WO2018037621A1

WO2018037621A1 - Light-modulating optical element

Info

Publication number: WO2018037621A1
Application number: PCT/JP2017/016157
Authority: WO
Inventors: 忠史鳥居; 敬介荻野
Original assignee: 伊藤光学工業株式会社
Priority date: 2016-08-23
Filing date: 2017-04-24
Publication date: 2018-03-01

Abstract

Provided is a light-modulating optical element that enables shortening of decolorization time through an interaction with a synthetic resin. This light-modulating optical element is used as an eyeglass material in which a functional resin layer 15 is integrated in one or both sides of an organic glass substrate 11 made of a resin molding, wherein the functional resin layer 15 contains a photochromic agent and a polyalkylene glycol-modified bisphenol A di(meth)acrylate represented by general formula (1). Transition energy in the photochromic agent that has transitioned as a result of irradiation with light (ultraviolet) is easily converted into thermal energy and received by the polyalkylene glycol-modified bisphenol A di(meth)acrylate represented by general formula (1) after shutting off the irradiation, whereby it becomes possible to shorten decolorization time.

Description

Light control optical element

The present invention relates to a light control optical element containing a photochromic agent.

The photochromic agent is an additive that undergoes a reversible color change in which the color of the photochromic agent changes by absorbing light (ultraviolet light) and returns to the original color when the light absorption stops. Patent Document 1 describes a method for producing a synthetic resin photochromic lens using a photochromic agent, and describes a synthetic resin photochromic lens that is excellent in weather resistance and has a uniform dimming effect over the entire lens. .

By adding a photochromic agent to the optical element, for example, in the case of eyeglass materials, it changes to a dark color when outdoors with strong ultraviolet rays, etc., resulting in an anti-glare effect for the user, and close to transparent in indoors where UV rays are weak. By changing, a clear view is given to the user and the light control function is exhibited.

An optical element having a dimming function (a dimming optical element) undergoes a reversible color change in which the color returns to its original state when light absorption stops, but the color is almost the original color after the light absorption stops. It took about 15 minutes to return to the time (decoloration time). In the photochromic lens described in Patent Document 2, a photochromic agent is dissolved in tetrahydrofuran to be uniformly dispersed in a synthetic resin so that the decoloring time can be reduced.

Further, in the resin lens manufacturing method described in Patent Document 3, a cavity for molding a functional resin layer is formed on one side or both sides of a base lens, and a thermoplastic elastomer is formed on the molding surface of the functional resin layer of the base lens. This is a manufacturing method in which a base lens and a functional resin layer are integrated. The resin lens manufactured by this manufacturing method can exhibit a photochromic function when the functional resin layer contains a photochromic agent or the like.

JP-A-8-216271 JP 2014-32273 A Japanese Patent Laid-Open No. 2014-156067

If the decoloring time of the dimming optical element is long, for example, in the case of eyeglass materials, when the user moves from the outside to the indoor, the dimming optical element exhibits a dark color until the decoloring time. And the appearance is uncomfortable with wearing colored glasses indoors. For this reason, it is preferable that the light control optical element has a short decoloring time. The photochromic lens described in Patent Document 2 can reduce the decoloring time by uniformly dispersing the photochromic agent in the synthetic resin. However, by improving the dispersion state, the original performance of the photochromic agent is extracted. However, the interaction with the synthetic resin was not studied.

The present invention has been made in view of the above points, and an object thereof is to provide a light control optical element capable of shortening the decoloring time by interaction with a synthetic resin.

The light control optical element of the present invention is a light control optical element in which a functional resin layer is integrated on one side or both sides of an organic glass base material that is a resin molded body, the functional resin layer includes a photochromic agent, It contains polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the following general formula (1).

The inventors of the present application disperse the photochromic agent in the resin containing the polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the general formula (1), thereby eliminating the light absorption of the photochromic agent. It has been found that the time until the color almost returns to the original time (decoloration time) is shortened. According to the light control optical element of the present invention, it is possible to provide a light control optical element capable of shortening the decoloring time by interaction with the synthetic resin.

Here, in the light modulation optical element, the functional resin layer may contain (poly) alkylene glycol di (meth) acrylate represented by the following general formula (2).

According to this, since the (poly) alkylene glycol di (meth) acrylate represented by the general formula (2) is excellent in dispersibility of the photochromic agent, the light control optical element can obtain a uniform light control function. it can.

In the light control optical element, the organic glass substrate is formed of a thiourethane-based, episulfide-based, or (meth) acrylate-based thermosetting resin material, and the functional resin layer has the following general formula (3 ) Represented by the formula (1).

According to this, since the thiourethane-based, episulfide-based or (meth) acrylate-based thermosetting resin material is a high refractive index material, the thickness of the light control optical element can be reduced. In addition, the alkylene diol diglycidyl ether acrylate represented by the general formula (3) is excellent in adhesion to thiourethane, episulfide, or (meth) acrylate thermosetting resin raw materials, and therefore a functional resin layer. Can be excellent in adhesion to the organic glass substrate.

In the light control optical element, the functional resin layer may have a thickness of 0.2 to 3.0 mm. According to this, since the thickness of the cavity for molding the functional resin layer is secured, cast molding can be performed instantaneously, and the injected functional resin layer is cured without uneven curing. Therefore, the dimming optical element can suppress the occurrence of striae (parts having different refractive indexes are generated).

According to the light control optical element of the present invention, the photochromic agent is dispersed in the resin containing the polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the general formula (1), thereby reducing the decoloring time. A dimming optical element that can be shortened can be provided.

It is a figure which shows the manufacturing process of the light control optical element of this invention. It is a figure which shows the manufacturing process which provides a protective resin layer. (A) is a figure which shows the up-and-down movement with a small blur width of the vibration immersion pattern which provides an ultraviolet absorber taper part, (b) shows the up-and-down movement with a large blur width of the vibration soak pattern which provides an ultraviolet absorber taper part. FIG. It is the figure which contrasted the performance of the Example and the comparative example.

Hereinafter, an embodiment of the present invention will be described. The light control optical element of the embodiment is a light control optical element in which a functional resin layer 15 is integrated on one or both sides of an organic glass substrate 11 that is a resin molded body. The functional resin layer 15 is a photochromic agent. And a polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the following general formula (1) (hereinafter sometimes abbreviated as general formula (1) BPAc). It is. In addition, (meth) acrylate is a general term for acrylate and methacrylate.

In the light control optical element of the embodiment, as shown in FIG. 1, an example in which a functional resin layer 15 is integrated by cast molding on the surface (convex surface) of an organic glass substrate 11 as a spectacle lens is taken. explain. Of course, the present invention is not limited to the use of spectacle lenses, but can be applied to any optical element such as telescope lenses, window glass for architectural or vehicle use. Moreover, the functional resin layer 15 of this invention is not limited to the use to the surface (convex surface) of the organic glass base material 11, The back surface (concave surface) or both surfaces (convex surface and concave surface) of the organic glass base material 11 It is possible to apply to.

The organic glass base material 11 is used as a base material for optical elements such as lenses and window glasses. The eyeglass material of the embodiment is made of organic glass (plastic) because it is lighter than inorganic glass. Shall.

As the organic glass substrate 11, polycarbonate (PC), polyurethane, polyurea, aliphatic allyl carbonate, aromatic allyl carbonate, polythiourethane, episulfide, (meth) acrylate, transparent polyamide (transparent Nylon), norbornene, polyimide, polyolefin, and other synthetic resins can be used. Among them, a thiourethane, episulfide, or (meth) acrylate synthetic resin has a high refractive index and can be used more favorably.

The thiourethane resin is a polymer (resin) having a bond (-NHCOS-, -NHCSO-, -NHCSS-) in which at least one oxygen atom of a polyurethane bond (-NHCOO-) is replaced with a sulfur atom. means. Examples of the resin material include one or more isocyanate components selected from polyisocyanate, polyisothiocyanate, polyisothiocyanate thioisocyanate, and one or more known active hydrogens selected from polythiol and a suitable polyol. A polymerizable component in combination with a compound component can be preferably used. Here, as the polyisocyanate, aliphatic, alicyclic, aromatic, and derivatives thereof, as well as sulfide, polysulfide, and thiocarbonyl (thioketone) derivatives in which sulfur is introduced into a part of their carbon chains are parent compounds. Can be mentioned. Of these, aliphatic or alicyclic polyisocyanates are desirable from the standpoint of yellowing resistance. Similarly, polythiols include aliphatic, alicyclic, aromatic, and derivatives thereof, and sulfides, polysulfides, and polythioethers in which sulfur is introduced into a part of their carbon chains as a base compound. Can be mentioned. Of these, aliphatic or alicyclic polythiols are desirable from the standpoint of yellowing resistance.

The episulfide resin means a polymer (resin) obtained by reacting a dithioepoxy compound, a curing agent, and another polymerizable compound, and is obtained by curing a linear alkyl sulfide type dithioepoxy compound. The well-known thing used can be used. As the curing agent, amines, organic acids, or inorganic acids that are ordinary epoxy resin curing agents can be used.

Specific examples of the organic glass substrate 11 include MR-6, MR-8, MR-20, MR-60, MR-95 (Mitsui Chemicals, thiourethane resin, refractive index: 1.60), MR -7, MR-10 (Mitsui Chemicals Co., Ltd. thiourethane resin, refractive index: 1.67), MR-174 (Mitsui Chemicals, Inc. episulfide resin, refractive index: 1.74), NK-11P, LS106S, LS420 (Nippon Shimizu Sangyo Co., Ltd. (meth) acrylate resin, refractive index: 1.56), NXT (Tribex Corporation (ICRX NXT Corporation) polyurea resin, refractive index: 1.53) and the like are suitable. Can be used for

The organic glass substrate 11 has a deterioration preventing agent for preventing resin deterioration of the organic glass, an ultraviolet absorber that absorbs ultraviolet rays, and an interior that improves releasability from the mold for molding the lens shape, which will be described in detail later. A mold release agent or a curing agent for curing the organic glass can be added according to the type of the organic glass.

The organic glass substrate 11 can be formed using a general forming method such as a polishing method or a casting method. The polishing method is a method in which a synthetic resin for forming the organic glass substrate 11 is molded into a block-like resin under suitable conditions, and then polished according to the lens design for obtaining the block-like resin. In the casting molding method, taking an uneven lens as an example, a cavity is formed by sealing the peripheral surface of the mold with taping or a gasket at an interval that requires a concave mold and a convex mold. In this method, a synthetic resin for molding the organic glass substrate 11 is injected and cured, and the organic glass substrate 11 is polished as necessary.

Next, the functional resin layer 15 will be described. The functional resin layer 15 is a layer that is integrated on one or both sides of the organic glass substrate 11, and is a layer that is thinner than the organic glass substrate 11. The functional resin layer 15 contains a photochromic agent and a polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the general formula (1) and, if necessary, represented by the general formula (2) (poly ) Alkylene glycol di (meth) acrylate, alkylene diol diglycidyl ether acrylate represented by the general formula (3). For the resin that forms the functional resin layer 15, a deterioration preventing agent, an ultraviolet absorber, a specific wavelength absorber, an internal mold release agent, a curing agent, a molecular weight adjusting agent, and the like are added depending on the type of resin. can do. Photochromic agents, ultraviolet absorbers and specific wavelength absorbers are expensive. For this reason, by containing a photochromic agent or the like in the functional resin layer 15 having a thickness smaller than that of the organic glass substrate 11, the content of the photochromic agent or the like can be reduced. Manufacturing cost can be reduced.

A photochromic agent is a compound that exhibits photochromism. By absorbing light (ultraviolet rays), it undergoes a structural change (isomerization) and a color change (shows a different absorption spectrum) without changing the molecular weight. It is an additive. In an embodiment, a preferred photochromic agent is a color that changes its color from colorless (or light) to blue, purple, magenta, black, etc. by absorbing light, and changes its color when light absorption stops. It has a reversible color change (T-type photochromic agent) that returns to its original colorless (or light color). As such a photochromic agent, an azobenzene photochromic agent, a spiropyran photochromic agent, a naphthopyran photochromic agent, a spirooxazine photochromic agent, a chromene photochromic agent, a hexaarylbisimidazole photochromic agent, or the like can be used. Among these, spiropyran-based photochromic agents, naphthopyran-based photochromic agents, spirooxazine-based photochromic agents, and chromene-based photochromic agents are more preferred because they become darker when they change color by absorbing light. can do. In addition, even if it contains only a single photochromic agent in the functional resin layer 15, the effect of this invention can be show | played, but in order to reduce the transmittance | permeability of the light of a visible light region uniformly, a photochromic agent has two or more. It is preferable to use a mixture of seed photochromic agents.

The deterioration preventing agent is an alkyl radical (R ·: R is generated when the organic glass resin is decomposed or deteriorated by light or heat while absorbing light of 280 to 320 nm, which is easily decomposed or deteriorated by the organic glass resin. By capturing or decomposing alkyl chains), peroxy radicals (ROO.), And peroxides (ROOH), the deterioration of the resin is prevented from proceeding at an accelerated rate. Examples of the deterioration inhibitor include benzophenone, diphenyl acrylate, sterically hindered amine, salicylic acid ester, benzotriazole, hydroxybenzoate, cyanoacrylate, hydroxyphenyl triazine, and the like. A suitable deterioration inhibitor can be added depending on the type of organic glass.

The ultraviolet absorber is an additive that absorbs ultraviolet rays and is added to the light control optical element for protecting the eyeball. This is because ultraviolet rays may cause cataracts and macular degeneration when entering the eyes. Depending on the absorption wavelength range of the ultraviolet absorber, it also functions as a deterioration preventing agent. Examples of the ultraviolet absorber include benzophenone series, diphenyl acrylate series, sterically hindered amine series, salicylic acid ester series, benzotriazole series, hydroxybenzoate series, cyanoacrylate series, and hydroxyphenyl triazine series. A suitable ultraviolet absorber can be added according to the type of organic glass.

The specific wavelength absorber is an additive that absorbs light of a specific wavelength. For example, as a specific wavelength absorber having a main absorption peak between 565 and 605 nm (especially 580 nm), NeoContrast (manufactured by Mitsui Chemicals, Inc.). Absorption peak wavelength: 580 nm). By using NeoContrast, the optical element has a function of selectively cutting dazzling light and can improve the appearance. Details of NeoContrast are described in Japanese Patent No. 5778109 and US Pat. No. 7,506,777. Specific wavelength absorbers include benzophenone, diphenyl acrylate, sterically hindered amine, salicylic acid ester, benzotriazole, hydroxybenzoate, cyanoacrylate, hydroxyphenyl triazine, porphyrin, and the like.

The internal mold release agent is an additive that is added to improve the release from the mold during mold removal after the organic glass substrate 11 is molded from the organic glass using the mold. A mold suitable for the organic glass material can be used.

The curing agent is an additive that cures (polymerizes) the organic glass that forms the organic glass substrate 11, and includes organic glass materials such as a tin-based catalyst, an amine-based catalyst, and a peroxide-based polymerization initiator. The one suitable for can be used.

The polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the following general formula (1) is a synthetic resin that can shorten the decoloring time of the photochromic agent.

The reason why the polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the general formula (1) can shorten the decoloring time of the photochromic agent cannot be determined, but the transition of the photochromic agent transitioned by light (ultraviolet rays) It is estimated that the polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the general formula (1) is easily converted into heat energy and received.

In the general formula (1), m + n (m is the degree of polymerization of alkylene glycol and n is the degree of polymerization of alkylene glycol) is preferably 1 or more and less than 50. The polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the general formula (1) within this range can shorten the decoloring time of the photochromic agent, and the strength of the functional resin layer 15 is maintained. is there. If m + n in the formula is less than 1, the effect of shortening the decoloring time of the photochromic agent may be insufficient. On the other hand, if it exceeds 50, the polyalkylene glycol represented by the general formula (1) Since the polyalkylene glycol which is a hydrophilic part of the modified bisphenol A di (meth) acrylate is long and easily contains water, the strength of the functional resin layer 15 may not be maintained. More preferably, m + n in the formula is 10 or more and less than 40, and even more preferably, m + n in the formula is 20 or more and less than 35.

In addition, R < ¹ > in General formula (1) is a hydrogen group or a methyl group. When R ¹ in the general formula (1) is a hydrogen group (acrylic), the photochromic decoloring time is slightly faster, but the hardness of the functional resin layer 15 tends to be slightly inferior. On the other hand, when R ¹ in the general formula (1) is a methyl group (methacrylic), the photochromic decoloring time is slightly longer, but the hardness of the functional resin layer 15 tends to be slightly harder. .

Moreover, it is preferable that R < ³ > O in General formula (1) is ethylene glycol and / or propylene glycol. The viscosity of the polyalkylene glycol-modified bisphenol A di (meth) acrylate monomer represented by the general formula (1) can be lowered, and the handling property of the resin for molding the functional resin layer 15 should be excellent. It is because it can do. More preferably, R ³ O in the general formula (1) is ethylene glycol.

The (poly) alkylene glycol di (meth) acrylate represented by the following general formula (2) (hereinafter sometimes abbreviated as general formula (2) ROAc) is a synthetic resin excellent in dispersibility of the photochromic agent. .

The reason why the (poly) alkylene glycol di (meth) acrylate represented by the general formula (2) is excellent in the dispersibility of the photochromic agent cannot be determined, but the (poly) alkylene glycol di represented by the general formula (2) It is estimated that the viscosity of the (meth) acrylate monomer is low and the compatibility with the photochromic agent is excellent. In addition, since the (poly) alkylene glycol di (meth) acrylate represented by the general formula (2) is not a volatile component but a component that is copolymerized with another synthetic resin, the functional resin layer 15 is formed. There is no possibility of causing “loss” due to volatilization, and there is no possibility of causing a decrease in physical strength of the formed functional resin layer 15. In addition, R < ² > in General formula (2) is a hydrogen group or a methyl group.

The viscosity of the (poly) alkylene glycol di (meth) acrylate monomer represented by the general formula (2) is preferably 15 mPa · s (25 ° C.) or less. This is because the compatibility with the photochromic agent is excellent. More preferably, it is 12 mPa * s (25 degreeC) or less, More preferably, it is 8 mPa * s (25 degreeC) or less. Further, n (the degree of polymerization of alkylene glycol) in the general formula (2) is preferably 4 or less. This is because when the viscosity is lowered, the compatibility with the photochromic agent is excellent. More preferably, n is 3 or less, and more preferably n is 2 or less.

In addition, R < ² > in General formula (2) is a hydrogen group or a methyl group. When R ² in the general formula (2) is a hydrogen group (acrylic), the strength of the functional resin layer 15 tends to be slightly inferior. On the other hand, when R ² in the general formula (2) is a methyl group (methacrylic), the hardness of the functional resin layer 15 tends to be slightly hard.

Further, R ⁴ O in the general formula (2) in is preferably ethylene glycol and / or propylene glycol. This is because the viscosity of the (poly) alkylene glycol di (meth) acrylate monomer represented by the general formula (2) can be reduced and the compatibility with the photochromic agent can be further improved. More preferably, R ⁴ O in the general formula (2) is ethylene glycol.

The alkylene diol diglycidyl ether acrylate represented by the following general formula (3) (hereinafter sometimes abbreviated as general formula (3) ROGAc) is a thiourethane, episulfide, or (meth) acrylate-based thermosetting. It is a synthetic resin that is excellent in adhesion to an adhesive resin raw material.

The reason why the alkylene diol diglycidyl ether acrylate represented by the general formula (3) is excellent in adhesion to a thiourethane-based, episulfide-based or (meth) acrylate-based thermosetting resin material cannot be determined, but the general formula (3) It is presumed that the OH group polarity of ROGAc is in close contact with the thiol group, episulfide group, and (meth) acrylate.

Integration of the functional resin layer 15 into the organic glass substrate 11 can be performed by a cast molding method as shown in FIG. The casting molding method is a method in which a mold cavity 21 is formed in the organic glass substrate 11 and molding is performed by injecting a functional resin. The integration of the functional resin layer 15 into the organic glass substrate 11 can also be performed by a general method such as a dipping method or a spray method. In the case where the functional resin is a material that reacts with oxygen in the air to cause curing inhibition, a cast molding method is preferable. Since the mold cavity 21 is a closed system closed by the first mold 13, the second mold 17, and the taping 19 made of the organic glass substrate 11, the oxygen in the air can be blocked to prevent inhibition of curing. Because it can.

As shown in FIG. 1, the cavity 21 in which the functional resin layer 15 is provided has the organic mold substrate 11 as the first mold 13 and the second mold 17 so that a certain gap is formed outside the first mold 13. In addition, the peripheral gap between the first mold 13 and the second mold 17 is sealed with a taping 19 or the like. By using the same mold as the mold used for molding the organic glass substrate 11, the functional resin layer 15 can have a certain thickness.

The gap between the cavities 21 where the functional resin layer 15 is provided is set depending on the flow characteristics of the functional resin and the functionality required for the functional resin layer 15, but is preferably 0.2 to 3.0 mm. Since the gap between the cavities 21 is secured to such an extent that injection is easy, casting can be performed instantaneously, and the injected functional resin can be cured without flowing. This is because it is possible to suppress the occurrence of reason (parts having different refractive indexes). If the gap between the cavities 21 is less than 0.2 mm, injection may be difficult even if the resin has excellent fluidity. On the other hand, if it exceeds 3.0 mm, striae may occur due to uneven curing due to the flow of the functional resin. More preferably, the gap of the cavity 21 is 0.3 to 1.5 mm, and more preferably 0.4 to 1.0 mm.

In addition, as shown in FIG. 2, it is good also as a structure by which the protective resin layer 16 was provided in the surface side seeing from the organic glass base material of the functional resin layer 15. FIG. This is because when the hardness of the functional resin layer 15 is inferior, the functional resin layer 15 can be protected by providing the protective resin layer 16 having a high hardness.

For the protective resin layer 16, a (meth) acrylate hard coat agent can be used, and a solvent-free (meth) acrylate hard coat agent commercially available from Hitachi Chemical Co., Ltd., Kyoeisha Chemical Co., Ltd. or the like can be used. it can. Further, for the protective resin layer 16, a resin mainly composed of (poly) alkylene glycol di (meth) acrylate represented by the general formula (2) can be used, and in particular, in the general formula (2) R ² is preferably a methyl group (methacrylic). This is because when R ² is a methyl group (methacrylic), the hardness of the protective resin layer 16 can be increased. Further, n (the degree of polymerization of alkylene glycol) in the general formula (2) is preferably 4 or less. This is because the viscosity of the protective resin forming the protective resin layer 16 is low, the fluidity is high, and injection into the cavity 23 described later becomes easy. More preferably, n is 3 or less, and more preferably n is 2 or less. The preferable viscosity of the (poly) alkylene glycol di (meth) acrylate represented by the general formula (2) is preferably 14 mPa · s (25 ° C.) (n = 4) or less, more preferably 9 mPa · It is s (25 degreeC) (n = 3) or less, More preferably, it is 6 mPa * s (25 degreeC) (n = 2) or less.

The integration of the protective resin layer 16 into the functional resin layer 15 can be performed by a casting method as shown in FIG. The casting molding method is performed by forming a mold cavity 23 in the functional resin layer 15 (organic glass substrate 11) and injecting a protective resin for forming the protective resin layer 16. The integration of the protective resin layer 16 into the functional resin layer 15 can also be performed by a general method such as a dipping method or a spray method. Note that, when the protective resin forming the protective resin layer 16 is a material that reacts with oxygen in the air to cause curing inhibition, a cast molding method is preferable. Since the cavity 23 of the mold is a closed system closed by the first mold 13, the second mold 17, and the taping 19 made of the organic glass base material 11 in which the functional resin layer 15 is integrated, This is because oxygen can be blocked to prevent curing inhibition.

The gap between the cavities 23 in which the protective resin layer 16 is provided is sufficient as the gap between the gaps forming the thickness of the protective resin layer 16 sufficient to protect the functional resin layer 15 and is preferably thin, but is set according to the flow characteristics of the protective resin. Therefore, the thickness is preferably 0.1 to 0.5 mm. Since the gap between the cavities 23 is secured to such an extent that the protective resin for forming the protective resin layer 16 can be easily injected, cast molding can be performed instantaneously, and the spectacles material has striae (parts with different refractive indices). This is because the occurrence of occurrence can be suppressed. More preferably, it is 0.15 to 0.3 mm.

The organic glass substrate (light control optical element) on which the functional resin layer 15 (and the protective resin layer 16) is formed has a hard coating process, an antifogging process, an antireflection process, a repellent process generally performed. General-purpose surface treatments such as water treatment and antistatic treatment can be appropriately performed.

Further, the functional resin layer 15 may be provided with a UV absorber gradually decreasing portion. The ultraviolet absorber gradually decreasing portion is configured to gradually decrease the ultraviolet absorbance on the surface due to the difference in the amount of penetration of the ultraviolet absorber on the surface side when viewed from the organic glass substrate of the functional resin layer 15.

By providing the ultraviolet absorber gradually decreasing portion in the functional resin layer 15, the light control optical element (glasses lens) exhibits a blurred color (gradation color) when irradiated with ultraviolet rays, and is functional and fashionable. It can be excellent. Specifically, the upper side (sky side) when using a spectacle lens reduces the amount of penetration of the UV absorber, making it easier for the photochromic agent to change to a dark color, and the lower side (ground side) penetrates the UV absorber. Increase the amount to make it difficult for the photochromic agent to turn dark. As a result, the upper side of the spectacle lens that is exposed to sunlight has a dark color and thus has an anti-glare effect, and the lower side of the spectacle lens has a light color and thus ensures the user's field of view.

The ultraviolet absorber gradually decreasing portion can be formed by oscillating the light-modulating optical element in an immersion bath in which the ultraviolet absorber is dissolved, and gradually decreasing and infiltrating the ultraviolet absorber on the surface side of the functional resin layer 15. As the solution of the immersion bath, for example, a solution in which a UV absorber such as benzotriazole can be dissolved can be used. The vibration immersion can be performed by, for example, vertical movement (vibration (reciprocating movement)) along the vibration immersion pattern shown in FIG.

The ultraviolet absorber gradually decreasing portion is a spectacle lens (photochromic member) having a gradually decreasing portion where the ultraviolet absorbance gradually decreases on the surface due to the difference in the amount of penetration of the ultraviolet absorber, and the details of the manufacturing method thereof are as follows. It is described in Japanese Patent Application Laid-Open No. 2016-212382 which is the applicant.

Hereinafter, the present invention will be described in more detail with reference to examples. As the functional resin for forming the functional resin layer 15, A-1 to A-23 shown in Table 1 were used. As the protective resin for forming the protective resin layer 16, A-24 shown in Table 1 was used.

In Table 1, abbreviations are used for polyalkylene glycol-modified bisphenol A di (meth) acrylate (general formula (1) BPAc) represented by general formula (1). Abbreviations, m + n, (meth) acrylic types, and polyalkylene glycol types are described below. BPAc1 (m + n = 30, acrylic, polyethylene glycol), BPAc2 (m + n = 30, methacryl, polyethylene glycol), BPAc3 (m + n = 17, methacryl, polyethylene glycol), BPAc4 (m + n = 10, methacryl, polyethylene glycol).

Abbreviations were used for (poly) alkylene glycol di (meth) acrylates (general formula (2) ROAc) represented by general formula (2). Abbreviations, n, viscosities, (meth) acrylic types, and polyalkylene glycol types are described below. ROAc1 (n = 1, 3 mPa · s (25 ° C.), methacryl, polyethylene glycol), ROAc2 (n = 2, 8 mPa · s (25 ° C.), acrylic, polyethylene glycol), ROAc3 (n = 2, 6 mPa · s ( 25 ° C.), methacryl, polyethylene glycol).

1,4-Butanediol diglycidyl ether acrylate was used for the alkylene diol diglycidyl ether acrylate represented by the general formula (3) (general formula (3) ROGAc). In Table 1, it was described as ROGAc1.

The photochromic agent was blended with a spiropyran photochromic agent and a spirooxazine photochromic agent (both manufactured by Yamada Chemical Co., Ltd.). NeoContrast (manufactured by Mitsui Chemicals, Inc., absorption peak wavelength: 580 nm) was used as the specific wavelength absorber.

The functional resin is a mixture of general formula (1) BPAc, general formula (2) ROAc, and general formula (3) ROGAc, a photochromic agent, other additives, and, if necessary, a specific wavelength absorber, and nitrogen gas. The mixture was stirred for 1 hour while adjusting the temperature to 15 ° C under an atmosphere. Subsequently, after deaeration for 1 hour with stirring at a liquid temperature of 15 ° C. and 133 Pa using a vacuum pump, a functional resin for forming the functional resin layer 15 was prepared by filtration through a 1 μm filter.

As the organic glass base material 11, one obtained by molding a resin raw material prepared as described below and a cast product molded in advance were used.
<Resin A (thiourethane resin)>
2,5-bicyclo [2,2,1] heptanebis (methylisocyanato): 100 parts, dibutyltin dichloride: 0.1 part as a curing agent, alkyl phosphate ester 2 parts as an internal mold release agent, and 3 parts as an ultraviolet absorber Monoester of -5-[(2-benzotriazole) -3-t-butyl-4-hydroxyphenyl] propionic acid and polyethylene glycol: 2.0 parts were sufficiently stirred for 1 hour in a nitrogen gas atmosphere at a liquid temperature of 15 ° C. . Thereafter, 50 parts of pentaerythritol tetrakis (3-mercaptopropionate): 50 parts and 4,7-bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol: 50 parts were further added. The mixture was stirred for 1 hour while adjusting the temperature to 15 ° C. in a nitrogen gas atmosphere. Subsequently, using a vacuum pump, degassing for 1 hour with stirring at a liquid temperature of 15 ° C and 133 Pa, and then filtering through a 1 µm filter to prepare a resin raw material for a thiourethane lens substrate with a refractive index (ne) of 1.60. did.
<Resin B (episulfide resin)>
Bis (2,3-epithiopropyl) disulfide: 90 parts, 4,7-bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol: 10 parts at 15 ° C. under nitrogen gas atmosphere The mixture was stirred for 30 minutes while adjusting the temperature, N, N-dimethylcyclohexylamine: 0.3 parts as a curing agent, isopulegol: 0.3 parts as a fragrance imparting agent, and 3-5 [-(2-benzotriazole as an ultraviolet absorber) ) -3-T-Butyl-4-hydroxyphenyl] propionic acid and polyethylene glycol: 1.5 parts were added respectively, and the mixture was further stirred for 30 minutes while adjusting the temperature to 15 ° C. in a nitrogen gas atmosphere. Subsequently, the mixture was degassed for 1 hour with stirring at a liquid temperature of 15 ° C. and 133 Pa using a vacuum pump, and then filtered through a 1 μm filter to prepare a resin raw material for an episulfide-based lens substrate having a refractive index (ne) of 1.74. .
<Resin C ((meth) acrylic resin)>
NK11P (manufactured by Nippon Shimizu Sangyo Co., Ltd., main component bisphenol MMA): 96 parts, α-methylstyrene dimer: 4 parts, mixed and stirred for 30 minutes while adjusting the temperature to 15 ° C. in a nitrogen gas atmosphere, and perbutyl ND: 1 as a curing agent 4 parts, 3-5 [-(2-benzotriazole) -3-tert-butyl-4-hydroxyphenyl] propionic acid: 1.0 part each as an ultraviolet absorber, and further added to 15 ° C. under nitrogen gas atmosphere The mixture was stirred for 30 minutes while adjusting the temperature. Subsequently, degassing for 1 hour with stirring at a liquid temperature of 15 ° C and 133 Pa using a vacuum pump, and filtering through a 1 µm filter, a resin raw material for a (meth) acrylic lens substrate having a refractive index (ne) of 1.56 Was prepared.

<Resin D (polyurea resin)>
As the polyurea resin, NXT (polyurea resin manufactured by Tribex Corporation (ICRX NXT)) cast molding was used.

The organic glass substrate 11 is molded by a cast molding method, and the mold is sealed with taping made of an adhesive tape so that the distance between the center of the lens is 1.0 mm between the convex mold and the concave mold. Thus, a mold having a cavity for forming an organic glass substrate was prepared.

The organic glass substrate 11 is prepared by mixing the resin raw materials with the above composition and injecting them into a mold. The thiourethane type and episulfide type are heated and cured at 120 ° C. for 2 hours, and the (meth) acrylate type is heated and cured at 80 ° C. for 1 hour. Was molded by.

As shown in FIG. 1, cast molding of the functional resin layer 15 onto the organic glass substrate 11 is performed by forming a mold cavity 21 in the organic glass substrate 11 and molding the functional resin layer 15. Molded by injecting resin and curing. The cavity 21 is a convex surface used when forming the organic glass substrate 11 as the second mold 17 so that the organic glass substrate 11 is the first mold 13 and a certain gap is formed outside the first mold 13. A side mold was disposed, and a circumferential gap between the first mold 13 and the second mold 17 was formed by sealing with a taping 19.

As shown in FIG. 2, casting molding of the protective resin layer 16 onto the organic glass substrate 11 (functional resin layer 15) is performed on the organic glass substrate 11 integrated with the functional resin layer 15. 23 was formed, and a protective resin for forming the protective resin layer 16 was injected and cured. The cavity 23 has an organic glass substrate 11 as the second mold 17 so that the organic glass substrate 11 integrated with the functional resin layer 15 is the first mold 13 and a certain gap is formed outside the first mold 13. The convex side mold used in molding the material 11 (functional resin layer 15) was disposed, and the peripheral gap between the first mold 13 and the second mold 17 was sealed with a taping 19 to be formed.

The organic glass substrate 11 (resin lens) on which the functional resin layer 15 (and the protective resin layer 16) is molded has its concave surface and outer periphery cut and polished, and a 70 mm diameter SPH (spherical surface (D)) is -8. 0.00 light control optical element (glasses lens).

The UV absorber gradually decreasing portion is a vibration immersion pattern described in FIG. 3B in an immersion bath in which 5% by mass of a benzotriazole UV absorber (absorption peak wavelength: 350 nm) is dissolved in distilled water. It was performed by moving up and down (vibrating (reciprocating movement)).

A dimming optical element of a test example is created by a combination of the organic glass substrate 11 and the functional resin layer 15 (and the protective resin layer 16) described below, and for these, photochromic characteristics and appearance evaluation are measured, Adhesion was measured as an evaluation of strength.
<Photochromic characteristics>
For photochromic properties, the light control optical element was colored by irradiation with ultraviolet rays and decolored by blocking ultraviolet rays, and the spectral average transmittance according to the colored state was measured. UV irradiation is FL4. BLB (Toshiba Lighttech Co., Ltd., black light fluorescent lamp, UV output 0.25 W, UV radiation intensity 2.7 μW / cm ² ) is irradiated from a position 20 cm away from the optical axis of the dimming optical element of the test piece and measured. Obtained the light control property, recoverability, and return amount from the spectral average transmittance. The spectral average transmittance was determined according to the following apparatus and standard, and the average transmittance for light of 380 to 780 nm was determined. The measurement position was the geometric center of the spectacle material.

・ Device: Spectrophotometer U-4100 (manufactured by Hitachi High-Tech Science Co., Ltd.)
Standard: Specification and test method of transmittance of refraction correcting spectacle lens (JIS T 7333: 2005 (ISO / DIS 8980-3: 2002))
The light control property was evaluated as follows by measuring the spectral average transmittance immediately after the light control optical element was irradiated with ultraviolet rays for 15 minutes. A: 10% or less, O: 15% or less, less than 10%, Δ: 20% or less, less than 15%, x: More than 20%.

Recoverability was evaluated as follows by measuring the spectral average transmittance 15 minutes after UV irradiation and measuring the spectral average transmittance 2 minutes after the UV irradiation. A: 70% or more, O: 50% or more and less than 70%, Δ: 40% or more and less than 50%, ×: less than 40%.

The amount of return was determined by obtaining a value (%) obtained by subtracting dimming property (%) from recoverability (%) and evaluated as follows. A: 50% or more, ○: 35% or more and less than 50%, Δ: 20% or more and less than 35%, ×: less than 20%.
<Lens appearance>
The external appearance of the lens was confirmed by visual inspection. And the lens external appearance was evaluated as follows. A: No abnormality, Δ: Streaks are observed but there are no problems in use, ×: Streaks and cracks are problematic in use.
<Adhesion>
The adhesion was evaluated by performing a forced peel test. In the forced peel test, a groove (Nyroll groove) on which a nylon thread is hung is provided on the outer peripheral surface (edge surface) of the lens corresponding to the interface between the functional substrate layer 15 and the organic glass substrate 11, and a minus driver is inserted into the Nyroll groove. The adhesiveness was evaluated by forcibly peeling. And adhesiveness was evaluated as follows. ○: No peeling (even if the functional base material layer 15 or the organic glass base material 11 has a defect, no peeling at the interface is seen), Δ: the functional base material layer 15 and the organic glass base Peeling is seen at the interface with the material 11 but no gap is confirmed. X: Peeling is seen at the interface between the functional base material layer 15 and the organic glass base material 11, and the occurrence of the gap can be confirmed.

The test example is described below. Test Example 1-1 to Test Example 1-22, Test Example 2-1 to Test Example 2-22, Test Example 3-1 to Test Example 3-22, Test Example 4-1 to Test Example 4-22 are examples The best examples are Test Example 1-7 and Test Example 1-8. Test Examples 1-23, 2-23, 3-23, and 4-23 are comparative examples.

(Test Example 1-1 to Test Example 1-23)
Test Examples 1-1 to 1-23 are test examples in which resin A (thiourethane resin) is used for the organic glass substrate. Among these, in Test Example 1-1 to Test Example 1-14 and Test Example 1-21 to Test Example 1-23, the functional resin layer 15 is provided but the protective resin layer 16 is not provided, and Test Examples 1-15 to In Test Example 1-20, the protective resin layer 16 is provided in addition to the functional resin layer 15. In Test Examples 1-7 and 1-8, a UV absorber gradually decreasing portion is provided and NeoContrast is contained as a functional drug. The evaluation performance results are listed in Table 2.

Test Examples 1-1 to 1-6 are obtained by changing the content ratio of the polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the general formula (1) in the functional resin layer. As the content ratio of the general formula (1) BPAc is small from Test Example 1-1 to Test Example 1-6, the recoverability (luminous transmittance) increases, the return amount increases, and the decoloring time increases. I understand that.

Test Examples 1-6 to 1-8 were obtained by changing the thickness of the functional resin layer. It can be seen that the dimming property (luminous transmittance) can be adjusted by changing the thickness. Test Example 1-7 and Test Example 1-8 were provided with a gradually decreasing portion of the ultraviolet absorber, and exhibited blurring coloring (gradation color) when irradiated with ultraviolet rays, and were excellent in functionality and fashionability. Further, Test Example 1-7 and Test Example 1-8 also contained NeoContrast as a functional drug, and the appearance of the optical element was improved.

Test Example 1-3 to Test Example 1-5, Test Example 1-9 to Test Example 1-11, Test Example 1-12 to Test Example 1-14 are represented by the general formula (1) in the functional resin layer. It compares by changing the value of m + n of the polyalkylene glycol modified bisphenol A di (meth) acrylate represented. The general formula (1) BPAc of Test Examples 1-3 to 1-5 is m + n = 30, the general formula (1) BPAc of Test Examples 1-9 to 1-11 is m + n = 17, The general formula (1) BPAc in Test Example 1-12 to Test Example 1-14 is m + n = 10. It can be seen that as m + n of the general formula (1) BPAc is larger, the recoverability (luminous transmittance) is higher, the return amount is higher, and the decoloring time is faster.

Test Example 1-4 to Test Example 1-5 and Test Example 1-15 to Test Example 1-16 are polyalkylene glycol-modified bisphenol A di (meth) represented by the general formula (1) in the functional resin layer. This is a comparison of the acrylate group and the methacryl group of the acrylate polymerization group. From the comparison of the recoverability (luminous transmittance) and the return amount, it can be seen that the general formula (1) BPAc, which is a slight acrylic group, is superior (faster) to the decoloring time. In addition, although the test body using the general formula (1) BPAc of the acrylic group for the functional resin layer was not described in the table, the hardness as the strength of the functional resin layer tended to be slightly inferior, A protective resin layer was provided.

Test Examples 1-15 to 1-16 and Test Examples 1-17 to 1-18 are (poly) alkylene glycol di (meth) acrylates represented by the general formula (2) in the functional resin layer. The value (and viscosity) of n was changed and compared. The general formula (2) ROAc in Test Examples 1-15 to 1-16 is n = 2 (6 mPa · s), and the general formula (2) ROAc in Test Examples 1-17 to 1-18 is n = 1 (3 mPa · s). The smaller the n (viscosity) of the general formula (2) ROAc, the better the compatibility with the photochromic agent, but it did not appear as a result in the photochromic properties.

Test Examples 1-15 to 1-16 and Test Examples 1-19 to 1-20 are (poly) alkylene glycol di (meth) acrylates represented by the general formula (2) in the functional resin layer. The methacrylic group and the acrylic group of the polymerized group are compared. No effect on the photochromic properties was observed due to the difference in the polymerization group of the general formula (2) ROAc.

Test Example 1-21 was one in which the alkylene diol diglycidyl ether acrylate represented by the general formula (3) was not contained. Adhesion to the organic glass substrate was slightly inferior.

Test Example 1-22 did not contain (poly) alkylene glycol di (meth) acrylate represented by general formula (2) and alkylene diol diglycidyl ether acrylate represented by general formula (3) It is. The dispersibility of the photochromic agent was slightly inferior, and the light control property and the lens appearance were slightly inferior. Further, the adhesion to the organic glass substrate was slightly inferior.

Test Example 1-23 does not contain the polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the general formula (1). There was no interaction with the general formula (1) BPAc, and the recoverability and return amount were not satisfied.

FIG. 4 is a graph comparing the performance of the example (Test Example 1-8) and the comparative example (Test Example 1-23). After the ultraviolet ray was irradiated for 15 minutes, it was blocked and irradiated (from 0 to 15 minutes). It is the figure which measured the visible light transmittance | permeability (Transmittance%) at the time of interruption | blocking (15 minutes to 20 minutes) with time, and represented the result. It can be seen that in Example (Test Example 1-8), the visible light transmittance after UV blocking is significantly recovered (discoloration time is significantly faster) than in Comparative Example (Test Example 1-23).

(Test Example 2-1 to Test Example 2-23, Test Example 3-1 to Test Example 3-23, Test Example 4-1 to Test Example 4-23)
Test Examples 2-1 to 2-23 are test examples in which resin B (episulfide resin) is used for the organic glass substrate. The evaluation performance results are listed in Table 3. Test Examples 3-1 to 3-23 are test examples in which resin C ((meth) acrylic resin) is used for the organic glass substrate. The evaluation performance results are listed in Table 4. Test Examples 4-1 to 4-23 are test examples in which resin D (polyurea resin) is used for the organic glass substrate. The evaluation performance results are listed in Table 5.

From the results of Test Example 2-1 to Test Example 2-23, Test Example 3-1 to Test Example 3-23, and Test Example 4-1 to Test Example 4-23, the functional resin layer of the embodiment is an organic glass. It was confirmed that the substrate can be used even if it is an episulfide resin, a (meth) acrylic resin, or a polyurea resin.

DESCRIPTION OF SYMBOLS 11 ... Organic glass base material, 13 ... 1st mold, 15 ... Functional resin layer, 16 ... Protective resin layer, 17 ... 2nd mold, 19 ... Taping, 21, 23 ... Cavity.

Claims

In the light control optical element in which the functional resin layer is integrated on one side or both sides of the organic glass substrate which is a resin molded body,
The functional resin layer contains a photochromic agent and a polyalkylene glycol-modified bisphenol A di (meth) acrylate represented by the following general formula (1).
The light control optical element according to claim 1, wherein the functional resin layer contains (poly) alkylene glycol di (meth) acrylate represented by the following general formula (2).
The organic glass substrate is molded from a thiourethane-based, episulfide-based or (meth) acrylate-based thermosetting resin raw material,
The light control optical element according to claim 1, wherein the functional resin layer contains an alkylene diol diglycidyl ether acrylate represented by the following general formula (3).
The light control optical element according to claim 1, wherein the thickness of the functional resin layer is 0.2 to 3.0 mm.