of .0]-5-nonene or the like can be used.
• This developer may contain, for example, a water-soluble organic solvent such as methanol or ethanol, an antifoaming agent, a surfactant, and the like.
• the development conditions are not particularly limited. In the development process, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid puddle) development method, or the like can be applied.
• the film is usually washed with water, dried, etc., and can be heat-treated if necessary.
• the activation energy when a 2.38% tetramethylammonium hydroxide aqueous solution (23 ° C.) was sprayed at 0.15 MPa on the cured film formed by irradiating the radiation under the conditions described later in [Example], the film thickness
• the retention can be preferably 86% or higher, more preferably 91% or higher, and even more preferably 94% or higher.
• Solid content A predetermined amount of the polymer solution was placed in a ventilation dryer, dried at 150°C for 1 hour, and the solid content was determined from the weight loss.
• Example 1-1 While maintaining the temperature of a pressurized stirred tank reactor equipped with an oil jacket at 221 ° C. and keeping the internal pressure of the reactor constant as a pressurized state, 53 parts of styrene (hereinafter referred to as “St”) and acrylic acid 22 parts of n-butyl (hereinafter referred to as “BA”), 25 parts of acrylic acid (hereinafter referred to as “AA”), 20 parts of methyl ethyl ketone (hereinafter referred to as "MEK”) as an organic solvent, and a polymerization initiator
• a monomer mixture consisting of 0.1 parts of di-tert-butyl peroxide "Perhexyl D” (trade name, hereinafter referred to as "DTBP”) manufactured by NOF Corporation, at a constant supply rate (48 g / min) Continuous supply was started from the raw material tank to the reactor, and the polymerization reaction proceeded with a residence time of 12 minutes (see Table 1).
• the reaction liquid corresponding to the supplied amount of the monomer mixture was continuously withdrawn from the outlet of the reactor and recovered.
• the reaction temperature was once lowered, but a temperature rise was observed due to the heat of polymerization. Therefore, by controlling the temperature of the oil jacket, the reaction temperature was kept at 226° C. to 228° C. (described as 227° C. in Table 1).
• the point at which the temperature of the liquid in the reactor stabilized after the start of supply of the monomer mixture was set as the starting point for collecting the reaction liquid, and the reaction was continued for 37 minutes.
• the supplied amount of the monomer mixture was 1.78 kg
• the recovered amount of the reaction liquid was 1.78 kg.
• copolymer p- 1 a (meth)acrylate polymer having a carboxyl group obtained 1.36 kg. Then, the weight average molecular weight (Mw) and glass transition temperature (Tg) of the obtained copolymer p-1 were measured (see Table 1).
• TPP triphenylphosphine
• Mn number average molecular weight
• Mw weight average molecular weight
• the polymer solution was added with 4-hydroxy-2,2,6,6 in an amount corresponding to 1000 ppm with respect to the vinyl polymer A-1.
• -Tetramethylpiperidine-1-oxyl was added and dissolved, and then the organic solvent was removed at 80°C under reduced pressure to use the product obtained.
• Examples 1-2 to 1-13 and Comparative Examples 1-1 to 1-4 The same operations as in Example 1-1 were performed except that the types and amounts of raw materials used for production were as shown in Tables 1, 2, 3 and 4 to obtain precursor polymers p-2 to p -10 and pp-1 to pp-4 and vinyl polymers A-2 to A-13 and AA-1 to AA-4 were obtained (see Tables 1 to 4).
• AMS in Table 1 is ⁇ -methylstyrene
• AN in Table 2 is acrylonitrile
• HA in Table 3
• TDA is tetradecyl acrylate.
• MAA is methacrylic acid and "MMA” in Table 4 is methyl methacrylate.
• Examples 1-14 While maintaining the temperature of a pressurized stirred tank reactor equipped with an oil jacket at 221° C. and keeping the internal pressure of the reactor constant as a pressurized state, 53 parts of St, 22 parts of BA, 25 parts of AA, A monomer mixture consisting of 13 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as "HEMA"), 20 parts of MEK, and 0.1 part of DTBP was added to the raw material tank at a constant supply rate (48 g / min). Continuous supply to the reactor was started from this point, and the polymerization reaction proceeded with a residence time of 12 minutes (see Table 3). Then, the reaction liquid corresponding to the supplied amount of the monomer mixture was continuously withdrawn from the outlet of the reactor and recovered.
• HEMA 2-hydroxyethyl methacrylate
• the reaction temperature was once lowered, but a temperature rise was observed due to the heat of polymerization. Therefore, by controlling the temperature of the oil jacket, the reaction temperature was kept at 226° C. to 228° C. (227° C. shown in Table 3). The point at which the temperature of the liquid in the reactor stabilized after the start of supply of the monomer mixture was set as the starting point for collecting the reaction liquid, and the reaction was continued for 37 minutes. As a result, the supplied amount of the monomer mixture was 1.78 kg, and the recovered amount of the reaction liquid was 1.78 kg.
• the reaction liquid is introduced into a thin film evaporator to separate volatile components such as unreacted monomers, and a (meth)acrylate polymer having a hydroxyl group and a carboxy group (hereinafter referred to as "copolymerization"), which is a precursor polymer.
• a (meth)acrylate polymer having a hydroxyl group and a carboxy group hereinafter referred to as "copolymerization”
• Mw weight average molecular weight
• Tg glass transition temperature
• a polymer solution containing coalescence A-14 was obtained. Then, in the same manner as in Example 1-1, the solid content, number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained vinyl polymer A-14, acid value, methacryloyl equivalent, per molecule The average value of methacryloyl groups and the glass transition temperature (Tg) were measured (see Table 3).
• Examples 1-15 Instead of 2-methacryloyloxyethyl isocyanate used in Example 1-14, 14.1 parts of 2-acryloyloxyethyl isocyanate "Karenzu AOI" (trade name) manufactured by Showa Denko Materials Co., Ltd. was used, and a catalyst was used. A polymer solution containing a vinyl polymer A-15 containing a structural unit having an acryloyl group in a side chain was obtained in the same manner as in Example 1-14, except that the amount was changed to 0.011 parts. rice field.
• Example 2-1 75.6 parts of the solution of the vinyl polymer A-1 obtained in Example 1-1 (75.6 parts of the polymer solution containing 50 parts of the vinyl polymer and 25.6 parts of butyl acetate);
• An active energy ray-curable composition was prepared by mixing 50 parts of a functional acrylate, 5 parts of a photoinitiator, and 30 parts of butyl acetate (see Table 5). After that, a cured product was produced using this active energy ray-curable composition, and tensile physical properties, substrate adhesion, film retention properties, and alkali solubility (uncured film) were evaluated. These results are also shown in Table 5.
• Tensile physical properties As a base film, a PET film “Lumirror T-60” manufactured by Toray Industries, Inc. (trade name, film thickness: 100 ⁇ m) was prepared, and a bar coater #0 was used to coat the surface of the film after drying. The active energy ray-curable composition was applied to a thickness of 30-40 ⁇ m. Then, the coating film was dried (90° C., 10 minutes) using a ventilation dryer to obtain a laminated film having a film (uncured film).
• a PET film “Lumirror T-60” manufactured by Toray Industries, Inc. (trade name, film thickness: 100 ⁇ m) was prepared, and a bar coater #0 was used to coat the surface of the film after drying. The active energy ray-curable composition was applied to a thickness of 30-40 ⁇ m. Then, the coating film was dried (90° C., 10 minutes) using a ventilation dryer to obtain a laminated film having a film (uncured film).
• the UVA illuminance was adjusted to 500 mW/cm 2 and the irradiation amount per time was adjusted to 800 mJ/cm 2 in an air atmosphere with a condensing type.
• the laminated film was passed twice on a conveyor, and the film was irradiated with ultraviolet rays to form a cured film.
• the film having the cured film was cut into strips having a width of 1 cm, and the cured film was peeled off from the base film.
• a tensile tester "Autograph AGS-J" (trade name) manufactured by Shimadzu Corporation, the elongation at break and the strength at break at a tensile speed of 5 mm/min were measured.
• the laminate was passed twice on a conveyer to irradiate the film with ultraviolet rays to form a cured film.
• the copper plate with the cured film was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution (23° C.) for 5 minutes, then washed with running ultrapure water for 1 minute, and then blown with nitrogen. Dried.
• the cured film after alkali treatment was subjected to a cross-cut peeling test according to JIS K 5600-5-6 to evaluate adhesion to the substrate. 100/100 was given when all of the 100 grids were in close contact with each other.
• Vinyl polymer (A) and (AA) are applied to the surface of a copper plate "C1020" (trade name) manufactured by Engineering Test Service Co., Ltd. using a spin coater so that the film thickness after drying is 4.0 ⁇ m. A butyl acetate solution or a precursor active energy ray-curable composition was applied. Then, the coating film was dried (90° C., 10 minutes) using an air drier to obtain a laminate having a film (uncured film).
• Examples 2-2 to 2-15 and Comparative Examples 2-1 to 2-4 Preparation of an active energy ray-curable composition, preparation of a cured product, and evaluation were carried out in the same manner as in Example 2-1, except that the vinyl polymer used was as shown in Tables 5 and 6. (See Tables 5 and 6).
• Examples 2-1 to 2-15 exhibited excellent breaking strength in terms of tensile properties, whereas Comparative Example 2-2 exhibited insufficient flexibility, and sample cracking occurred in the tensile test. measurement was not possible due to Examples 2-1 to 2-15 exhibited excellent adhesion to the substrate, whereas Comparative Example 2-2 exhibited insufficient adhesion.
• the film remaining properties after alkali development were excellent, while in Comparative Examples 2-1 and 2-4, the results were inferior.
• Examples 2-1 to 2-5 development was possible within the predetermined time of 1 minute, whereas in Comparative Example 2-3 development was not possible within the predetermined time. , the alkali solubility was insufficient.
• the vinyl-based polymer of the present invention is used for interlayer insulating films, planarizing films, surface protective films, spacers, colored layers of color filters, color resists used in colored layers of color filters, and pixel formation such as black matrices in display devices such as liquid crystal and organic EL.
• Materials materials for forming a patterned cured resin layer having contact holes arranged around electrodes of a touch panel; materials for insulating between wirings of flexible printed circuit boards in semiconductors, materials for forming interlayer insulating films, planarizing films, photo It is suitable as a raw material component of an active energy ray-curable composition useful as a pattern-forming material such as a resist, solder resist, etching resist, and the like.
• the active energy ray-curable composition of the present invention can also be used as a coating agent or the like.

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