JP7685909B2 - Lenses and glasses - Google Patents

Description

The present invention relates to an aqueous primer composition for optical articles, an optical laminate, an optical article, a lens, and glasses.

Eyeglasses are optical articles used to correct refractive errors and protect the eyes. Functional layers may be laminated on the surfaces of plastic or glass lenses used in eyeglasses to provide functions other than those mentioned above. For example, a hard coat layer is a functional layer that protects the lens surface from scratches, etc. A photochromic layer is a functional layer that gives the lens photochromic properties.

To improve adhesion between the functional layer and the lens, a primer layer may be provided between them. The primer layer is formed by applying a primer composition onto the lens surface and curing the resulting coating. The primer composition contains, for example, an adhesive component such as a urethane resin, and a solvent for dispersing this adhesive component.

International Publication No. 2015/016313

The object of the present invention is to provide an aqueous primer composition for optical articles that has the ability to absorb light of a specific wavelength and has a small environmental impact, and an optical laminate, optical article, lens, and eyeglasses that contain a cured product of this aqueous primer composition for optical articles.

According to an embodiment, a water-based primer composition for optical articles is provided. This water-based primer composition for optical articles contains at least one compound selected from the group consisting of urethane acrylate, acrylic monomer, acrylic resin, urethane resin, and ester resin, a water-soluble functional dye, and water.

According to an embodiment, an optical laminate is provided. The optical laminate includes an optical substrate, a primer layer, and a resin layer. The primer layer is provided on at least one main surface of the optical substrate, and includes a cured product of the aqueous primer composition for optical articles according to the embodiment. The resin layer is provided on the surface of the primer layer opposite to the surface in contact with the optical substrate, and includes at least one resin selected from the group consisting of (meth)acrylic resins, urethane resins, urethane urea resins, and resins having siloxane bonds.

According to an embodiment, an optical article is provided that includes an optical laminate according to the embodiment.

According to an embodiment, a lens is provided. The lens includes an optical laminate according to an embodiment, in which the optical substrate is a plastic lens substrate.

According to an embodiment, a lens is provided. The lens includes at least one polymer selected from the group consisting of urethane acrylates and urethane resins, and a water-soluble functional dye.

According to an embodiment, eyeglasses are provided that include a lens according to the embodiment.

The present invention provides an aqueous primer composition for optical articles that has light absorption capability at a specific wavelength and has a small environmental impact, and an optical laminate, optical article, lens, and eyeglasses that contain a cured product of the aqueous primer composition for optical articles.

FIG. 1 is a cross-sectional view illustrating an example of an optical laminate according to an embodiment. FIG. 1 is a perspective view illustrating an example of glasses according to an embodiment.

The aqueous primer composition for optical articles according to the embodiment contains at least one compound selected from the group consisting of urethane acrylate, acrylic monomer, acrylic resin, urethane resin, and ester resin, a water-soluble functional dye, and water.

The primer composition according to the embodiment contains a water-soluble functional dye, and therefore can form a primer layer capable of absorbing light of specific wavelengths, such as ultraviolet light and blue light. In addition, because a water-soluble functional dye is used, water can be used as a dispersion medium. Therefore, this primer composition is less toxic and has a smaller environmental impact than primer compositions that use an organic solvent as a dispersion medium. In addition, it is less likely to cause cracks in plastic lenses, and can be applied to any type of plastic lens.

The photocurable composition according to the embodiment is described in detail below.

[Water-based primer composition for optical articles]
(1) Adhesive component At least one compound selected from the group consisting of urethane acrylate, acrylic monomer, acrylic resin, urethane resin, and ester resin is a main component that provides adhesion to the primer layer. Among these compounds, it is preferable to use urethane acrylate from the viewpoint of improving weather-resistant adhesion.

The proportion of the above compounds in the aqueous primer composition for optical articles is, for example, 5% by mass or more and 70% by mass or less, and preferably 20% by mass or more and 50% by mass or less. If this proportion is high, the film thickness will be large when applied, making it difficult to obtain a primer layer with a uniform film thickness. If this proportion is low, the film thickness will be too thin when applied, making it difficult to obtain a primer layer with sufficient light absorption ability. This proportion can be calculated, for example, by a known method for measuring solid content concentration.

These compounds are preferably in the form of particles, and more preferably in the form of colloidal particles. The average particle size of the compounds as measured by the light scattering method is, for example, 0.001 μm or more and 0.100 μm or less, and preferably 0.005 μm or more and 0.050 μm or less.

The number average molecular weight of these compounds is preferably 1,000 or more and 100,000 or less. If the number average molecular weight is large, a strong primer film with good adhesion can be formed, but the viscosity is high and it tends to be difficult to obtain a primer layer with a uniform thickness. If the average molecular weight is small, the adhesion tends to be insufficient. This average molecular weight can be measured by dynamic light scattering using, for example, a Zetasizer Nano ZS manufactured by Malvern Panalytical.

These compounds preferably have an anionic group. The presence of an anionic group increases dispersibility in an aqueous solvent. Specific examples of the anionic group include a carboxyl group, a sulfonyl group, a phosphate group, and a betaine structure-containing group such as sulfobetaine. The number of anionic groups contained in one molecule of the compound is preferably one or more.

(1-1) Urethane acrylate Urethane acrylate is an oligomer having a polyurethane skeleton and a (meth)acryloyl group at the end of the main chain. The (meth)acryloyl group includes at least one of an acryloyl group and a methacryloyl group. The number of (meth)acryloyl groups in the urethane acrylate is preferably 2 or more, and more preferably 4 to 30, per molecule.

(1-2) Acrylic Monomer The acrylic monomer is a monomer that forms a (meth)acrylic resin by polymerization. The acrylic monomer has one or more (meth)acryloyl groups. The acrylic monomer preferably has two or more (meth)acryloyl groups in one molecule. Here, the (meth)acryloyl group means at least one of an acryloyl group and a methacryloyl group.

(1-3) Acrylic Resin The acrylic resin is a polymer of an acrylic monomer. The acrylic resin is preferably one obtained by emulsion polymerization of an acrylic acid ester monomer with an emulsifier.

(1-4) Urethane resin The urethane resin is a polymer having a urethane bond in the main chain of the molecule. The urethane resin is preferably a reaction product of a polyisocyanate and a polyol. As the polyol, it is preferable to use at least one selected from the group consisting of polyalkylene glycol, polyester polyol, polyether polyol, polyether ester polyol, and polycarbonate polyol. The polyisocyanate may be an aromatic polyisocyanate or an aliphatic polyisocyanate. The polyisocyanate is preferably an aliphatic polyisocyanate.

(1-5) Ester resin The ester resin is a polymer having an ester bond in the main chain of the molecule. The ester resin is a resin produced by polycondensation of a polybasic acid and a polyhydric alcohol, and is preferably a resin that does not contain a urethane bond (-NHCOO-) in the molecule.

(2) Water-soluble functional dye The functional dye is a dye that absorbs light of a specific wavelength. The functional dye includes ultraviolet absorbers, blue light absorbers, dyes, near-infrared absorbers, and infrared absorbers. The functional dye may be of only one type, or may contain a mixture of multiple types. The water-soluble functional dye is a dye that can be dissolved when 0.5 g of the water-soluble functional dye is added to 100 g of water and stirred at 20° C. for 3 hours. The water-soluble functional dye preferably contains at least one of a water-soluble ultraviolet absorber and a water-soluble blue light absorber.

In the aqueous primer composition for optical articles, the proportion of the water-soluble functional dye is, for example, 0.01% by mass or more and 20% by mass or less, preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.3% by mass or more and 7% by mass or less. In addition, the proportion of the water-soluble functional dye in the solid matter of the aqueous primer composition for optical articles is 1% by mass or more and 50% by mass or less, and preferably 5% by mass or more and 30% by mass or less.

The water-soluble functional dye preferably has a hydrophilic group. Examples of the hydrophilic group include a hydroxyl group, a sulfo group, an amino group, and a carboxyl group. The water-soluble functional dye may have one hydrophilic group in one molecule, or may have two or more hydrophilic groups.

(2-1) Water-soluble ultraviolet absorber The water-soluble ultraviolet absorber exhibits a maximum absorption peak in the wavelength region of 250 nm or more and less than 420 nm. The maximum absorption peak of the water-soluble ultraviolet absorber can be confirmed by ultraviolet-visible absorption spectroscopy (UV-Vis). Specifically, first, a 0.01 mmol/L aqueous solution of the water-soluble ultraviolet absorber is prepared. The absorption spectrum of this aqueous solution is measured with a UV-Vis spectrophotometer using a 1 cm quartz cell.

In the aqueous primer composition for optical articles, the proportion of the water-soluble UV absorber is, for example, 0.01% by mass or more and 20% by mass or less, preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less.

Examples of water-soluble UV absorbers include pyrimidine derivatives, benzophenone derivatives, and benzimidazole derivatives having hydrophilic functional groups. More specifically, pyrimidine derivatives represented by the following formula (1), methylobamine represented by the following formula (2), benzophenone derivatives represented by the following formula (3), sodium hydroxymethoxybenzophenone sulfonate represented by the following formula (4), and COMFOGUARD UV002 manufactured by Fujifilm Corporation can be used.

In the above formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a methyl group or an ethyl group.

Using a water-based primer composition for optical articles that contains a water-soluble UV absorber can improve the weather resistance and adhesion of the optical laminate.

(2-2) Water-soluble blue light absorber The water-soluble blue light absorber exhibits a maximum absorption peak in the wavelength region of 420 nm or more and 500 nm or less. The maximum absorption peak of the water-soluble blue light absorber can be confirmed by UV-Vis spectroscopy. Specifically, first, a 0.01 mmol/L aqueous solution of the water-soluble blue light absorber is prepared. The absorption spectrum of this aqueous solution is measured with a UV-Vis spectrophotometer using a 1 cm quartz cell.

In the aqueous primer composition for optical articles, the proportion of the water-soluble UV absorber is, for example, 0.01% by mass or more and 20% by mass or less, preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less.

It is preferable that the water-soluble blue light absorbing agent has a maximum absorption peak in the wavelength range of 420 nm or more and 480 nm or less.

An example of a water-soluble blue light absorbing agent is COMFOGUARD VIS-001 manufactured by Fujifilm Corporation.

(3) Water Water is a dispersion medium of the aqueous primer composition for optical articles. The aqueous primer composition for optical articles according to the embodiment uses water as a dispersion medium, and therefore can realize a primer composition that is safer and has a smaller environmental impact than those that use an organic solvent as a dispersion medium.

In the aqueous primer composition for optical articles, the proportion of water is, for example, 20% by mass or more and 95% by mass or less, and preferably 30% by mass or more and 80% by mass or less. If the proportion of water is high, the film thickness at the time of application tends to be too thin, making it difficult to impart the desired light absorption ability. If the proportion of water is low, the viscosity of the primer composition increases, making it difficult to impart a primer layer of uniform thickness. This proportion can be measured, for example, by gas chromatography.

(4) Other Additives The aqueous primer composition for optical articles may contain other additives in addition to the above-mentioned compounds. Examples of the other additives include a photopolymerization initiator, a neutralizing agent, and an organic solvent.

(4-1) Photopolymerization initiator When a photopolymerizable monomer such as urethane acrylate and acrylic monomer is used, the primer composition may contain a photopolymerization initiator. The ratio of the photopolymerization initiator in the primer composition is, for example, 0.01 parts by mass or more and 5.0 parts by mass or less, preferably 0.05 parts by mass or more and 2.0 parts by mass or less, relative to 100 parts by mass of the polymerizable monomer. If the ratio of the photopolymerization initiator is high, the resulting primer layer tends to be hard and insufficient adhesion is not obtained. If the ratio of the photopolymerization initiator is low, the resulting primer layer tends to be insufficiently cured and insufficient hardness and adhesion is not obtained.

Specific examples of photopolymerization initiators include benzophenone; acetophenone compounds such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; α-dicarbonyl compounds such as 1,2-diphenylethanedione and methylphenylglycoxylate; 2,6-dimethylbenzoyldiphenylphosphine oxide, bis(2,4,6- acylphosphine oxide compounds such as bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, and 2,6-dimethoxybenzoyldiphenylphosphine oxide; 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester, and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester.

Among these photopolymerization initiators, it is preferable to use a liquid or water-soluble photopolymerization initiator. Specific examples of liquid or water-soluble photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR1173 manufactured by BASF), a mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone (IRGACURE500 manufactured by BASF), and a mixture of oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2- Examples include a mixture of [2-hydroxy-ethoxy]-ethyl esters (IRGACURE 754 manufactured by BASF), a water dispersion of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE 819DW manufactured by BASF), and a mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 4265 manufactured by BASF).

These photopolymerization initiators may be used alone or in combination of two or more. It is also possible to use them in combination with known polymerization accelerators such as tertiary amines.

(5-1) Neutralizing Agent The neutralizing agent can be blended in order to disperse at least one compound selected from the group consisting of the urethane acrylate, acrylic monomer, acrylic resin, urethane resin, and ester resin.

Neutralizing agents include trialkylamines such as trimethylamine and triethylamine; N,N-dialkylalkanolamines such as N,N-dimethylethanolamine; trialkanolamines such as triethanolamine; sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, trimethylammonium hydroxide, etc.

(5-2) Organic Solvent The organic solvent is blended in order to disperse at least one compound selected from the group consisting of the above-mentioned urethane acrylate, acrylic monomer, acrylic resin, urethane resin, and ester resin.

Examples of organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and 2-butanol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and dioxane; and ketones such as diacetone alcohol.

In the manufacturing process of the primer layer, taking into consideration the occurrence of cracks in the optical substrate and high safety, it is preferable that the proportion of organic solvent in the primer composition is low. The proportion of organic solvent in the aqueous primer composition for optical articles is preferably 30% by mass or less, and more preferably 20% by mass or less. The lower limit of the proportion of organic solvent is 0% by mass.

(6) Method for Producing Aqueous Primer Composition for Optical Articles The aqueous primer composition for optical articles can be produced, for example, by the following method.
First, each raw material is prepared. As the raw material of at least one compound selected from the group consisting of urethane acrylate, acrylic monomer, acrylic resin, urethane resin, and ester resin, it is preferable to use a dispersion of each compound. The dispersion of each compound may contain each compound particle, a solvent, and a neutralizing agent. As the solvent, water is preferably used. As the neutralizing agent, the above-mentioned one is used. In the dispersion of the compound particles, the ratio of the solid content is preferably 10% by mass or more and 80% by mass or less. That is, the primer composition for optical articles according to the embodiment may contain a dispersion of at least one compound selected from the group consisting of urethane acrylate, acrylic monomer, acrylic resin, urethane resin, and ester resin, a water-soluble functional dye, and any other additives.

Next, the prepared raw materials are mixed, for example, under normal pressure and temperature to obtain a photocurable composition. There are no particular limitations on the order in which the prepared raw materials are mixed.

The aqueous primer composition for optical articles obtained by the above method contains a water-soluble functional dye, so by using this primer composition, a primer layer that is both safe and functional can be obtained.

As a raw material for the aqueous primer composition for optical articles, it is preferable to use at least one of a urethane acrylate dispersion and a urethane resin dispersion. The urethane acrylate dispersion and the urethane resin dispersion are described in detail below.

In the urethane acrylate dispersion, the amount of solids is preferably 10 to 70% by mass, and more preferably 20 to 50% by mass.

As a dispersion of urethane acrylate, Ucecoat (registered trademark) manufactured by Daicel Allnex Corporation can be suitably used.

It is preferable to use a urethane acrylate dispersion in which the elongation of the cured urethane acrylate at 25°C is 0.1% or more and 10% or less. By using a primer composition containing such a urethane acrylate, a cured product that is highly crosslinked in three dimensions can be obtained. It is more preferable that the elongation of the cured product at 25°C is 0.5% or more and 5.0% or less. In addition, it is preferable that the tensile strength of the cured urethane acrylate at 25°C is 10 MPa or more and 50 MPa or less, and more preferably 15 MPa or more and 30 MPa or less.

The elongation and tensile strength of the water-dispersible urethane (meth)acrylate single-cured body can be measured by the following method. First, 2-hydroxy-2-methyl-1-phenylpropan-1-one, a photopolymerization initiator, is added to a dispersion of urethane (meth)acrylate in an amount of 0.3 parts by mass per 100 parts by mass of solid content to obtain a mixed solution. This mixed solution is separated into a container such as a petri dish so that the film thickness of the solid content after drying is about 500 μm. The separated mixture is left to stand in a dark place at room temperature for 24 hours, further left to stand in a dark place at 80° C. for 6 hours, and further left to stand in a dark place at 120° C. for 20 minutes to thoroughly dry and obtain a residue. This residue is irradiated with light for 90 seconds in a nitrogen gas atmosphere so that the output at 405 nm is 200 mW/cm ² to obtain a film. For the light irradiation, for example, an F3000SQ equipped with a D bulb manufactured by Fusion UV Systems is used. The obtained film is cut into a size of 15 mm wide and 200 mm long, and then marks are made at 50 mm intervals in the center to prepare a measurement sample. The measurement sample is attached to a tensile tester, and the grip interval of the tester is set to 100 mm, and the sample is pulled at a speed of 200 mm/min until it breaks, to measure the elongation. The stress at which the sample breaks is taken as the tensile strength, and the elongation is calculated by the following formula.

Elongation (%) = ((gauge length at break - gauge length before test) / (gauge length before test)) x 100.

The urethane acrylate contained in the urethane acrylate dispersion is obtained, for example, by reacting a polyisocyanate compound, a polyol compound, an anionic group-active hydrogen group-containing compound, and a hydroxyl group-containing (meth)acrylate compound.

Specific examples of polyisocyanate compounds include aliphatic diisocyanate compounds such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, and 2,2,4-trimethylhexane-1,6-diisocyanate; cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 4,4'-methylenebisisocyanate. Alicyclic diisocyanate compounds such as an isomer mixture of (cyclohexyl isocyanate), hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, 1,9-diisocyanato-5-methylnonane, 1,1-bis(isocyanatomethyl)cyclohexane, 2-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]-1-methylcyclohexane, 2-(3-isocyanatopropyl)cyclohexyl isocyanate, and norbornane diisocyanate ; Phenylcyclohexylmethane diisocyanate, isomeric mixture of 4,4'-methylenebis(phenylisocyanate), toluene-2,3-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, 1,3-bis(isocyanatomethyl)benzene, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, 1,3-diisocyanatomethylbenzene, 4,4'-diisocyanato-3,3'-dimethoxy Examples of aromatic diisocyanate compounds include 1,1'-biphenyl, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 1,2-diisocyanatobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrachlorobenzene, 2-dodecyl-1,3-diisocyanatobenzene, 1-isocyanato-4-[(2-isocyanatocyclohexyl)methyl]-2-methylbenzene, 1-isocyanato-3-[(4-isocyanatophenyl)methyl)-2-methylbenzene, 4-[(2-isocyanatophenyl)oxy]phenyl isocyanate, and diphenylmethane diisocyanate.

In addition, polymers of the above polyisocyanate compounds (e.g., dimers, trimers, etc.); biuret modified products produced by the reaction of a polymer of a polyisocyanate compound with water; allophanate modified products or polyol modified products produced by the reaction of a polymer of a polyisocyanate compound with an alcohol or a low molecular weight polyol described below; oxadiazinetrione modified products produced by the reaction of a polymer of a polyisocyanate compound with carbon dioxide gas, and polymers of these modified products can also be used as raw materials for the water-dispersible urethane (meth)acrylate of the present invention. These polyisocyanate compounds can be used alone or in combination of two or more types of polyisocyanate compounds.

Among the above polyisocyanate compounds, it is preferable to use aliphatic diisocyanate compounds and/or alicyclic diisocyanate compounds from the viewpoint of weather resistance.

Specific examples of polyol compounds include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, dipropylene glycol, and diethylene glycol; polyalkylene glycols such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol; poly(alkylene adipates) such as poly(diethylene adipate), poly(tetramethylene adipate), poly(hexamethylene adipate), and poly(neopentylene adipate); poly-ε-caprolactone, polycaprolactone diol ... Examples of the polyol compounds include polycaprolactone polyols such as ethylene glycol; polybutadiene glycols such as poly(1,4-butanediene) glycol and poly(1,2-butanediene) glycol; poly(alkylene carbonates) such as poly(hexamethylene carbonate); polyester polyols; polyols containing three or more hydroxy groups in one molecule such as trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol, and pentaerythritol; and silicone polyols. These polyol compounds can be used alone or in combination of two or more kinds.

Among these polyol compounds, polyalkylene glycols, polyols containing three or more hydroxyl groups, polyalkylene adipates, polyalkylene carbonate polyols, polycaprolactone polyols, and polyester polyols are preferred because they allow the heating temperature during curing to be lower and can more reliably prevent thermal deformation and discoloration of the substrate.

An anionic active hydrogen group-containing compound is a compound that has one or more anionic groups such as a carboxyl group, a sulfonyl group, a phosphate group, or a betaine structure-containing group such as sulfobetaine, and has two or more active hydrogen groups that can react with an isocyanate group. Specific examples of such anionic active hydrogen group-containing compounds include dihydroxyl carboxylic acids such as 2,2-dimethylol acetic acid, 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol butyric acid, and 2,2-dimethylol valeric acid, and diamino carboxylic acids such as lysine, cystine, and arginine.

A hydroxyl group-containing (meth)acrylate compound is a (meth)acrylate compound having one or more hydroxyl groups in the molecule. Specific examples of such hydroxyl group-containing (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2, Examples include 2-dihydroxymethylbutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 1,4-butylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, propylene glycol mono(meth)acrylate, polycaprolactone glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polyhydroxyalkyl maleate, and polyhydroxyalkyl fumarate.

The amounts of the above-mentioned components to be mixed when producing a urethane acrylate may be appropriately determined depending on the target structure. From the viewpoint of making it easier to obtain a urethane acrylate, it is preferable to select the total equivalent of the isocyanate groups of the polyisocyanate compound from the range of 0.95 to 2.0 equivalents, particularly 1.0 to 1.5 equivalents, relative to the total equivalent of the hydroxyl groups contained in the polyol compound, the hydroxyl groups and active hydrogen groups such as amino groups contained in the anionic group-active hydrogen group-containing compound, and the hydroxyl groups contained in the hydroxyl group-containing (meth)acrylate compound.

In addition, when the total equivalent of the isocyanate groups of the polyisocyanate compound exceeds 1.0 relative to the total equivalent of the hydroxyl groups contained in the polyol compound, the hydroxyl groups contained in the anionic active hydrogen group-containing compound, active hydrogen groups such as amino groups, and the hydroxyl groups contained in the hydroxyl group-containing (meth)acrylate compound, the chain can be extended using a chain extender after dispersion in water. As the chain extender, a known chain extender can be used. Specific examples of such chain extenders include water, short-chain diols such as ethylene glycol and 1,4-butanediol, and polyamines such as hydrazine, ethylenediamine, diethyltriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, hexamethylenediamine, cyclohexylenediamine, piperazine, 2-methylpiperazine, phenylenediamine, tolylenediamine, xylenediamine, α,α'-methylenebis(2-chloroaniline), 3,3'-dichloro-α,α'-biphenylamine, m-xylenediamine, isophoronediamine, and N-methyl-3,3'-diaminopropylamine.

The aqueous dispersion of urethane acrylate is prepared by mixing the above-mentioned urethane acrylate with a neutralizing agent and dispersing it in water, and is in the form of an emulsion, dispersion, colloidal dispersion, etc. of urethane acrylate.

The urethane resin contained in the urethane resin dispersion is preferably a water-dispersible polyurethane resin obtained by reacting a polyol compound, an anionic group-active hydrogen group-containing compound, and a polyisocyanate compound.

It is even more preferable to mix a water-dispersible polyurethane resin, which is obtained by reacting an active hydrogen group-containing acrylate compound and/or an alkoxysilyl group-containing polyamine compound, as described in Japanese Patent Publication No. 5016266 and International Publication No. 2008/001875.

The raw materials of the water-dispersible polyurethane resin, that is, the polyol compound, the anionic group active hydrogen group-containing compound, the polyisocyanate compound, and the hydroxyl group-containing (meth)acrylate compound, can be the same as those of the water-dispersible urethane (meth)acrylate. In addition, the alkoxysilyl group-containing polyamine compound can be an alkoxysilyl compound having a primary amino group and a secondary amino group, specifically, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropyldimethoxysilane, γ-(2-aminoethyl aminopropyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyldiethoxysilane, N,N'-bis[α-(trimethoxysilyl)propyl]ethylenediamine, etc.

The water-dispersible urethane resin can be synthesized by reacting an active hydrogen group-containing component (i.e., at least a polyol compound, an anionic active hydrogen group-containing compound, a hydroxyl group-containing (meth)acrylate compound, and/or an alkoxysilyl group-containing polyamine compound) with a polyisocyanate component (i.e., a polyisocyanate compound) by a one-shot method or a prepolymer method in the same manner as for the water-dispersible urethane (meth)acrylate, with the prepolymer method being more preferred. A chain extender can also be used.

The surface hardness of the urethane resin layer obtained by photocuring the water-dispersible polyurethane resin is the same as that obtained without photocuring, and no improvement in surface hardness was observed due to photocuring.

Among the above water-dispersible urethane resins, from the viewpoint of the appearance and adhesion of the photochromic laminate, it is preferable to use a water-dispersible urethane resin in which the tensile strength of the urethane resin film obtained by drying the water-dispersible urethane resin at 25°C is 20 MPa or more and 70 MPa or less, particularly 30 MPa or more and 60 MPa or less, and the elongation percentage at 25°C is 100% or more and 1000% or less, particularly 200% or more and 800% or less. The tensile strength and elongation percentage of the urethane resin film of the water-dispersible urethane resin can be measured in the same manner as for the urethane acrylate.

Furthermore, from the viewpoint of improving the appearance of the resulting photochromic laminate and of adhesion, it is preferable for the water-dispersible urethane resin to have a Vickers hardness of a dry coating of 1 or more and less than 8, and particularly 2 or more and 6 or less. The Vickers hardness of the dry coating of the water-dispersible urethane resin can also be measured in the same manner as for the water-dispersible urethane (meth)acrylate.

When using the above water-dispersible polyurethane resin, the mixing ratio of the water-dispersible polyurethane resin is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and most preferably 30 to 100 parts by mass, of the water-dispersible urethane resin per 100 parts by mass of the water-dispersible urethane (meth)acrylate in order to prevent a decrease in surface hardness after lamination of the photochromic layer due to a decrease in the surface hardness of the resulting primer coat layer, and to obtain a sufficient effect of improving adhesion.

The water-dispersible urethane resin can be blended as is, or an aqueous dispersion in which the urethane resin is dispersed in water can be blended.

As a dispersion of water-dispersible urethane resin, Superflex 420 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., NJ-321A manufactured by Tokuyama Corporation, etc. can be suitably used.

[Optical laminate]
The optical laminate according to the embodiment includes an optical substrate, a primer layer provided on at least one main surface of the optical substrate and including a cured product of the aqueous primer composition for optical articles according to the embodiment, and a resin layer provided on the surface of the primer layer opposite to the surface in contact with the optical substrate and including a (meth)acrylic resin, a urethane resin, an epoxy resin, a resin having a siloxane bond, or the like.

Figure 1 is a cross-sectional view that shows a schematic example of an optical laminate according to an embodiment. The optical laminate 1 shown in Figure 1 includes an optical substrate 2, a primer layer 3 provided on one of the main surfaces of the optical substrate 2, and a resin layer provided on the primer layer 3. The optical substrate 2 has an uneven shape. The primer layer 3 and the resin layer 4 cover the convex side of the optical substrate 2.

(1) Optical Substrate The optical substrate can be any substrate having optical transparency, without any particular limitation. Examples of optical substrates include glass lenses, plastic lenses, and glass and resins used in windows of houses or vehicles. The aqueous primer composition for optical articles according to the embodiment uses water as a dispersion medium, and therefore is less likely to affect plastics than a primer composition using an organic solvent as a dispersion medium. Therefore, the primer composition according to the embodiment is suitable for an optical laminate using a plastic lens as the optical substrate.

The plastic lens may be any of the known lenses, such as thermoplastic resin lenses made of (meth)acrylic resins, polycarbonate resins, etc.; and crosslinkable resin lenses made of polyfunctional (meth)acrylic resins, allyl resins, thiourethane resins, urethane resins, and thioepoxy resins, etc. The plastic lens is preferably a methacrylic plastic lens or a thiourethane plastic lens. That is, the primer layer obtained by the aqueous primer composition for optical articles according to the embodiment is suitable as a primer layer for bonding a resin layer to an optical substrate made of these plastic lenses.

The shape of the plastic lens substrate is not particularly limited, and any known shape can be used. Examples of the shape of the plastic lens substrate include minus lenses, plus lenses, and oblique-angle lenses.

(2) Primer layer The primer layer may include a cured product of the aqueous primer composition for optical articles according to the embodiment, and may be made of this cured product. The primer layer may be provided on one main surface of the optical substrate, or on both main surfaces. The primer layer enhances the adhesion between the optical substrate and the resin layer. In addition, the primer layer contains a water-soluble functional dye, and therefore has a function due to this functional dye. The function of the primer layer may be the same as or different from that of the resin layer.

The thickness of the primer layer is, for example, 0.1 μm or more and 10 μm or less.

The primer layer preferably contains at least one of a water-soluble ultraviolet absorber and a water-soluble blue light absorber. That is, the aqueous primer composition for optical articles according to the embodiment preferably contains at least one of a water-soluble ultraviolet absorber and a water-soluble blue light absorber.

Providing a primer layer containing a water-soluble ultraviolet absorber tends to improve the weather resistance and adhesion of the optical laminate. That is, ultraviolet rays can cause deterioration of the plastic optical substrate and the primer layer itself. If the primer layer contains a water-soluble ultraviolet absorber, such ultraviolet rays can be absorbed, making it difficult for the ultraviolet rays to reach the primer layer itself and the optical substrate located inside the primer layer with respect to the ultraviolet irradiator. In addition, ultraviolet rays can be harmful to human eyes. Therefore, an optical laminate provided with a primer layer containing a water-soluble ultraviolet absorber is suitable as a plastic lens for glasses.

A primer layer containing a water-soluble blue light absorbent can absorb blue light. Blue light is a type of light that has high energy among visible light rays and can have a negative effect on the human eye. Therefore, an optical laminate having a primer layer containing a water-soluble blue light absorbent is suitable as a spectacle lens with blue light blocking function.

(3) Resin layer The resin layer contains a resin. The resin layer may contain at least one selected from the group consisting of functional dyes, silicon compounds, metal compounds, and additives. The resin layer may have various functions by containing a specific component. For example, a resin layer containing a resin, a silicon compound, and a transition metal compound may function as a hard coat layer for protecting an optical substrate from scratches. A resin layer containing a functional dye can absorb light of a specific wavelength. The resin layer is a cured product of a resin layer forming composition described later.

The resin layer may be a single layer or may have a multi-layer structure. For example, the resin layer may include a first resin layer that is provided on the primer layer and contains a photochromic compound, and a second resin layer that is provided on the first resin layer and functions as a hard coat layer.

The resin layer is preferably a photochromic resin layer containing a photochromic compound, or a hard coat layer containing a silicon compound. That is, the primer layer obtained by the aqueous primer composition for optical articles according to the embodiment is suitable as a primer layer for bonding a photochromic resin layer or a hard coat layer to an optical substrate.

(3-1) Resin Examples of the resin contained in the resin layer include (meth)acrylic resin, urethane resin, epoxy resin, and resin having a siloxane bond. Note that the (meth)acrylic resin means at least one of an acrylic resin and a methacrylic resin.

(3-2) Functional Dye (3-2-1) Photochromic Compound A photochromic compound is a compound that undergoes a reversible structural change upon irradiation with ultraviolet light. An optical substrate containing a photochromic compound can change from a colorless and transparent state to a colored state upon irradiation with ultraviolet light.

Examples of photochromic compounds include fulgide compounds, chromene compounds, and spirooxazine compounds.

(3-2-2) Thermochromic Material Thermochromic materials are materials that undergo a reversible structural change in response to a change in temperature. An optical substrate containing a thermochromic material can change color in response to a change in temperature.

Examples of thermochromic materials include leuco dyes.

(3-2-3) Porphyrin Compound A porphyrin compound is a compound having a porphyrin skeleton. An optical substrate containing a porphyrin compound can absorb a specific wavelength in the visible light range of 400 to 800 nm.

Examples of the porphyrin compound include compounds in which Zn ²⁺ , Cu ²⁺ , Ni ²⁺ , Co ²⁺ or the like is coordinated to a porphyrin skeleton as a central metal.

(3-2-4) Near-infrared absorbing agent Near-infrared absorbing agents are compounds having an absorption peak at a wavelength of 800 nm or more and 2000 nm or less. When an optical substrate containing a near-infrared absorbing agent is used, near-infrared rays contained in sunlight and the like can be efficiently cut off.

Examples of near-infrared absorbers include cyanine dyes, phthalocyanine dyes, nickel dithiolene complexes, squarium dyes, quinone compounds, diimmonium compounds, and azo compounds.

(3-2-5) Blue light absorbing agent A blue light absorbing agent is a compound having an absorption peak at a wavelength of 420 nm or more and 480 nm or less. Blue light can cause glare to the human eye and can cause sleep disorders. Glasses using an optical substrate containing a blue light absorbing agent can prevent such blue light from reaching the human eye.

An example of a blue light absorbing agent is a porphyrin compound that has an absorption peak at a wavelength of 420 nm or more and 480 nm or less.

(3-2-6) Polarizer A polarizer is an optical element that can extract linearly polarized light from natural light. By using an optical substrate containing a polarizer, the transmittance of reflected light can be reduced. Glasses using an optical substrate containing a polarizer can prevent reflected light from reaching the human eye, thereby reducing glare.

Examples of polarizers include dichroic substances such as iodine and dichroic dyes. The dichroic substance may be dispersed in a film such as polyvinyl alcohol or polyethylene terephthalate. In other words, a polarizing film in which a dichroic substance is dispersed may be used as the resin layer.

(3-2-7) UV absorber The UV absorber may be a water-soluble UV absorber, a hydrophobic UV absorber, or a mixture thereof. When the primer layer contains a UV absorber, it is preferable that the absorption peak of the UV absorber contained in the resin layer is different from the absorption peak of the UV absorber contained in the primer layer. By using such a UV absorber, an optical laminate capable of blocking a wide range of UV rays can be obtained. As the water-soluble UV absorber, the same type as that described in the primer composition can be used.

Examples of hydrophobic UV absorbers include benzotriazoles, benzophenones, benzoates, and triazines.

(3-2-8) Dyes Dyes are dyes other than the functional dyes described above. Dyes are used to dye the optical substrate to a desired color. Examples of dyes include azo dyes and anthraquinone dyes.

(3-3) Silicon Compound The resin layer containing a silicon compound can function as a hard coat layer. The silicon compound contains an organic silane and silicon dioxide. Examples of the organic silane include γ-glycidoxypropyltrimethoxysilane, tetraethoxysilane, and methyltriethoxysilane. One type of organic silane may be used, or multiple types may be used. The silicon compound preferably contains an organic silane and silicon dioxide.

The proportion of silicon compounds in the resin layer is, for example, 10% by mass or more and 99% by mass or less, and preferably 30% by mass or more and 95% by mass or less.

(3-4) Metal Compound The resin layer containing a metal compound can function as a hard coat layer. Examples of the metal compound include oxides of metal elements. As the metal compound, fine particles made of an inorganic oxide or a composite inorganic oxide containing at least one element selected from Si, Al, Ti, Fe, In, Zr, Au, Sn, Sb, W, and Ce are suitable.

The proportion of the metal compound in the resin layer is, for example, 5% by mass or more and 80% by mass or less, and preferably 10% by mass or more and 60% by mass or less.

(3-5) Other Additives Other additives include a photopolymerization initiator, a leveling agent, and a light stabilizer. As the photopolymerization initiator, the same type as that explained in the primer composition can be used.

(3-5-1) Leveling Agent The leveling agent is blended for the purpose of smoothing the resin layer.
As the leveling agent, a silicone-based surfactant having a silicone chain, a fluorine-based surfactant having a fluorocarbon chain, etc. can be used. Specific examples of the leveling agent include "L-7001", "L-7002", "L-7604", and "FZ-2123" manufactured by Toray Dow Corning Co., Ltd., "Megafac F-470", "Megafac F-1405", and "Megafac F-479" manufactured by Dainippon Ink and Chemicals, Inc., and "Florad FC-430" manufactured by Sumitomo 3M Limited. Only one type of leveling agent may be used, or multiple types may be mixed and used.

The proportion of the leveling agent in the resin layer is, for example, 1 ppm or more and 1000 ppm or less, and preferably 10 ppm or more and 500 ppm or less.

(3-5-2) Light Stabilizers As the light stabilizer, hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants can be used. Suitable examples include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87, 2,6-di-t-butyl-4-methyl-phenol, 2,6-ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate] manufactured by Asahi Denka Kogyo Co., Ltd., and IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, and 565 manufactured by Ciba Specialty Chemicals. The light stabilizer may be used alone or in combination of two or more kinds.

The proportion of the light stabilizer in the resin layer is, for example, 0.01% by mass or more and 5% by mass or less, and preferably 0.05% by mass or more and 3% by mass or less.

(4) Method for Producing Optical Laminate The optical laminate can be produced, for example, by the following method.
First, an optical substrate is prepared. In order to enhance adhesion to the primer layer, the surface of the optical substrate may be subjected to a chemical treatment using an alkaline solution, an acid solution, or the like, or a physical treatment using corona discharge, plasma discharge, polishing, or the like.

Next, the aqueous primer composition for optical articles according to the embodiment is applied on the optical substrate by, for example, spin coating to obtain a first coating film. A resin layer forming composition is applied on the first coating film by, for example, spin coating to obtain a second coating film. The laminate of the first coating film and the second coating film is irradiated with ultraviolet light to cure the first and second coating films to obtain an optical laminate. The ultraviolet light irradiation is, for example, performed under a nitrogen atmosphere, with an atmospheric temperature of, for example, 10°C or more and 80°C or less, and an ultraviolet light irradiation time of, for example, 5 seconds or more and 120 seconds or less. The ultraviolet light intensity is, at a wavelength of 365 nm, 50 mW/ ^cm2 or more and 500 mW/ ^cm2 or less. Alternatively, the first and second coating films are cured by heating to obtain an optical laminate. The heat treatment is, for example, performed under air or a nitrogen atmosphere, with an atmospheric temperature of, for example, 70°C or more and 130°C or less, and a heating time of, for example, 30 minutes or more and 3 hours or less.

In addition, after the first coating film is thermally or photocured to form a primer layer, a resin layer-forming composition may be applied onto the primer layer to form a second coating film, and then the second coating film may be thermally or photocured to obtain an optical laminate.

The composition for forming the resin layer contains at least one of a resin and a monomer, and an optional component. It is preferable to use an acrylic monomer as the monomer. When an acrylic monomer is used, the resin layer can be cured by irradiating it with ultraviolet light, so that an optical laminate can be produced efficiently in a short time compared to when the resin layer is cured by heat.

As the acrylic monomer, any known (meth)acrylic monomer can be used without any particular restrictions. Specifically, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, bisphenol A dimethacrylate, 2,2-bis(4-methacryloyloxyethoxyphenyl)propane, 2,2-bis(4-methacryloyloxypolyethylene glycol phenyl)propane having an average molecular weight of 628, 2,2-bis(4-methacryloyloxypolyethylene glycol phenyl)propane having an average molecular weight of 804, 2,2-bis(4-acryloyloxypolyethylene glycol phenyl)propane having an average molecular weight of 776, methoxypolyethylene glycol methacrylate having an average molecular weight of 468, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol ethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, polyethylene glycol dimethacrylate having an average molecular weight of 330, polyethylene glycol dimethacrylate having an average molecular weight of 536, polytetramethylene glycol dimethacrylate having an average molecular weight of 736, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate having an average molecular weight of 536, polyethylene glycol diacrylate having an average molecular weight of 258, polyethylene glycol diacrylate having an average molecular weight of 308, polyethylene glycol diacrylate having an average molecular weight of 508, polyethylene glycol diacrylate having an average molecular weight of 708, polycarbonate di(meth)acrylate which is a reaction product of polycarbonate diol and (meth)acrylic acid, urethane Examples of such compounds include polyfunctional urethane (meth)acrylates such as oligomer tetraacrylate, urethane oligomer hexamethacrylate, and urethane oligomer hexaacrylate, polyfunctional polyester (meth)acrylates such as polyester oligomer hexaacrylate, silsesquioxane monomers having (meth)acrylic groups and various structures such as cage-shaped, ladder-shaped, and random structures, 2-isocyanatoethyl methacrylate, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and glycidyl methacrylate.

In addition, the resin layer forming composition may include 1) polycarbonate di(meth)acrylate, 2) polyfunctional (meth)acrylates such as trimethylolpropane trimethacrylate and ditrimethylolpropane tetramethacrylate, and 3) di(meth)acrylates having a bisphenol A skeleton such as 2,2-bis[4-(methacryloxy-polyethoxy)phenyl]propane (the average chain length of the ethylene glycol chain is 10 and the average molecular weight is 804), or 4) trimethylolpropane trimethacrylate and ditrimethylolpropane tetramethacrylate. acrylate, 5) a di(meth)acrylate having a bisphenol A skeleton such as 2,2-bis[4-(methacryloxy-polyethoxy)phenyl]propane (the average chain length of the ethylene glycol chain is 10, and the average molecular weight is 804), and 6) a composition for forming a resin layer containing at least one long-chain (meth)acrylic monomer selected from the group consisting of a polyalkylene glycol di(meth)acrylate having a molecular weight of 600 to 2000, and a urethane di(meth)acrylate having a molecular weight of 600 to 2000. Furthermore, when the total of the (meth)acrylate monomers 1) to 3) is taken as 100% by mass, it is more preferable that 1) is 10 to 30% by mass, 2) is 35 to 50% by mass, and 3) is 10 to 65% by mass; or when the total of the (meth)acrylate monomers 3) to 6) is taken as 100% by mass, it is more preferable that 3) is 35 to 70% by mass, 2) is 10 to 40% by mass, and 3) is 10 to 40% by mass.

[Optical articles]
The optical article includes the optical laminate according to the embodiment. Examples of the optical article include a plastic eyeglass lens, eyeglasses equipped with the lens, an automobile window, a house window, and the like.

The lens according to the embodiment includes at least one polymer selected from the group consisting of urethane acrylate, urethane resin, acrylic resin, and epoxy resin, a water-soluble functional dye, and a photopolymerization initiator. Such a lens is considered to include a cured product of the aqueous primer composition for optical articles according to the embodiment. That is, when an ultraviolet absorber is contained in an optical substrate such as a plastic lens or a resin layer that covers the optical substrate, a hydrophobic ultraviolet absorber is typically used, and a water-soluble ultraviolet absorber is not used, in consideration of compatibility with the resin, etc. In the composition for forming a primer layer, the proportion of the resin component, etc. is low, and the water-soluble resin component, etc. exhibits high adhesion, so water can be used as a dispersion medium. The primer layer, which is a cured product of such a composition for forming a primer layer, may include a water-soluble functional dye.

Figure 2 is a perspective view that shows a schematic example of glasses according to an embodiment. The glasses 10 shown in Figure 3 include two lenses 11 and a frame 12 that fixes the lenses 11. At least one of the two lenses 11 includes an optical laminate according to an embodiment.

Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples.

<Water-based primer composition for optical articles>
The following materials were used for the aqueous primer composition for optical articles.

(A: water-soluble functional dye)
A1: Sodium hydroxymethoxybenzophenone sulfonate (a water-soluble dye having a series maximum at about 285 nm)
A2: Methylobamine (a water-soluble functional dye having an absorption maximum around 360 nm)
A3: COMFOGUARD UV-002 (a water-soluble functional dye with an absorption maximum around 360 nm) manufactured by Fujifilm
(B: Water-soluble blue light absorbing agent)
B1: COMFOGUARD VIS-001 (a water-soluble functional dye having an absorption maximum around 465 nm) manufactured by Fujifilm
(C: Water Dispersion of Water-Dispersible Urethane (Meth)acrylate)
C1: Carboxyl group-containing water-dispersible urethane acrylate dispersion (Ucecoat 7655, manufactured by Daicel Allnex Corporation, average particle size 150 nm, solid content 35%, tensile strength 25 MPa, elongation 1.5%).

C2: Carboxyl group-containing water-dispersible urethane acrylate dispersion (Daicel-Allnex's "Ucecoat 7849", average particle size 150 nm, solid content 35%, tensile strength 15 MPa, elongation 1.3%).

C3: Carboxyl group-containing water-dispersible urethane acrylate dispersion (Daicel-Allnex's "Ucecoat 7674", average particle size 150 nm, solid content 40%, tensile strength 24 MPa, elongation 18%).

(D: Photopolymerization initiator)
D1: Phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (BASF Corporation's "Irgacure 819").

D2: 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR1173, manufactured by BASF)
D3: A mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone (IRGACURE 500 manufactured by BASF)
D4: A mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR4265 manufactured by BASF)
(E: Water-dispersible urethane resin dispersion)
E1: Water-dispersible urethane resin dispersion ("Superflex 420" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solids concentration 32%, tensile strength 30 MPa, elongation 280%).

E2: Water-dispersible urethane resin dispersion (Tokuyama Corporation's "NJ-321A", solids concentration 35%, tensile strength 50 MPa, elongation 400%).

The tensile strength and elongation of the water-dispersible urethane (meth)acrylate and the water-dispersible urethane resin cured bodies were measured by the methods described above.
<Photochromic curable composition>
As materials for the photochromic curable composition, the following materials were used.

((Meth)acrylic monomer)
TMPT; trimethylolpropane trimethacrylate.
14G: Polyethylene glycol dimethacrylate (the average chain length of the ethylene glycol chain is 14, and the average molecular weight is 736).
A-400: Polyethylene glycol diacrylate (average chain length of ethylene glycol chain: 9, average molecular weight: 508)
SI-1: γ-methacryloyloxypropyltrimethoxysilane GMA: glycidyl methacrylate RX-1: polyrotaxane having a (meth)acrylate group (A polyrotaxane having a (meth)acrylate group satisfying the following characteristics was synthesized according to the method described in International Publication No. WO2018/030275.
Weight average molecular weight Mw (GPC) of polyrotaxane having (meth)acrylate groups: 880,000
Acrylate group modification ratio: 85 mol%
Proportion of OH groups remaining in side chains: 15 mol%)
Axle molecule: linear polyethylene glycol (PEG) with a molecular weight of 20,000
Inclusion ring: α-cyclodextrin (α-CD) introduction ratio: 0.25
End of the axis molecule; Side chain introduced into the sealed inclusion ring with adamantane; (average) molecular weight of the side chain is about 600
(Photochromic Compound)
PC1: a compound represented by the following formula:

(Polymerization initiator)
CGI: phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (product name: Omnirad 819, manufactured by IGM)
(Other added ingredients)
HALS: Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (molecular weight 508) (ultraviolet stabilizer)
HP: Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (manufactured by Ciba Specialty Chemicals, Irganox 245) (ultraviolet light stabilizer)
L7001: Product name: L7001 (leveling agent), manufactured by Dow Corning Toray Co., Ltd.
<Optical laminate>
Lens substrate A: a thiourethane-based plastic lens having a center thickness of 2.0 mm and a refractive index of 1.60.
Lens substrate C: center thickness 2.0 mm, refractive index 1.67, thiourethane-based plastic lens. Lens substrate D: center thickness 2.0 mm, refractive index 1.59, polycarbonate plastic lens.
Lens substrate E: center thickness 2.0 mm, refractive index 1.50, methacrylic plastic lens.
Lens substrate F: plastic lens with center thickness of 2.0 mm, refractive index of 1.60, and with a methacrylic resin coating layer (photochromic coating layer) Example 1
(Preparation of photocurable primer composition for optical articles (P1))
A mixture was obtained by thoroughly mixing 3 parts by mass of the water-soluble functional dye (A1), 100 parts by mass of the water-dispersible urethane acrylate (C1), and 0.1 parts by mass of 2-hydroxy-2-methyl-1-phenylpropan-1-one (D2). This mixture was filtered through a cellulose acetate filter paper (mesh size: 0.8 μm) to obtain a photocurable primer composition for optical articles (P1). In this composition P1, the water-soluble functional dye A1 was dissolved.

(Preparation of Photochromic Curable Composition (F1))
30 parts by mass of TMPT, 21 parts by mass of A-400, 3 parts by mass of RX-1, 40 parts by mass of 14G, 3 parts by mass of SI-1, 1 part by mass of GMA, 2 parts by mass of PC1, 0.3 parts by mass of CGI, 3 parts by mass of HALS, 1 part by mass of HP, and 0.1 part by mass of L7001 were mixed and stirred and mixed at 70° C. for 15 minutes, to obtain a photochromic curable composition (F1).

(Production of optical laminate)
A thiourethane plastic lens (lens substrate A) having a center thickness of 2.0 mm and a refractive index of 1.60 was prepared as the lens substrate. This lens substrate was subjected to alkaline etching using a 10% aqueous sodium hydroxide solution at 50° C. for 5 minutes, and then thoroughly washed with distilled water.

Using a spin coater (1H-DX2, manufactured by MIKASA), the water-based primer composition for optical articles (P1) was spin-coated onto the surface of the lens substrate to obtain a coating film. This coating film was dried at room temperature (20-25°C) for 10 minutes to obtain a laminate in which an uncured primer layer was laminated on the lens substrate. The film thickness of the uncured primer layer was adjusted to 10 μm.

Next, about 2 g of the photochromic curable composition (F1) was spin-coated on the surface of the uncured primer layer to obtain a laminate in which the lens substrate, the uncured primer layer, and the uncured photochromic resin layer (PC resin layer) were laminated in this order. The film thickness of the photochromic resin layer was adjusted to 40±1 μm. In a nitrogen gas atmosphere, the uncured photochromic resin layer of this laminate was irradiated with light to cure the uncured primer layer and the uncured photochromic resin layer. During the light irradiation, the output at 405 nm was adjusted to 200 mW/cm ^2. The light irradiation time was 90 seconds. For the light irradiation, an F3000SQ equipped with a D bulb manufactured by Fusion UV Systems was used.

Next, the photocured laminate was subjected to a heat treatment for 1 hour in a thermostatic oven at 100°C to obtain a photochromic optical laminate.

<Examples 2 to 8, Comparative Example 1>
Photochromic optical laminates according to Examples 2 to 8 and Comparative Example 1 were produced in the same manner as described in Example 1, except that the materials shown in Table 1 were used.

<Example 9>
A photochromic optical laminate was obtained in the same manner as described in Example 1, except that the materials shown in Table 1 were used and the uncured primer layer formed on the lens substrate by spin coating was dried at 80° C. for 20 minutes and cured.

<Example 10, Comparative Example 2>
Photochromic optical laminates according to Example 10 and Comparative Example 2 were produced in the same manner as described in Example 9, except that the materials shown in Table 1 were used.

Example 11
A photochromic optical laminate was produced in the same manner as in Example 1, except that a coating film of the aqueous primer composition for optical articles (P1) applied onto a lens substrate was cured by light irradiation, a photochromic curable composition was applied onto the cured primer layer, and the coating film of the photochromic curable composition was cured by light irradiation. The primer layer and the photochromic resin layer were photocured under the same conditions as those for the photocuring of the photochromic resin layer described in Example 1.

Example 12
An optical laminate was produced in the same manner as described in Example 11, except that a hard coat layer was laminated on the cured primer layer instead of providing a photochromic resin layer, and the thickness of the primer layer was set within the range of 2.0 to 3.0 μm.

The hard coat layer was formed by applying the hard coat composition onto the cured primer layer by dip coating, and then heating the resulting coating at 110°C for 2 hours. The thickness of the hard coat layer was 3 μm. The dip coating was performed at a pull-up speed of 15 cm/min.

The hard coat composition was prepared in the following manner.
First, 58.8 g of γ-glycidoxypropyltrimethoxysilane, 47.3 g of methyltriethoxysilane, 47.5 g of ethylene glycol monoisopropyl ether, 25.2 g of acetylacetone, 82.8 g of t-butyl alcohol, and 0.25 g of a silicon-based surfactant (manufactured by Toray Dow Corning Co., Ltd., trade name "L-7001") were mixed to obtain a mixture. 25 g of 0.05 N hydrochloric acid, 13.9 g of 0.1 N tetramethylammonium chloride methanol solution, 198.0 g of methanol-dispersed silica sol, and 1.4 g of tris(2,4-pentanedionato)aluminum(III) were added in order to this mixture at 40°C while stirring, and further stirred for 48 hours. 0.59 g of tris(2,4-pentanedionato)aluminum(III) was mixed into the mixture after stirring to prepare a hard coat composition.

<Examples 13 to 16>
Photochromic optical laminates according to Examples 13 to 16 were produced in the same manner as described in Example 12, except that the lens substrates shown in Table 1 were used.

[Evaluation test]
<Vickers hardness>
A Vickers hardness test was carried out on the optical laminate according to Example 1. As a result, the Vickers hardness of the optical laminate according to Example 1 was 12.0.

<Photochromic property evaluation test>
The maximum absorption wavelength, color density, and fading density were measured for the optical laminates according to Examples 1 to 11 and Comparative Examples 1 and 2. As a result, the maximum absorption wavelength was 588 nm, the color density was 1.0, and the fading speed was 56 seconds for the optical laminates according to Examples 1 to 11 and Comparative Examples 1 and 2. Details of each measurement method are as follows.

1) Photochromic properties The photochromic properties were measured by irradiating the optical laminate surface with a xenon lamp L-2480 (300 W ⁾ SHL-100 manufactured by Hamamatsu Photonics K.K. at 20±1°C through an Aeromass filter (manufactured by Corning) for 120 seconds at a beam intensity of 365 nm = 2.4 mW/ ^cm2 and 245 nm = 24 μW/cm2 at the surface to cause color development.
Maximum absorption wavelength (λmax):
This is the maximum absorption wavelength after color development, determined using a spectrophotometer (instantaneous multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd.
Color density {ε(120)-ε(0)}:
The difference between the absorbance {ε(120)} after 120 seconds of light irradiation and the absorbance ε(0) before light irradiation at the maximum absorption wavelength. The higher this value, the better the photochromic properties.
・Fading speed [t1/2 (sec.)]:
The time required for the absorbance of the sample at the maximum absorption wavelength to decrease to 1/2 of {ε(120)-ε(0)} when the light irradiation is stopped after 120 seconds of light irradiation. The shorter this time, the better the photochromic property.

<Transmittance at 350 nm and transmittance at 465 nm>
The primer compositions used in Examples 1 to 16 and Comparative Examples 1 and 2 were coated on quartz glass to the same thickness as in the respective Examples and Comparative Examples, and the UV-vis spectrum of the resulting laminate was obtained by ultraviolet-visible spectroscopy. From this spectrum, the transmittance at 350 nm and the transmittance at 465 nm were calculated. The results are shown in Table 1.

<Adhesion>
The optical laminates according to Examples 1 to 16 and Comparative Examples 1 and 2 were evaluated for adhesion by a cross-cut tape test in accordance with Japanese Industrial Standard JIS D-0202. That is, a cutter knife was used to make cuts at intervals of about 1 mm on the surface of the photochromic layer or hard coat layer of the obtained optical laminate to form 100 grids. Cellophane adhesive tape (Cellotape (registered trademark) manufactured by Nichiban Co., Ltd.) was firmly attached onto the grids, and then the tape was pulled in a 90° direction from the surface to peel it off, and the number of grids where the photochromic layer or hard coat layer remained was counted. The results are shown in Table 1.

<Weather resistance and adhesion>
The weather-resistant adhesion of the optical laminates according to Examples 1 to 16 and Comparative Examples 1 and 2 was evaluated by the following method. First, the optical laminate was placed in an ultraviolet fluorescent lamp type accelerated weather resistance tester (QUV) manufactured by Q Lab Corporation, and irradiated with a UVA-340 lamp of 0.89 w/m ² at a temperature of 60° C. for 8 hours. Thereafter, UV irradiation to the optical laminate was stopped, and the laminate was left to stand for 4 hours under humidified conditions at a temperature of 50° C. A series of these tests was regarded as one cycle, and adhesion was evaluated in two cycles, that is, every 24 hours, by the same method as in the above-mentioned adhesion test. The maximum time during which a state in which 95 or more squares remained without peeling out of 100 squares was maintained is shown in Table 1. The maximum test time was 360 hours.

As is clear from the above Examples 1 to 16, the plastic lenses obtained using the aqueous primer composition for optical articles containing a water-soluble UV absorber have excellent weather-resistant adhesion. However, in Comparative Examples 1 and 2, the weather-resistant adhesion was insufficient.

Claims (6)

A plastic lens substrate;
A primer layer provided on at least one of the main surfaces of the plastic lens substrate and including a cured product of an aqueous primer composition for optical articles;
a resin layer provided on the surface of the primer layer opposite to the surface in contact with the plastic lens substrate, the resin layer including at least one resin selected from the group consisting of (meth)acrylic resins, urethane resins, urethane urea resins, and resins having a siloxane bond;
The optical laminate includes
The aqueous primer composition for optical articles comprises
at least one compound selected from the group consisting of urethane acrylate, acrylic monomer, acrylic resin, urethane resin, and ester resin;
A water-soluble functional dye, and
Lenses containing water. The lens according to claim 1 , wherein the water-soluble functional dye contains a water-soluble ultraviolet absorbing agent having a maximum absorption peak in a wavelength region of 250 nm or more and less than 420 nm. The lens according to claim 1 or 2, wherein the water-soluble functional dye contains a water-soluble blue light absorbing agent having a maximum absorption peak in a wavelength region of 420 nm or more and 500 nm or less. The lens according to claim 1 , wherein the content of the water-soluble functional dye is from 0.1% by mass to 10% by mass. 3. The lens according to claim 1 , comprising at least one polymer selected from the group consisting of urethane acrylates and urethane resins, and a water-soluble functional dye. A pair of spectacles comprising a lens according to claim 1 or 2 .