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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts

Definitions

• the present disclosure relates to compositions and eyeglass lenses.
• Patent Document 1 discloses a copolymer that contains both a segment (A) that contains a repeating unit of a silicone structure represented by general formula (1) and a segment (B) that contains a repeating unit having a cage silsesquioxane structure in its side chain represented by general formula (2).
• composition of the first embodiment comprising a polymer S of a silsesquioxane having a polymerizable group, a monomer M, and a compound X selected from the group consisting of a polymer P of the monomer M, wherein the monomer M is selected from the group consisting of polyalkylene glycol di(meth)acrylates and urethane (meth)acrylates, and in a molecular weight distribution curve of the polymer S obtained by gel permeation chromatography, the peak top molecular weight of the polymer S is 2800 or more, and in a molecular weight distribution curve of the polymer P obtained by gel permeation chromatography, the peak top molecular weight of the polymer P is 3500 or more.
• composition of a second embodiment comprising a polymer P of a silsesquioxane having a polymerizable group and a monomer M selected from the group consisting of polyalkylene glycol di(meth)acrylates and urethane (meth)acrylates, wherein the polymer P has a peak top molecular weight of 3,500 or more in a molecular weight distribution curve of the polymer P obtained by gel permeation chromatography.
• 1 is an example showing a cross section of a spectacle lens.
• the compositions of the present disclosure are described in detail below.
• the composition of the present disclosure is preferably used to form a hard coat layer of an eyeglass lens, for example.
• the layer (e.g., hard coat layer) formed by using the composition of the present disclosure has excellent interlayer adhesion.
• interlayer adhesion means that when the composition of the present disclosure is used to form a hard coat layer on a substrate, the hard coat layer is not easily peeled off from the substrate, or when another layer (e.g., primer layer) is formed on the substrate, and the composition of the present disclosure is used to form a hard coat layer on the other layer, the hard coat layer is not easily peeled off from the substrate.
• halogen atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• halogenation includes, for example, fluorination, chlorination, bromination and iodination.
• (meth)acrylic is a concept that includes both acrylic and methacrylic
• (meth)acryloyl group is a concept that includes both acryloyl group and methacryloyl group
• (meth)acrylate” is a concept that includes both acrylate and methacrylate.
• the solid content refers to components other than the solvent, and even if the components are in a liquid state at room temperature and normal pressure (25° C., 101.3 kPa), they are counted as solids.
• the solid content may be a component that undergoes a chemical change during the curing process.
• the composition and the living polymerization mixture described later contain a specific compound selected from the group consisting of a surfactant that is liquid at room temperature and normal pressure, a living polymerization catalyst that is liquid at room temperature and normal pressure, and a co-catalyst that is liquid at room temperature and normal pressure, the solid content of the composition and the living polymerization mixture described later does not include the specific compound.
• the composition of a first embodiment comprises a polymer S of a silsesquioxane having a polymerizable group, a monomer M, and a compound X selected from the group consisting of a polymer P of the monomer M, wherein the monomer M is selected from the group consisting of polyalkylene glycol di(meth)acrylate and urethane (meth)acrylate, and in a molecular weight distribution curve of the polymer S obtained by gel permeation chromatography, the peak top molecular weight of the polymer S is 2800 or more, and in a molecular weight distribution curve of the polymer P obtained by gel permeation chromatography, the peak top molecular weight of the polymer P is 3500 or more.
• the composition of the first embodiment contains a polymer S and a monomer M, or contains a polymer S and a polymer P.
• the composition of the first embodiment may contain a polymer S, a monomer M, and a polymer P.
• the composition of the first embodiment contains polymer S.
• the polymer S is a polymer of a silsesquioxane having a polymerizable group.
• the polymer S is preferably a polymer obtained by polymerization via the polymerizable group of a silsesquioxane.
• the polymer S is a so-called prepolymer, which is a polymer that can be further cured by a curing treatment such as a light irradiation treatment when forming a hard coat layer.
• the polymer S preferably has a polymerizable group. Examples of the polymerizable group that the polymer S has include polymerizable groups that remain when the polymer S is formed, among the polymerizable groups that the silsesquioxane having a polymerizable group has.
• the peak top molecular weight of the polymer S is 2,800 or more, preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more.
• the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 10,000 or less.
• the polymer S has multiple peak top molecular weights, it is preferable that at least one of the multiple peak top molecular weights falls within the above-mentioned peak top molecular weight range, and it is more preferable that all of the peak top molecular weights fall within the above-mentioned peak top molecular weight range.
• the peak top molecular weight of the polymer S can be measured by the following method.
• the polymer S is dissolved in a solvent to prepare a measurement solution.
• the measurement solution may be a solution obtained by living polymerization of a mixture for living polymerization described later.
• the solvent may be any solvent in which the polymer S dissolves, and is preferably a solvent that can be contained in a solution obtained by living polymerization of a mixture for living polymerization described later.
• the molecular weight is measured using a GPC analyzer under the following conditions, and the molecular weight at each elution time is calculated from the obtained retention time using an elution curve of monodisperse polystyrene.
• the molecular weight of polymer S is preferably in the region of 2,000 or more, more preferably in the region of 3,000 or more, and even more preferably in the region of 4,000 or more.
• the upper limit is preferably in the region of 70,000,000 or less, more preferably in the region of 2,000,000 or less, even more preferably in the region of 1,000,000 or less, particularly preferably in the region of 30,000 or less, and most preferably in the region of 20,000 or less.
• Methods for adjusting the molecular weight of polymer S include, for example, known methods.
• the polymerizable group of the silsesquioxane may be, for example, a radical polymerizable group or a cationic polymerizable group.
• the radical polymerizable group is preferably a (meth)acryloyl group.
• the cationic polymerizable group may be, for example, an alicyclic ether group such as an epoxy group or an oxetanyl group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group, and the epoxy group or the oxetanyl group is preferred.
• the number of polymerizable groups contained in the silsesquioxane is preferably 2 or more, and more preferably 2 to 10.
• Silsesquioxanes are silane compounds obtained by hydrolysis of trifunctional silane compounds such as alkoxysilanes, chlorosilanes, and silanols.
• Examples of the silsesquioxane structure include irregular structures such as random structures, ladder structures, cage (completely condensed cage) structures, and incomplete cage structures (partially cleaved cage structures in which some of the silicon atoms are missing from the cage structure and some of the silicon-oxygen bonds in the cage structure are broken).
• the silsesquioxane having a polymerizable group is preferably a compound having a basic skeleton represented by formula (Q).
• RQ represents a monovalent organic group, and at least one of them represents a polymerizable group or a group having a polymerizable group.
• the group having a polymerizable group is preferably an -alkylene group-O-polymerizable group.
• the alkylene group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms.
• the polymerizable group the above-mentioned polymerizable group contained in the silsesquioxane is preferable.
• silsesquioxanes having polymerizable groups examples include the SQ series (e.g., AC-SQ series and MAC-SQ series, manufactured by Toagosei Co., Ltd.).
• the average particle size of the silsesquioxane having a polymerizable group is preferably from 0.5 to 200 nm, and more preferably from 1 to 50 nm.
• methods for measuring the average particle size include a method of measuring the particle sizes of 100 arbitrary silsesquioxanes having polymerizable groups using a scanning electron microscope and calculating the arithmetic average thereof, and a method of measuring the particle size using a dynamic light scattering method under the following conditions.
• the dispersion liquid containing the silsesquioxane having a polymerizable group to be measured is diluted with a dilution solvent as necessary.
• a dilution solvent for example, MEK (methyl ethyl ketone) is used as the dilution solvent, and if the use of MEK causes problems such as aggregation of the silsesquioxane having a polymerizable group, other suitable dilution solvents are used.
• the average particle size means the average particle size based on volume distribution.
• Silsesquioxanes having polymerizable groups may be used alone or in combination of two or more types.
• Examples of the method for producing the polymer S include known polymerization methods such as living polymerization, and living polymerization is preferred.
• Examples of the living polymerization include living radical polymerization such as atom transfer radical polymerization using a mixture for living polymerization.
• the living polymerization mixture includes a silsesquioxane having a polymerizable group.
• the mixture for living polymerization preferably further contains at least one selected from the group consisting of a living polymerization catalyst, a polymerization initiator, a solvent, and a co-catalyst, and more preferably further contains a living polymerization catalyst, a polymerization initiator, a solvent, and a co-catalyst.
• the silsesquioxane having a polymerizable group is as described above.
• the content of the silsesquioxane having a polymerizable group is preferably from 10 to 90 mass %, more preferably from 20 to 70 mass %, based on the total solid content of the mixture for living polymerization.
• Living polymerization catalysts include, for example, transition metals and transition metal compounds.
• the transition metal in the transition metal and transition metal compound include copper, iron, cobalt, chromium, manganese, molybdenum, silver, zinc, palladium, rhodium, platinum, ruthenium, iridium, ytterbium, samarium, rhenium and nickel, with copper, iron or ruthenium being preferred.
• the transition metal compound may be a transition metal complex comprising the transition metal and a ligand.
• the living polymerization catalyst copper, copper compounds such as ferrocenes, iron, or iron compounds such as ferrocenes are preferred.
• the living polymerization catalyst is preferably a compound represented by formula (F1) or a compound represented by formula (F2).
• M represents copper or iron
• CP1 and CP2 each independently represent a cyclopentadienyl ring which may have a substituent.
• the number of substituents on the cyclopentadienyl ring is preferably 0 to 5, and more preferably 1.
• the substituent that the cyclopentadienyl ring may have is preferably -P(R P ) 2 .
• P is a phosphorus atom
• the two R Ps each independently represent a hydrogen atom or a substituent.
• the above substituent is preferably an organic group, more preferably an alkyl group or a phenyl group.
• the above alkyl group may be either linear or branched.
• the number of carbon atoms in the above alkyl group is preferably 1 to 3.
• CP 1 represents a cyclopentadienyl ring which may have a substituent.
• CP1 in formula (F2) has the same meaning as CP1 in formula (F1), and the preferred embodiments are also the same.
• Each of the three R and Q independently represents -CO, a halogen atom, or -PPh3 .
• P is a phosphorus atom
• Ph is a phenyl group which may have a substituent.
• the substituent which the phenyl group may have is preferably an alkyl group.
• the alkyl group may be either linear or branched, and the number of carbon atoms of the alkyl group is preferably 1 to 3.
• the number of substituents on the phenyl group is preferably 0 to 5.
• copper compounds examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, and cuprous perchlorate.
• the living polymerization catalysts may be used alone or in combination of two or more.
• the content of the living polymerization catalyst is preferably from 0.00001 to 5 mass %, more preferably from 0.00005 to 2 mass %, based on the total solid content of the mixture for living polymerization.
• polymerization initiators examples include 1-chloroethylbenzene, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, ⁇ , ⁇ '-dichloroxylene, ⁇ , ⁇ '-dibromoxylene, hexakis( ⁇ -bromomethyl)benzene, and alkyl ester compounds of halogenated carboxylic acids (e.g., diethylchloromalonic acid, 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, and 2-bromoisobutyric acid, etc.).
• halogenated carboxylic acids e.g., diethylchloromalonic acid, 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, and 2-bromoisobutyric acid, etc.
• the polymerization initiator may be used alone or in combination of two or more.
• the content of the polymerization initiator is preferably 0.01 to 1% by mass based on the total mass of the monomers (for example, silsesquioxane having a polymerizable group and monomer M).
• Solvents include, for example, organic solvents such as tetrahydrofuran, ethyl acetate, toluene, acetone, dimethylformamide, ketones, and alcohols, as well as water.
• organic solvents such as tetrahydrofuran, ethyl acetate, toluene, acetone, dimethylformamide, ketones, and alcohols, as well as water.
• the solvent may be used alone or in combination of two or more.
• the content of the solvent is preferably from 0 to 95% by mass, more preferably from 10 to 90% by mass, based on the total mass of the mixture for living polymerization.
• co-catalyst examples include triamine compounds such as pentamethyldiethylenetriamine, phosphine compounds such as diphenylphosphine oxide, triazine compounds having at least one triazine ring, benzotriazole compounds having at least one benzotriazole ring, and imidazole compounds having at least one imidazole ring (for example, 1-methylimidazole).
• phosphine compounds such as diphenylphosphine oxide, Tri(m-tolyl)phosphine and Tri(o-tolyl)phosphine, or triamine compounds such as N,N,N',N'',N''-Pentamethyldiethylenetriamine, tripropylamine and Tris(2-pyridylmethyl)amine.
• the promoter include Tinuvin 400, Tinuvin 384-2, and Tinuvin 477 (all manufactured by BASF).
• the promoter may be used alone or in combination of two or more.
• the content of the co-catalyst is preferably from 0.000001 to 10 mass %, more preferably from 0.00001 to 5 mass %, based on the total solid content of the mixture for living polymerization.
• the content of the promoter is preferably 0.1 to 1000% by mass based on the total mass of the catalyst.
• the reaction time for the living polymerization is preferably from 0.5 to 24 hours, more preferably from 1 to 10 hours.
• the reaction temperature for the living polymerization is preferably from 25 to 100°C, more preferably from 25 to 60°C.
• the polymer S may be used alone or in combination of two or more.
• the content of the polymer S is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, and even more preferably from 30 to 60% by mass, based on the total solid content of the composition.
• composition of the first embodiment comprises compound X.
• the compound X is a compound selected from the group consisting of a monomer M and a polymer P of the monomer M.
• the composition of the first embodiment may contain a monomer M.
• Monomer M is a monomer selected from the group consisting of polyalkylene glycol di(meth)acrylates and urethane (meth)acrylates.
• Polyalkylene glycol di(meth)acrylate is a monomer having (meth)acryloyl groups at both ends of a polyalkylene glycol chain.
• the urethane (meth)acrylate may also be an oligomer.
• the polyalkylene glycol di(meth)acrylate is preferably a compound represented by formula (II).
• n represents a number from 0 to 30.
• R3 and R4 each independently represent a hydrogen atom or a methyl group. When a plurality of R 3 's are present, the plurality of R 4 's may be the same or different.
• n is preferably a number from 1 to 25, more preferably a number from 4 to 25, and even more preferably a number from 9 to 20.
• polyalkylene glycol di(meth)acrylates examples include NK ester bifunctional polyethylene glycol acrylate (A-200, A-400, A-600, A-1000, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate 4EG-A, Light Acrylate 9EG-A, and Light Acrylate 14EG-A (all manufactured by Kyoeisha Chemical Co., Ltd.).
• the molecular weight of the polyalkylene glycol di(meth)acrylate is preferably less than 3000, more preferably 2000 or less, and even more preferably 1500 or less.
• the lower limit is preferably 400 or more, and more preferably 600 or more.
• the urethane (meth)acrylate is a monomer having a urethane bond and a (meth)acryloyl group.
• the urethane (meth)acrylate may also be an oligomer.
• the number of (meth)acryloyl groups in the urethane (meth)acrylate is preferably 1 or 2 or more, and more preferably 2 or 3.
• the urethane (meth)acrylate may be either a urethane di(meth)acrylate or a urethane tri(meth)acrylate.
• the number of urethane bonds in the urethane (meth)acrylate is preferably 1 or 2 or more, more preferably 2 or more, and even more preferably 3 or more.
• the upper limit is preferably 100 or less, and more preferably 50 or less.
• the urethane (meth)acrylate is preferably obtained by reacting a polyol, a diisocyanate, and a (meth)acrylate having a hydroxyl group.
• polyols include 1,6-hexane diglycidyl ether, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone diol, polycarbonate diol, polybutadiene polyol, and polyester diol.
• Diisocyanates include, for example, toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
• the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol (meth)acrylate, and caprolactone-modified 2-hydroxyethyl (meth)acrylate.
• urethane (meth)acrylate a compound represented by formula (I) is preferred.
• R represents a bifunctional polyester polyol residue or a bifunctional polyether polyol residue.
• R1 represents a hydrogen atom or a methyl group.
• R2 represents an alkylene group having 2 to 4 carbon atoms.
• L represents a group represented by any one of formulas (I-1) to (I-3).
• R represents a difunctional polyester polyol residue or a difunctional polyether polyol residue.
• the bifunctional polyester polyol residue is a group obtained by removing two hydroxyl groups (OH) from a polyester polyol having two hydroxyl groups.
• the polyester polyol include polyester polyols obtained by dehydration condensation of adipic acid or phthalic acid with a glycol having 2 to 6 carbon atoms.
• the bifunctional polyether polyol residue is a group obtained by removing two hydroxyl groups (OH) from a polyether polyol having two hydroxyl groups.
• the polyether polyol include polyethylene glycol and polypropylene glycol.
• R 2 represents an alkylene group having 2 to 4 carbon atoms.
• the alkylene group may be either linear or branched.
• L represents a group represented by any one of formulas (I-1) to (I-3).
• * represents a bonding position.
• the multiple groups represented by the same symbol may be the same or different.
• urethane (meth)acrylates examples include CN9002, CN910A70, CN9167, CN9170A86, CN9200, CN963B80, CN964A85, CN965, CN966H90, CN9761, CN9761A75, CN981, CN991 and CN996 (all manufactured by Sartomer Arkema); UF8001G, UF8002G, UF8003G and DAUA-167 (all manufactured by Kyoei Chemical); SC2404, SC2565, PU-2560 and UA-5210 (all manufactured by Miwon); UA-122P and UA-232P (all manufactured by Shin-Nakamura Chemical).
• the weight average molecular weight of the urethane (meth)acrylate is preferably less than 4000, more preferably 3800 or less, and even more preferably 3500 or less.
• the lower limit is preferably 300 or more, and more preferably 500 or more.
• the monomer M may be used alone or in combination of two or more.
• the content of the monomer M is preferably from 1 to 99 mass %, more preferably from 5 to 90 mass %, and even more preferably from 10 to 70 mass %, based on the total solid content of the composition.
• the composition of the first embodiment may contain a polymer P.
• the polymer P is a polymer of a monomer M.
• the polymer P is preferably a polymer obtained by polymerization via a polymerizable group (e.g., a (meth)acryloyl group) contained in the monomer M.
• the polymer P is a so-called prepolymer, which is a polymer that can be further cured by a curing treatment such as a light irradiation treatment when forming a hard coat layer.
• the polymer P preferably has a polymerizable group. Examples of the polymerizable group that the polymer P has include polymerizable groups that remain among the polymerizable groups that the monomer M has when the polymer P is formed.
• the monomer M is as described above.
• the peak top molecular weight of the polymer P is 3,500 or more, and preferably 4,000 or more.
• the upper limit is preferably 600,000 or less, more preferably 45,000 or less, and even more preferably 25,000 or less.
• the molecular weight of polymer P is preferably in the region of 2,000 or more, more preferably in the region of 4,000 or more, even more preferably in the region of 4,500 or more, and particularly preferably in the region of 5,000 or more.
• the upper limit is preferably in the region of 2,000,000 or less, more preferably in the region of 400,000 or less, even more preferably in the region of 50,000 or less, and particularly preferably in the region of 30,000 or less.
• the peak top molecular weight and the molecular weight of the polymer P can be measured by the same method as that for the polymer S described above.
• polymer P for example, there is a method in which, in the above-mentioned method for producing polymer S, monomer M is used instead of silsesquioxane having a polymerizable group.
• the polymer P may be used alone or in combination of two or more.
• the content of the polymer P is preferably from 1 to 99% by mass, more preferably from 5 to 90% by mass, and even more preferably from 10 to 70% by mass, based on the total solid content of the composition.
• the composition of the first embodiment may contain a polymerization initiator.
• the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and a photopolymerization initiator is preferred.
• Examples of the polymerization initiator include Omnirad 127, 184, 907, 651, 1700, 1800, 819, 369, and TPO (manufactured by IGM Resins B.V.); DAROCUR 1173 (manufactured by Sigma-Aldrich); Ezacure KIP 150 and TZT (manufactured by Nippon SiberHegner Co., Ltd.); Kayacure BMS and Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.); Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, and Tinuvin 1577 (manufactured by BASF).
• Examples of the cationic polymerization initiator include onium salts composed of one or more cations selected from the group consisting of aromatic sulfonium, aromatic iodonium, aromatic diazonium, and pyridinium, and one or more anions selected from the group consisting of BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , and B(C 6 F 5 ) 4 ⁇ ; and thermal cationic polymerization initiators such as aluminum complexes such as aluminum chloride.
• the polymerization initiator may be used alone or in combination of two or more.
• the content of the polymerization initiator is preferably from 0.001 to 5 mass %, more preferably from 0.01 to 5 mass %, based on the total solid content of the composition.
• the composition of the first embodiment may include a sensitizer.
• the composition contains a polymerization initiator, it is preferable that the composition further contains a sensitizer.
• the sensitizer may, for example, be the Anthracure series (manufactured by Kawasaki Chemical Industries, Ltd.).
• the sensitizers may be used alone or in combination of two or more.
• the content of the sensitizer is preferably from 0.001 to 5% by mass, and more preferably from 0.05 to 2% by mass, based on the total solid content of the composition.
• the composition of the first embodiment may contain a surfactant.
• the surfactant may, for example, be a silicone compound such as silicone oil.
• the surfactant may be, for example, the DOWSIL series (manufactured by Dow).
• the surfactants may be used alone or in combination of two or more.
• the content of the surfactant is preferably from 0.001 to 5 mass %, more preferably from 0.01 to 0.5 mass %, based on the total solid content of the composition.
• the composition of the first embodiment may contain an ultraviolet absorbing agent.
• the ultraviolet absorber include triazine compounds and benzotriazole compounds.
• the triazine compound and the benzotriazole compound include the triazine compound and the benzotriazole compound that can be contained in the above-mentioned living polymerization mixture. Therefore, when the living polymerization mixture is used for preparing the composition of the first embodiment, the triazine compound and the benzotriazole compound contained in the living polymerization mixture may be used as an ultraviolet absorber in the composition of the first embodiment.
• the ultraviolet absorbents may be used alone or in combination of two or more.
• the content of the ultraviolet absorber is preferably from 0.01 to 5 mass %, more preferably from 0.1 to 3 mass %, based on the total solid content of the composition.
• the composition of the first embodiment may contain a solvent.
• the solvent includes, for example, water and organic solvents.
• the organic solvent include alcohol-based solvents, ketone-based solvents such as methyl ethyl ketone, ether-based solvents such as tetrahydrofuran, ester-based solvents, hydrocarbon-based solvents, halogenated hydrocarbon-based solvents, amide-based solvents, sulfone-based solvents, and sulfoxide-based solvents.
• the solvent may be used alone or in combination of two or more.
• the content of the solvent is preferably from 10 to 90% by mass, and more preferably from 30 to 80% by mass, based on the total mass of the composition.
• the composition of the first embodiment may contain other components in addition to the various components described above.
• other components include various components that may be contained in the living polymerization mixture, their reaction products and decomposition products, silsesquioxanes having no polymerizable groups, inorganic oxide particles (excluding silsesquioxanes having polymerizable groups and silsesquioxanes having no polymerizable groups), anti-aging agents, coating film modifiers, light stabilizers, antioxidants, color inhibitors, dyes, fillers, and internal release agents.
• the composition of the first embodiment comprises a silsesquioxane having a polymerizable group and satisfies requirement A1, or It is preferable that the composition of the first embodiment does not contain a silsesquioxane having a polymerizable group and satisfies the requirement B1.
• requirement A1 the requirement A2 or the requirement A3 is preferable, and the requirement A4 is more preferable.
• requirement B1 the requirement B2 or the requirement B3 is preferable, and the requirement B4 is more preferable.
• Requirement A1 The total content of the polymer S and the silsesquioxane having a polymerizable group is 30 mass % or more based on the total content of the polymer S, the silsesquioxane having a polymerizable group, and the compound X.
• Requirement A2 The total content of the polymer S and the silsesquioxane having a polymerizable group is 50 mass % or more based on the total content of the polymer S, the silsesquioxane having a polymerizable group, and the compound X.
• Requirement A3 The total content of the polymer S and the silsesquioxane having a polymerizable group is 30 to 90 mass % based on the total content of the polymer S, the silsesquioxane having a polymerizable group, and the compound X.
• Requirement A4 The total content of the polymer S and the silsesquioxane having a polymerizable group is 50 to 70 mass % based on the total content of the polymer S, the silsesquioxane having a polymerizable group, and the compound X.
• Requirement B1 The content of the polymer S is 5% by mass or more based on the total content of the polymer S and the compound X.
• Requirement B2 The content of the polymer S is 10 mass % or more based on the total content of the polymer S and the compound X.
• Requirement B3 The content of the polymer S is 5 to 20% by mass based on the total content of the polymer S and the compound X.
• Requirement B4 The content of the polymer S is 10 to 15 mass % based on the total content of the polymer S and the compound X.
• the total content of the polymer S, the silsesquioxane having a polymerizable group, and the compound X is preferably 80 to 100 mass%, more preferably 95 to 100 mass%, and even more preferably 98 to 100 mass%, based on the total solid content of the composition.
• the total content of the polymer S and the compound X is preferably 80 to 100 mass%, more preferably 95 to 100 mass%, and even more preferably 98 to 100 mass%, based on the total solid content of the composition.
• the composition of the second embodiment comprises a silsesquioxane having a polymerizable group, A polymer P of a monomer M selected from the group consisting of polyalkylene glycol di(meth)acrylate and urethane (meth)acrylate, A composition, wherein the peak top molecular weight of polymer P is 3,500 or more in a molecular weight distribution curve of polymer P obtained by gel permeation chromatography.
• the composition of the second embodiment contains a silsesquioxane having a polymerizable group and a polymer P.
• silsesquioxane having a polymerizable group, the monomer M, and the polymer P are as described in the first embodiment.
• the second embodiment may contain components selected from the group consisting of polymerization initiators, sensitizers, surfactants, UV absorbers, solvents, and other components described in the first embodiment.
• the composition of the second embodiment further comprises a monomer M selected from the group consisting of polyalkylene glycol di(meth)acrylates and urethane (meth)acrylates, and satisfies requirement C1; or Furthermore, it is preferable that the composition does not contain a monomer M selected from the group consisting of polyalkylene glycol di(meth)acrylates and urethane (meth)acrylates, and satisfies requirement D1.
• the requirement C1 the requirement C2 or the requirement C3 is preferable, and the requirement C4 is more preferable.
• the requirement D1 the requirement D2 or the requirement D3 is preferable, and the requirement D4 is more preferable.
• Requirement C1 The total content of the polymer P and the monomer M is 30 mass % or more based on the total content of the polymer P, the monomer M, and the silsesquioxane having a polymerizable group.
• Requirement C2 The total content of the polymer P and the monomer M is 50 mass % or more based on the total content of the polymer P, the monomer M, and the silsesquioxane having a polymerizable group.
• Requirement C3 The total content of the polymer P and the monomer M is 30 to 90 mass % based on the total content of the polymer P, the monomer M, and the silsesquioxane having a polymerizable group.
• Requirement C4 The total content of the polymer P and the monomer M is 50 to 70 mass % based on the total content of the polymer P, the monomer M, and the silsesquioxane having a polymerizable group.
• Requirement D1 The content of the polymer P is 10 mass % or more based on the total content of the polymer P and the silsesquioxane having a polymerizable group.
• Requirement D2 The content of the polymer P is 20 mass % or more based on the total content of the polymer P and the silsesquioxane having a polymerizable group.
• Requirement D3 The content of the polymer P is 10 to 80 mass % based on the total content of the polymer P and the silsesquioxane having a polymerizable group.
• Requirement D4 The content of the polymer P is 20 to 70 mass % based on the total content of the polymer P and the silsesquioxane having a polymerizable group.
• the total content of polymer P, monomer M, and silsesquioxane having a polymerizable group is preferably 80 to 100 mass%, more preferably 95 to 100 mass%, and even more preferably 98 to 100 mass%, based on the total solid content of the composition.
• the total content of the polymer P and the silsesquioxane having a polymerizable group is preferably 80 to 100 mass%, more preferably 95 to 100 mass%, and even more preferably 98 to 100 mass%, based on the total solid content of the composition.
• compositions of the first and second embodiments examples include a method in which the various components that may be contained in the composition of the first or second embodiment described above are mixed together in one go, and a method in which the various components are mixed in portions and in stages.
• the composition of the first or second embodiment may be prepared using a solution obtained by living polymerization of the mixture for living polymerization. In other words, when the above liquid is used, various components contained in the above liquid are brought into the composition of the first or second embodiment.
• compositions of the first and second embodiments are suitably used as a composition for forming a hard coat layer on a substrate (a composition for forming a hard coat layer).
• the substrate is preferably a spectacle lens substrate as described below.
• the hard coat layer formed using the composition of the first embodiment or the second embodiment may be used for a spectacle lens.
• the spectacle lens is preferably a spectacle lens including a spectacle lens substrate (e.g., a spectacle lens substrate, etc.) and a hard coat layer formed using the composition of the first embodiment or the second embodiment and disposed on the spectacle lens substrate.
• FIG. 1 is a cross-sectional view of one embodiment of a spectacle lens.
• the spectacle lens 10 includes a spectacle lens substrate 12, a primer layer 14 disposed on both sides of the spectacle lens substrate 12, and a hard coat layer 16 disposed on both sides of the primer layer 14.
• the hard coat layer 16 is a layer formed using the composition of the first or second embodiment.
• the spectacle lens 10 includes a primer layer 14, but is not limited to this form and may not include the primer layer 14.
• the spectacle lens 10 has the primer layer 14 disposed on both sides of the spectacle lens substrate 12, but the primer layer 14 may be disposed on only one side of the spectacle lens substrate 12.
• the spectacle lens 10 has the hard coat layer 16 disposed on both sides of the primer layer 14, but the hard coat layer 16 may be disposed on only one side of the primer layer 14.
• One type of spectacle lens substrate is, for example, a finished lens in which both the convex and concave surfaces are optically finished and molded to a desired diopter.
• the resins constituting the spectacle lens substrate include (meth)acrylic resins, thiourethane resins, allyl resins, episulfide resins, polycarbonate resins, polyurethane resins, polyester resins, polystyrene resins, polyethersulfone resins, poly-4-methylpentene-1 resins, diethylene glycol bisallyl carbonate resins (CR-39), and polyvinyl chloride resins.
• the thickness of the spectacle lens substrate is preferably 1 to 30 mm from the viewpoint of ease of handling.
• the refractive index of the spectacle lens substrate is not particularly limited.
• the spectacle lens substrate may be opaque or colored so long as it has light-transmitting properties.
• the hard coat layer is a layer disposed on the spectacle lens substrate, and is a layer that imparts scratch resistance to the spectacle lens substrate.
• the hard coat layer is a layer formed from the composition of the first or second embodiment.
• Examples of a method for forming a hard coat layer include a method in which the composition of the first or second embodiment is applied onto a spectacle lens substrate to form a coating film, and then the coating film is subjected to a curing treatment such as a light irradiation treatment and a heat treatment. After the coating film is formed, a drying treatment such as a heating treatment may be carried out, if necessary, in order to remove the solvent from the coating film.
• a curing treatment such as a light irradiation treatment and a heat treatment.
• a drying treatment such as a heating treatment may be carried out, if necessary, in order to remove the solvent from the coating film.
• Methods for applying the composition of the first or second embodiment onto a spectacle lens substrate include known methods (e.g., dipping coating, spin coating, spray coating, inkjet coating, flow coating, etc.).
• a spectacle lens substrate is immersed in the composition of the first or second embodiment, and then the spectacle lens substrate is pulled up and dried, whereby a coating film of a predetermined thickness can be formed on the spectacle lens substrate.
• the thickness of the coating film formed on the spectacle lens substrate can be appropriately adjusted.
• the conditions for the light irradiation treatment can be selected appropriately depending on the type of polymerization initiator used.
• the type of light used for the light irradiation may be, for example, ultraviolet light or visible light, and the light source may be, for example, a high-pressure mercury lamp.
• the integrated light quantity during light irradiation is preferably from 100 to 3000 mJ/cm 2 , more preferably from 100 to 1500 mJ/cm 2 , from the viewpoints of productivity and curability of the coating film.
• the thickness of the hard coat layer is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more.
• the upper limit is preferably 30 ⁇ m or less.
• the above film thickness is an average film thickness, and is measured by measuring the film thickness at any five points on the hard coat layer and calculating the arithmetic average of the measured values.
• the spectacle lens may further include a primer layer disposed between the substrate and the hard coat layer.
• the primer layer is a layer that improves the adhesion of the hard coat layer to the substrate.
• An example of the material constituting the primer layer is a resin. Specific examples include urethane-based resins, epoxy-based resins, phenol-based resins, polyimide-based resins, polyester-based resins, bismaleimide-based resins, and polyolefin-based resins.
• the primer layer can be formed by, for example, a known method. Specifically, a method can be mentioned in which a primer layer-forming composition containing a resin is applied onto a substrate, and then cured as necessary to form a primer layer.
• a primer layer-forming composition onto the spectacle lens substrate to form a first coating film
• the adhesion between the primer layer and the hard coat layer is likely to be excellent.
• a heat treatment may be performed during the formation of the first coating film and the formation of the second coating film.
• the curing treatment the above-mentioned curing treatment for the hard coat layer is preferable.
• a heat treatment is preferable.
• the thickness of the primer layer may be 0.3 to 2 ⁇ m.
• the spectacle lenses may include an anti-reflective layer.
• the anti-reflection layer is a layer having a function of preventing reflection of incident light. Specifically, it has low reflectance characteristics (broadband low reflectance characteristics) over the entire visible region of 400 to 700 nm.
• the antireflection layer may have a single-layer structure or a multi-layer structure.
• the antireflection layer is preferably an inorganic antireflection layer, which means an antireflection layer made of an inorganic compound.
• the multi-layered antireflection layer may have a structure in which low refractive index layers and high refractive index layers are alternately laminated.
• Examples of materials constituting the high refractive index layer include titanium, zirconium, aluminum, niobium, tantalum, and lanthanum oxides, and examples of materials constituting the low refractive index layer include silica oxides.
• Examples of methods for producing the anti-reflection layer include dry methods such as vacuum deposition, sputtering, ion plating, ion beam assisted deposition, and CVD.
• composition of the present disclosure will be explained in more detail below with reference to examples and comparative examples, but the composition of the present disclosure is not limited in any way by these examples.
• Example 1 Preparation of primer layer-forming composition
• Pure water 83 parts by mass
• UW-1013D-C1 manufactured by UBE, solid content 34% by mass
• Carbodilite V-02 manufactured by Nisshinbo Chemical Inc., solid content 39.9%
• a 10% by mass aqueous solution of DOWSIL 501W Additive 0.8 parts by mass
• a 10% by mass aqueous solution of DOWSIL L-7604 0.8 parts by mass
• DOWSIL 501WA Additive aqueous solution- Pure water 9 parts by mass
• DOWSIL 501W Additive manufactured by Dow Corp.
• DOWSIL L-7604 aqueous solution- Pure water (9 parts by mass) and DOWSIL L-7604 (manufactured by Dow Corp.) (1 part by mass) were added and stirred to prepare a 10% by mass aqueous solution of DOWSIL L-7604.
• a spectacle lens substrate with a refractive index of 1.74 (S-7.00D, manufactured by Nikon Essilor Co., Ltd.) was used.
• a primer layer forming composition (1.0 mL) was dropped onto one side of the spectacle lens substrate, and spin-coated.
• the spectacle lens substrate coated with the primer layer forming composition was rotated in this order at 500 rpm for 10 seconds, at 2000 rpm for 0.5 seconds, and finally at 0 rpm over 1 second.
• the obtained substrate was heated at 90° C. for 20 minutes to form a first coating film.
• the first coating film was formed on the other surface of the obtained spectacle lens substrate in the same manner as above.
• the obtained substrate was used as a spectacle lens substrate with a first coating film.
• Copper complex solution Tetrahydrofuran (89 parts by mass), copper(I) bromide (Tokyo Chemical Industry Co., Ltd., 0.05 parts by mass), and diphenylphosphine oxide (Tokyo Chemical Industry Co., Ltd., 5.28 parts by mass) were added and stirred to prepare a copper complex solution.
• Ominirad 127 solution- Methyl ethyl ketone (18.0 parts by mass) and an Ominirad 127 solution (manufactured by IGM Resins B.V., 2.0 parts by mass) were added and stirred to prepare a 10% by mass Ominirad 127 solution.
• a hard coat layer-forming composition J1 (2.0 mL) was dropped onto one of the first coatings of the obtained eyeglass lens substrate with the first coating, and spin-coated to form a second coating.
• the substrate was rotated in this order at 500 rpm for 10 seconds, at 2000 rpm for 0.5 seconds, and finally at 0 rpm over 1 second.
• the first coating film and the second coating film were irradiated with ultraviolet light (accumulated light amount: 0.8 J/cm 2 ) using a high-pressure mercury lamp (Fusion UV, LIGHT HAMMER 6, manufactured by Heraeus) as a light source.
• the hard coat layer forming composition J1 was dropped on the surface of the obtained substrate opposite to the side on which the hard coat layer forming composition J1 was applied, and spin-coated and irradiated with ultraviolet light under the same conditions as the side on which the hard coat layer forming composition J1 was applied.
• the obtained substrate was heated at 100° C. for 20 minutes to obtain a spectacle lens of Example 1 having a hard coat layer, a primer layer, a spectacle lens substrate, a primer layer, and a hard coat layer in this order.
• Examples 5 to 7 Each spectacle lens was obtained in the same manner as in Example 1, except that prepolymer liquid 2-1 or 2-2 was prepared in the following manner and used instead of prepolymer liquid 1-1.
• Prepolymer Liquid 2-1 Tetrahydrofuran (634.1 parts by mass), copper(I) bromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.0052 parts by mass), diphenylphosphine oxide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.54 parts by mass), NK Ester A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd., 71.3 parts by mass), and N,N,N',N'',N''-pentamethyldiethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd., 1.25 parts by mass) were added and stirred for 16 hours. Next, 581.1 parts by mass of tetrahydrofuran was removed from the resulting liquid using an evaporator (NE-1101, manufactured by Tokyo Rikakikai Co., Ltd.) to prepare prepolymer liquid 2-1.
• evaporator NE-1101, manufactured by Tokyo Rikakikai Co., Ltd
• Prepolymer solution 2-2 was obtained in the same manner as prepolymer solution 2-1, except that the various components and their contents were changed as shown in the table below.
• the interlayer adhesion of the hard coat layer in each of the eyeglass lenses was evaluated using a cross-cut tape test according to the following procedure.
• the obtained eyeglass lens was cut with a knife from the concave side of the sample at intervals of 1 mm to the eyeglass lens substrate, forming 25 grids.
• Scotch tape manufactured by 3M was pressed strongly onto the cut hard coat layer, and the Scotch tape was quickly pulled once with a load of 4 kg in a 45° direction from the surface to which the tape was attached, to peel it off.
• the total number of grids remaining on the substrate (the total number of grids consisting of the substrate, the primer layer and the hard coat layer) was counted, and the interlayer adhesion of the hard coat layer was evaluated according to the following evaluation criteria.
• Copper complex solution As described above.
• AC-SQ TA-100 silsesquioxane having a polymerizable group, manufactured by Toagosei Co., Ltd.
• NK Ester A-600 polyalkylene glycol di(meth)acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
• NK Oligo UA-232P mixture of urethane (meth)acrylate and AMP-20GY (phenoxydiethylene glycol acrylate) (70:30 (mass ratio), manufactured by Shin-Nakamura Chemical Co., Ltd.
• each description is as follows.
• the content of each component is indicated as the value (mass %) relative to the total solid content of the composition.
• the column “Polymer S + TA100” indicates the total content (mass %) of Polymer S and AC-SQ TA-100 relative to the total solid content of the composition.
• the column “Polymer P + A600” indicates the total content (mass %) of Polymer P and NK Ester A-600 relative to the total solid content of the composition.
• the column indicates the value of the total content of the polymer S and the silsesquioxane having a polymerizable group relative to the total content of the polymer S, the silsesquioxane having a polymerizable group, and the compound X (the value of any one of requirements A1 to A4).
• the column indicates the value of the content of the polymer S relative to the total content of the polymer S and the compound X (the value of any one of requirements B1 to B4).
• the "Requirement C or Requirement D” column in each example indicates the value of the total content of polymer P and monomer M relative to the total content of polymer P, monomer M, and silsesquioxane having a polymerizable group when the composition contains monomer M (any value of requirements C1 to C4). Also, when the composition does not contain monomer M, indicates the value of the content of polymer P relative to the total content of polymer P and silsesquioxane having a polymerizable group (any value of requirements D1 to D4).
• the "Mp" column indicates the peak top molecular weight of each compound. Note that TA100 had two peak top molecular weights, and the other components other than TA100 had one peak top molecular weight.
• the “Mw” column indicates the weight average molecular weight of each compound. It should be noted that the Mp and molecular weight distribution for "UA232P (urethane (meth)acrylate)" in the table are values for only the urethane (meth)acrylate contained in UA232P, and do not include AMP-20GY (phenoxydiethylene glycol acrylate).
• the column "Molecular weight distribution” indicates the region (molecular weight range) in which the molecular weight of each polymer exists in the molecular weight distribution curve of each polymer obtained by GPC method.
• composition of the present disclosure can form a hard coat layer with excellent interlayer adhesion.

Landscapes

• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Ophthalmology & Optometry (AREA)
• Physics & Mathematics (AREA)
• General Health & Medical Sciences (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Macromonomer-Based Addition Polymer (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=93938895

Family Applications (1)

Country Status (4)

Citations (6)

• 2024
  • 2024-06-14 WO PCT/JP2024/021677 patent/WO2025004856A1/ja not_active Ceased
  • 2024-06-14 JP JP2025529643A patent/JPWO2025004856A1/ja active Pending
  • 2024-06-14 EP EP24831720.8A patent/EP4737494A1/en active Pending
  • 2024-06-14 CN CN202480043289.7A patent/CN121443654A/zh active Pending

Patent Citations (6)

Also Published As

Similar Documents

Legal Events