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
  • C08F122/00—Homopolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
  • C08F122/10—Esters
  • C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
• • 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
• • 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
  • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5397—Phosphine oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0806—Silver
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0831—Gold
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2237—Oxides; Hydroxides of metals of titanium
  • C08K2003/2241—Titanium dioxide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/02—Ingredients treated with inorganic substances

Definitions

• the present invention relates to a composition containing a photopolymerizable compound (A) and an inorganic particle (B), a photosensitive composition, and a cured product of the photosensitive composition.
• compositions used to form materials with various functionalities for the purpose of imparting functionality to the materials For example, high refractive index materials are used to form optical members.
• high refractive index materials are used to form optical members.
• the high refractive material for example, a composition in which metal oxide particles such as titanium oxide particles and zirconium oxide particles are dispersed in an organic component is used.
• an energy beam containing a metal oxide (A) with a specific particle size, a (meth)acrylate (B), and a photopolymerization initiator (C) is used.
• a curable composition has been proposed (see Patent Document 1).
• the present invention has been made in view of the above-mentioned problems, and includes components in a composition or photosensitive composition (components other than the solvent if the composition or photosensitive composition contains a solvent) even when heated.
• An object of the present invention is to provide a composition, a photosensitive composition, and a cured product of the photosensitive composition, in which an excessive decrease in weight is unlikely to occur and in which inorganic particles are stably dispersed over a long period of time.
• the present inventors created a composition containing a photopolymerizable compound (A) and an inorganic particle (B), or a photopolymerizable compound (A), an inorganic particle (B), and an initiator (C).
• the present inventors have discovered that the above problems can be solved by using a compound with a specific structure having a radically polymerizable group-containing group as the photopolymerizable compound (A) in a photosensitive composition containing a photosensitive composition, and have completed the present invention. .
• the present invention provides the following.
• the first aspect of the present invention includes a photopolymerizable compound (A) and inorganic particles (B),
• the photopolymerizable compound (A) has the following formula (A1): R a01 -X a01 -R a02 -Ar-X a02 -(Ar-R a02 -X a01 -R a01 ) n ...(A1)
• R a01 is each independently a radical polymerizable group-containing group
• R a02 is each independently an alkylene group having 1 to 3 carbon atoms
• X a01 is each is independently O or S
• X a02 is an n+1 valent organic group having 1 to 3 carbon atoms, O, or S
• each Ar may independently have a substituent It is an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is 1 or 2, and when X a02 is O or S, n is 1.
• the second aspect of the present invention includes a photopolymerizable compound (A), an inorganic particle (B), and an initiator (C),
• the photopolymerizable compound (A) has the following formula (A1): R a01 -X a01 -R a02 -Ar-X a02 -(Ar-R a02 -X a01 -R a01 ) n ...(A1)
• R a01 is each independently a radical polymerizable group-containing group
• R a02 is each independently an alkylene group having 1 to 3 carbon atoms
• X a01 is each is independently O or S
• X a02 is an n+1 valent organic group having 1 to 3 carbon atoms, O, or S
• each Ar may independently have a substituent It is an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is 1 or 2, and when X a02 is O or S, n is 1.
• the third aspect of the present invention is a cured product of the photosensitive composition according to the second aspect.
• the weight of the composition or components in the photosensitive composition is unlikely to decrease excessively, and the inorganic fine particles remain stable for a long period of time.
• a composition that is stably dispersed, a photosensitive composition, a cured product of the photosensitive composition, the aforementioned composition, a compound preferably blended into the photosensitive composition, and a method for producing the compound. can be provided.
• the composition includes a photopolymerizable compound (A) and inorganic particles (B).
• a composition is essentially an inorganic particle dispersion composition, and after being appropriately blended with an initiator for curing the photopolymerizable compound (A), a function having properties depending on the type of the inorganic particles (B) is added. used in the formation of synthetic materials.
• the photopolymerizable compound (A) includes a compound represented by the following formula (A1). R a01 -X a01 -R a02 -Ph-X a02 -(Ph-R a02 -X a01 -R a01 ) n ...(A1)
• R a01 each independently represents a radically polymerizable group-containing group.
• R a02 each independently represents an alkylene group having 1 or more and 3 or less carbon atoms.
• X a01 is each independently O or S.
• X a02 is an n+1-valent organic group having 1 to 3 carbon atoms, O, or S.
• Ar is each independently an aromatic hydrocarbon group having 6 or more and 12 or less carbon atoms which may have a substituent.
• n is 1 or 2. When X a02 is O or S, n is 1.
• the composition may contain, as the photopolymerizable compound (A), a photopolymerizable compound (A2) other than the compound (A1) together with the compound (A1).
• the photopolymerizable compound (A) a photopolymerizable compound (A2) other than the compound (A1) together with the compound (A1).
• the composition contains a photopolymerizable compound (A).
• the photopolymerizable compound (A) is a compound having a radically polymerizable group-containing group.
• the radically polymerizable group-containing group typically includes a group containing an ethylenically unsaturated double bond.
• an alkenyl group-containing group including an alkenyl group such as a vinyl group and an allyl group is preferable, and a (meth)acryloyl group-containing group is more preferable.
• (meth)acrylic means both acrylic and methacrylic.
• (Meth)acryloyl means both acryloyl and methacryloyl.
• (Meth)acrylate means both acrylate and methacrylate.
• the photopolymerizable compound (A) includes a compound represented by the following formula (A1). R a01 -X a01 -R a02 -Ar-X a02 -(Ar-R a02 -X a01 -R a01 ) n ...(A1)
• R a01 each independently represents a radically polymerizable group-containing group.
• R a02 each independently represents an alkylene group having 1 or more and 3 or less carbon atoms.
• X a01 is each independently O or S.
• X a02 is an n+1-valent organic group having 1 to 3 carbon atoms, O, or S.
• Ar is each independently an aromatic hydrocarbon group having 6 or more and 12 or less carbon atoms which may have a substituent.
• n is 1 or 2. When X a02 is O or S, n is 1.
• the compound represented by formula (A1) is also referred to as "compound (A1)."
• R a01 is a radically polymerizable group-containing group.
• the radically polymerizable group-containing group typically includes a group containing an ethylenically unsaturated double bond.
• an alkenyl group-containing group including an alkenyl group such as a vinyl group and an allyl group is preferable, and a (meth)acryloyl group-containing group is more preferable.
• Suitable examples of the alkenyl group-containing group include an alkenyl group having 3 to 10 carbon atoms, and an alkenylcarbonyl group having 3 to 10 carbon atoms.
• alkenyl groups and alkenylcarbonyl groups may be linear or branched.
• Preferred specific examples of the alkenyl group include allyl group, but-3-en-1-yl group, pent-4-en-1-yl group, hex-5-en-1-yl group, hept-6-ene -1-yl group, oct-7-en-1-yl group, non-8-en-1-yl group, and dec-9-en-1-yl group.
• alkenylcarbonyl group examples include an acryloyl group, a methacryloyl group, a but-3-en-1-ylcarbonyl group, a pent-4-en-1-ylcarbonyl group, and a hex-5-en-1-ylcarbonyl group. group, hept-6-en-1-ylcarbonyl group, oct-7-en-1-ylcarbonyl group, and non-8-en-1-ylcarbonyl group.
• radically polymerizable group-containing groups allyl, acryloyl, and methacryloyl groups are preferred, and acryloyl and methacryloyl groups are particularly preferred. That is, among radically polymerizable group-containing groups, a (meth)acryloyl group is particularly preferred.
• a plurality of R a01s exist.
• a plurality of R a01s may be the same or different.
• the plurality of R a01s are the same.
• R a02 each independently represents an alkylene group having 1 or more and 3 or less carbon atoms.
• the alkylene group include methylene group, ethane-1,2-diyl group (ethylene group), ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group. group, propane-1,1-diyl group, and propane-2,2-diyl group.
• methylene group, ethane-1,2-diyl group (ethylene group), propane-1,3-diyl group, and propane-1,2-diyl group are preferable, and methylene group is more preferable.
• a plurality of R a02s exist.
• a plurality of R a02 's may be the same or different.
• the plurality of R a02s are the same.
• X a01 is O or S, preferably O.
• a plurality of X a01s exist.
• the plurality of X a01s may be the same or different.
• the plurality of X a01s are the same.
• X a02 is an n+1 valent organic group having 1 to 3 carbon atoms, O, or S. Further, n is 1 or 2, and 1 is preferable. When X a02 is O or S, n is 1.
• the organic group as X a02 is a divalent organic group.
• divalent organic groups include alkylene groups having 1 to 3 carbon atoms, -CH 2 -CO-, -CH 2 -CH 2 -CO-, -CH 2 -CO-CH 2 -, -CH 2 - O-, -CH 2 -CH 2 -O-, -CH 2 -CH 2 -CH 2 -O-, -O-CH 2 -O-, -O-CH 2 -CH 2 -O-, -O- CH 2 -CH 2 -CH 2 -O-, -CH 2 -O-CH 2 -, -CH 2 -O-CH 2 -CH 2 -, -CH 2 -NH-, -CH 2 -CH 2 -NH -, -CH 2 -CH 2 -CH 2 -NH-, -NH-CH 2 -NH-, -NH-CH 2 -NH-, -NH-CH 2
• alkylene group having 1 to 3 carbon atoms as X a02 are the same as the specific examples of the alkylene group having 1 to 3 carbon atoms as R a02 .
• Examples of the alkylene group having 1 to 3 carbon atoms as X a02 include methylene group, ethane-1,2-diyl group (ethylene group), propane-1,3-diyl group, and propane-1,2-diyl group.
• a group is preferable, and a methylene group is more preferable.
• X a02 is a methylene group, O, or S.
• the organic group as X a02 is a trivalent organic group.
• the trivalent organic group an alkantriyl group having 1 or more and 3 or less carbon atoms is preferable.
• the alkantriyl group include methanetriyl group, ethane-1,1,1-tolyyl group, ethane-1,1,2-tolyyl group, propane-1,1,1-tolyyl group, propane-1, Examples include 1,2-tolyyl group, propane-1,1,3-tolyl group, propane-1,2,2-tolyyl group, and propane-1,2,3-tolyyl group.
• methanetriyl group is preferred.
• Ar is an aromatic hydrocarbon group having 6 or more and 12 or less carbon atoms that may have a substituent.
• the aromatic hydrocarbon group include a phenylene group, a naphthalenediyl group, and a biphenyldiyl group.
• the aromatic hydrocarbon group includes o-phenylene group, m-phenylene group, p-phenylene group, naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene- 1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3-diyl group group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, biphenyl-4,4'-diyl group, biphenyl-3,3'-diyl group, and biphenyl-3,4'-diyl group can be mentioned.
• aromatic hydrocarbon groups m-phenylene group, p-phenylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, biphenyl- 4,4'-diyl group and biphenyl-3,3'-diyl group are preferred, p-phenylene group, naphthalene-2,6-diyl group, and biphenyl-4,4'-diyl group are more preferred; -Phenylene group is particularly preferred.
• the aromatic hydrocarbon group as Ar may have a substituent.
• the type of the substituent is not particularly limited as long as the desired effect is not impaired.
• substituents include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, nitro groups, and monovalent organic groups.
• halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the monovalent organic group include an alkyl group, an alkoxy group, an alkoxyalkyl group, an aliphatic acyl group, an aliphatic acyloxy group, an alkoxycarbonyl group, an alkylthio group, and an aliphatic acylthio group.
• the number of carbon atoms in the monovalent organic group as a substituent is not particularly limited as long as the desired effect is not impaired.
• the number of carbon atoms in the monovalent organic group as a substituent is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less.
• the alkoxyalkyl group aliphatic acyl group, aliphatic acyloxy group, alkoxycarbonyl group, alkoxyalkylthio group, and aliphatic acylthio group
• the lower limit of the number of carbon atoms is 2.
• alkyl group as a substituent examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include n-hexyl group, n-heptyl group, and n-octyl group.
• alkoxy group as a substituent examples include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n- Examples include pentyloxy group, n-hexyloxy group, n-heptyloxy group, and n-octyloxy group.
• alkoxyalkyl group as a substituent examples include methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, n-butyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2- n-propyloxyethyl group, 2-n-butyloxyethyl group, 3-methoxy-n-propyloxy group, 3-ethoxy-n-propyloxy group, 3-n-propyloxy-n-propyloxy group, 3 -n-butyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, 4-n-propyloxy-n-butyloxy group, and 4-n-butyloxy-n- A butyloxy group is mentioned.
• Preferred specific examples of the aliphatic acyl group as a substituent include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, and an octanoyl group.
• Preferred specific examples of the aliphatic acyloxy group as a substituent include an acetoxy group, a propionyloxy group, a butanoyloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoyloxy group, and an octanoyloxy group.
• alkoxycarbonyl group as a substituent examples include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxy Examples include carbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, and n-octyloxycarbonyl group.
• alkylthio group as a substituent examples include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group. n-hexylthio, n-heptylthio, and n-octylthio.
• Preferred specific examples of the aliphatic acylthio group as a substituent include an acetylthio group, a propionylthio group, a butanoylthio group, a pentanoylthio group, a hexanoylthio group, a heptanoylthio group, and an octanoylthio group.
• the number of substituents is not particularly limited as long as the desired effect is not impaired.
• the number of substituents is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.
• the aromatic hydrocarbon group as Ar has a plurality of substituents, the plurality of substituents may be different from each other.
• Preferred specific examples of compound (A1) include the following compounds.
• the composition may contain other photopolymerizable compound (A2) together with compound (A1). Since the compound (A1) has a radically polymerizable group-containing group, the other photopolymerizable compound (A2) also has a radically polymerizable group-containing group.
• the other photopolymerizable compound (A2) may be a monofunctional compound having one radically polymerizable group or a polyfunctional compound having two or more radically polymerizable groups.
• the other photopolymerizable compound (A2) having a radically polymerizable group-containing group is preferably a compound having one or more (meth)acryloyl groups, such as a (meth)acrylate compound or a (meth)acrylamide compound; A (meth)acrylate compound having a (meth)acryloyl group is more preferred.
• Examples of monofunctional compounds having a radically polymerizable group-containing group include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxy Methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, anhydride Citraconic acid, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Cyclohexyl (meth)
• polyfunctional compounds having radically polymerizable group-containing groups include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.
• tolylene diisocyanate reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether , polyfunctional compounds such as a condensate of polyhydric alcohol and N-methylol (meth)acrylamide, and triacryl formal. These polyfunctional compounds can be used alone or in combination of two or more.
• photopolymerizable compounds (A2) having a radically polymerizable group-containing group trifunctional or higher-functional polyfunctional compounds are preferred because they tend to increase the strength of the material formed using the composition.
• a polyfunctional compound having four or more functionalities is more preferred, and a polyfunctional compound having five or more functionalities is even more preferred.
• the photopolymerizable compound (A) includes a monofunctional compound as another photopolymerizable compound (A2)
• the ratio of the mass of the monofunctional compound to the mass of the photopolymerizable compound (A) is less than 20% by mass. is preferable, and 10% by mass or less is more preferable.
• the composition contains a compound represented by the following formula (A-2a) or the following formula (A-2b) as the photopolymerizable compound (A) having a radically polymerizable group-containing group. It is preferable to include. (MA-(O-R a1 ) na1 -X-CH 2 ) 2 -CH-X-(R a1 -O) na1 -MA...(A-2b)
• MA each independently represents a (meth)acryloyl group.
• Each X is independently an oxygen atom, -NH-, or -N(CH 3 )-.
• R a1 is each independently an ethane-1,2-diyl group, a propane-1,2-diyl group, or a propane-1,3-diyl group.
• R a2 is a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or a group represented by -X-(R a1 -O) na1 -MA.
• X is the same as above.
• na1 and na2 are each independently 0 or 1.
• the alkyl group having 1 to 4 carbon atoms as R a2 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. group, and tert-butyl group.
• methyl and ethyl groups are preferred.
• Preferred examples of the compound represented by formula (A-2a) and the compound represented by formula (A-2b) include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and trimethylolpropane. Examples include tri(meth)acrylate, glycerin tri(meth)acrylate, and the following compounds 1) to 32). In the compounds 1) to 32) below, MA is a (meth)acryloyl group.
• the mass of the compound represented by formula (A-2a) and the mass of the compound represented by formula (A-2b) with respect to the mass of the photopolymerizable compound (A) is preferably 20% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 50% by mass or less, and even more preferably 40% by mass or more and 50% by mass or less.
• the composition preferably contains another photopolymerizable compound (A2) having a radically polymerizable group-containing group, since it is easy to form a material with a high refractive index using the composition.
• the photopolymerizable compound (A2) preferably includes a diaryl sulfide compound having a structure in which two aryl groups substituted with a radically polymerizable group-containing group are connected via -S-. Such a diaryl sulfide compound may have a substituent other than the radically polymerizable group-containing group on the aryl group. Substituents other than the radically polymerizable group-containing group are the same as the substituents that the aromatic hydrocarbon group as Ar may have in the above formula (A1).
• aryl group examples include a phenyl group, a naphthalen-1-yl group, a naphthalen-2-yl group, a 4-phenylphenyl group, a 3-phenylphenyl group, and a 2-phenylphenyl group.
• phenyl group is preferred.
• the above diaryl sulfide compound preferably includes, for example, a compound represented by the following formula (A-2c).
• R 1 and R 2 are each independently a hydrogen atom or a methyl group.
• R 3 and R 4 are each independently an alkyl group having 1 or more and 5 or less carbon atoms.
• p and q are each independently 0 or 1.
• R 1 and R 2 are each independently a hydrogen atom or a methyl group. R 1 and R 2 may be different from each other or may be the same. Since the compound represented by formula (A-2c) is easy to synthesize and obtain, it is preferable that R 1 and R 2 are the same.
• R 3 and R 4 are each independently an alkyl group having 1 or more and 5 or less carbon atoms. R 3 and R 4 may be different from each other or may be the same. Since the compound represented by formula (A-2c) is easy to synthesize and obtain, it is preferable that R 3 and R 4 are the same.
• the alkyl group having 1 to 5 carbon atoms as R 3 and R 4 may be linear or branched.
• Examples of the alkyl group having 1 to 5 carbon atoms as R 3 and R 4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Examples include tert-butyl group, n-pentyl group, isopentyl group, and tert-pentyl group.
• Preferred specific examples of the compound represented by formula (A-2c) include the following compounds.
• the composition contains a compound represented by formula (A-2c) as another photopolymerizable compound (A2) having a radically polymerizable group-containing group
• the mass ratio of the compound represented by -2c) is preferably 10% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 50% by mass or less.
• the composition contains a sulfur-containing compound represented by the following formula (A-2d) as another photopolymerizable compound (A2) having a radically polymerizable group-containing group.
• a sulfur-containing compound represented by the following formula (A-2d) as another photopolymerizable compound (A2) having a radically polymerizable group-containing group.
• it contains (meth)acrylate.
• Ar a1 -R a21 -S-R a22 -O-CO-CR a23 CH 2 ...(A-2d)
• Ar a1 is a phenyl group optionally substituted with a halogen atom.
• R a21 is a single bond or an alkylene group having 1 or more and 6 or less carbon atoms.
• R a22 is an alkylene group having 1 or more and 6 or less carbon atoms.
• R a23 is a hydrogen atom or a methyl group.
• Ar a1 is a phenyl group which may be substituted with a halogen atom.
• the number of halogen atoms bonded to the phenyl group is not particularly limited.
• the number of halogen atoms bonded to the phenyl group is preferably 1 or 2, more preferably 1.
• the plurality of halogen atoms bonded to the phenyl group may consist of only the same type of halogen atoms, or may consist of two or more types of halogen atoms.
• Ar a1 an unsubstituted phenyl group is preferable.
• R a21 is a single bond or an alkylene group having 1 or more and 6 or less carbon atoms.
• alkylene groups having 1 to 6 carbon atoms include methylene group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group. group, pentane-1,5-diyl group, and hexane-1,6-diyl group.
• R a21 a single bond and a methylene group are preferable, and a single bond is more preferable.
• R a22 is an alkylene group having 1 or more and 6 or less carbon atoms.
• alkylene groups having 1 to 6 carbon atoms include methylene group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group. group, pentane-1,5-diyl group, and hexane-1,6-diyl group.
• a methylene group, an ethane-1,2-diyl group, and a propane-1,3-diyl group are preferable, and an ethane-1,2-diyl group and a propane-1,3-diyl group are more preferable.
• Ar a1 is a phenyl group and R a21 is a single bond. is particularly preferred.
• sulfur-containing (meth)acrylate represented by formula (A-2d) include 2-phenylthioethyl (meth)acrylate, 3-phenylthiopropyl (meth)acrylate, and 2-benzylthioethyl ( meth)acrylate, 3-benzylthiopropyl(meth)acrylate, 2-(2-chlorophenyl)ethyl(meth)acrylate, 2-(3-chlorophenyl)ethyl(meth)acrylate, 2-(4-chlorophenyl)ethyl(meth)acrylate ) acrylate, 3-(2-chlorophenyl)propyl (meth)acrylate, 3-(3-chlorophenyl)propyl (meth)acrylate, 3-(4-chlorophenyl)propyl (meth)acrylate, 2-(2-fluorophenyl) Ethyl (meth)acrylate, 2-(3-fluorophenyl)
• the composition contains a sulfur-containing (meth)acrylate represented by formula (A-2d) as another photopolymerizable compound (A2) having a radically polymerizable group-containing group
• the photopolymerizable compound (A) The ratio of the mass of the sulfur-containing (meth)acrylate represented by formula (A-2d) to the mass is preferably 40% by mass or more and 50% by mass or less.
• the composition preferably contains a compound represented by the following formula (A-2e) as the other photopolymerizable compound (A2), since it is easy to form a material with a high refractive index using the composition.
• R A1 , R A2 , and R A3 are each independently an organic group. At least two of the organic group as R A1 , the organic group as R A2 , and the organic group as R A3 have radically polymerizable group-containing groups.
• Preferred examples of the compound represented by formula (A-2e) include compounds represented by formula (A-2e-a) below.
• R A01 is a quinolinyl group which may have a substituent, an isoquinolinyl group which may have a substituent, or a 2-substituted benzothiazolyl group which may have a substituent. It is.
• the 2-substituted benzothiazolyl group has a group represented by -SR A0 at the 2-position.
• R A0 is a hydrogen atom or a radically polymerizable group-containing group.
• R A02 and R A03 are both aromatic ring-containing groups having a radically polymerizable group-containing group.
• the -NH- group bonded to the triazine ring is bonded to the aromatic rings in R A02 and R A03 .
• R A01 is a quinolinyl group which may have a substituent, an isoquinolinyl group which may have a substituent, or a 2-substituted benzothiazolyl group which may have a substituent. It is thought that this contributes to the high refractive index of the material formed using this method.
• the quinolinyl group as R A01 includes quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5-yl group, quinolin-6-yl group, quinolin-7-yl group. , and quinolin-8-yl group.
• the compound represented by formula (A2e-a) is easily available as a raw material, and the compound represented by formula (A2e-a) is easily synthesized.
• quinolin-3-yl group, and quinolin-4-yl group are preferred.
• the isoquinolinyl group as R A01 includes an isoquinolin-1-yl group, an isoquinolin-3-yl group, an isoquinolin-4-yl group, an isoquinolin-5-yl group, an isoquinolin-6-yl group, an isoquinolin-7-yl group , and isoquinolin-8-yl group.
• the substituents that the quinolinyl group and isoquinolinyl group as R A01 may have are not particularly limited as long as the desired effect is not impaired.
• substituents include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, nitro groups, and monovalent organic groups.
• halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the monovalent organic group include an alkyl group, an alkoxy group, an alkoxyalkyl group, an aliphatic acyl group, an aliphatic acyloxy group, an alkoxycarbonyl group, an alkylthio group, and an aliphatic acylthio group. Further, a radically polymerizable group-containing group described below is also preferable as a monovalent organic group.
• the number of carbon atoms in the monovalent organic group as a substituent is not particularly limited as long as the desired effect is not impaired.
• the number of carbon atoms in the monovalent organic group as a substituent is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less.
• the alkoxyalkyl group aliphatic acyl group, aliphatic acyloxy group, alkoxycarbonyl group, alkoxyalkylthio group, and aliphatic acylthio group
• the lower limit of the number of carbon atoms is 2.
• alkyl group as a substituent examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include n-hexyl group, n-heptyl group, and n-octyl group.
• alkoxy group as a substituent examples include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n- Examples include pentyloxy group, n-hexyloxy group, n-heptyloxy group, and n-octyloxy group.
• alkoxyalkyl group as a substituent examples include methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, n-butyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2- n-propyloxyethyl group, 2-n-butyloxyethyl group, 3-methoxy-n-propyloxy group, 3-ethoxy-n-propyloxy group, 3-n-propyloxy-n-propyloxy group, 3 -n-butyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, 4-n-propyloxy-n-butyloxy group, and 4-n-butyloxy-n- A butyloxy group is mentioned.
• Preferred specific examples of the aliphatic acyl group as a substituent include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, and an octanoyl group.
• Preferred specific examples of the aliphatic acyloxy group as a substituent include an acetoxy group, a propionyloxy group, a butanoyloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoyloxy group, and an octanoyloxy group.
• alkoxycarbonyl group as a substituent examples include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxy Examples include carbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, and n-octyloxycarbonyl group.
• alkylthio group as a substituent examples include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group. n-hexylthio, n-heptylthio, and n-octylthio.
• Preferred specific examples of the aliphatic acylthio group as a substituent include an acetylthio group, a propionylthio group, a butanoylthio group, a pentanoylthio group, a hexanoylthio group, a heptanoylthio group, and an octanoylthio group.
• the number of substituents is not particularly limited as long as the desired effect is not impaired.
• the number of substituents is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.
• the plurality of substituents may be different from each other.
• the 2-substituted benzothiazolyl group as R A01 has a group represented by -S-R A0 at the 2-position.
• the 2-substituted benzothiazolyl group as R A01 may have a substituent other than the group represented by -S-R A0 at a position other than 2.
• R A0 is a hydrogen atom or a radically polymerizable group-containing group. The radically polymerizable group-containing group will be described later.
• Preferred examples of the 2-substituted benzothiazolyl group include the following groups.
• the substituents that the 2-substituted benzothiazolyl group as R A01 may have are the same as the substituents that the quinolinyl group and isoquinolinyl group may have.
• the number of substituents is not particularly limited as long as the desired effect is not impaired.
• the number of substituents is preferably 1 or 2, and more preferably 1.
• the 2-substituted benzothiazolyl group has multiple substituents, the multiple substituents may be different from each other.
• R A02 and R A03 are both aromatic ring-containing groups having a radically polymerizable group-containing group. Note that the -NH- group bonded to the triazine ring is bonded to the aromatic rings in R A02 and R A03 .
• the bonding position of the radically polymerizable group-containing group in the aromatic ring-containing group as R A02 and R A03 is not particularly limited.
• the number of radically polymerizable group-containing groups in the aromatic ring-containing group as R A02 and the number of radically polymerizable group-containing groups in the aromatic ring-containing group as R A03 are not particularly limited.
• the number of radically polymerizable group-containing groups in the aromatic ring-containing group as R A02 and the number of radically polymerizable group-containing groups in the aromatic ring-containing group as R A03 are preferably an integer of 1 or more and 3 or less, and 1 or 2 is more preferred, and 1 is particularly preferred.
• the aromatic ring-containing group as R A02 and R A03 may contain only one monocyclic aromatic ring or one fused aromatic ring, and may include a monocyclic aromatic ring and/or a fused aromatic ring. It may contain two or more.
• the aromatic ring-containing groups as R A02 and R A03 contain two or more monocyclic aromatic rings and/or fused aromatic rings, the monocyclic aromatic rings may be combined with each other, the fused aromatic rings may be combined with each other, or the monocyclic aromatic rings may be combined with each other.
• the type of the linking group that connects the aromatic ring and the fused aromatic ring is not particularly limited.
• the linking group may be a divalent linking group, a trivalent or higher valent linking group, and a divalent linking group is preferred.
• a group represented by -CR a001 R a002 - is also preferable.
• R a001 and R a002 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms.
• R a001 and R a002 may be combined with each other to form a ring.
• Specific examples of the group represented by -CR a001 R a002 - include a methylene group, an ethane-1,1-diyl group, a propane-2,2-diyl group, a butane-2,2-diyl group, and a 1,1-diyl group. , 1,3,3,3-hexafluoropropane-2,2-diyl group, cyclopentylidene group, cyclohexylidene group, and cycloheptylidene group.
• the aromatic ring-containing groups as R A02 and R A03 have a radically polymerizable group-containing group.
• the radically polymerizable group-containing group is as described above.
• Suitable examples of the radically polymerizable group-containing group include groups represented by the following formula (AI) or the following formula (A-II), which do not fall under the vinyloxy group-containing group. -(A 01 ) na -R 01 ...(A-I) -(A 01 ) na -R 02 -A 02 -R 01 ...(A-II)
• R 01 is an alkenyl group having 2 or more and 10 or less carbon atoms.
• R 02 is an alkylene group having 1 or more and 10 or less carbon atoms.
• a 01 is -O-, -S-, -CO-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -CO-NH-, -NH-CO -, or -NH-.
• a 02 is -O-, -S-, -CO-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -CO-NH-, -NH-CO -, or -NH-.
• na is 0 or 1.
• Preferred specific examples of radically polymerizable group-containing groups include: -OR 03 , -SR 03 , -O-CH 2 CH 2 -O-R 03 , -O-CH 2 CH 2 CH 2 -O-R 03 , -O-CH 2 CH 2 CH 2 CH 2 -O-R 03 , -CO-O-CH 2 CH 2 -O-R 03 , -CO-O-CH 2 CH 2 CH 2 CH 2 -O-R 03 , -CO-O-CH 2 CH 2 CH 2 CH 2 -O-R 03 , -O-CH 2 CH 2 -NH-R 03 , -O-CH 2 CH 2 CH 2 -NH-R 03 , -O-CH 2 CH 2 CH 2 CH 2 -NH-R 03 , -CO-O-CH 2 CH 2 -NH-R 03 , -CO-O-CH 2 CH 2 CH 2 -NH-R 03 , -CO-O-CH 2 CH 2 CH 2 -NH-R
• R A02 and R A03 have one radically polymerizable group-containing group
• suitable examples of R A02 and R A03 include groups of the following formulas.
• PG is a radically polymerizable group-containing group.
• Preferred specific examples of the compound represented by formula (A-2e) include compounds of the following formula.
• X A is a group selected from the group consisting of (meth)acryloyloxy group, (meth)acryloylthio group, and 3-(meth)acryloyloxy-2-hydroxy-n-propyloxycarbonyl group. be.
• the method for producing the compound represented by formula (A-2e-a) is not particularly limited. Typically, it can be produced by reacting cyanuric halides such as cyanuric chloride with aromatic amines represented by R A01 --NH 2 , R A02 --NH 2 , and R A03 --NH 2 . These multiple types of amines may be reacted with cyanuric halides simultaneously or sequentially with cyanuric halides, and it is preferable to react with cyanuric halides sequentially.
• cyanuric halides such as cyanuric chloride
• aromatic amines represented by R A01 --NH 2 , R A02 --NH 2 , and R A03 --NH 2 .
• R A02 and R A03 in formula (A-2e-a) are expressed by reacting an aromatic amine having a functional group such as a hydroxyl group, a mercapto group, a carboxy group, or an amino group with a cyanuric halide; It can also be produced by reacting these functional groups with a compound that provides a radically polymerizable group-containing group.
• the compound that provides a radically polymerizable group-containing group include compounds having a radically polymerizable group such as (meth)acrylic acid, (meth)acrylic acid halide, and halogenated olefin.
• reaction between a functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group and a compound having a polymerizable group there is a well-known reaction that produces an ether bond, a carboxylic acid ester bond, a carboxylic acid amide bond, and a thioether bond. Reactions can be adopted.
• the reaction for forming the radically polymerizable group-containing group may be a multistep reaction.
• a cyanuric halide is reacted with an aromatic amine having a phenolic hydroxyl group. Thereafter, the phenolic hydroxyl group is reacted with epichlorohydrin to glycidylate it.
• a radically polymerizable group-containing group represented by the following formula can be introduced onto the aromatic ring.
• -O-CH 2 -CHOH-CH 2 -O-CO-CH CH 2
• the above reaction is an example, and the radically polymerizable group-containing group can be formed by combining various reactions.
• the compound represented by formula (A-2e-a) is usually synthesized in an organic solvent.
• an organic solvent is not particularly limited as long as it is an inert solvent that does not react with cyanuric halides, aromatic amines, radically polymerizable groups, and the like.
• organic solvents such as those exemplified as specific examples of the solvent (S) described later can be used.
• cyanuric halide and aromatic amines represented by R A01 -NH 2 , R A02 -NH 2 , R A03 -NH 2 , etc.
• the temperature at which the aromatic amines are reacted is not particularly limited. Typically, the reaction temperature is preferably from 0°C to 150°C.
• R A11 , R A12 , and R A13 are each an aromatic ring-containing group. At least one of R A12 and R A13 is a group represented by the following formula (A-2e-b1). The -NH- group bonded to the triazine ring is bonded to the aromatic ring in R A11 , R A12 , and R A13 , respectively.
• R a11 and R a12 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
• nA1 and nA2 are each independently an integer of 0 or more and 4 or less.
• R a13 and R a14 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group.
• R a13 and R a14 may be combined with each other to form a ring.
• R A14 is a radically polymerizable group-containing group.
• R A12 and R A13 are both groups represented by formula (A-2e-b1), R A12 and R A13 both have a radically polymerizable group-containing group.
• R A11 , R A12 , and R A13 are each aromatic ring-containing groups.
• the -NH- groups bonded to the triazine ring are bonded to the aromatic rings in R A11 , R A12 , and R A13 , respectively.
• the aromatic ring-containing group is a group other than the group represented by formula (A-2e-b1), the aromatic ring-containing group is not particularly limited as long as it satisfies the above predetermined requirements.
• the aromatic ring-containing group other than the group represented by formula (A-2e-b1) may contain only one monocyclic aromatic ring or one fused aromatic ring, and may include a monocyclic aromatic ring, and/or may contain two or more fused aromatic rings.
• monocyclic aromatic rings may be mixed together, fused aromatic rings may be fused together, or a monocyclic aromatic ring and a fused aromatic ring.
• the linking group may be a divalent linking group, a trivalent or higher valent linking group, and a divalent linking group is preferable.
• Preferred examples of the aromatic ring-containing group include a quinolinyl group which may have a substituent, an isoquinolinyl group which may have a substituent, and a 2-substituted benzothiazolyl group which may have a substituent.
• These groups include the quinolinyl group which may have a substituent, the isoquinolinyl group which may have a substituent, and the isoquinolinyl group which may have a substituent, as explained for R A01 in formula (A-2e-a). This is the same as the 2-substituted benzothiazolyl group.
• aromatic ring-containing group examples include a phenyl group that may have a substituent, a naphthyl group that may have a substituent, a biphenylyl group that may have a substituent, and a phenyl group that may have a substituent.
• phenylthiophenyl group that may have a substituent
• phenoxyphenyl group that may have a substituent
• phenylsulfonylphenyl group examples include a benzoxazolyl group which may have a substituent
• terphenyl group which may have a substituent.
• Preferred specific examples of the naphthyl group which may have a substituent include a naphthalen-1-yl group and a naphthalen-2-yl group.
• biphenylyl groups which may have substituents include 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4-(4-nitrophenyl)phenyl group, 3-(4 -nitrophenyl) phenyl group, 2-(4-nitrophenyl) phenyl group, 4-(4-cyanophenyl) phenyl group, 3-(4-cyanophenyl) phenyl group, and 2-(4-cyanophenyl) phenyl group Examples include groups.
• Preferred specific examples of the phenylthiophenyl group which may have a substituent include 4-phenylthiophenyl group, 3-phenylthiophenyl group, and 2-phenylthiophenyl group.
• Preferred specific examples of the phenoxyphenyl group which may have a substituent include 4-phenoxyphenyl group, 3-phenoxyphenyl group, and 2-phenoxyphenyl group.
• Preferred specific examples of the phenylsulfonylphenyl group which may have a substituent include 4-phenylsulfonylphenyl group, 3-phenylsulfonylphenyl group, and 2-phenylsulfonylphenyl group.
• Suitable examples of the terphenyl group which may have a substituent include 4-(4-phenylphenyl)phenyl group, 3-(4-phenylphenyl)phenyl group, and 2-(4-phenylphenyl)phenyl group. , 4-(3-phenylphenyl)phenyl group, 3-(3-phenylphenyl)phenyl group, 2-(3-phenylphenyl)phenyl group, 4-(2-phenylphenyl)phenyl group, 3-(2- phenyl phenyl) phenyl group, and 2-(2-phenylphenyl) phenyl group.
• the aromatic ring-containing group other than the group represented by formula (A-2e-b1) may have a radically polymerizable group-containing group as a substituent.
• the bonding position of the radically polymerizable group-containing group in the aromatic ring-containing group is not particularly limited.
• the number of radically polymerizable group-containing groups in the aromatic ring-containing group is not particularly limited.
• the number of radically polymerizable group-containing groups in the aromatic ring-containing group is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and particularly preferably 1.
• aromatic ring-containing group has one radically polymerizable group-containing group
• suitable examples of such a group include groups of the following formula.
• PG is a radically polymerizable group-containing group.
• R A12 and R A13 are a group represented by the following formula (A-2e-b1).
• R a11 and R a12 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
• nA1 and nA2 are each independently an integer of 0 or more and 4 or less.
• R a13 and R a14 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group.
• R a13 and R a14 may be combined with each other to form a ring.
• R A14 is a radically polymerizable group-containing group.
• Examples of the alkyl group having 1 to 4 carbon atoms as R a11 and R a12 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert -butyl group.
• Examples of the alkoxy group having 1 to 4 carbon atoms as R a11 and R a12 include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group , and tert-butyloxy group.
• Examples of the halogen atom as R a11 and R a12 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• alkyl groups having 1 to 4 carbon atoms as R a13 and R a14 are the same as specific examples of alkyl groups having 1 to 4 carbon atoms as R a11 and R a12 .
• halogenated alkyl groups having 1 to 4 carbon atoms as R a13 and R a14 include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, Examples include fluoromethyl group, difluoromethyl group, trifluoromethyl group, 3,3,3-trifluoroethyl, pentafluoroethyl group, and heptafluoropropyl group.
• Suitable examples of the group represented by formula (A-2e-b1) include groups represented by the following formula.
• the group represented by formula (A-2e-b1) has a radically polymerizable group-containing group as R A14 .
• the radically polymerizable group-containing group is as described above.
• Preferred specific examples of the radically polymerizable group-containing group are the same as the preferred specific examples of the radically polymerizable group-containing group described for the compound represented by formula (A-2e-a).
• Preferred specific examples of the compound represented by formula (A-2e-b) include compounds of the following formula.
• X A is selected from the group consisting of (meth)acryloyloxy group, (meth)acryloylthio group, 3-(meth)acryloyloxy-2-hydroxy-n-propyloxycarbonyl group, and glycidyloxy group. This is the group that is used.
• Y A is quinolin-3-yl group, phenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 2-cyanophenyl group, 3,4-dicyanophenyl group, 4-nitrophenyl group, 4-methoxyphenyl group group, 4-phenylthiophenyl group, 4-phenylsulfonylphenyl group, 4-iodophenyl group, benzothiazol-2-yl group, 2-mercaptobenzothiazol-5-yl group, 4-phenylphenyl group, 4-( It is a group selected from the group consisting of 4-nitrophenyl)phenyl group, 4-(4-cyanophenyl)phenyl group, naphthalen-1-yl group, and 4-(4-phenylphenyl)phenyl group.
• the method for producing the compound represented by formula (A-2e-b) is not particularly limited. Typically, it can be produced by reacting cyanuric halides such as cyanuric chloride with aromatic amines represented by R A11 --NH 2 , R A12 --NH 2 , and R A13 --NH 2 . These multiple types of amines may be reacted with cyanuric halides simultaneously or sequentially with cyanuric halides, and it is preferable to react with cyanuric halides sequentially.
• cyanuric halides such as cyanuric chloride
• aromatic amines represented by R A11 --NH 2 , R A12 --NH 2 , and R A13 --NH 2 .
• the aromatic amine having a functional group such as a hydroxyl group, mercapto group, carboxy group, or amino group can be A radically polymerizable group-containing group can also be generated by reacting these functional groups with a compound that provides a radically polymerizable group-containing group after the reaction with cyanuric acid.
• the compound that provides a radically polymerizable group-containing group include compounds having a radically polymerizable group such as (meth)acrylic acid, (meth)acrylic acid halide, and halogenated olefin.
• reaction between a functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group and a compound having a polymerizable group there is a well-known reaction that produces an ether bond, a carboxylic acid ester bond, a carboxylic acid amide bond, and a thioether bond. Reactions can be adopted.
• the reaction for forming the radically polymerizable group-containing group may be a multistep reaction.
• a cyanuric halide is reacted with an aromatic amine having a phenolic hydroxyl group. Thereafter, the phenolic hydroxyl group is reacted with epichlorohydrin to glycidylate it.
• a radically polymerizable group-containing group represented by the following formula can be introduced onto the aromatic ring.
• -O-CH 2 -CHOH-CH 2 -O-CO-CH CH 2
• the above reaction is an example, and the radically polymerizable group-containing group can be formed by combining various reactions.
• the compound represented by formula (A-2e-b) is usually synthesized in an organic solvent.
• an organic solvent is not particularly limited as long as it is an inert solvent that does not react with cyanuric halides, aromatic amines, radically polymerizable groups, and the like.
• organic solvents and the like illustrated as specific examples of the solvent (S) can be used.
• the temperature at which the aromatic amines are reacted is not particularly limited. Typically, the reaction temperature is preferably 0°C or higher and 150°C or lower.
• the content of the photopolymerizable compound (A) in the composition is not particularly limited as long as the desired effect is not inhibited.
• the content of the photopolymerizable compound (A) in the composition is 0.1 parts by mass or more and 50 parts by mass or less when the mass of the composition excluding the mass of the solvent (S) described below is 100 parts by mass. It is preferably 0.5 parts by mass or more and 40 parts by mass or less, more preferably 1 part by mass or more and 25 parts by mass or less.
• the composition includes inorganic particles (B).
• the material of the inorganic particles (B) is not particularly limited as long as it is an inorganic material.
• the inorganic particles (B) are preferably one or more selected from the group consisting of metal oxide particles (B1) and metal particles (B2).
• metal oxide particles (B1) it is easy to form a cured product with a high refractive index using the composition.
• the composition contains metal particles (B2), conductivity is imparted to a material formed using the composition, or the light absorption of a specific wavelength of a material formed using the composition is enhanced.
• the composition containing metal particles (B2) is used to form a material that can be applied to a bandpass filter.
• the type of metal oxide constituting the metal oxide particles (B1) is not particularly limited as long as the desired effect is not impaired.
• Preferred examples of the metal oxide particles (B1) include at least one selected from the group consisting of zirconium oxide particles, titanium oxide particles, barium titanate particles, cerium oxide particles, and niobium pentoxide particles.
• the type of metal constituting the metal particles (B2) is not particularly limited as long as the desired effect is not impaired.
• the metal constituting the metal particles (B2) may be a single substance or an alloy.
• Preferred examples of the metal particles (B2) include gold particles and platinum particles.
• Other preferred inorganic particles (B) include silicon particles (silicon nanoparticles) that are semimetal particles.
• the composition may contain one type of these inorganic particles (B) alone, or a combination of two or more types.
• the average particle diameter of the inorganic particles (B) is preferably 500 nm or less from the viewpoint of transparency of the material formed using the composition and stability of dispersion of the inorganic particles (B) in the composition. , preferably 2 nm or more and 100 nm or less.
• the metal oxide particles (B1) preferably have surfaces modified with ethylenically unsaturated double bond-containing groups. It is preferable that the surface of the metal oxide particles (B1) is modified with an ethylenically unsaturated double bond-containing group, since aggregation of the metal oxide particles (B1) is less likely to occur.
• the ethylenically unsaturated double bond can be bonded to the surface through chemical bonds such as covalent bonds.
• Metal oxide particles (B1) modified with a containing group are obtained.
• the method of bonding the capping agent containing an ethylenically unsaturated double bond to the surface of the metal oxide particles (B1) via a chemical bond such as a covalent bond is not particularly limited.
• a hydroxyl group usually exists on the surface of the metal oxide particles (B1).
• the capping agent is covalently bonded to the surface of the metal oxide particles (B1).
• trialkoxysilyl groups such as trimethoxysilyl group and triethoxylyl group
• the trialkoxysilyl group, dialkoxysilyl group, monoalkoxysilyl group, trihalosilyl group, dihalosilyl group, and monohalosilyl group form a siloxane bond with the surface of the metal oxide particles (B1).
• the carboxyl group and the halocarbonyl group form a bond represented by (metal oxide-O-CO-) with the surface of the metal oxide particle (B1).
• the hydroxyl group forms a bond represented by (metal oxide-O-) with the surface of the metal oxide particle (B1).
• examples of the group that binds to the above-mentioned reactive group include a hydrogen atom and various organic groups.
• the organic group may contain a heteroatom such as O, N, S, P, B, Si, or a halogen atom.
• Groups that bond to the above-mentioned reactive groups include, for example, alkyl groups that may be linear or branched, and may be interrupted by an oxygen atom (-O-); an alkenyl group which may be straight-chain or branched and which may be interrupted by an oxygen atom (-O-); Examples thereof include an alkynyl group, a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group, which may be substituted.
• substituents such as a halogen atom, an epoxy group-containing group such as a glycidyl group, a hydroxyl group, a mercapto group, an amino group, a (meth)acryloyl group, and an isocyanate group.
• substituents such as a halogen atom, an epoxy group-containing group such as a glycidyl group, a hydroxyl group, a mercapto group, an amino group, a (meth)acryloyl group, and an isocyanate group.
• substituents such as a halogen atom, an epoxy group-containing group such as a glycidyl group, a hydroxyl group, a mercapto group, an amino group, a (meth)acryloyl group, and an isocyanate group.
• the number of substituents is not particularly limited.
• R b1 , R b2 , R b3 , and Rb4 are each organic groups that may be the same or different.
• Suitable examples of organic groups include alkyl groups such as methyl group and ethyl group; alkenyl groups such as vinyl group and allyl group; aromatic hydrocarbon groups such as phenyl group, naphthyl group and tolyl group; 3-glycidoxy Examples include epoxy group-containing groups such as propyl groups; and (meth)acryloyloxy groups.
• r and s in the above formula are each independently an integer of 0 or more and 60 or less. Both r and s in the above formula are never 0.
• Preferred specific examples of the capping agent include vinyltrimethoxylane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 1-hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane.
• Unsaturated groups such as silane, 1-octenyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloylpropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, etc.
• alkoxysilane Containing alkoxysilane; unsaturated group-containing alcohols such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, allyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, and 3-allyloxypropanol (meth)acrylic acid; and (meth)acrylic acid halides such as (meth)acrylic acid chloride.
• unsaturated group-containing alcohols such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, allyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, and 3-allyloxypropanol (meth)acrylic acid
• (meth)acrylic acid halides such as (meth)acrylic acid chloride.
• the amount of the capping agent used when bonding the capping agent to the surface of the metal oxide particles (B1) via a chemical bond such as a covalent bond is not particularly limited.
• a sufficient amount of capping agent is used to react with substantially all of the hydroxyl groups on the surface of the metal oxide particles (B1).
• the content of the inorganic particles (B) in the composition is not particularly limited as long as it does not impede the object of the present invention.
• the content of the inorganic particles (B) in the composition is preferably 5% by mass or more and 95% by mass or less, and 35% by mass or more and 93% by mass or less, based on the mass excluding the mass of the solvent (S) of the composition. is more preferable, and even more preferably 40% by mass or more and 90% by mass or less.
• the compositions also facilitate forming materials that have the desired effects provided by the use of inorganic particles (B).
• the content of the metal oxide particles (B1) in the composition is determined from the viewpoint that it is easy to form a material with a particularly high refractive index.
• the amount is preferably 70% by mass or more based on the mass excluding the mass of the solvent (S).
• the content of metal oxide particles in the composition may be 75% by mass or more and 98% by mass or less, and 80% by mass or more and 95% by mass, based on the mass excluding the mass of the solvent (S) of the composition. % or less.
• the surface of the metal oxide particles (B1) is modified with an ethylenically unsaturated double bond-containing group
• the ethylenically unsaturated double bond-containing group present on the surface of the metal oxide particles (B1)
• the mass of the capping agent having the following is included in the mass of the metal oxide particles (B1).
• the composition may also contain a plasticizer (D).
• the plasticizer (D) is a component that lowers the viscosity of the composition without significantly impairing various physical properties such as a high refractive index of the material formed using the composition.
• plasticizer (D) a compound represented by the following formula (d-1) is preferred.
• R d1 and R d2 are each independently a phenyl group which may have 1 or more and 5 or less substituents.
• the substituent is selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.
• R d3 and R d4 are each independently a methylene group or an ethane-1,2-diyl group.
• r and s are each independently 0 or 1.
• X d is an oxygen atom or a sulfur atom.
• the viscosity of the composition can be reduced without significantly impairing various physical properties such as a high refractive index of a material formed using the composition.
• the viscosity of the plasticizer (D) measured at 25° C. using an E-type viscometer is preferably 10 cP or less, more preferably 8 cP or less, and even more preferably 6 cP or less.
• the plasticizer (D) preferably has a boiling point of 250° C. or higher at atmospheric pressure, from the viewpoint that the plasticizer (D) is difficult to volatilize and the effect of lowering the viscosity of the composition is easily maintained. It is more preferable that the temperature is at least °C.
• the upper limit of the boiling point of the plasticizer (D) under atmospheric pressure is not particularly limited, but may be, for example, 300°C or lower, or 350°C or lower.
• R d1 and R d2 in formula (d-1) are each independently a phenyl group which may have 1 or more and 5 or less substituents.
• the substituent bonded to the phenyl group is a group selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.
• the number of substituents is not particularly limited.
• the number of substituents is 1 or more and 5 or less, preferably 1 or 2, and preferably 1. From the viewpoint of reducing the viscosity of the composition, it is preferable that R d1 and R d2 are each unsubstituted phenyl groups.
• Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. Can be mentioned.
• Examples of the alkoxy group having 1 to 4 carbon atoms as a substituent include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, and tert- A butyloxy group is mentioned.
• Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• R d3 and R d4 in formula (d-1) are each independently a methylene group or an ethane-1,2-diyl group. Further, r and s are each independently 0 or 1.
• X d in formula (d-1) is an oxygen atom or a sulfur atom.
• Preferred specific examples of the compound represented by formula (d-1) described above include diphenyl ether, diphenyl sulfide, dibenzyl ether, dibenzyl sulfide, diphenethyl ether, and diphenethyl sulfide. Among these, diphenyl sulfide and/or dibenzyl ether are more preferred.
• the content of the plasticizer (D) in the composition is preferably more than 0% by mass and 35% by mass or less, based on the mass of the entire composition, from the viewpoint of achieving both viscosity adjustment and dispersibility of the inorganic particles (B). , more preferably 5% by mass or more and 15% by mass or less.
• the composition contains an amine compound (E1) represented by the following formula (e1) and/or an amine compound represented by the following formula (e2).
• the imine compound (E2) may be contained as the nitrogen-containing compound (E).
• R e1 , R e2 , and R e3 are each independently a hydrogen atom or an organic group.
• R e4 , R e5 , and R de6 are each independently a hydrogen atom or an organic group.
• R e1 , R e2 , R e3 , R e4 , R e5 , and R de6 are organic groups
• the organic groups have a range that does not impair the desired effect. can be selected from a variety of organic groups.
• the organic group is preferably a carbon atom-containing group, with one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Suitable examples of the organic group include an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, Examples include a naphthylalkyl group which may have a substituent, and a heterocyclyl group which may have a substituent.
• the number of carbon atoms in the alkyl group as an organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less.
• the structure of the alkyl group may be linear or branched. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group.
• the alkyl group may contain an ether bond (-O-) in the carbon chain.
• alkyl group having an ether bond in the carbon chain examples include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.
• the number of carbon atoms in the cycloalkyl group as an organic group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less.
• Specific examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.
• the number of carbon atoms in the phenylalkyl group as an organic group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less.
• the number of carbon atoms in the naphthylalkyl group as an organic group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less.
• Specific examples of the phenylalkyl group include benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group.
• the naphthylalkyl group examples include ⁇ -naphthylmethyl group, ⁇ -naphthylmethyl group, 2-( ⁇ -naphthyl)ethyl group, and 2-( ⁇ -naphthyl)ethyl group.
• the phenylalkyl group or naphthylalkyl group may further have a substituent on the phenyl group or naphthyl group.
• the heterocyclyl group is the same as when R c4 in formula (c3) is a heterocyclyl group, and the heterocyclyl group may further have a substituent.
• the heterocyclyl group as an organic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group.
• the heterocyclyl group is preferably a 5- or 6-membered monocyclic ring containing one or more of N, S, and O, or a heterocyclyl group in which such monocycles are fused together, or such monocycles and a benzene ring are condensed.
• the heterocyclyl group is a fused ring, the number of rings is up to 3.
• heterocycle constituting such a heterocyclyl group examples include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It will be done.
• substituents include an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.
• halogenated alkyl group having 1 to 6 carbon atoms halogenated alkoxy group having 1 to 6 carbon atoms
• saturated aliphatic acyl group having 2 to 7 carbon atoms halogenated alkyl group having 1 to 6 carbon atoms
• saturated aliphatic acyl group having 2 to 7 carbon atoms Alkoxycarbonyl group, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms , benzoyl group, halogen atom, nitro group, and cyano group.
• the number of the substituents is not particularly limited, and is preferably 1 or more and 4 or less.
• the phenyl group, naphthyl group, and heterocyclyl group contained in the organic group have a plurality of substituents, the plurality of substituents may be the same or different.
• R e1 , R e2 , and R e3 are each independently a hydrogen atom or an organic group. At least one of R e1 , R e2 , and R e3 is an aromatic group-containing group.
• R e4 , R e5 , and R de6 are each independently a hydrogen atom or an organic group. At least one of R e4 , R e5 , and R de6 is an aromatic group-containing group.
• the aromatic ring in the aromatic group-containing group may be an aromatic hydrocarbon ring or an aromatic heterocycle.
• the aromatic group-containing group is preferably a hydrocarbon group.
• an aromatic hydrocarbon group (aryl group) and an aralkyl group are preferable.
• the aromatic hydrocarbon group include a phenyl group, a naphthalen-1-yl group, and a naphthalen-2-yl group.
• phenyl group is preferred.
• the aralkyl group include benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group.
• R e1 is an aromatic group which may have a substituent.
• the aromatic group as Ar e1 may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
• the aromatic group as Ar e1 is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthalen-1-yl group, and a naphthalen-2-yl group. Among these aromatic hydrocarbon groups, phenyl group is preferred.
• the substituent that the aromatic group as Ar e1 may have is a phenyl group, a naphthyl group , or a heterocyclyl group, and The same applies to the substituents that these groups may have in some cases.
• Preferred specific examples of the amine compound represented by formula (e1) include triphenylamine, N,N-diphenylbenzylamine, N-phenyldibenzylamine, tribendialmine, N,N-dimethylphenylamine, N -Methyldiphenylamine, N,N-dimethylbenzylamine, N-methyldibenzylamine, N-methyl-N-benzylphenylamine, N,N-diethylphenylamine, N-ethyldiphenylamine, N,N-diethylbenzylamine, N-ethyldibenzylamine and N-ethyl-N-benzylphenylamine are mentioned.
• Preferred specific examples of the imine compound represented by formula (e2) include N-benzylphenylmethanimine, N-benzyldiphenylmethanimine, N-benzyl-1-phenylethanimine, and N-benzylpropan-2-imine. can be mentioned.
• the content of the nitrogen-containing compound (E) in the composition is not particularly limited as long as the desired effect is not impaired.
• the content of the nitrogen-containing compound (E) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 5% by mass or less, based on the mass of the photopolymerizable compound (A). .
• the composition may contain a compound represented by the following formula (F1) as the triazine compound (F).
• R F1 , R F2 , and R F3 are each independently a monocyclic aromatic group which may have a substituent, or a fused aromatic group which may have a substituent. It is. However, R F1 , R F2 , and R F3 do not contain a radically polymerizable group-containing group. When a monocyclic aromatic group or a fused aromatic group has a substituent, the substituent does not include an aromatic ring.
• the three -NH- groups bonded to the triazine ring are bonded to the aromatic rings in R F1 , R F2 and R F3 , respectively.
• the monocyclic aromatic groups as R F1 , R F2 , and R F3 may be aromatic hydrocarbon groups or aromatic heterocyclic groups.
• Examples of the monocyclic aromatic group include a phenyl group, a pyridinyl group, a pimidinyl group, a pyrazinyl group, a pyridazinyl group, a furanyl group, a thienyl group, an oxazolyl group, and a thiazolyl group.
• substituents that the monocyclic aromatic group may have include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a nitro group, and a monovalent organic group.
• the monovalent organic group does not contain an aromatic ring.
• the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the monovalent organic group include an alkyl group, an alkoxy group, an alkoxyalkyl group, an aliphatic acyl group, an aliphatic acyloxy group, an alkoxycarbonyl group, an alkylthio group, and an aliphatic acylthio group.
• the number of carbon atoms in the monovalent organic group as a substituent is not particularly limited as long as the desired effect is not impaired.
• the number of carbon atoms in the monovalent organic group as a substituent is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less.
• the alkoxyalkyl group aliphatic acyl group, aliphatic acyloxy group, alkoxycarbonyl group, alkoxyalkylthio group, and aliphatic acylthio group
• the lower limit of the number of carbon atoms is 2.
• alkyl group as a substituent examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include n-hexyl group, n-heptyl group, and n-octyl group.
• alkoxy group as a substituent examples include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n- Examples include pentyloxy group, n-hexyloxy group, n-heptyloxy group, and n-octyloxy group.
• alkoxyalkyl group as a substituent examples include methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, n-butyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2- n-propyloxyethyl group, 2-n-butyloxyethyl group, 3-methoxy-n-propyloxy group, 3-ethoxy-n-propyloxy group, 3-n-propyloxy-n-propyloxy group, 3 -n-butyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, 4-n-propyloxy-n-butyloxy group, 4-n-butyloxy-n-butyloxy Examples include groups.
• Preferred specific examples of the aliphatic acyl group as a substituent include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, and an octanoyl group.
• Preferred specific examples of the aliphatic acyloxy group as a substituent include an acetoxy group, a propionyloxy group, a butanoyloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoyloxy group, and an octanoyloxy group.
• alkoxycarbonyl group as a substituent examples include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxy Examples include carbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, and n-octyloxycarbonyl group.
• alkylthio group as a substituent examples include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group. n-hexylthio, n-heptylthio, and n-octylthio.
• Preferred specific examples of the aliphatic acylthio group as a substituent include an acetylthio group, a propionylthio group, a butanoylthio group, a pentanoylthio group, a hexanoylthio group, a heptanoylthio group, and an octanoylthio group.
• the number of substituents is not particularly limited as long as the desired effect is not impaired.
• the number of substituents is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.
• the monocyclic aromatic group has a plurality of substituents, the plurality of substituents may be different from each other.
• phenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 2-cyanophenyl group, 4-nitrophenyl group, 3-nitrophenyl group, and 2-nitrophenyl group are preferred, and phenyl and 4-cyanophenyl group are more preferred.
• the fused aromatic groups as R F1 , R F2 , and R F3 are groups obtained by removing one hydrogen atom from a fused polycycle in which two or more aromatic monocycles are fused.
• the number of aromatic monocycles constituting the fused aromatic group is not particularly limited.
• the number of aromatic monocycles constituting the fused aromatic group is preferably 2 or 3, and more preferably 2. That is, the fused aromatic group is preferably a two-ring fused aromatic group or a three-ring fused aromatic group, and more preferably a two-ring fused aromatic group.
• the fused aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
• bicyclic fused aromatic group examples include naphthalen-1-yl group, naphthalen-2-yl group, quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5 -yl group, quinolin-6-yl group, quinolin-7-yl group, quinolin-8-yl group, isoquinolin-1-yl group, isoquinolin-3-yl group, isoquinolin-4-yl group, isoquinolin-5-yl group yl group, isoquinolin-6-yl group, isoquinolin-7-yl group, isoquinolin-8-yl group, benzoxazol-2-yl group, benzoxazol-4-yl group, benzoxazol-5-yl group, benzoxazole -6-yl group, benzoxazol-7-yl group, benzothiazol-2-yl group, benzothiazol-4-yl group,
• tricyclic fused aromatic group examples include anthracen-1-yl group, anthracen-2-yl group, anthracen-9-yl group, phenanthren-1-yl group, phenanthren-2-yl group, phenanthrene-3 -yl group, phenanthren-4-yl group, phenanthren-9-yl group, acridin-1-yl group, acridin-2-yl group, acridin-3-yl group, acridin-4-yl group, and acridin-9 -yl group is mentioned.
• a polycyclic fused aromatic group such as a bicyclic fused aromatic group and a tricyclic fused aromatic group may have are the same as the substituents that a monocyclic aromatic group may have. The same is true.
• the fused cyclic aromatic group which may have a substituent as described above includes naphthalen-1-yl group, naphthalen-2-yl group, quinolin-2-yl group, quinolin-3-yl group, quinolin-3-yl group, and quinolin-2-yl group.
• -4-yl group, quinolin-5-yl group, quinolin-6-yl group, quinolin-7-yl group, quinolin-8-yl group, benzothiazol-2-yl group, and 2-mercaptobenzothiazol-6 -yl group is preferred.
• naphthalen-1-yl group quinolin-3-yl group, quinolin-4-yl group, and 2-mercaptobenzothiazol-6-yl group are preferred, and naphthalen-1-yl group is preferred. More preferred.
• R F1 , R F2 , and R F3 is a naphthyl group which may have a substituent, and one or two of R F1 , R F2 , and R F3 is a 4-cyanophenyl group, or Compounds that are benzothiazolyl groups are preferred.
• a naphthalen-1-yl group is preferable.
• Preferable specific examples of the compound represented by formula (F1) include compounds of the following formula.
• the method for producing the compound represented by formula (F1) is not particularly limited. Typically, it can be produced by reacting cyanuric halides such as cyanuric chloride with aromatic amines represented by R F1 --NH 2 , R F2 --NH 2 , and R F3 --NH 2 . These multiple types of amines may be reacted with cyanuric halides simultaneously or sequentially with cyanuric halides, and it is preferable to react with cyanuric halides sequentially.
• cyanuric halides such as cyanuric chloride
• aromatic amines represented by R F1 --NH 2 , R F2 --NH 2 , and R F3 --NH 2 .
• the compound represented by formula (F1) is usually synthesized in an organic solvent.
• an organic solvent is not particularly limited as long as it is an inert solvent that does not react with cyanuric halides, aromatic amines, radically polymerizable groups, and the like.
• organic solvents, etc. which are exemplified as specific examples of the solvent (S) described later, can be used.
• cyanuric halide and aromatic amines such as aromatic amines represented by R F1 -NH 2 , R F2 -NH 2 , and R F3 -NH 2 are used.
• the temperature at which the reaction is performed is Typically, the reaction temperature is preferably 0°C or higher and 150°C or lower.
• the content of the triazine compound (F) in the composition is not particularly limited as long as the desired effect is not inhibited.
• the content of the triazine compound (F) in the composition is, for example, 0.1 parts by mass or more and 30 parts by mass or less when the mass of the composition excluding the mass of the solvent (S) described below is 100 parts by mass. It is preferably 0.3 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less.
• the composition may contain a solvent (S) for the purpose of adjusting coating properties.
• the type of solvent (S) is not particularly limited as long as the desired effect is not inhibited.
• Suitable examples of the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol.
• the solvent (S) contains a solvent with a boiling point of 140°C or higher under atmospheric pressure, and a high-temperature solvent with a boiling point of 170°C or higher under atmospheric pressure. It is more preferable to include a boiling point solvent (S1).
• solvents with a boiling point of 140°C or higher at atmospheric pressure include ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether (HO-CH 2 CH 2 CH 2 -O-CH 3 ), propylene glycol monoethyl ether (HO -CH 2 CH 2 CH 2 -O-CH 2 CH 3 ), propylene glycol mono-n-propyl ether (HO-CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 3 ), propylene glycol mono-n- Propyl ether (HO-C(CH 3 )HCH 2 -O-CH 2 CH 2 CH 3 , or H 3 CH 2 CH 2 CH
• the high boiling point solvent (S1) include ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol monoethyl ether, propylene glycol mono-n-butyl ether (HO-CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 CH 3 ), propylene glycol mono-n-butyl ether (HO-C(CH 3 ) )HCH 2 -O-CH 2 CH 2 CH 2 CH 3 , or H 3 CH 2 CH 2 CH 2 C-O-C(CH 3 )HCH 2 -OH), dipropylene glycol monoethyl ether (HO-(CH 2 CH 2 CH 2 -O) 2 -CH 3 ), dipropylene glycol monomethyl ether (HO-(C(CH 3 )
• the ratio of the mass of the solvent with a boiling point of 140° C. or higher or the high-boiling point solvent (S1) with a boiling point of 170° C. or higher to the mass of the solvent (S) is preferably 20% by mass or more, and 30% by mass or more. It is more preferably at least 50% by mass, even more preferably at least 70% by mass, particularly preferably at least 90% by mass, and most preferably at least 100% by mass.
• the content of the solvent (S) is preferably such that the concentration of components other than the solvent (S) in the composition is 1% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 50% by mass or less. , more preferably 10% by mass or more and 30% by mass or less.
• the composition may contain various additives as other components other than the above-mentioned components, if necessary.
• Additives include sensitizers, curing accelerators, fillers, dispersants, adhesion promoters such as silane coupling agents, antioxidants, anti-aggregation agents, thermal polymerization inhibitors, antifoaming agents, surfactants, etc. can be mentioned.
• the amounts of these additives to be used are appropriately determined in consideration of the amounts in which these additives are normally used in the composition.
• the photosensitive composition includes a photopolymerizable compound (A), inorganic particles (B), and an initiator (C).
• the initiator (C) is a component that cures the photopolymerizable compound. Preferred embodiments and usage amounts of the photopolymerizable compound (A) and the inorganic particles (B) are as described above for the above composition.
• the photosensitive composition is further selected from the group consisting of a plasticizer (D), a nitrogen-containing compound (E), a triazine compound (F), a solvent (S), and other components, each of which is described above in the above composition. It may contain one or more components. Preferred embodiments and usage amounts of these components are as described above for the above composition.
• the photosensitive composition contains an initiator (C). Since the photopolymerizable compound (A) has a radically polymerizable group, a radical polymerization initiator is used as the initiator (C). As the initiator (C), a photoinitiator is used because it can perform position-selective curing of the photosensitive composition and there is no concern about thermal deterioration, volatilization, sublimation, etc. of the components of the photosensitive composition. is used.
• the initiator (C) is not particularly limited, and various conventionally known polymerization initiators can be used.
• photoradical polymerization initiators useful as radical polymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-( 2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4 -dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O-acetyl-1 -[6-(2-methylbenzoyl)-9-ethyl
• oxime ester compounds are preferred from the viewpoint of sensitivity of the photosensitive composition.
• a compound having a partial structure represented by the following formula (c1) is preferable.
• n1 is 0 or 1.
• R c2 is a monovalent organic group.
• R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. * is a bond.
• the compound having a partial structure represented by formula (c1) preferably has a carbazole skeleton, a fluorene skeleton, a diphenyl ether skeleton, or a phenyl sulfide skeleton.
• the compound having a partial structure represented by formula (c1) preferably has one or two partial structures represented by formula (c1).
• Examples of the compound having a partial structure represented by formula (c1) include a compound represented by formula (c2) below.
• R c1 is a group represented by the following formula (c3), (c4), or (c5).
• n1 is 0 or 1.
• R c2 is a monovalent organic group.
• R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.
• R c4 is a monovalent organic group.
• R c5 is a monovalent organic group, a halogen atom, or a nitro group.
• n2 is an integer from 0 to 3. When n2 is 2 or 3, the plurality of R c5s may be the same or different, and the plurality of R c5s may be bonded to each other to form a ring. * is a bond.
• R c6 and R c7 each independently represent a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, or a chain alkyl group which may have a substituent.
• R c6 and R c7 may be combined with each other to form a ring.
• R c7 and the benzene ring in the fluorene skeleton may be bonded to each other to form a ring.
• R c8 is a nitro group or a monovalent organic group.
• n3 is an integer from 0 to 4. * is a bond.
• R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group.
• A is S or O.
• n4 is an integer from 0 to 4. * is a bond.
• R c4 is a monovalent organic group.
• R c4 can be selected from various organic groups within the range that does not impede the purpose of the present invention.
• the organic group is preferably a carbon atom-containing group, with one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• R c4 examples include an alkyl group which may have a substituent having 1 to 20 carbon atoms, a cycloalkyl group which may have a substituent having 3 to 20 carbon atoms, and a carbon atom.
• a saturated aliphatic acyl group which may have a substituent of 2 or more and 20 or less, an alkoxycarbonyl group which may have a substituent of 2 or more and 20 or less carbon atoms, a phenyl group which may have a substituent , a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a phenylalkyl group which may have a substituent naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted naphthyl alkyl group having 11 to
• R c4 an alkyl group having 1 or more and 20 or less carbon atoms is preferred.
• the alkyl group may be linear or branched.
• the number of carbon atoms in the alkyl group as R c4 is preferably 2 or more, more preferably 5 or more, and 7 The above is particularly preferable.
• the number of carbon atoms in the alkyl group as R c4 is 15 or less. is preferable, and 10 or less is more preferable.
• R c4 has a substituent
• suitable examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms.
• the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group.
• the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O, or such monocycles are fused together, or such monocycles are fused with a benzene ring. It is a heterocyclyl group.
• the heterocyclyl group is a fused ring, the number of rings is up to 3.
• heterocycle constituting such a heterocyclyl group examples include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran.
• R c4 is a heterocyclyl group
• substituents that the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, and the like.
• R c4 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl group, neopentyl group, pentan-3-yl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and 2-ethylhexyl group.
• n-octyl group and 2-ethylhexyl group are preferable, and 2-ethylhexyl group is more preferable.
• R c5 is a monovalent organic group, a halogen atom, or a nitro group.
• the monovalent organic group as R c5 can be selected from various organic groups as long as the purpose of the present invention is not impaired.
• the organic group is preferably a carbon atom-containing group, with one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Examples of monovalent organic groups suitable as R c5 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and those having substituents.
• R c5 is an alkyl group
• the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less.
• R c5 is an alkyl group, it may be a straight chain or a branched chain.
• Specific examples when R c5 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group.
• alkyl group having an ether bond in the carbon chain examples include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.
• R c5 is an alkoxy group
• the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, when R c5 is an alkoxy group, it may be a straight chain or a branched chain.
• R c5 is an alkoxy group
• R c5 is an alkoxy group
• R c5 is an alkoxy group
• R c5 is an alkoxy group
• R c5 is an alkoxy group
• R c5 is an alkoxy group
• R c5 is an alkoxy group
• R c5 is an alkoxy group
• R c5 is an alkoxy group
• R c5 is an alkoxy group
• R c5 is an alkoxy group.
• R c5 is an alkoxy group
• the alkoxy group may contain an ether bond (-O-) in the carbon chain.
• the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, and methoxypropyloxy group.
• R c5 is a cycloalkyl group or a cycloalkoxy group
• the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less.
• Specific examples when R c5 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
• R c5 is a cycloalkoxy group
• R c5 is a cycloalkoxy group
• R c5 is a cycloalkoxy group
• R c5 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group
• the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less.
• R c5 is a saturated aliphatic acyl group
• R c5 is a saturated aliphatic acyl group
• examples when R c5 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanoyl group
• Examples thereof include a noyl group and an n-hexadecanoyl group.
• R c5 is a saturated aliphatic acyloxy group
• R c5 is a saturated aliphatic acyloxy group
• examples when R c5 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n Examples include -dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexa
• R c5 is an alkoxycarbonyl group
• the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less.
• Specific examples when R c5 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl group.
• R c5 is a phenylalkyl group
• the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less.
• R c5 is a naphthylalkyl group
• the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less.
• Specific examples when R c5 is a phenylalkyl group include benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group.
• R c5 is a naphthyl alkyl group
• R c5 is a naphthyl alkyl group
• R c5 may further have a substituent on the phenyl group or naphthyl group.
• R c5 is a heterocyclyl group
• the heterocyclyl group is the same as when R c4 in formula (c3) is a heterocyclyl group, and the heterocyclyl group may further have a substituent.
• R c5 is a heterocyclylcarbonyl group
• the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R c5 is a heterocyclyl group.
• R c5 is an amino group substituted with 1 or 2 organic groups
• suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, Saturated aliphatic acyl group having 2 to 21 carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, 7 to 20 carbon atoms which may have a substituent
• amino groups substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoyla
• the substituent includes a group represented by HX 2 C- or H 2 XC-, and the number of carbon atoms.
• the number of the substituent is not limited as long as it does not impede the object of the present invention, and is preferably 1 or more and 4 or less.
• the phenyl group, naphthyl group, and heterocyclyl group contained in R c5 have a plurality of substituents, the plurality of substituents may be the same or different.
• R c5 When the benzoyl group contained in R c5 further has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a 2-thenoyl group. (thiophen-2-ylcarbonyl group), furan-3-ylcarbonyl group, phenyl group, and the like.
• halogen atom represented by X examples include fluorine atom, chlorine atom, bromine atom, etc., and fluorine atom is preferable.
• substituents containing a group represented by HX 2 C- or H 2 XC- include a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-, HX 2 C- or H 2 XC-; A group having a halogenated alkoxy group including a group represented by -, a halogenated alkyl group including a group represented by HX 2 C- or H 2 Examples include groups having a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-, or a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 A group having a halogenated alkoxy group containing a group is more preferable.
• the group having a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC- is a group substituted with a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC- aromatic groups (e.g., phenyl group, naphthyl group, etc.), cycloalkyl groups substituted with halogenated alkyl groups (e.g., cyclopentyl group, cyclohexyl group, etc. )
• the aromatic group is preferably an aromatic group substituted with a halogenated alkyl group including a group represented by HX 2 C- or H 2 XC-.
• the group having a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC- is a group substituted with a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC- (e.g., phenyl group, naphthyl group, etc.), an alkyl group substituted with a halogenated alkoxy group (e.g., methyl group, ethyl group, etc.) containing a group represented by HX 2 C- or H 2 XC- , n-propyl group, i-propyl group, etc.), a cycloalkyl group substituted with a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC- (for example, cyclopentyl group, cyclohexyl group, etc.) ), and is preferably an aromatic group substituted with a halogenated alkoxy
• R c5 are a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring.
• the substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group included in R c5 may have.
• R c5 is an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, even if it has a substituent on an aromatic ring.
• Good phenylthioalkyl groups are preferred.
• the alkyl group an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is the most preferable. preferable.
• methylphenyl is preferred, and 2-methylphenyl is more preferred.
• the number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6.
• the number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2.
• a cyclopentylethyl group is preferred.
• the number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2.
• 2-(4-chlorophenylthio)ethyl group is preferred.
• examples of the formed ring include a hydrocarbon ring, a heterocycle, etc. It will be done.
• the heteroatom contained in the heterocycle include N, O, and S.
• the ring formed by bonding a plurality of R c5 to each other is particularly preferably an aromatic ring.
• Such an aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. As such an aromatic ring, an aromatic hydrocarbon ring is preferable.
• formula (c3) a specific example where a plurality of R c5s combine with each other to form a benzene ring is shown below.
• R c8 is a nitro group or a monovalent organic group.
• R c8 is bonded to a 6-membered aromatic ring different from the aromatic ring bonded to the group represented by -(CO) n1 - on the condensed ring in formula (c4).
• the bonding position of R c8 is not particularly limited.
• the group represented by formula (c4) has one or more R c8 , one of the one or more R c8 is fluorene because the compound represented by formula (c4) is easily synthesized. It is preferable to bond to the 7th position of the skeleton.
• the group represented by formula (c4) when the group represented by formula (c4) has one or more R c8 , the group represented by formula (c4) is preferably represented by the following formula (c6).
• the plurality of R c8s may be the same or different.
• R c6 , R c7 , R c8 , and n3 are the same as R c6 , R c7 , R c8 , and n3 in formula (c4), respectively.
• R c8 is not particularly limited as long as it does not impede the object of the present invention.
• the organic group is preferably a carbon atom-containing group, with one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Preferable examples of R c8 being a monovalent organic group include the same groups as the preferable examples of the monovalent organic group as R c5 in formula (c3).
• R c6 and R c7 are a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, and a cyclic alkyl group which may have a substituent, respectively. It is an organic group or a hydrogen atom. R c6 and R c7 may be bonded to each other to form a ring. Among these groups, R c6 and R c7 are preferably chain alkyl groups which may have a substituent. When R c6 and R c7 are chain alkyl groups which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.
• R c6 and R c7 are chain alkyl groups without substituents
• the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, particularly 1 or more and 6 or less.
• Specific examples when R c6 and R c7 are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.
• n-pentyl group isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group.
• R c6 and R c7 are alkyl groups
• the alkyl groups may contain an ether bond (-O-) in the carbon chain.
• alkyl group having an ether bond in the carbon chain examples include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.
• R c6 and R c7 are chain alkyl groups having a substituent
• the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, particularly preferably 1 or more and 6 or less.
• the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group.
• the chain alkyl group having a substituent is preferably linear.
• the substituent that the alkyl group may have is not particularly limited as long as it does not impede the object of the present invention.
• Suitable examples of the substituent include an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, and an alkoxycarbonyl group.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atom, chlorine atom, and bromine atom are preferred.
• Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group.
• cycloalkyl group are the same as the preferred examples when R c8 is a cycloalkyl group.
• aromatic hydrocarbon group include phenyl group, naphthyl group, biphenylyl group, anthryl group, and phenanthryl group.
• heterocyclyl group are the same as the preferred examples when R c8 is a heterocyclyl group.
• R c8 is an alkoxycarbonyl group
• the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and preferably linear.
• the number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
• the number of substituents is not particularly limited.
• the preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group.
• the number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
• R c6 and R c7 are chain alkoxy groups without substituents
• the number of carbon atoms in the chain alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, particularly 1 or more and 6 or less. preferable.
• R c6 and R c7 are chain alkoxy groups include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert -butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, Examples include sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group.
• R c6 and R c7 are alkoxy groups
• the alkoxy groups may contain an ether bond (-O-) in the carbon chain.
• the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, and methoxypropyloxy group.
• R c6 and R c7 are chain alkoxy groups having substituents
• the substituents that the alkoxy groups may have are the same as in the case where R c6 and R c7 are chain alkyl groups.
• the cyclic organic group may be an alicyclic group or an aromatic group.
• the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group.
• the substituents that the cyclic organic groups may have are the same as when R c6 and R c7 are chain alkyl groups.
• the aromatic hydrocarbon group is a phenyl group or a group formed by combining multiple benzene rings via carbon-carbon bonds. , is preferably a group formed by condensing a plurality of benzene rings.
• the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing multiple benzene rings
• the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, It is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.
• Preferred specific examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, biphenylyl group, anthryl group, and phenanthryl group.
• R c6 and R c7 are aliphatic cyclic hydrocarbon groups
• the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic.
• the number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less.
• Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, Examples include a tetracyclododecyl group and an adamantyl group.
• R c6 and R c7 are heterocyclyl groups
• the same groups as the heterocyclyl group as R c5 in formula (c3) can be mentioned.
• R c6 and R c7 may be bonded to each other to form a ring.
• the group formed by the ring formed by R c6 and R c7 is preferably a cycloalkylidene group.
• the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.
• the ring When forming a ring with R c7 and the benzene ring of the fluorene skeleton, the ring may be an aromatic ring or an aliphatic ring.
• the cycloalkylidene group may be fused with one or more other rings.
• rings that may be fused with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, and a pyridine ring.
• a 1 is a linear alkylene group
• a 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.
• the number of carbon atoms in the linear alkylene group of A 1 is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
• a 2 is an alkoxy group
• the alkoxy group may be linear or branched, preferably linear.
• the number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
• a 2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferable, and a fluorine atom, a chlorine atom, or a bromine atom is more preferable.
• the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom.
• the halogenated alkyl group may be linear or branched, preferably linear.
• a 2 is a cyclic organic group
• examples of the cyclic organic group are the same as the cyclic organic groups that R c6 and R c7 have as substituents.
• a 2 is an alkoxycarbonyl group
• examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that R c6 and R c7 have as substituents.
• R c6 and R c7 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-
• R c6 and R c7 preferred groups among the above include ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta It is a fluoro-n-pentyl group.
• R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group.
• R c9 in formula (c5) is a monovalent organic group, it can be selected from various organic groups as long as it does not impede the object of the present invention.
• the organic group is preferably a carbon atom-containing group, with one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Suitable examples of the case where R c9 in formula (c5) is an organic group include the same monovalent organic group as R c5 in formula (c3).
• R c9 substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group.
• benzoyl group; nitro group; benzofuranylcarbonyl group which may have a substituent is preferred; benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group ; and 4-(phenyl)phenylcarbonyl group are more preferred.
• n4 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.
• the bonding position of R c9 is preferably at the para position with respect to the bond where the phenyl group to which R c9 is bonded is bonded to an oxygen atom or a sulfur atom.
• the monovalent organic group as R c2 is not particularly limited as long as it does not impede the object of the present invention.
• the organic group is preferably a carbon atom-containing group, with one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Suitable examples of the monovalent organic group as R c2 include the same groups as the monovalent organic group as R c5 in formula (c3).
• R c2 a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring.
• the substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the substituents contained in R c5 in formula (c3) when the phenyl group, naphthyl group, and heterocyclyl group further have a substituent. Same as base.
• R c2 is a substituent containing the group represented by HX 2 C- or H 2 XC-, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or A cycloalkylalkyl group and a phenylthioalkyl group which may have a substituent on the aromatic ring are preferred.
• the number of carbon atoms in the alkylene group included in the phenylthioalkyl group that may have a substituent on the ring, or the phenylthioalkyl group that may have a substituent on the aromatic ring, is determined by the formula (c3 ) is similar to R c5 .
• a 3 is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group.
• a 4 is a monovalent organic group, preferably a monovalent hydrocarbon group.
• the alkylene group may be linear or branched, preferably linear.
• the number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.
• Suitable examples of A4 include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms.
• Preferred specific examples of A4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group.
• Examples include phenyl group, naphthyl group, benzyl group, phenethyl group, ⁇ -naphthylmethyl group, and ⁇ -naphthylmethyl group.
• Preferred specific examples of the group represented by -A 3 -CO-O-A 4 include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group,
• R c2 a group represented by the following formula (c7) or (c8) is also preferable.
• R c10 and R c11 each independently represent a monovalent organic group.
• n5 is an integer from 0 to 4.
• R c10 and R c11 may be bonded to each other to form a ring.
• R c12 is a monovalent organic group.
• n6 is an integer of 1 or less and 8 or less.
• n7 is an integer of 1 or more and 5 or less.
• n8 is an integer from 0 to (n7+3).
• R c10 and R c11 in formula (c7) are the same as R c8 in formula (c4).
• R c10 is a halogenated alkoxy group containing a group represented by HX 2 C- or H 2 XC-, a halogenated alkyl group containing a group represented by HX 2 C- or H 2 XC-, an alkyl group, or A phenyl group is preferred.
• the ring may be an aromatic ring or an aliphatic ring.
• Suitable examples of the group represented by formula (c7) in which R c10 and R c11 form a ring include naphthalen-1-yl group and 1,2,3,4- Examples include tetrahydronaphthalen-5-yl group.
• n7 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.
• R c12 is an organic group.
• the organic group include the same groups as the organic group explained for R c8 in formula (c4).
• alkyl groups are preferred.
• the alkyl group may be linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less.
• Preferred examples of R c12 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and the like, and among these, a methyl group is more preferred.
• n7 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2.
• n8 is 0 or more and (n7+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0.
• n6 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.
• R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.
• Preferred examples of the substituent that R c3 may have when it is an aliphatic hydrocarbon group include a phenyl group and a naphthyl group.
• R c3 is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group
• Preferred examples include a cyclohexylmethyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, and among these, a methyl group or a phenyl group is more preferred.
• Preferred specific examples of the compound represented by formula (c2) and having a group represented by formula (c3) as R c1 include the following compounds.
• Preferred specific examples of the compound represented by formula (c2) and having a group represented by formula (c4) as R c1 include the following compounds.
• Preferred specific examples of the compound represented by formula (c2) and having a group represented by formula (c5) as R c1 include the following compounds.
• phosphine oxide compounds are also preferred since the photosensitive composition has good deep curability.
• a phosphine oxide compound containing a partial structure represented by the following formula (c9) is preferable.
• R c21 and R c22 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 to 20 carbon atoms, or an aromatic group having 7 to 20 carbon atoms. It is a group acyl group. However, both R c21 and R c22 are not aliphatic acyl groups or aromatic acyl groups.
• the number of carbon atoms in the alkyl group as R c21 and R c22 is preferably 1 or more and 12 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 4 or less.
• the alkyl groups as R c21 and R c22 may be linear or branched.
• alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert- Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2,4,4,-trimethylpentyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, and Examples include n-dodecyl group.
• the number of carbon atoms in the cycloalkyl group as R c21 and R c22 is preferably 5 or more and 12 or less.
• Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group.
• the number of carbon atoms in the aryl group as R c21 and R c22 is preferably 6 or more and 12 or less.
• the aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and the like. Specific examples of the aryl group include phenyl group and naphthyl group.
• the number of carbon atoms in the aliphatic acyl group as R c21 and R c22 is 2 or more and 20 or less, preferably 2 or more and 12 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 6 or less.
• the aliphatic acyl group may be linear or branched.
• aliphatic acyl groups include acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group, dodecanoyl group, tridecanoyl group, and tetradecanoyl group.
• the number of carbon atoms in the aromatic acyl group as R c21 and R c22 is 7 or more and 20 or less.
• the aromatic acyl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and the like.
• aromatic acyl group examples include benzoyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,6-dimethylbenzoyl group, 2,6-dimethoxybenzoyl group, 2,4,6- Examples include trimethylbenzoyl, ⁇ -naphthoyl, and ⁇ -naphthoyl.
• Preferred specific examples of the phosphine oxide compound containing the structural moiety represented by formula (c9) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphos Examples include fin oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.
• the phosphine oxide compound containing the structural moiety represented by formula (c9) is an ⁇ -hydroxyalkylphenone compound such as 2-hydroxy-2-methylpropiophenone. It is also preferred to use it with an initiator.
• the mass ratio of the phosphine oxide compound containing the structural moiety represented by formula (c9) to the total is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and 40% by mass. % or more and 60% by mass or less is more preferable.
• the content of the initiator (C) in the photosensitive composition is not particularly limited.
• the content of the initiator (C) is appropriately determined depending on the type of radically polymerizable group and the type of the initiator (C).
• the content of the initiator (C) in the photosensitive composition is 0.01 part by mass or more and 20 parts by mass when the mass of the photosensitive composition excluding the mass of the solvent (S) described below is 100 parts by mass.
• the following is preferable, 0.1 part by weight or more and 15 parts by weight or less is more preferable, and even more preferably 1 part by weight or more and 10 parts by weight or less.
• Photosensitization is achieved by uniformly mixing and dispersing the photopolymerizable compound (A), inorganic particles (B), initiator (C), and optional components blended as necessary in desired amounts.
• a sexual composition is obtained.
• a cured product After the photosensitive composition described above is molded into a desired shape, a cured product can be produced by exposing the photosensitive composition to light depending on the type of initiator (C).
• the method for molding the photosensitive composition is not particularly limited.
• the molding method is appropriately selected depending on the shape of the cured product. Examples of the molding method include coating, casting into a mold, and the like.
• a method for manufacturing a cured film will be described as a typical example of a method for manufacturing a cured product.
• a photosensitive composition is applied onto a desired substrate to form a coating film, and then, if necessary, at least a portion of the solvent (S) is removed from the coating film to form a coating film.
• the method of applying the photosensitive composition onto the substrate is not particularly limited.
• a curable composition is applied to a substrate using a contact transfer coating device such as a roll coater, reverse coater, bar coater, or slit coater, or a non-contact coating device such as a spinner (rotary coating device) or curtain flow coater.
• a coating film can be formed by coating the film to a desired thickness.
• printing methods such as screen printing method and inkjet printing method can also be applied.
• the photosensitive composition described above is difficult to dry rapidly, thicken or solidify in an inkjet head. Therefore, by using the above-mentioned photosensitive composition, coating by the inkjet printing method can be performed satisfactorily.
• the coating film After applying the photosensitive composition onto the substrate, it is preferable to bake the coating film as necessary to remove at least a portion of the solvent (S) from the coating film.
• the baking temperature is appropriately determined in consideration of the boiling point of the solvent (S), etc. Baking may be performed at low temperature under reduced pressure conditions.
• the baking method is not particularly limited. Examples of the baking method include a method of drying using a hot plate at a temperature of 80° C. or more and 150° C. or less, preferably 85° C. or more and 120° C. or less, for a period of 60 seconds or more and 500 seconds or less.
• the thickness of the coating film formed as described above is not particularly limited.
• the thickness of the coating film is appropriately determined depending on the use of the cured film.
• the thickness of the coating film is typically appropriately adjusted so that a cured film having a thickness of preferably 0.1 ⁇ m or more and 10 ⁇ m or less, more preferably 0.2 ⁇ m or more and 5 ⁇ m or less is formed.
• a cured film can be obtained by exposing the coating film to light.
• the conditions for exposing the coating film are not particularly limited as long as the curing progresses satisfactorily. Exposure is performed, for example, by irradiating active energy rays such as ultraviolet rays and excimer laser light.
• the energy dose to be irradiated is not particularly limited, but may be, for example, 30 mJ/cm 2 or more and 5000 mJ/cm 2 or less.
• the exposed coating film may be baked by the same method as the heating after coating.
• the photopolymerizable compound (A) has the following formula (A1): R a01 -X a01 -R a02 -Ar-X a02 -(Ar-R a02 -X a01 -R a01 ) n ...(A1)
• R a01 is each independently a radical polymerizable group-containing group
• R a02 is each independently an alkylene group having 1 to 3 carbon atoms
• X a01 is each is independently O or S
• X a02 is an n+1 valent organic group having 1 to 3 carbon atoms, O, or S
• each Ar may independently have a substituent It is an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is 1 or 2, and when X a02 is O or S, n is 1.
• the photopolymerizable compound (A) has the following formula (A1): R a01 -X a01 -R a02 -Ar-X a02 -(Ar-R a02 -X a01 -R a01 ) n ...(A1)
• R a01 is each independently a radically polymerizable group-containing group
• R a02 is each independently an alkylene group having 1 to 3 carbon atoms
• X a01 is each is independently O or S
• X a02 is an n+1 valent organic group having 1 to 3 carbon atoms, O, or S
• each Ar may independently have a substituent It is an aromatic hydrocarbon group having 6 to 12 carbon atoms, n is 1 or 2, and when X a02 is O or S, n is 1.
• the obtained solution was dropped onto a weighed glass substrate, heated at 110° C. for 10 minutes, and the glass substrate was weighed again.
• the mass of the photopolymerizable compound (A) decreased by heating was calculated from the weight of the glass substrate before and after heating.
• the rate of decrease in the mass of the photopolymerizable compound (A) due to heating was calculated from the mass of the photopolymerizable compound (A) that decreased due to heating.
• the reduction rate values are shown in Table 1.
• the composition containing the photopolymerizable compound (A) having the structure included in the above formula (A1) is It can be seen that the weight of raw materials of components other than the solvent (S) due to heating is significantly suppressed compared to the composition containing a photopolymerizable compound having a structure that does not correspond to the structure of A1).
• Examples 9 to 40 and Comparative Examples 3 to 10 5 parts by mass of the photopolymerizable compound (A) of the type listed in Table 2, 20 parts by mass of inorganic particles (B) made of the material listed in Table 2, and bis(2,4, 0.5 parts by mass of 6-trimethylbenzoyl)-phenylphosphine oxide was dissolved and dispersed in the type of solvent (S) listed in Table 2 so that the solid content concentration was 10% by mass.
• Photosensitive compositions of Examples 9 to 40 and Comparative Examples 3 to 10 were obtained.
• the average particle diameters of the gold particles, platinum particles, zirconium oxide particles, and titanium oxide particles used as the inorganic particles (B) were all 10 nm.
• the obtained photosensitive composition was left standing in a constant temperature device at a temperature of 40° C. for 3 months.
• the state of dispersion of the inorganic particles in the photosensitive composition was visually confirmed after one month and after three months.
• the dispersion stability of the inorganic particles (B) in the photosensitive composition was evaluated according to the following criteria. A: There is no separation or sedimentation of inorganic particles (B). B: Slight separation or sedimentation of the inorganic particles (B) is confirmed. C: Significant separation and sedimentation of inorganic particles (B) is confirmed.
• Examples 41 to 44, Comparative Example 11, and Comparative Example 12 2.3 parts by mass of the photopolymerizable compound (A) of the type listed in Table 3, 7.5 parts by mass of titanium oxide particles as inorganic particles (B), and bis(2,4, 0.2 parts by mass of 6-trimethylbenzoyl)-phenylphosphine oxide, and the total mass of the photopolymerizable compound (A), inorganic particles (B), and initiator (C) relative to the mass of the photosensitive composition.
• the photosensitive compositions of Examples 41 to 44, Comparative Example 11, and Comparative Example 12 were prepared by dispersing and dissolving them in the aforementioned solvent S-1 (propylene glycol monomethyl ether acetate) so that the ratio of 10% by mass was obtained.
• a photosensitive composition was applied onto a glass substrate using a spin coater. Next, the film made of the photosensitive composition was heated at 110° C. for 2 minutes to obtain a coating film having a thickness such that a cured film with a thickness of 0.3 ⁇ m was formed. The obtained coating film was exposed using a high-pressure mercury lamp so that the cumulative exposure amount was 100 mJ/cm 2 . The exposed coating film was heated at 110° C. for 2 minutes to obtain a cured film with a thickness of 0.3 ⁇ m. The light transmittance of the obtained cured film was measured using a multichannel spectrometer (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.). From the measurement results, the average transmittance of light with a wavelength of 400 to 700 nm was determined.
• MCPD-3000 multichannel spectrometer
• the average transmittance of light with a wavelength of 400 to 700 nm determined in the above-mentioned transmittance evaluation of the cured film was defined as T0.
• the cured film was then heated at 180°C for 2 minutes. After heating, the average transmittance of the cured film to light having a wavelength of 400 to 700 nm was measured at the same position where the average transmittance T0 was measured.
• the average transmittance was defined as T1. Based on the measured values of T0 and T1, the rate of change in transmittance was determined according to the following formula.
• Transmittance change rate (%)
• Remaining film rate (%) (film thickness after immersion / film thickness before immersion) x 100 Based on the calculated residual film rate, solvent resistance was evaluated according to the following criteria. A: Remaining film rate 98% or more B: Remaining film rate 90% or more and less than 98% C: Remaining film rate 80% or more and less than 90%
• the photosensitive composition containing the photopolymerizable compound (A) having the structure represented by the above formula (A1) produces a cured product having excellent light transmittance, heat resistance, and solvent resistance. I know I can give.
• the photosensitive composition containing only the photopolymerizable compound (A) having a structure that does not correspond to the structure of formula (A1) described above has good surface appearance, heat resistance, It can be seen that a cured product with poor solvent resistance is obtained.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Inorganic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=88419577

Family Applications (1)

Country Status (3)

Citations (8)

• 2023
  • 2023-02-07 JP JP2024516092A patent/JPWO2023203837A1/ja active Pending
  • 2023-02-07 WO PCT/JP2023/003931 patent/WO2023203837A1/ja not_active Ceased
  • 2023-02-07 US US18/857,594 patent/US20250282900A1/en active Pending

Patent Citations (8)

Also Published As

Similar Documents

Legal Events