Patent Application
20210079163
The present disclosure relates to a polymerizable composition for an optical component, an optical component, and a method for producing the optical component.
A cured product obtained by curing a polymerizable composition containing a polyene compound and a polythiol compound is widely used as various optical components such as lenses (refer to Patent Literature 1, for example).
One of the physical properties desired for the optical component is to have excellent heat resistance. This is due to the following reason, for example. The optical component is generally used as a substrate for various optical products. The optical products are usually produced by forming one or more functional films (for example, a hard coat, an antireflection film, and the like) on the optical component (substrate). The functional film is formed by various film forming methods, and many film forming methods involve a heat treatment. If an optical component which is a substrate has poor heat resistance, the quality of an optical product may be deteriorated due to deformation and/or deterioration of the substrate by the heat treatment. For example, when the substrate is deformed, a functional film formed on the substrate cannot follow the deformation of the substrate and a crack may be generated in the functional film. Meanwhile, if the substrate is to be heated at a heating temperature at which the substrate can withstand in order to prevent such deterioration in quality, film forming conditions are restricted, and usable film forming materials are also limited.
According to one aspect of the present disclosure, there is provided an optical component obtained by curing a polymerizable composition containing a polyene compound and a polythiol compound, which is excellent in heat resistance.
One aspect of the present disclosure relates to a polymerizable composition for an optical component containing a polyene compound, a polyiso(thio)cyanate compound, and a polythiol compound (excluding those subjected to a photopolymerization treatment). Hereinafter, the “polymerizable composition for an optical component” is also simply referred to as “polymerizable composition”.
A polymerizable composition for an optical component to be subjected to photopolymerization treatment is excluded from the above-described polymerizable composition for an optical component according to one aspect of the present disclosure. The polymerizable composition for an optical component that is subjected to a photopolymerization treatment refers to a composition that includes a polymerization treatment by light irradiation in a producing process of an optical component that is a cured product of this polymerizable composition. On the other hand, a polymerization treatment by light irradiation is not included in the step of producing a cured product (optical component) by curing the above-described polymerizable composition for an optical component according to one aspect of the present disclosure.
Here, “the polymerization treatment by light irradiation is not included” means that the polymerizable composition is intentionally irradiated with light as a polymerization treatment, and the polymerizable composition is allowed to be unintentional irradiated with light by the incidence of natural light, illumination light, or the like.
In the present disclosure and the specification, the “polyene compound” is referred to as a compound having two or more carbon-carbon double bonds per molecule, and the “polythiol compound” is referred to as a compound having two or more thiol groups per molecule. The cured product of the polymerizable composition containing a polyene compound and a polythiol compound has a carbon-carbon double bond of the polyene compound and a bond formed by a reaction (hereinafter, described as “thiol-ene reaction”) with a thiol group of the polythiol compound.
As a result of repeated intensive studies by the present inventors, heat resistance of a cured product obtained by curing the polymerizable composition can be increased by further adding a polyiso(thio)cyanate compound to the polymerizable composition containing a polyene compound and a polythiol compound. The reason for this is considered that the cured product obtained by curing the polymerizable compound has a thiourethane bond obtained by the reaction between the polyiso(thio)cyanate compound and the polythiol compound, in addition to the bond obtained by the thiol-ene reaction.
In the present disclosure and the present specification, the “polyiso(thio)cyanate compound” refers to a compound having two or more iso(thio)cyanate groups per molecule. “Iso(thio)cyanate” means isocyanate and/or isothiocyanate. Further, the “thiourethane bond” in the present disclosure and the present specification means a bond represented by the following Formula 1:
In Formula 1, Z represents an oxygen atom or a sulfur atom. A reaction between the thiol group and the isocyanate group forms the bond in which Z is an oxygen atom. A reaction between the thiol group and the isothiocyanate group forms the bond in which Z is a sulfur atom. In the present disclosure and the present specification, these reactions are referred to as “thiourethane reaction”. In Formula 1, * indicates the position where the thiourethane bond is bonded to another adjacent structure.
According to one aspect of the present disclosure, there is provided an optical component obtained by curing a polymerizable composition containing a polyene compound and a polythiol compound, which is excellent in heat resistance.
The polymerizable composition contains a polyene compound, a polyiso(thio)cyanate compound, and a polythiol compound. These compounds will be further described in detail below.
(Polyene Compound)
The number of carbon-carbon double bonds contained in the polyene compound is two or more per molecule, can be three or more, for example, three to five. The polyene compound can contain a carbon-carbon double bond in a carbon-carbon double bond-containing group such as a (meth)acrylic group, a vinyl group, and an allyl group. The carbon-carbon double bond-containing groups contained in the polyene compound may be the same as or different from each other.
Specific examples of the polyene compound include vinyl compounds such as divinylbenzene and divinyltoluene, (meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetraethylene glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and allyl compounds such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, and tetraallyloxyethane. As the polyene compound, the polyene compound may be used singly or in combination of two or more kinds thereof.
The polyene compound can be, for example, an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like. In one aspect, the polyene compound can be a cyclic structure-containing compound. The cyclic structure-containing compound may be a carbocyclic compound, a heterocyclic compound, a monocyclic compound, or a bicyclic or higher polycyclic compound. Moreover, the polyene compound may include a plurality of cyclic structures. In one aspect, the polyene compound can be a heteroalicyclic compound or a heteroaromatic compound, and specifically, an isocyanuric ring-containing compound or a cyanuric ring-containing compound.
The content of the polyene compound in the polymerizable composition can be, for example, more than 0% by mass and 50.00% by mass or less, or 10.00% to 35.00% by mass with respect to the mass (100% by mass) of the polymerizable composition. In the present disclosure and the present specification, the mass of the polymerizable composition means the mass excluding the solvent when the polymerizable composition contains the solvent.
(Polyiso(thio)cyanate Compound)
The polyiso(thio)cyanate compound can be, for example, an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like. The number of iso(thio)cyanate groups contained in the polyiso(thio)cyanate compound is two or more, and can be two to four, or two or three per one molecule.
The polyiso(thio)cyanate compound can be, for example, an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like. Specific examples of the polyiso(thio)cyanate compound include: an aliphatic polyisocyanate compound such as hexamethylene diisocyanate, 1,5-pentane diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, bis(4-isocyanatocyclohexyl) methane, 1,3-bis(isocyanatomethyl) cyclohexane, or 1,4-bis(isocyanatomethyl) cyclohexane; and an aromatic polyisocyanate compound such as xylylene diisocyanate, 1,3-diisocyanatobenzene, tolylene diisocyanate, or diphenylmethane diisocyanate. Furthermore, a halogen substitution product of the polyiso(thio)cyanate compound such as a chlorine substitution product thereof or a bromine substitution product thereof, an alkyl substitution product thereof, an alkoxy substitution product thereof, a prepolymer type modified product thereof with a nitro substitution product or a polyhydric alcohol, a carbodiimide modified product thereof, a urea modified product thereof, a biuret modified product thereof, a dimerization or trimerization reaction product thereof, and the like can be used. As the polyiso(thio)cyanate compound, only one kind of polyiso(thio)cyanate compound may be used, or two or more kinds of polyiso(thio)cyanate compounds may be mixed to be used. In one aspect, the polymerizable composition can contain a cyclic structure-containing compound as a polyiso(thio)cyanate compound. The cyclic structure-containing compound may be a carbocyclic compound, a heterocyclic compound, a monocyclic compound, or a bicyclic or higher polycyclic compound. Moreover, the polyiso(thio)cyanate compound may include a plurality of cyclic structures. In one aspect, the polyiso(thio)cyanate compound can be an aromatic compound (aromatic polyiso(thio)cyanate compound).
The content of the polyiso(thio)cyanate compound in the polymerizable composition can be, for example, more than 0% by mass and 50.00% by mass or less, or in a range of 10.00% to 35.00% by mass with respect to the mass (100% by mass) of the polymerizable composition.
(Polythiol Compound)
The polythiol compound can be, for example, an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like. The number of thiol groups contained in the polythiol compound is two or more, and can be two to four per molecule. In addition, the number of thiol groups contained in the polythiol compound can be three or more per molecule.
Examples of the polythiol compound include aliphatic polythiol compounds such as methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, tetrakis(mercaptomethyl)methane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, thiomalic acid bis(2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), and 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane; aromatic polythiol compounds such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2-bis(mercaptomethoxy)benzene, 1,3-bis(mercaptomethoxy)benzene, 1,4-bis(mercaptomethoxy)benzene, 1,2-bis(mercaptoethoxy)benzene, 1,3-bis(mercaptoethoxy)benzene, 1,4-bis(mercaptoethoxy)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 1,2,3-tris(mercaptomethoxy)benzene, 1,2,4-tris(mercaptomethoxy)benzene, 1,3,5-tris(mercaptomethoxy)benzene, 1,2,3-tris(mercaptoethoxy)benzene, 1,2,4-tris(mercaptoethoxy)benzene, 1,3,5-tris(mercaptoethoxy)benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyl)benzene, 1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptoethyl)benzene, 1,2,4,5-tetrakis(mercaptoethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptomethoxy)benzene, 1,2,4,5-tetrakis(mercaptomethoxy)benzene, 1,2,3,4-tetrakis(mercaptoethoxy)benzene, 1,2,3,5-tetrakis(mercaptoethoxy)benzene, 1,2,4,5-tetrakis(mercaptoethoxy)benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1, 3-dithiol, 9,10-anthracene dimethanethiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-di(p-mercaptophenyl)pentane; halogen-substituted aromatic polythiol compounds such as a chlorine substitution product and a bromine substitution product such as 2,5-dichlorobenzene-1,3-dithiol, 1,3-di(p-chlorophenyl)propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, and 2,3,4,6-tetrachloro-1,5-bis(mercaptomethyl)benzene; aromatic polythiol compounds containing a sulfur atom in addition to a thiol group (also referred to as “mercapto group”) such as 1,2-bis(mercaptomethylthio)benzene, 1,3-bis(mercaptomethylthio)benzene, 1,4-bis(mercaptomethylthio)benzene, 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, 1,3,5-tris(mercaptoethylthio)benzene, 1,2,3,4-tetrakis(mercaptomethylthio)benzene, 1,2,3,5-tetrakis(mercaptomethylthio)benzene, 1,2,4,5-tetrakis(mercaptomethylthio)benzene, 1,2,3,4-tetrakis(mercaptoethylthio)benzene, 1,2,3,5-tetrakis(mercaptoethylthio)benzene, 1,2,4,5-tetrakis(mercaptoethylthio)benzene, and nuclear alkylated product thereof; aliphatic polythiol compounds containing a sulfur atom in addition to a thiol group such as bis(mercaptomethyl)sulfide, bis(mercaptoethyl)sulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio) ethane, 1,2-bis(3-mercaptopropylthio)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)disulfide, and esters of these thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxypropyl ulfide bis(2-mercaptoacetate), hydroxypropyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxypropyl disulfide bis(2-mercaptoacetate), hydroxypropyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol bis(2-mercaptoacetate), 1,4-dithiane-2,5-diol bis(3-mercaptopropionate), thioglycolic acid (2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), 4,4′-thiodibutyric acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 4,4′-dithiodibutyric acid bis(2-mercaptoethyl ester), thiodiglycolic acid bis(2,3-dimercaptopropyl ester), thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithiodiglycolic acid bis(2,3-dimercaptopropyl ester), dithiodipropionic acid bis(2,3-dimercaptopropyl ester), 4-mercaptomethyl-3,6-dithiaoctane-1,8-dithiol, bis(1,3-dimercapto-2-propyl) sulfide, bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol (also known as “bis(mercaptomethyl)-3,6,9-trithia-1,11-undecandithiol”; one of the isomers selected from the group consisting of 4,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis(mercaptomethyl)-3,6,9-trithial undecane-1,11-dithiol, and 5,7-bis(mercaptomethyl)-3,6,9-trithial undecane-1,11-dithiol, or a mixture of two or three of these isomers); and heterocyclic compounds containing a sulfur atom in addition to a thiol group such as 3,4-thiophenedithiol, tetrahydrothiophene-2,5-dimercaptomethyl, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,4-dithiane, and 2,5-dimercaptomethyl-1,4-dithiane.
In one aspect, the polythiol compound contained in the polymerizable composition can be an aliphatic compound. Further, in one aspect, the polythiol compound can be an ester bond-containing compound. The polythiol compound containing an ester bond can contain, for example, two or more ester bonds per molecule, for example, 2 to 5 ester bonds. In one aspect, the polythiol compound can be an ester bond-containing aliphatic compound.
The content of the polythiol compound in the polymerizable composition can be, for example, 20.00% to 80.00% by mass, or 30.00% to 70.00% by mass, with respect to the mass (100% by mass) of the polymerizable composition.
(Other Components)
The polymerizable composition can optionally contain one or more known components such as additives and polymerization catalysts that are generally used for producing an optical component. Examples of the additives include various additives such as an ultraviolet absorber, an antioxidant, and a release agent. Further, an organic phosphorus compound such as a phosphine derivative can also be used as an additive. The amount of the additive used can be set appropriately.
Further, the polymerizable composition can include, as a polymerization catalyst, a first polymerization catalyst that catalyzes a thiol-ene reaction between a polyene compound and a polythiol compound, and a second polymerization catalyst which catalyzes a thiourethane reaction between a polyiso(thio)cyanate compound and a polythiol compound. As the first polymerization catalyst which catalyzes the thiol-ene reaction and the second polymerization catalyst which catalyzes the thiourethane reaction, known polymerization catalysts can be used.
Examples of the first polymerization catalyst for catalyzing thiol-ene reaction inlcude azobis compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2′-azobisisoobtylate, 1,1′-azobis(cyclohexane-1-carbonitrile), 1,1′-azobis(1-acetoxyl-phenylethane), and 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile); and peroxide compounds such as benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, propionyl peroxide, lauroyl peroxide, peracetic acid tert-butyl, tert-butyl perbenzoate, tert-butyl hydroperoxide, tert-butyl peroxypivalate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylperoxide oxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-amylperisononanoate, t-amylperoxyacetate, and t-amylperoxybenzoate. The polymerizable composition can contain, for example, the first polymerization catalyst in an amount of 0.01% to 0.10% by mass with respect to the mass (100% by mass) of the polymerizable composition.
Examples of the second polymerization catalyst that catalyzes the thiourethane reaction include organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, tributyltin fluoride, and dimethyltin dibromide. The polymerizable composition can contain, for example, the second polymerization catalyst in an amount of 0.01% to 0.50% by mass with respect to the mass (100% by mass) of the polymerizable composition.
The above-mentioned polymerizable composition can be prepared by simultaneously or sequentially mixing the above-described various components at the same time or in any order. The preparation method is not particularly limited, and any known method for preparing a polymerizable composition can be adopted. Further, the polymerizable composition may be prepared without adding a solvent, or may be prepared by adding an optional amount of the solvent. As the solvent, it is possible to use one or more of known solvents that can be used in the polymerizable composition.
<Method for Manufacturing Cured Product>
The polyene compound, the polyiso(thio)cyanate compound, and the polythiol compound described above are all polymerizable compounds, and by polymerizing these compounds, the polymerizable composition can be cured to obtain a cured product. The cured product thus obtained can be used as various optical components.
For example, examples of the optical component include various lenses such as a spectacle lens, a telescope lens, a binocular lens, a microscope lens, an endoscope lens, and an imaging system lens of various cameras. The “lens” in the present disclosure and the present specification includes a “lens substrate” in which one or more layers are optionally layered.
For example, cast polymerization can be conducted for producing a cured product (also referred to as “plastic lens”) having a lens shape. In cast polymerization, a polymerizable composition is injected into a cavity of a molding die having two molds facing each other with a predetermined gap and a cavity formed by closing the gap, and the polymerizable compound contained in the polymerizable composition is polymerized (curing reaction) in the cavity to obtain a cured product. For details of a molding die usable for cast polymerization, for example, refer to paragraphs 0012 to 0014 and FIG. 1 of JP 2009-262480 A. Note that the publication describes a molding die in which the gap between the two molds is closed with a gasket as a sealing member, but a tape can also be used as the sealing member.
In an aspect, cast polymerization can be performed as follows. The polymerizable composition is injected into a molding die cavity from an injection port formed on a side surface of the molding die. After the injection, by polymerizing (curing reaction) the polymerizable compound contained in the polymerizable composition by heating, the polymerizable composition is cured to obtain a cured product having an internal shape of the cavity transferred thereon. A polymerization condition is not particularly limited, and can be appropriately set depending on the composition of a polymerizable composition or the like. As an example, a molding die having a polymerizable composition injected into a cavity can be heated at a heating temperature of 20° C. to 150° C. for about 1 to 72 hours, but the polymerization condition is not limited thereto. In the present disclosure and the present specification, the temperature such as a heating temperature for cast polymerization refers to a temperature of an atmosphere in which a molding die is placed. In addition, it is possible to raise the temperature at an arbitrary temperature rising rate during heating, and to lower the temperature (cooling) at an arbitrary temperature falling rate. After completion of the polymerization (curing reaction), the cured product inside the cavity is released from the molding die. The cured product can be released from the molding die by removing the upper and lower molds forming the cavity and a gasket or a tape in an arbitrary order as usually performed in cast polymerization. The cured product released from the molding die can be used as an optical component after post-treatment as necessary, and can be used as, for example, various lenses (for example, lens substrate). As an example, the cured product used as a lens substrate of a spectacle lens can be usually subjected to a post-step such as annealing, a dyeing treatment, a grinding step such as a rounding step, a polishing step, or a step of forming a coat layer such as a primer coat layer for improving impact resistance or a hard coat layer for improving surface hardness after releasing. Furthermore, various functional layers such as an antireflection layer and a water-repellent layer can be formed on the lens substrate. A known technique can be applied to any of these steps. In this way, a spectacle lens of which a lens substrate is the cured product can be obtained. Furthermore, by mounting this spectacle lens in a frame, eyeglasses can be obtained.
For example, in a case where the cured product obtained by curing the above polymerizable composition is a spectacle lens (spectacle lens substrate), the spectacle lens can be a finished lens (both sides are optically finished lens blanks) in one aspect. In another aspect, the spectacle lens can be a semi-finished lens in which one surface is an optical surface and the other surface is a non-optical surface (lens blanks in which only one surface is optically finished). In the semi-finished lens, a front surface (object-side surface; for example, a convex surface) is usually an optically finished surface, and a rear surface (eyeball-side surface; for example, a concave surface) is polished to have a desired lens power according to a lens prescription value. Therefore, the semi-finished lens is molded to have a larger wall thickness (for example, a center wall thickness of 3 to 10 mm) than that of the finished lens. As the polymerization treatment for obtaining such a cured product having a large wall thickness, a polymerization treatment by a heat treatment can be conducted.
One aspect of the present disclosure relates to an optical component that is a cured product obtained by curing the above polymerizable composition.
Further, one aspect of the present disclosure relates to a method for producing an optical component, which includes curing the polymerizable composition by the heat treatment.
The above description can be referred to for details of the method for producing the polymerizable composition and the cured product.
The optical component can have excellent heat resistance. The optical component having excellent heat resistance has, for example, little deformation and/or deterioration of the optical component as the substrate even if the heat treatment is performed in a film forming step of forming one or more various functional films on the optical component. Examples of an index of the heat resistance include a glass transition temperature (Tg). The glass transition temperature (Tg) in the present disclosure and the present specification refers to a glass transition temperature measured by a thermomechanical analysis (TMA) penetration method according to JIS K7196-2012. For a specific measurement method, refer to Examples described later. The optical component can have a glass transition temperature of 70° C. or higher or 80° C. or higher. The glass transition temperature can be high, from the viewpoint of heat resistance.
The optical component is a cured product of a polymerizable composition containing a polyene compound, a polyiso(thio)cyanate compound, and a polythiol compound, and thus can have a thiourethane bond formed by the reaction between an iso(thio)cyanate group of the polyiso(thio)cyanate compound and a thiol group of the polythiol compound (hereinafter, also described as “thiourethane reaction”).
From the viewpoint of further improving heat resistance, the content of the thiourethane bond of the optical component can be 9.00% by mass or more, 10.00% by mass or more, 12.00% by mass or more, 14.00% by mass or more, 16.00% by mass or more, 18.00% by mass or more, 20.00% by mass or more, 22.00% by mass or more, 24.00% by mass or more, 26.00% by mass or more, or 28.00% by mass or more. The content of the thiourethane bonds in the optical component can be, for example, 35.00% by mass or less or 30.00% by mass or less. The content of the thiourethane bond is a value with respect to the mass (100% by mass) of the optical component. The content of the thiourethane bond in the optical component can be determined by a known method. In a case where the composition of the polymerizable composition for obtaining the optical component (cured product) is known, the content of the thiourethane bond in the optical component can be calculated based on the known composition. The content of the thiourethane bond in the cured product can be adjusted by the composition of the polymerizable composition used to obtain the cured product.
Hereinafter, the present disclosure will be described in more detail with Examples, but the present disclosure is not limited to aspects indicated by Examples. Operation and evaluation described below were performed in air at room temperature (about 20° C. to 25° C.) unless otherwise specified. In addition, % described below are on a mass basis unless otherwise specified.
10.9 g of 2,4-tolylene diisocyanate (TDI) as a polyiso(thio)cyanate compound, 32.8 g of triallyl isocyanurate (TRIC) as a polyene compound, and 0.30 g of triphenylphosphine (TPP) as an organic phosphorus compound, 0.15 g of butoxyethyl acid phosphate as a release agent (JP-506H, available from Johoku Chemical Co., Ltd), 0.01 g of dimethyltin dichloride, and 0.02 g of 2,2′-azobis-2,4-dimethylvaleronitrile as a polymerization catalyst were added to a 300 ml eggplant-shaped flask, and stirring was continued for one hour under nitrogen purge at 20° C. When these were completely dissolved, 56.3 g of pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) was added as a polythiol compound, and the mixture was stirred under reduced pressure for 20 minutes at 0.13 kPa (1.0 Torr) to prepare a polymerizable composition 1 which contains a polyene compound, a polyiso(thio)cyanate compound, and a polythiol compound.
This polymerizable composition 1 was injected into the cavity of the molding die through a polytetrafluoroethylene membrane filter having a pore diameter of 1.0 μm, and cast polymerization was carried out for 24 hours at a temperature program from an initial temperature of 25° C. to a final temperature of 120° C. to produce a plastic lens having a center thickness of 2 mm.
The content of thiourethane bonds in the plastic lens thus produced is 9.41% by mass.
22.0 g of 2,4-tolylene diisocyanate (TDI) as a polyiso(thio)cyanate compound, 22.0 g of triallyl isocyanurate (TRIC) as a polyene compound, and 0.30 g of triphenylphosphine (TPP) as an organic phosphorus compound, 0.15 g of butoxyethyl acid phosphate as a release agent (JP-506H, available from Johoku Chemical Co., Ltd), 0.02 g of dimethyltin dichloride, and 0.02 g of 2,2′-azobis-2,4-dimethylvaleronitrile as a polymerization catalyst were added to a 300 ml eggplant-shaped flask, and stirring was continued for one hour under nitrogen purge at 20° C. When these were completely dissolved, 56.0 g of pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) was added as a polythiol compound, and the mixture was stirred under reduced pressure for 20 minutes at 0.13 kPa (1.0 Torr) to prepare a polymerizable composition 2 which contains a polyene compound, a polyiso(thio)cyanate compound, and a polythiol compound.
This polymerizable composition 2 was injected into the cavity of the molding die through a polytetrafluoroethylene membrane filter having a pore diameter of 1.0 μm, and cast polymerization was carried out for 24 hours at a temperature program from an initial temperature of 25° C. to a final temperature of 120° C. to produce a plastic lens having a center thickness of 2 mm.
The content of thiourethane bonds in the plastic lens thus produced is 18.98% by mass.
33.2 g of 2,4-tolylene diisocyanate (TDI) as a polyiso(thio)cyanate compound, 11.1 g of triallyl isocyanurate (TRIC) as a polyene compound, and 0.30 g of triphenylphosphine (TPP) as an organic phosphorus compound, 0.15 g of butoxyethyl acid phosphate as a release agent (JP-506H, available from Johoku Chemical Co., Ltd), 0.03 g of dimethyltin dichloride, and 0.02 g of 2,2′-azobis-2,4-dimethylvaleronitrile as a polymerization catalyst were added to a 300 ml eggplant-shaped flask, and stirring was continued for one hour under nitrogen purge at 20° C. When these were completely dissolved, 55.7 g of pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) was added as a polythiol compound, and the mixture was stirred under reduced pressure for 20 minutes at 0.13 kPa (1.0 Torr) to prepare a polymerizable composition 3 which contains a polyene compound, a polyiso(thio)cyanate compound, and a polythiol compound.
This polymerizable composition 3 was injected into the cavity of the molding die through a polytetrafluoroethylene membrane filter having a pore diameter of 1.0 μm, and cast polymerization was carried out for 24 hours at a temperature program from an initial temperature of 25° C. to a final temperature of 120° C. to produce a plastic lens having a center thickness of 2 mm.
The content of thiourethane bonds in the plastic lens thus produced is 28.74% by mass.
24.0 g of 2,4-tolylene diisocyanate (TDI) as a polyiso(thio)cyanate compound, 24.0 g of triallyl isocyanurate (TRIC) as a polyene compound, and 0.30 g of triphenylphosphine (TPP) as an organic phosphorus compound, 0.15 g of butoxyethyl acid phosphate as a release agent (JP-506H, available from Johoku Chemical Co., Ltd), 0.01 g of dimethyltin dichloride, and 0.08 g of 2,2′-azobis-2,4-dimethylvaleronitrile as a polymerization catalyst were added to a 300 ml eggplant-shaped flask, and stirring was continued for one hour under nitrogen purge at 20° C. When these were completely dissolved, 52.0 g of bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol as a polythiol compound was added, and the mixture was stirred under reduced pressure for 20 minutes at 0.13 kPa (1.0 Torr) to prepare a polymerizable composition 4 which contains a polyene compound, a polyiso(thio)cyanate compound, and a polythiol compound.
This polymerizable composition 4 was injected into the cavity of the molding die through a polytetrafluoroethylene membrane filter having a pore diameter of 1.0 μm, and cast polymerization was carried out for 24 hours at a temperature program from an initial temperature of 25° C. to a final temperature of 125° C. to produce a plastic lens having a center thickness of 2 mm.
The content of thiourethane bonds in the plastic lens thus produced is 20.71% by mass.
11.5 g of 2,4-tolylene diisocyanate (TDI) as a polyiso(thio)cyanate compound, 35.0 g of triallyl isocyanurate (TRIC) as a polyene compound, and 0.30 g of triphenylphosphine (TPP) as an organic phosphorus compound, 0.15 g of butoxyethyl acid phosphate as a release agent (JP-506H, available from Johoku Chemical Co., Ltd), 0.01 g of dimethyltin dichloride, and 0.08 g of 2,2′-azobis-2,4-dimethylvaleronitrile as a polymerization catalyst were added to a 300 ml eggplant-shaped flask, and stirring was continued for one hour under nitrogen purge at 20° C. When these were completely dissolved, bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol 52.5 g was blended as a polythiol compound, and stirred under reduced pressure for 20 minutes at 0.13 kPa (1.0 Torr). Then, a polymerizable composition 5 containing a polyene compound, a polyiso(thio)cyanate compound and a polythiol compound was prepared.
This polymerizable composition 5 was injected into the cavity of the molding die through a polytetrafluoroethylene membrane filter having a pore diameter of 1.0 μm, and cast polymerization was carried out for 24 hours at a temperature program from an initial temperature of 25° C. to a final temperature of 125° C. to produce a plastic lens having a center thickness of 2 mm.
The content of thiourethane bonds in the plastic lens thus produced is 9.93% by mass.
43.5 g of triallyl isocyanurate (TRIC) as a polyene compound, 0.30 g of triphenylphosphine (TPP) as an organic phosphorus compound, 0.15 g of butoxyethyl acid phosphate as a release agent (JP-506H, available from Johoku Chemical Co., Ltd), and 0.02 g of 2,2′-azobisu 2,4-dimethylvaleronitrile as a polymerization catalyst were added to a 300 ml eggplant-shaped flask, and stirring was continued for one hour under nitrogen purge at 20° C. When these were completely dissolved, 56.5 g of pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) was blended as a polythiol compound, and the mixture was stirred under reduced pressure for 20 minutes at 0.13 kPa (1.0 Torr) to prepare a polymerizable composition 6 which contains a polyene compound and a polythiol compound and does not contain a polyiso(thio)cyanate compound.
This polymerizable composition 6 was injected into the cavity of the molding die through a polytetrafluoroethylene membrane filter having a pore diameter of 1.0 μm, and cast polymerization was carried out for 24 hours at a temperature program from an initial temperature of 25° C. to a final temperature of 120° C. to produce a plastic lens having a center thickness of 2 mm.
The content of thiourethane bonds in the plastic lens thus produced is 0% by mass.
The plastic lenses of Examples 1 to 5 and Comparative Example 1 were released from the molding die and then subjected to measurement of glass transition temperature. The glass transition temperatures (Tg) was measured by a penetration method using a thermal instrument analyzer TMA 8310 manufactured by Rigaku Corporation. A temperature rising rate at the time of measurement was 10 K/min, and an indenter having a diameter of 0.5 mm was used as an indenter for the penetration method. Results of the measurement are illustrated in Table 1.
As indicated in Table 1, the glass transition temperature of the plastic lens of Comparative Example 1 was 65° C., whereas the glass transition temperature of the plastic lenses of Examples 1 to 5 was 70° C. or higher.
The plastic lenses of Examples 1 to 5 and the plastic lens of Comparative Example 1 were both produced from a polymerizable composition containing a polyene compound and a polythiol compound, but the plastic lenses of Examples 1 to 5 produced from a polymerizable composition also containing a polyiso(thio)cyanate compound had a higher glass transition temperature (excellent heat resistance) than the plastic lens of Comparative Example 1. The plastic lenses of Examples 1 to 5 described above are suitable as various optical components such as spectacle lenses that are desired to have excellent heat resistance. For example, a spectacle lens can be produced by using the plastic lens of Examples 1 to 5 as a lens substrate.
The polymerizable compositions 1 to 5 include various polymerizable compounds at a molar ratio at which the total amount of the isocyanate groups of the polyiso(thio)cyanate compound is able to react with the thiol group contained in the polythiol compound. The content of the thiourethane bond is a value calculated by the following formula, assuming that the total amount of the isocyanate groups of the polyiso(thio)cyanate compound reacts to generate a thiourethane bond.
The content of thiourethane bond=(mass of thiourethane bond to be generated/total mass of polymerizable composition)×100
As the polymerizable composition 6 does not contain a polyiso(thio)cyanate compound, the content of the thiourethane bond of the plastic lens of Comparative Example 1 obtained from this polymerizable composition 4 is 0% by mass.
Finally, the above-described aspects will be summarized.
According to one aspect, there is provided a polymerizable composition for an optical component containing a polyene compound, a polyiso(thio)cyanate compound, and a polythiol compound (excluding those subjected to a photopolymerization treatment).
By curing the polymerizable composition by heating, an optical component having excellent heat resistance can be produced.
In one aspect, the polyene compound can be a cyclic structure-containing compound.
In one aspect, the cyclic structure can be an isocyanuric ring.
In one aspect, the polyene compound can be an allyl compound.
In one aspect, the polyene compound can be a compound containing three or more carbon-carbon double bonds per molecule.
In one aspect, the polythiol compound can be an aliphatic compound.
In one aspect, the polythiol compound can be an ester bond-containing compound.
In one aspect, the polythiol compound can be a compound containing three or more thiol groups per molecule.
In one aspect, the polyiso(thio)cyanate compound can be an aromatic compound.
In one aspect, the optical component can be a lens.
In one aspect, the lens can be a spectacle lens.
According to one aspect, there is provided an optical component that is a cured product obtained by curing the above polymerizable composition.
The optical component can have excellent heat resistance.
In one aspect, the glass transition temperature of the optical component may be 70° C. or higher.
In one aspect, the content of the thiourethane bond may be 9.00% by mass or more.
According to one aspect, there is provided a method for producing an optical component, which includes curing the polymerizable composition by the heat treatment.
The various aspects described in this specification can be combined in two or more in any combination.
The embodiment disclosed here is exemplary in all respects, and it should be considered that the embodiment is not restrictive. The scope of the present disclosure is defined not by the above description but by claims, and intends to include all modifications within meaning and a scope equal to claims.
An aspect of the present disclosure is useful in the field of producing various kinds of optical components such as a spectacle lens.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-125589 | Jun 2018 | JP | national |
This application is a Continuation of PCT International Application No. PCT/JP2019/025549 filed on Jun. 27, 2019, which was published under PCT Article 21(2) in Japanese. The above application is hereby expressly incorporated by reference, in its entirety, into the present application.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2019/025549 | Jun 2019 | US |
| Child | 17104567 | US |
