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
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

• the present invention relates to a curable composition and a cured film.
• Patent Document 1 aims to provide a curable composition having a high refractive index, for example, 45% by mass of zirconia nanoparticles and 25% by mass of tricyclodecanedimethanol dimethacrylate as a ring structure polyfunctional compound.
• a curable composition containing 14% by mass of 1,9-nonandiol dimethacrylate as a non-ring structure polyfunctional compound and 10% by mass of isobutylmethacrylate as a monofunctional compound together with a polymerization initiator and a surfactant. ing.
• the curable composition may not be sufficiently cured.
• An object of the present invention is to provide a curable composition having excellent curability.
• the polymerizable compound (B) contains the compound (B1).
• the compound (B1) has a (meth) acryloyl group (K1) to which an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms may be bonded, and an aryl group having 6 to 20 carbon atoms. It has at least two groups in the same molecule that are independently selected from the group consisting of unsaturated hydrocarbon groups (K2) having 2 to 20 carbon atoms that may be bonded, but of the at least two groups.
• the average value of the transmittance of the film formed from the curable composition under predetermined conditions at a wavelength of 400 to 700 nm is 90% or more per 1.0 ⁇ m film thickness.
• the curable composition is applied onto a glass substrate so that the average thickness of the cured film falls within the range of 1.0 ⁇ 0.2 ⁇ m, and ultraviolet rays having a wavelength of 385 nm are used using an LED lamp.
• a curable composition comprising irradiating with an integrated light intensity of 2000 J / m 2 .
• the curability of the curable composition can be improved.
• One aspect of the present invention is a curable composition containing inorganic fine particles (A), a polymerizable compound (B), and a polymerization initiator (C), and specific monomers are used as the polymerizable compound (B). It is characterized by its content.
• Such a curable composition is excellent in curability, and the film (specifically, the cured film) obtained from the curable composition is excellent in visible light transmittance.
• the inorganic fine particles (A) are preferably particles having no wavelength conversion ability to the visible light region, and preferably particles having a refractive index of 1.6 or more.
• the refractive index is preferably 1.8 or more, more preferably 2.0 or more.
• the refractive index may be, for example, 3.5 or less, or 3.0 or less.
• the refractive index is the value of sodium on the D line.
• the inorganic fine particles (A) contain oxides, nitrides, and the like, and specifically, TIO 2 (titanium oxide; refractive index 2.3 to 2.7) and Nb 2 O 5 (niobium oxide; refractive index 2).
• Ta 2 O 5 tantal oxide; refractive index 2.3), BN (boron nitride; refractive index 2.2), ZrO 2 (zinc oxide; refractive index 2.1), SnO 2 (tin oxide; tin oxide; Refractive index 2.0), ITO (tin -doped indium oxide; refractive index 2.0), Si 3N 4 ( silicon nitride; refractive index 2.0), CeO 2 (cerium oxide; refractive index 1.9 to 2.0) ), ZnO (zinc oxide; refractive index 1.9), Y2 O 3 ( ittrium oxide; refractive index 1.9), ATO (antimond-doped tin oxide; refractive index 1.7-1.9), SbO 5 ( Antimon oxide; refractive index 1.8), Al 2 O 3 (aluminum oxide; refractive index 1.8), TiN (titanium nitride; refractive index 1.6), and the like can be mentioned.
• the inorganic fine particles (A) are preferably oxides of elements 3 to 5 and 12 to 15 of the periodic table or nitrides of elements of group 4 of the periodic table, and more preferably titanium oxide, zirconium oxide, aluminum oxide and oxidation. It is niobium or silicon nitride, more preferably titanium oxide or zirconium oxide. These inorganic fine particles (A) may be used alone or in combination of two or more.
• the volume average particle diameter of the inorganic fine particles (A) is, for example, 100 nm or less, preferably 50 nm or less, and more preferably 30 nm or less.
• the lower limit of the volume average particle diameter of the inorganic fine particles (A) is not particularly limited, but is, for example, 0.1 nm or more, preferably 0.5 nm or more, and more preferably 1.0 nm or more.
• the content of the inorganic fine particles (A) is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more in the curable composition.
• the content of the inorganic fine particles (A) is, for example, 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less.
• the inorganic fine particles (A) may be surface-treated with a coupling agent.
• a coupling agent include a silane-based coupling agent, a zirconium-based coupling agent, a titanium-based coupling agent, a phosphorus-based coupling agent, and the like, and one of these may be used alone or two or more of them may be used. It may be combined.
• silane coupling agent examples include ⁇ - (meth) acryloyloxypropyldimethylmethoxysilane, ⁇ - (meth) acryloyloxypropylmethyldimethoxysilane, ⁇ - (meth) acryloyloxypropyltrimethoxysilane, diphenyldimethoxysilane, and diphenyldi.
• Examples thereof include ethoxysilane, phenyldimethylmethoxysilane, phenylmethyldimethoxysilane, phenyldiethylmethoxysilane, phenylethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane.
• zirconium-based coupling agent examples include tetrapropylzirconate, tetrabutylzirconate, tetra (triethanolamine) zirconate, tetraisopropylzirconate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium stearate, and zirconium stearate.
• Butyrate, monoalkoxyzircoaluminate, trialkoxyzircoaluminate, tetraalkoxyzircoaluminate and the like can be mentioned.
• titanium-based coupling agent examples include isopropyltriisostearoyl titanate, isopropyltristearoyl titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyldiacyl titanate, and isopropyltri. (Dioctyl phosphate) Titanium, isopropyltitanium triisostearate and the like can be mentioned.
• Examples of the phosphorus-based coupling agent include isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, and tetra (2,2-diallyloxy).
• Examples thereof include methyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, and acryloyloxyethylphthaloxyethyldiethyl phosphate.
• the inorganic fine particles (A) may be contained in the curable composition together with the dispersant.
• the dispersant any type of dispersant such as nonionic, anionic, and cationic dispersants can be used, and anionic dispersants are preferable.
• anion-based dispersant a phosphoric acid ester-based dispersant can be preferably used.
• DISPERBYK registered trademark
• DISPERBYK registered trademark
• DISPERBYK registered trademark
• DISPERBYK registered trademark
• DISPERBYK registered trademark
• DISPERBYK registered trademark
• DISPERBYK registered trademark
• DISPERBYK registered trademark
• DISPERBYK registered trademark
• DISPERBYK registered trademark
• DISPERBYK registered trademark
• the amount of the dispersant is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the inorganic fine particles (A). As the amount of the dispersant increases, the dispersibility of the inorganic fine particles (A) can be improved.
• the amount of the dispersant is, for example, 100 parts by mass or less, preferably 60 parts by mass or less, and more preferably 40 parts by mass or less with respect to 100 parts by mass of the inorganic fine particles (A). The smaller the amount of dispersant, the higher the refractive index of the curable composition.
• the polymerizable compound (B) contains the compound (B1).
• the compound (B1) has a (meth) acryloyl group (K1) to which an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms may be bonded, and an aryl group having 6 to 20 carbon atoms bonded to the compound (B1). It has at least two groups in the same molecule, which are independently selected from the group A consisting of unsaturated hydrocarbon groups (K2) having 2 to 20 carbon atoms which may be used.
• the (meth) acryloyl group (K1) and the unsaturated hydrocarbon group (K2) may have a substituent.
• condition 1 the case where all the groups selected from the group A are the same (meth) acryloyl group (K1) is excluded (hereinafter referred to as condition 1), and this condition 1 applies to all of the following preferred embodiments. There is no limitation other than this condition 1.
• two or more groups are the unsaturated hydrocarbon group (K2), they may be the same or different from each other.
• group X the different groups are the (meth) acryloyl group (K1) and the unsaturated hydrocarbon.
• the compound (B1) may have two or more of the same (meth) acryloyl groups (K1) (referred to as group X).
• group X The curable composition containing such a compound (B1) has excellent curability, and the film obtained from the curable composition has excellent visible light transmittance.
• all the groups selected from group A are an acryloyl group (hereinafter, may be referred to as an acryloyl group in a narrow sense) to which an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms is not bonded.
• the alkyl group having 1 to 20 carbon atoms may be either linear or branched.
• specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. Examples thereof include a decyl group, a heptadecyl group and an undecyl group.
• the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms.
• Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a xylyl group, a trimethylphenyl group, and a naphthyl group.
• the aryl group preferably has 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 9 carbon atoms.
• a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; -NR a R b (R a and R b are independently hydrogen atoms or 1 to 20 carbon atoms, respectively). ); Nitro group; alkoxy group having 1 to 10 carbon atoms such as methoxy group and ethoxy group; alkoxycarbonyl group having 2 to 10 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; and the like.
• the substituent may be directly bonded to the (meth) acryloyl group (K1) or the unsaturated hydrocarbon group (K2), and these (meth) acryloyl group (K1) and the unsaturated hydrocarbon group (K2) may be bonded. It may be optionally bonded to the alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 20 carbon atoms which is optionally bonded to.
• the (meth) acryloyl group (K1) to which the alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 20 carbon atoms may be bonded is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. It contains an acryloyl group (K11) to which an aryl group may be bonded, and a methacryloyl group (K12) to which an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms may be bonded.
• the unsaturated hydrocarbon group (K2) to which the aryl group having 6 to 20 carbon atoms may be bonded has an aryl group having 6 to 20 carbon atoms and / or an alkyl group having 1 to 18 carbon atoms bonded thereto.
• a good vinyl group (K21), an aryl group having 6 to 20 carbon atoms and / or an alkyl group having 1 to 17 carbon atoms may be bonded to the 1-methylvinyl group (K22), an aryl group having 6 to 20 carbon atoms.
• a group and / or an aryl group having 1 to 17 carbon atoms may be bonded to an aryl group (K23), an aryl group having 6 to 20 carbon atoms and / or an alkyl group having 1 to 16 carbon atoms may be bonded to the aryl group. It preferably contains a good metallicyl group (K24) and the like.
• the (meth) acryloyl group (K1) preferably does not have an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms (referred to as a (meth) acryloyl group in a narrow sense), and an acryloyl group (K11).
• a (meth) acryloyl group in a narrow sense preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms (acryloyl group in a narrow sense)
• the methacryloyl group (K12) is an alkyl group having 1 to 20 carbon atoms or 6 carbon atoms.
• the unsaturated hydrocarbon group (K2) has no aryl group of 6 to 20 carbon atoms (called an unsaturated hydrocarbon group in a narrow sense).
• the vinyl group (K21) does not have an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 18 carbon atoms (referred to as a vinyl group in a narrow sense), and a 1-methylvinyl group (K22).
• the metalyl group (K24) has an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 16 carbon atoms.
• Those that do not exist are preferable.
• the polymerizable compound (B1) is a group consisting of an acryloyl group (K11), a methacryloyl group (K12), a vinyl group (K21), a 1-methylvinyl group (K22), an allyl group (K23), and a metalyl group (K24). It is preferable that at least two groups independently selected from A'are contained in the same molecule. In addition, the polymerizable compound (B1) needs to satisfy the above-mentioned condition 1, and may have preferred embodiment 1, preferred embodiment 2 or preferred embodiment 3 (similar to the following preferred embodiments).
• the groups selected from group A' is a vinyl group (K21), a 1-methylvinyl group (K22), an allyl group (K23), or a metalyl group (K24), preferably from group A'.
• the selected groups is a vinyl group (K21) or an allyl group (K23)
• preferred embodiments 1 and 2 are satisfied.
• the compound (B1) is an example corresponding to the preferred embodiment 3, for example, at least one group selected from an acryloyl group (K11) and a methacryloyl group (K12), and a vinyl group (K21) and a 1-methylvinyl group (K22).
• the polymerizable compound (B1) preferably does not have a ring structure.
• the number of groups selected from group A is preferably 4 or less, more preferably 3 or less, and most preferably 2.
• the polymerizable compound (B1) is more preferably a compound represented by the formula (1) or the formula (2).
• R 1a , R 2a , and R 2b each independently represent a single bond or a methylene group.
• L 11 and L 21 represent an alkanediyl group having 1 to 10 carbon atoms.
• n1 and n2 represent integers from 0 to 4.
• R 11 to R 13 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
• R 14 to R 16 and R 21 to R 26 independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 20 or 6 to 18 carbon atoms.
• the total number of carbon atoms of R 1a and R 14 to R 16 is 18 or less, the total number of carbon atoms of R 2a and R 24 to R 26 is 18 or less, and the total number of carbon atoms of R 2b and R 21 to R 23 is 18 or less. The total is 18 or less.
• R 1a , R 2a , R 2b , L 11 , L 21 , R 11 to R 16 or R 21 to R 26 have a carbon atom, a substituent may be bonded to the carbon atom.
• the alkanediyl group having 1 to 10 carbon atoms represented by L 11 and L 21 may be either linear or branched.
• Specific examples of the linear or branched alkanediyl group include a methylene group, an ethanediyl group, an n-propanediyl group, an isopropanediyl group, an n-butanediyl group, an isobutanediyl group, and a trimethylmethanediyl group.
• Examples thereof include a hexanediyl group, a heptanediyl group, an octanediyl group, a nonandiyl group, a decandyl group and the like.
• the number of carbon atoms of the alkanediyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 2 to 3.
• the alkyl groups having 1 to 20 carbon atoms represented by R 11 to R 13 and the alkyl groups having 1 to 16 carbon atoms represented by R 14 to R 16 and R 21 to R 26 are linear and branched chains. It may be any of. Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. Examples thereof include a decyl group, a heptadecyl group and an undecyl group.
• the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms.
• the aryl group having 6 to 20 carbon atoms represented by R 11 to R 13 and the aryl group having 6 to 20 or 6 to 18 carbon atoms represented by R 14 to R 16 and R 21 to R 26 are phenyl groups. , Xylyl group, trimethylphenyl group, naphthyl group and the like.
• the aryl group preferably has 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 9 carbon atoms.
• a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; -NR a R b (R a and R b are independently hydrogen atoms or 1 to 20 carbon atoms, respectively). ); Nitro group; alkoxy group having 1 to 10 carbon atoms such as methoxy group and ethoxy group; alkoxycarbonyl group having 2 to 10 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; and the like.
• N1 is preferably 0 to 3, more preferably 0 to 2.
• N2 is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 to 1.
• the compound represented by the formula (1) includes one group selected from an acryloyl group in a narrow sense and a methacryloyl group in a narrow sense, a vinyl group in a narrow sense, a 1-methylvinyl group in a narrow sense, an allyl group in a narrow sense, and a narrow sense.
• a compound having one group selected from a methylene group is preferable, and specifically, R 11 , R 12 , R 14 , and R 15 are hydrogen atoms, and R 13 and R 16 are independently hydrogen atoms or A compound which is a methyl group and R 1a is a single bond or a methylene group is preferable.
• n1 is 0 to 3 and L 11 is an ethylene group, a linear propylene group, or a branched propylene group are preferable, and specifically, R 1a , R 11 to R 16 , n 1, and No. 1 in which L 11 is a combination of Tables 1 and 2.
• Compounds 1 to 104 are more preferable. No. Compounds 1 to 8, 27 to 34, 53 to 60, and 79 to 86 are even more preferable, and No. Compounds 1 to 8 and 27 to 34 are particularly preferable, and No. 1 to No. The compounds of 2, 5, 28, and 31 are most preferred.
• a compound having two groups selected from a vinyl group in a narrow sense, a 1-methylvinyl group in a narrow sense, an allyl group in a narrow sense, and a metallicyl group in a narrow sense is preferable, and specifically.
• R 21 , R 22 , R 24 , and R 25 are hydrogen atoms
• R 23 and R 26 are independently hydrogen atoms or methyl groups
• R 2a and R 2b are independently single-bonded or Compounds that are methylene groups are preferred.
• the number of repetitions n2 is 0 to 3 and L 21 is an ethylene group, a linear propylene group, or a branched propylene group, and specifically, R 21 to R 26 , R 2a , and R 2b .
• the compounds of 201 to 356 are more preferable.
• No. The compounds of 201 to 208, 227 to 234, 253 to 260, 279 to 286, 305 to 312, 331 to 338 are more preferable, and No. Compounds 201 to 208, 227 to 234 are particularly preferred.
• the polymerizable compound (B) may contain a compound having an ethylenic double bond (hereinafter, may be referred to as another polymerizable compound) other than the polymerizable compound (B1).
• the ratio of the polymerizable compound (B1) in the polymerizable compound (B) is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, or 80% by mass or more, still more preferably 90. It is mass% or more, particularly preferably 95% by mass or more, and may be 100% by mass.
• Examples of other polymerizable compounds include a polyfunctional compound (B2) having a non-ring structure, a polyfunctional compound (B3) having a ring structure, and a monofunctional compound (B4). These other polymerizable compounds may be used alone or in combination of two or more.
• Examples of the polyfunctional compound (B2) having an acyclic structure include compounds having the same (meth) acryloyl group having two or more polymerizable groups, and examples of the bifunctional compound having an acyclic structure include ethylene glycol di.
• Examples thereof include di (meth) acrylates of alkanediols having 1 to 40 carbon
• Examples of the trifunctional or higher functional compound having an acyclic structure include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol.
• Esters with acrylic acid can be mentioned.
• Examples of the polyfunctional compound (B3) having a ring structure include compounds having two or more identical (meth) acryloyl groups having a polymerizable group, and examples of the bifunctional compound having a ring structure include tricyclodecanedimethanol.
• Di (meth) acrylate of cycloalkhandiol having about 4 to 8 carbon atoms such as di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, cyclopentane dimethanol di (meth) acrylate; Di (meth) acrylates of diols obtained by hydroxyalkylene etherifying the OH groups of bisphenols, such as meth) acrylates and ethoxylated bisphenol A di (meth) acrylates; 9,9-bis [4- (2- (2-) Acryloyloxyethoxy) phenyl] fluorene and the like.
• trifunctional or higher functional compound having a ring structure examples include ethoxylated isocyanurate tri (meth) acrylate, ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, and the like.
• Examples of the monofunctional compound (B4) include ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate, which have 1 to 1 to carbon atoms. Twelve alkanol (meth) acrylates; alkylene glycol monoether (meth) acrylates such as ethyldiethylene glycol (meth) acrylates; dicyclopentadiene (meth) acrylates, isobornyloxyethyl (meth) acrylates, isobornyl (meth) acrylates.
• Monofunctional compounds with a ring structure such as dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; (meth) acryloylmorpholin, 7-amino-3,7.
• Monofunctional compounds having a nitrogen atom such as dimethyloctyl (meth) acrylate.
• a polyfunctional compound (B2) having an acyclic structure, a monofunctional compound (B4) and the like are preferable.
• the polymerizable compound (B) contains a polymerizable compound (B1), a polyfunctional compound (B2) having an acyclic structure and / or a monofunctional compound (B4)
• the compound (B1) has a polycyclic structure.
• the total content of the functional compound (B2) and the monofunctional compound (B4) is, for example, 40% by mass or more, preferably 60% by mass or more, more preferably 80% by mass or more, in the polymerizable compound (B). Even more preferably, it is 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass.
• the content of the polymerizable compound (B) is, for example, 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less in the curable composition.
• the content of the polymerizable compound (B) is, for example, 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more.
• the polymerization initiator (C) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light or heat, and a known polymerization initiator can be used. Photopolymerization initiators are preferred. Examples of the polymerization initiator that generates an active radical include an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, a phosphinic acid ester compound, and a biimidazole compound. These polymerization initiators may be used alone or in combination of two or more.
• the O-acyloxime compound is a compound having a partial structure represented by the formula (c1).
• * represents a bond.
• O-acyloxym compound examples include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane.
• the alkylphenone compound is a compound having a partial structure represented by the formula (c2) or a partial structure represented by the formula (c3).
• the benzene ring may have a substituent.
• Examples of the compound having a partial structure represented by the formula (c2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4).
• -Morholinophenyl) -2-benzylbutane-1-one 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one
• Commercially available products such as Irgacure (registered trademark) 369, 907, 379 (all manufactured by BASF) may be used.
• Examples of the compound having a partial structure represented by the formula (c3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, ⁇ , ⁇ -diethoxy Examples thereof include acetophenone and benzyldimethylketal.
• triazine compound examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-). Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy) Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethyla
• acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• Commercially available products such as Irga Cure (registered trademark) 819 (manufactured by BASF) may be used.
• phosphinic acid ester compound examples include phenyl (2,4,6-trimethylbenzoyl) ethyl phosphinate and the like.
• Commercially available products such as Omnirad (registered trademark) TPO-L (manufactured by IGM Resins BV) may be used.
• biimidazole compound examples include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl)-.
• benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-methyl benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoyl compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthlenquinone, Kinone compounds such as 2-ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, and titanosen compounds. These are preferably used in combination with the polymerization initiation aid (C1) (particularly an amine compound
• the polymerization initiator (C) also includes an acid generator.
• the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, and 4-acetoxyphenylmethylbenzylsulfonium.
• Onium salts such as hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylate, benzointosylatekind and so on.
• the polymerization initiator (C) contains at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, a phosphinic acid ester compound, and a biimidazole compound. Is preferable, and a polymerization initiator containing at least one selected from the group consisting of an acylphosphine oxide compound and a phosphinic acid ester compound is preferable.
• the polymerization initiator (C) contains at least one selected from the group consisting of an acylphosphine oxide compound and a phosphinic acid ester compound, the total amount of the acylphosphine oxide compound and the phosphinic acid ester compound in the polymerization initiator (C).
• the content is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and may be 100% by mass.
• the content of the polymerization initiator (C) is, for example, 0.1% by mass or more, preferably 1% by mass or more, more preferably 10% by mass or more, based on 100 parts by mass of the polymerizable compound (B). For example, it is 40% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.
• the polymerization initiator (C1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound initiated by the polymerization initiator.
• the curable composition contains a polymerization initiator (C1), it is usually used in combination with the polymerization initiator (C).
• Examples of the polymerization initiation aid (C1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
• Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michelers ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (Ethylmethylamino) Benzophenone and the like can be mentioned.
• Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.
• alkoxyanthracene compound examples include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-di. Butoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.
• thioxanthone compound examples include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.
• carboxylic acid compound examples include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, and dichlorophenylsulfanylacetic acid.
• Examples thereof include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.
• the content thereof is, for example, 0.1% by mass or more, preferably 1% by mass or more, and more preferably 10% by mass with respect to 100 parts by mass of the polymerizable compound (B). % Or more, for example, 40% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.
• the curable composition may contain a resin (D), a solvent (E) and the like, if necessary.
• the resin (D) is not particularly limited, but is preferably an alkali-soluble resin.
• Examples of the resin (D) include the following resins [K1] to [K6].
• Resin [K1] a structural unit derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter, may be referred to as “(a)”), and 2 carbon atoms.
• a polymer having a cyclic ether structure of ⁇ 4 and a structural unit derived from a monomer (b) having an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”); Resin [K2]; a structural unit derived from (a), a structural unit derived from (b), and a monomer (c) copolymerizable with (a) (however, (a) and (b) Is different.)
• (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexendicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-e, 5-
• acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerizability and solubility of the obtained resin in an alkaline aqueous solution.
• (B) is a polymerizable compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond.
• a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group is preferable.
• (meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.
• Examples of (b) include a monomer (b1) having an oxylanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single having an oxetanyl group and an ethylenically unsaturated bond.
• a metric (b2) hereinafter sometimes referred to as "(b2)
• b3 a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond
• (b1) for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”). There is), and a monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter, may be referred to as “(b1-2)”).
• Examples of (b1-1) include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, ⁇ -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p.
• Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, seroxide (registered trademark) 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth).
• Acrylic eg, Cyclomer® A400; manufactured by Dycel Co., Ltd.
• 3,4-epoxycyclohexylmethyl (meth) acrylate eg, Cyclomer® M100; manufactured by Dycel Co., Ltd.
• formula ( Examples thereof include a compound represented by I) and a compound represented by formula (II).
• Ra and R b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be good.
• X a and X b represent a single bond, * -R c-, * -R c-O-, * -R c-S- or * -R c - NH- .
• R c represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O.
• alkyl group having 1 to 4 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like.
• the alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
• R a and R b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.
• the alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. Examples include 1,6-diyl group.
• Examples of X a and X b are preferably a single bond, a methylene group, an ethylene group, * -CH 2 -O- and * -CH 2 CH 2 -O-, and more preferably a single bond and * -CH 2 .
• CH 2 -O- can be mentioned (* represents a bond with O).
• Examples of the compound represented by the formula (I) include compounds represented by any of the formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15).
• the compound represented by the formula (I-1) is preferable, and the compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15) is more preferable.
• Examples of the compound represented by the formula (II) include compounds represented by any of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15). The compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the compound represented by the formula (II-15) is more preferable.
• the compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more.
• the content ratio thereof [the compound represented by the formula (I): the compound represented by the formula (II)] is On a molar basis, it is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.
• (b2) a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable.
• Examples of (b2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3-acryloyloxymethyloxetane.
• (b3) a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.
• Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscort V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.
• (B) is preferably (b1) in that the reliability of the heat resistance, chemical resistance, etc. of the film obtained from the curable composition can be further increased. Further, (b1-2) is more preferable in that the curable composition has excellent storage stability.
• Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth).
• Tricyclo [5.2.1.0 2,6 ] decene-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate”.
• Dicyclopentanyloxyethyl (meth) acrylate isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (Meta) acrylic acid esters such as (meth) acrylate; Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid; Bicyclo
• styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are selected from the viewpoint of copolymerization reactivity and heat resistance. preferable.
• the ratio of each structural unit is the total number of moles of all the structural units constituting the resin [K1].
• the curable composition tends to be excellent in storage stability, developability when forming a pattern, and solvent resistance of the obtained developed product. ..
• the resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis” (written by Takayuki Otsu, Kagaku-Dojin Publishing Co., Ltd., 1st edition, 1st printing, published on March 1, 1972). And, it can be manufactured with reference to the cited documents described in the relevant document.
• a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and the mixture is stirred. Examples thereof include a method of heating and keeping warm.
• the polymerization initiator, solvent and the like used here are not particularly limited, and those usually used in the art can be used.
• an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.
• an organic peroxide benzoyl peroxide, etc.
• any solvent may be used as long as it dissolves each monomer, and examples of the solvent (E) of the curable composition include a solvent described later.
• the obtained copolymer may be used as it is after the reaction, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as reprecipitation. May be used.
• a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as reprecipitation. May be used.
• the solvent (E) contained in the curable composition as the solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the curable composition, so that the curable composition can be used.
• the manufacturing process of goods can be simplified.
• the ratio of each structural unit is the total number of moles of all the structural units constituting the resin [K2].
• the storage stability of the curable composition, the developability when forming a pattern, and the solvent resistance, heat resistance and heat resistance of the obtained developed product are obtained. It tends to have excellent mechanical strength.
• the resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].
• the ratio of each structural unit is the total number of moles of all the structural units constituting the resin [K3].
• the resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].
• the resin [K4] is a carboxylic acid and / or a carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms having (b) obtained by obtaining a copolymer of (a) and (c). It can be manufactured by adding it to.
• the copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1].
• the ratio of each structural unit is preferably the same as the ratio mentioned in the resin [K3].
• the resin [K4] is obtained by placing a catalyst (for example, tris (dimethylaminomethyl) phenol, etc.), a polymerization inhibitor (for example, hydroquinone, etc.) and the like in a flask and reacting them at, for example, 60 to 130 ° C. for 1 to 10 hours. Can be manufactured.
• a catalyst for example, tris (dimethylaminomethyl) phenol, etc.
• a polymerization inhibitor for example, hydroquinone, etc.
• the amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a).
• the amount of (b) used in this range By setting the amount of (b) used in this range, the storage stability of the curable composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained developed product are set. Tends to be well-balanced. Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K4], and (b1-1) is more preferable.
• the amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
• the amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
• reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment and the calorific value due to the polymerization.
• a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production method of the resin [K1].
• the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation. ) May be used.
• the ratio of the structural units derived from (b) and (c) is the total number of moles of all the structural units constituting the copolymer.
• the carboxylic acid or carboxylic acid anhydride of (a) is added to the cyclic ether derived from (b) of the copolymer of (b) and (c).
• the resin [K5] can be obtained by reacting an object.
• the amount of (a) used to react with the above-mentioned copolymer is preferably 5 to 80 mol with respect to (b) 100 mol. Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K5], and (b1-1) is more preferable.
• the resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. Specifically, the carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction between the cyclic ether and the carboxylic acid or the carboxylic acid anhydride.
• carboxylic acid anhydride examples include maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride and the like.
• the amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mol with respect to 1 mol of the amount used in (a).
• the resin (D) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 2,6 . ] Resins such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decylacrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3-( Resin [K2] such as meta) acrylic loyloxymethyloxetane / (meth) acrylic acid / sty
• Resins with glycidyl (meth) acrylate added to the coalescence resins such as tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) acrylate added [ K4]; Co-weight of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate, a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid.
• a resin such as a resin obtained by reacting a (meth) acrylic acid with a coalescence [K5]; a resin obtained by reacting a (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and further tetrahydro.
• a resin [K6] such as a resin obtained by reacting with phthalic acid anhydride.
• the resin [K1] and the resin [K2] are preferable, and the resin [K2] is particularly preferable.
• the polystyrene-equivalent weight average molecular weight of the resin (D) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. ..
• the molecular weight is within the above range, the hardness of the film obtained from the curable composition is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution of the pattern tends to be improved. There is.
• the degree of dispersion [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (D) is preferably 1.1 to 6, and more preferably 1.2 to 4.
• the acid value of the resin (D) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and even more preferably 70 to 135 mg-KOH / g in terms of solid content.
• the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (D), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution. can.
• the solid content of the resin (D) in the curable composition is, for example, 200 parts by mass or less, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the polymerizable compound (B). Even more preferably, it is 30 parts by mass or less, particularly preferably 10 parts by mass or less, and it may be 0 parts by mass.
• the solvent (E) is not particularly limited, and a solvent usually used in the art can be used.
• a solvent usually used in the art can be used.
• an ester solvent solvent containing -COO- in the molecule and not containing -O-
• an ether solvent solvent containing -O- in the molecule and not containing -COO-
• an ether ester solvent intramolecular
• Solvent containing -COO- and -O- Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- Examples thereof include CO- and -COO-free solvents), alcohol ketone solvents (solvents containing OH and -CO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.
• Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, ⁇ -butyrolactone and the like.
• ether solvent examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.
• ether ester solvent examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy.
• Ethyl propionate methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.
• ketone solvent examples include 4-hydroxy-4-methyl-2-pentanone, acetone, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Can be mentioned.
• alcohol solvent examples include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
• Examples of the alcohol ketone solvent include a dimer of a ketone selected from the above-mentioned ketone solvents such as diacetone alcohol.
• aromatic hydrocarbon solvent examples include benzene, toluene, xylene, mesitylene and the like.
• amide solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
• an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable from the viewpoint of workability and dryness.
• the solvent propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone , Methyl ethyl ketone, butyl acetate, 2-heptanone, diacetone alcohol and N, N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate ethyl ketone and ethyl 3-ethoxypropionate are more preferred.
• the content of the solvent (E) in the curable composition is, for example, 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less. It is even more preferably 15% by mass or less, particularly preferably 10% by mass or less, and most preferably 5% by mass or less.
• the curable composition according to the above aspect of the present invention has high fluidity and excellent workability even if it does not contain a solvent.
• the curable composition may contain a surfactant (F).
• the surfactant (F) can be used as a leveling agent, and examples thereof include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
• silicone-based surfactant examples include a surfactant having a siloxane bond in the molecule.
• examples of the surfactant having a siloxane bond in the molecule include octamethylcyclotetrasiloxane.
• Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KF994, KP321, KP322, KP323, KP324, KP326, Using commercially available products such as KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) May be good.
• fluorine-based surfactant examples include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554.
• R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.) and the like.
• silicone-based surfactant having a fluorine atom examples include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megafuck (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).
• the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably, with respect to the total amount of the curable composition. Is 0.002% by mass or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.07% by mass or less.
• the curable composition according to the above aspect of the present invention is known in the art as a filler, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like, if necessary. Additives may be included.
• the viscosity of the curable composition according to the above aspect of the present invention at a temperature of 23 ° C. is, for example, 50 mPa ⁇ s or less, preferably 45 mPa ⁇ s or less, and more preferably 40 mPa ⁇ s or less.
• the viscosity is, for example, 1 mPa ⁇ s or more.
• the viscosity can be measured, for example, by using an E-type viscometer and optimizing the rotor rotation speed (preferably 1 rpm).
• the curable composition according to the above aspect of the present invention has excellent visible light transmittance.
• the average value of the transmittance of the cured film obtained by the following film forming method 1 at a wavelength of 400 to 700 nm is 90% or more, preferably 93% or more, more preferably 95% or more per 1.0 ⁇ m film thickness. become.
• the total transmittance of the cured film obtained by the following film forming method 1 in the wavelength range of 400 to 700 nm is preferably 90% or more, more preferably 93% or more per 1.0 ⁇ m film thickness. , 95% or more is more preferable.
• a curable composition is applied onto a glass substrate so that the average thickness of the cured film falls within the range of 1.0 ⁇ 0.2 ⁇ m, and an ultraviolet (UV) having a wavelength of 385 nm is integrated with an integrated light amount of 2000 J / using an LED lamp. Irradiate with m 2 .
• UV ultraviolet
• the transmittance T (when the film thickness is 1.0 ⁇ m) is treated as it is as the transmittance per 1.0 ⁇ m film thickness.
• the transmittance T'(thickness x ⁇ m). Hour) is converted to absorbance A'(at film thickness x ⁇ m) based on A' -log 10 T', and this absorbance A'(at film thickness x ⁇ m) is multiplied by the reciprocal of film thickness x ( ⁇ m).
• the absorbance A when the film thickness is 1.0 ⁇ m
• the transmittance T when the film thickness is 1.0 ⁇ m
• the average value of the transmittance per 1.0 ⁇ m film thickness at a wavelength of 400 to 700 nm is calculated.
• the curable composition according to the above aspect of the present invention has a high refractive index.
• the refractive index of the cured film obtained by the following film forming method 2 measured with a spectroscopic ellipsometer at a wavelength of 550 nm is, for example, 1.5 or more, preferably 1.6 or more, more preferably 1.7.
• the above is, for example, 3.0 or less, preferably 2.5 or less, and more preferably 2.0 or less.
• a curable composition is applied onto a 4-inch Si wafer substrate using a spin coater so that the average thickness of the cured film is 0.5 ⁇ m. Using an LED lamp, UV with a wavelength of 385 nm is irradiated with an integrated light amount of 2000 J / m 2 .
• cured film can be produced by treating the curable composition by a wet method such as a printing method, a capillary coating method, or a nozzle coating method. Further, a patterned cured film may be produced by using a photolithography method, an inkjet printing method, or the like.
• the thickness of the cured film is usually about 1 nm to 50 ⁇ m, preferably 1 ⁇ m to 50 ⁇ m.
• the cured film can be used as a microlens, a sealing material, etc., and is particularly preferable to be used as a microlens, a sealing material, etc. of a light emitting element.
• VEEA manufactured by Nippon Catalyst Co., Ltd., hereinafter referred to as VEEA
• Example 2 A curable composition 2 was obtained in the same manner as in Example 1 except that allyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of VEEA as the polymerizable compound.
• allyl methacrylate manufactured by Tokyo Chemical Industry Co., Ltd.
• Example 3 The curable composition 3 was prepared in the same manner as in Example 2 except that 3 parts by mass of methyl ethyl ketone remained in the cured composition as a solvent and the mass of allyl methacrylate was 43 parts by mass.
• Comparative Example 1 As the polymerizable compound, instead of VEEA, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., hereinafter referred to as A-DCP), 1,10-decanediol diacrylate (A-DCP).
• A-DCP tricyclodecanedimethanol diacrylate
• A-DCP 1,10-decanediol diacrylate
• A-DOD-N DOD-N
• isobutyl methacrylate manufactured by Tokyo Kasei Kogyo Co., Ltd.
• octamethylcyclotetrasiloxane manufactured by Tokyo Kasei Kogyo Co., Ltd.
• TPO-L TPO-L
• the comparatively curable composition 1 contains 37 parts by mass of zirconium oxide particles, 9 parts by mass of a dispersant, 24 parts by mass of A-DCP, 14 parts by mass of A-DOD-N, 10 parts by mass of isobutylmethacrylate, and IRG819. It contained 5 parts by mass and 1 part by mass of octamethylcyclotetrasiloxane.
• the obtained cured film and curable composition were evaluated as follows. The evaluation results are shown in Table 6. 1.
• Curability taciness
• the case where the cured film did not have the marks of the protective gloves was evaluated as ⁇
• the case where the cured film had the marks of the protective gloves was evaluated as x.
• Applyability Measure the thickness of the cured film at two locations, and mark ⁇ when the difference between the film thicknesses at the two locations is within 5% of the average value of the film thickness at the two locations, and ⁇ when it is greater than 5%. evaluated.

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• 2021
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