WO2018123077A1

WO2018123077A1 - Optical element

Info

Publication number: WO2018123077A1
Application number: PCT/JP2017/006188
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: 2016-12-28
Filing date: 2017-02-20
Publication date: 2018-07-05
Also published as: JP6585850B2; JPWO2018124063A1

Abstract

The purpose of the present invention is to provide an optical element that exhibits excellent adhesion of a functional resin layer in which a fracture is unlikely to occur even when the optical element is subjected to excessive force. This optical element has a functional resin layer (15) integrated in one or both surfaces of an organic glass substrate (11) which is a resin molding, wherein the functional resin layer (15) contains a functional chemical agent, an isocyanate compound, and a polyol compound, and the polyol compound contains a polyhydric alcohol polymer compound having an average molecular weight of 180 or more. Since the polyhydric alcohol polymer compound having an average molecular weight of 180 or more is highly hydrophilic, and a polymer that is formed from the polyhydric alcohol polymer compound and the isocyanate compound that is lipophilic is used as a binder; the functional resin layer (15) has a well-balanced combination between hydrophilicity and lipophilicity and exhibits excellent adhesion to the organic glass substrate (11).

Description

Optical element

The present invention relates to an optical element in which a functional resin layer is integrated on one side or both sides of an organic glass substrate that is a resin molded body.

The performance required for eyeglass materials (lenses) of optical elements includes vision correction performance, light control performance, and specific wavelength absorption performance. In order for a spectacle material to have dimming performance and specific wavelength absorption performance, it is necessary to include functional drugs such as a photochromic agent and a specific wavelength absorber in the spectacle material. However, when a functional drug is mixed in the eyeglass material, if the eyeglass material is a vision correction lens (a lens with a degree), the density difference (color tone difference) of the functional drug occurs due to the difference in thickness between the inner and outer circumferences. As a result, there is a problem that a difference in performance occurs between the inner and outer circumferences.

On the other hand, Patent Document 1 describes a manufacturing method of a resin lens (vision correction lens) including a functional resin layer. This manufacturing method comprises a cavity for molding a functional resin layer on one side or both sides of a base lens, and is provided with a thermoplastic elastomer adhesive layer on the side surface of the functional resin layer of the base lens. This is a method of manufacturing a resin lens in which a lens and a functional resin layer are integrated. The resin lens manufactured by this manufacturing method is provided with a light control performance and a specific wavelength absorption performance by the functional resin layer containing a functional drug, and the functional resin layer has a constant thickness. This solves the problem of light and shade differences caused by the difference in thickness between the inner and outer circumferences of a prescription lens.

Japanese Patent Laid-Open No. 2014-156067

In recent years, supple spectacle frames that do not deform even if they are stepped on by mistake have come to be used as spectacle materials (lenses) for optical elements. Depending on the conditions when stepped on, the lens will receive excessive force. However, conventional resin lenses with a functional resin layer are not supposed to be stepped on by humans, but are examined until abnormalities such as defects occur in the functional resin layer when excessive force is applied. Was not.

In addition, with the diversification of eyeglass frame designs, rimless (frameless frame) and half rim (upper half frame) eyeglass frames have come to be used as optical element eyeglass materials (lenses). In these cases, a frame mounting hole is formed at the outer periphery of the lens, or a groove (ny roll groove) for tying nylon thread is formed on the outer peripheral surface (edge surface) of the lens. However, a conventional resin lens having a functional resin layer is one in which the functional resin layer is bonded to the base lens with an adhesive layer of a thermoplastic elastomer, and is used for a processing tool in drilling or grooving. Depending on the handling, there is an undeniable risk that the functional resin layer may be damaged due to excessive force.

The present invention has been made in view of the above points, and even when the spectacle material (lens) of the optical element receives an excessive force, the functional resin layer is less likely to be damaged, and the functional resin layer is closely attached. It aims at providing the optical element excellent in property.

The optical element of the present invention is an optical element in which a functional resin layer is integrated on one side or both sides of an organic glass substrate that is a resin molded body. The functional resin layer comprises a functional agent, an isocyanate compound, The polyol compound contains a polyhydric alcohol polymer compound having an average molecular weight of 180 or more.

The inventors of the present invention have a function in which the polyol compound of the functional resin layer (urethane resin layer) containing the isocyanate compound and the polyol compound contains a polyhydric alcohol polymer compound having an average molecular weight of 180 or more. It was discovered that the adhesive resin layer is excellent in adhesion to the organic glass substrate. Since the polyhydric alcohol polymer compound has an average molecular weight of 180 or more, the polyhydric alcohol polymer compound has higher hydrophilicity than a compound having a small average molecular weight (less than 180). A functional resin layer having a polymer formed from a polyhydric alcohol polymer compound and an oleophilic isocyanate compound as a binder has a good balance between hydrophilicity and oleophilicity. For this reason, it is thought that a functional resin layer becomes the thing excellent in the adhesiveness to an organic glass base material. According to the optical element of the present invention, since the polyhydric alcohol polymer compound having an average molecular weight of 180 or more is contained, even if the optical element receives an excessive force, a defect or the like is hardly generated in the functional resin layer. It is possible to provide an optical element having excellent durability.

Here, in the above optical element, the polyhydric alcohol polymer compound may contain a polyalkylene glycol (polyoxyalkylene) compound. According to this, since the polyalkylene glycol compound has ether (alkyleneoxy), the hydrophilicity is stronger, and the functional resin layer has a better balance between hydrophilicity and lipophilicity. Excellent adhesion due to Thereby, the optical element can be made more excellent in durability.

In the optical element, the polyhydric alcohol polymer compound may contain a phenol skeleton-containing polyalkylene glycol (polyoxyalkylene) compound. According to this, since the thermal expansion coefficient of the functional resin containing the phenol skeleton-containing polyalkylene glycol compound is low, the optical element is reduced in distortion due to heat at the time of production drying and the like.

In the above optical element, the polyhydric alcohol polymer compound may contain a polyalkylene glycol (polyoxyalkylene) compound and a phenol skeleton-containing polyalkylene glycol (polyoxyalkylene) compound. According to this, the optical element can be reduced in distortion due to heat at the time of drying during manufacture, and can be excellent in durability.

In the above optical element, the functional resin layer may contain a thiol compound. According to this, by containing a thiol compound, the functional resin layer (thiourethane resin layer) can have excellent optical properties such as a high refractive index.

Further, in the optical element, the functional drug can contain a photochromic agent. Conventionally, when a photochromic agent is contained in a urethane resin or a thiourethane resin, there is a problem that the resin becomes cloudy. In contrast, the inventors of the present application can prevent the resin from becoming clouded by containing a polyhydric alcohol polymer compound having an average molecular weight of 180 or more of the polyol compound of the urethane resin or thiourethane resin. It was discovered that we can do it. According to this, even if it is a functional resin layer made of urethane resin or thiourethane resin, the functional resin layer can contain the photochromic agent, so that the optical element has photochromic characteristics (light controllability). It can have.

In the above optical element, a polarizing film may be provided between the organic glass substrate and the functional resin layer. According to this, since the polarizing film can exhibit polarization characteristics, the optical element can have polarization characteristics.

In the optical element, the functional resin layer may have a thickness of 0.2 to 3.0 mm. According to this, at the time of manufacture, the thickness of the cavity for molding the functional resin layer can be ensured, and the functional resin layer can be cast and molded instantly. Since it can be cured without causing unevenness in curing, the optical element can suppress the occurrence of striae (parts having different refractive indexes).

According to the optical element of the present invention, since the polyhydric alcohol polymer compound having an average molecular weight of 180 or more is contained, even if the optical element receives an excessive force, a defect or the like is hardly generated in the functional resin layer. An optical element having excellent adhesion of the functional resin layer can be provided.

It is the schematic which shows the manufacturing process of the optical element of this invention.

Hereinafter, an embodiment of the present invention will be described. The optical element of the embodiment is an optical element in which the functional resin layer 15 is integrated on one side or both sides of the organic glass substrate 11 that is a resin molded body. An isocyanate compound and a polyol compound are contained, and the polyol compound contains a polyhydric alcohol polymer compound having an average molecular weight of 180 or more.

In the optical element of the embodiment, as shown in FIG. 1, an example in which the functional resin layer 15 is integrated with the surface (convex surface) of the organic glass substrate 11 as a spectacle lens by casting is described. . 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 substrate 11 is used as a substrate of an optical element such as a lens or a window glass. The optical element 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.

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), Iupilon CLS3400 (Mitsubishi Engineering Plastics polycarbonate resin, refractive index: 1.59), Grillamide TR XE3805 (Nylon-based resin, refractive index: 1.53 manufactured by Emschemy Japan Co., Ltd.), NXT (Tribex Corporation (ICRX) XT Co.) made by polyurea resin, refractive index: 1.53) can be suitably used and the like.

The organic glass substrate 11 includes a deterioration inhibitor that prevents resin degradation of organic glass, an ultraviolet absorber that absorbs ultraviolet rays, an internal mold release agent that improves releasability from a mold for molding a lens shape, and organic glass. A bluing agent for imparting a bluish tint, a curing agent for curing organic glass, and the like can be added depending on the type of organic glass.

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. Depending on the absorption wavelength range of the deterioration preventing agent, it also functions as an ultraviolet absorber.

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 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, when an uneven lens is taken as an example, a cavity 21 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 into the cavity 21 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 functional agent, an isocyanate compound, and a polyol compound, and if necessary, a thiol compound. The resin for forming the functional resin layer 15 can be added with the above-described deterioration preventing agent, internal mold release agent, curing agent, molecular weight adjusting agent, or the like, depending on the type of resin. .

A functional drug is a drug that imparts a function to an optical element, a photochromic agent that imparts photochromic properties, an ultraviolet absorber that imparts ultraviolet absorption performance, a specific wavelength absorber that imparts specific wavelength absorption or cut performance, Examples include pigments or dyes that impart coloring performance. These are expensive, and it is possible to reduce the content of the functional drug by containing the functional drug in the functional resin layer 15 having a smaller thickness than the organic glass substrate 11, Optical elements can reduce manufacturing costs.

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 ultraviolet absorber is an additive that absorbs ultraviolet rays and is added to the 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.

The specific wavelength absorber is an additive that absorbs light of a specific wavelength, and is added to an optical element, for example, to reduce the transmission of blue light. This is because blue light may cause tired eyes. Specific wavelength absorbers include benzophenone, diphenyl acrylate, sterically hindered amine, salicylic acid ester, benzotriazole, hydroxybenzoate, cyanoacrylate, hydroxyphenyl triazine, porphyrin, and the like.

Also, NeoContrast (manufactured by Mitsui Chemicals, absorption peak wavelength: 580 nm) is a specific wavelength absorber having a main absorption peak between 565 and 605 nm (especially 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.

The isocyanate compound and the polyol compound form a polyurethane resin that is a resin of the functional resin layer 15. In addition, the isocyanate compound, the polyol compound, and the thiol compound form a thiourethane resin that is a resin of the functional resin layer 15. As the polyurethane resin or thiourethane resin, one or two or more isocyanate components selected from polyisocyanate, polyisothiocyanate and polyisothiocyanate thioisocyanate, a polyol compound and an appropriate polythiol are used. A polymerizable component in combination with the above known active hydrogen 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 polyol compound is a polyhydric alcohol polymer compound having an average molecular weight of 180 or more, a polyalkylene glycol (polyoxyalkylene) compound represented by the following general formula (1) and / or a phenol represented by the following general formula (2). A skeleton-containing polyalkylene glycol (polyoxyalkylene) compound can be preferably used.

The inventors of the present application include an isocyanate compound and a polyol compound by containing the polyhydric alcohol polymer compound represented by the general formula (1) and / or the general formula (2) having an average molecular weight of 180 or more. It has been found that the functional resin layer 15 contained is excellent in adhesion to the organic glass substrate 11.

Since the polyhydric alcohol polymer compound has an average molecular weight of 180 or more, the polyhydric alcohol polymer compound has stronger hydrophilicity than a compound having a small average molecular weight (less than 180). The functional resin layer 15 having a polymer (polyurethane resin) formed from a polyhydric alcohol polymer compound and an oleophilic isocyanate compound as a binder has a good balance between hydrophilicity and oleophilicity. is there. For this reason, the functional resin layer 15 is considered to have excellent adhesion to the organic glass substrate 11. As a result, the optical element of the embodiment can be made excellent in durability because the functional resin layer 15 is less likely to be damaged even when the optical element receives an excessive force. When the average molecular weight of the polyol compound is less than 180, the functional resin layer 15 may shrink during curing, and the adhesion of the functional resin layer 15 to the organic glass substrate 11 may be insufficient. is there. On the other hand, the larger the average molecular weight of the polyol compound, the smaller the shrinkage when the functional resin layer 15 is cured, and the functional resin layer 15 has better adhesion to the organic glass substrate 11. In addition, when the average molecular weight of the polyol compound exceeds 15000, it is estimated that the polyhydric alcohol compound that is a hydrophilic portion becomes long, easily contains water, and the strength of the functional resin layer 15 may not be maintained. The In the examples described later, it has been confirmed that the functional resin layer 15 having an average molecular weight of 14,000 of the polyol compound is excellent in adhesion to the organic glass substrate 11. However, it has not been confirmed with polyol compounds having an average molecular weight higher than this. For this reason, even if the average molecular weight of a polyol compound exceeds 15000, it is possible that the functional resin layer 15 is excellent in adhesiveness to the organic glass substrate 11. Therefore, as a confirmed range, the average molecular weight of the polyol compound is preferably 180 to 15000, more preferably 500 to 15000, and still more preferably 1000 to 15000.

The polyhydric alcohol polymer compound may contain a polyalkylene glycol (polyoxyalkylene) compound. According to this, since the polyalkylene glycol compound has ether, the hydrophilicity is stronger, and the functional resin layer is provided with a better balance between hydrophilicity and lipophilicity, so that it adheres to the organic glass substrate. Will be better. Thereby, the optical element can be made more excellent in durability.

The polyhydric alcohol polymer compound may contain a phenol skeleton-containing polyalkylene glycol compound. Thereby, the functional resin layer 15 can reduce distortion caused by heat at the time of drying during manufacture. This is because the functional resin layer 15 containing the phenol skeleton-containing polyalkylene glycol compound has a low coefficient of thermal expansion. Polyoxyalkylene-bisphenol A ether and the like can be used as the phenol skeleton-containing polyalkylene glycol compound.

The polyhydric alcohol polymer compound contains a polyalkylene glycol (polyoxyalkylene) compound and a phenol skeleton-containing polyalkylene glycol (polyoxyalkylene) compound, so that the optical element is distorted by heat during drying of production. Can be reduced, and the durability can be improved.

In the polyol compounds of the general formulas (1) and (2), m + n (m is an average polymerization degree of alkylene glycol, n is an average polymerization degree of alkylene glycol) is preferably 1 or more and 300 or less. The polyol compounds represented by the general formulas (1) and (2) in this range can shorten the decoloring time of the photochromic agent when the functional agent is a photochromic agent, and the functional resin layer 15 This is because the strength is maintained. If m + n in the formula is less than 1, the effect of shortening the decoloring time of the photochromic agent may not be sufficiently obtained. On the other hand, if m + n exceeds 300, it is represented by the general formula (1) or (2). Since the polyalkylene glycol which is a hydrophilic part of the polyol compound to be produced is long and easily contains water, it is presumed that the strength of the functional resin layer 15 may not be maintained. More preferably, m + n in the formula is from 10 to 270, and even more preferably, m + n is from 30 to 250.

(OR) _n and (OR) _{m in} the polyol compounds of the general formulas (1) and (2) are polyoxyethylene (hereinafter referred to as EO) and / or polyoxypropylene (hereinafter referred to as PO). Is preferred. This is because EO and PO have high hydrophilicity and the functional resin layer 15 has excellent adhesion to the organic glass substrate 11. In particular, (OR) n and (OR) m in the polyol compounds of the general formulas (1) and (2) are preferably a copolymer (block copolymer) of EO and PO. The ratio of EO and PO is preferably EO / (EO + PO) = 20 to 90% by mass. This is because when the functional agent is a photochromic agent, the photochromic agent can be excellent in dispersibility and photochromic properties. When the ratio of EO and PO is less than EO / (EO + PO) = 20% by mass, the dispersibility of the photochromic agent may be inferior, and the functional resin layer may become cloudy. On the other hand, when EO / (EO + PO) = 90 mass% is exceeded, the photochromic characteristics may be inferior. More preferably, the ratio of EO and PO is EO / (EO + PO) = 30 to 85% by mass, and more preferably EO / (EO + PO) = 40 to 80% by mass.

The 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 functional resin layer 15 can be integrated with the organic glass substrate 11 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.

In the cavity 21 in which the functional resin layer 15 is provided, the organic glass substrate 11 is the first mold 13, and the second mold 17 is arranged so that a certain gap is formed outside the first mold 13. A gap between the peripheral surfaces of the mold 13 and the second mold 17 is formed by sealing with a taping 19 or the like. By using the same mold as that used for forming the organic glass substrate 11 as the second mold 17, 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 it can be easily injected, cast molding can be performed instantaneously, and the injected functional resin can be cured without flowing, so that the optical element has a pulse. 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, it is 0.3 to 1.5 mm, and still more preferably 0.4 to 1.0 mm.

The optical element has a polarizing film provided on the side of the organic glass substrate 11 provided with the functional resin layer 15 and a polarizing film provided between the organic glass substrate 11 and the functional resin layer 15. An optical element having characteristics can be obtained. The polarizing film is preferably composed of polyvinyl alcohol. This is because the adhesion between the organic glass substrate 11, the polarizing film, and the functional resin layer 15 is ensured by the isocyanate compound containing polyvinyl alcohol in the functional resin layer 15. The thickness of the polarizing film is preferably 10 to 50 μm. This is because the polarizing film has elongation characteristics that follow the curved surface of the optical element while having polarization characteristics.

In addition, the organic glass substrate 11 (optical element) on which the functional resin layer 15 is formed generally has a hard coat process, an antifogging process, an antireflection process, a water repellent process, and an antistatic process. General-purpose surface treatment such as processing can be appropriately performed.

Hereinafter, the present invention will be described in more detail with reference to examples. As functional resins for forming the functional resin layer 15, A-1 to A-24 shown in Table 1-1 and A-25 to A-31 shown in Table 1-2 were used.

In Table 1-1 and Table 1-2, abbreviations are used for isocyanate compounds, and names and the like for the abbreviations are described in parentheses. NBDI ((2,5) -bis (isocyanatomethyl) bicyclo [2.2.1] heptane), HDI (hexamethylene diisocyanate), MBDI (methylene bis (4,1 cyclohexylene) diisocyanate), MXDI (metaxylene diisocyanate) ).

An abbreviation is used for the thiol compound, and the name of the abbreviation is written in parentheses. PEMP (pentaerythritol tetrakis (3-mercaptopropionate)), FSH (4,7 (5,7 or 4,8) -bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11 A reaction product of 1-chloro-2,3 epoxypropane, 2-mercaptoethanol, sodium sulfide and thiourea based on dithiol).

* Abbreviations are used for polyol compounds, and names for abbreviations are written in parentheses. PEG200 (polyethylene glycol (average molecular weight 200, m + n≈4, bifunctional)), PEG400 (polyethylene glycol (average molecular weight 400, m + n≈9, bifunctional)), PEG1000 (polyethylene glycol (average molecular weight 1000, m + n≈22, 2) Functional)), PPG400 (polypropylene glycol (average molecular weight 400, m + n≈6, bifunctional)), PPG1000 (polypropylene glycol (average molecular weight 1000, m + n≈17, bifunctional)), PEPG1500 (polyethylene glycol-polypropylene glycol copolymer) (Average molecular weight 1500, m + n≈30, EO≈40 mass%, bifunctional)), PEPG2000 (polyethylene glycol-polypropylene glycol copolymer (average molecular weight 2000, m + n≈40, O≈20 mass%, bifunctional)), PEPG 2500 (polyethylene glycol-polypropylene glycol copolymer (average molecular weight 2500, m + n≈50, EO≈20 mass%, bifunctional)), PEPG 3500 (polyethylene glycol-polypropylene glycol copolymer) Combined (average molecular weight 3500, m + n≈70, EO≈40 mass%, bifunctional)), PEPG 10000 (polyethylene glycol-polypropylene glycol copolymer (average molecular weight 10,000, m + n≈200, EO≈80 mass%, bifunctional)) PEPG 13000 (polyethylene glycol-polypropylene glycol copolymer (average molecular weight 13000, m + n≈250, EO≈70 mass%, bifunctional)), PEPG 14000 (polyethylene glycol-polypropylene glycol Copolymer (average molecular weight 14000, m + n≈270, EO≈70% by mass, bifunctional)), EPPE4000 (polyoxyethylene / polyoxypropylene-pentaerythritol-ether (average molecular weight 4000, tetrafunctional)), EPH400 (polyoxyethylene-bisphenol A ether (average molecular weight 400, m + n≈4, bifunctional)), EPH700 (polyoxyethylene-bisphenol A ether (average molecular weight 660, m + n≈10, bifunctional)), PPH400 (polyoxy Propylene-bisphenol A ether (average molecular weight 400, m + n≈4, bifunctional)), EPPH800 (polyoxyethylene-polyoxypropylene-bisphenol A ether (average molecular weight 750, m + n≈10, bifunctional)).

∙ Photochromic agent and specific wavelength absorber were used as functional drugs. 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 an isocyanate compound, a thiol compound and a polyol compound, a functional agent and other additives (molecular weight modifier, curing agent, etc.), and the temperature is adjusted to 15 ° C. in a nitrogen gas atmosphere. The mixture was stirred for 1 hour. Subsequently, after degassing for 1 hour while stirring at a liquid temperature of 15 ° C. and 133 Pa using a vacuum pump, a functional resin that forms the functional resin layer 15 by filtration through a 1 μm filter was prepared.

The organic glass base material 11 was prepared as follows.

<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, after deaeration for 1 hour with stirring at a liquid temperature of 15 ° C. and 133 Pa using a vacuum pump, the resin raw material for a thiourethane liquid lens substrate having a refractive index (ne) of 1.60 is filtered through a 1 μm filter. Was prepared.

<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 deaerated 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 liquid resin raw material of an episulfide resin 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, 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 having a refractive index (ne) of 1.56.

<Resin D (nylon-based resin)>
As the nylon resin, a grill amide TR XE3805 (polyamide resin manufactured by EMS Chemie Japan Co., Ltd.) cast molding was used.

<Resin E (polycarbonate resin)>
As the polycarbonate resin, Iupilon CLS3400 (Mitsubishi Engineering Plastics polycarbonate resin) cast molding was used.

<Resin F (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 mixed by the above-described composition and injected into a mold, and the thiourethane and episulfide are molded by heating and curing at 120 ° C. for 2 hours, and the (meth) acrylate system is heated and cured at 80 ° C. for 1 hour. did.

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. The interval between the first mold 13 and the second mold 17 (the thickness of the functional resin layer 15) was 0.8 mm unless otherwise specified.

When the optical element (glasses lens) has polarization characteristics, a polarizing film is disposed on the side of the organic glass substrate 11 on which the functional resin layer 15 is provided, and then a mold cavity 21 is formed. The functional resin for forming the functional resin layer 15 was injected. When the functional resin is cured, the optical element is provided with a polarizing film between the organic glass substrate 11 and the functional resin layer 15 and has polarizing characteristics. The polarizing film used was a 38 μm thick polyvinyl alcohol stretched polarizing film.

The organic glass substrate 11 (resin lens) on which the functional resin layer 15 is molded has its concave surface and outer periphery cut and polished, and an optical element (glasses) having a diameter of 70 mm and SPH (spherical surface (D)) of −8.00. Lens).

The optical element was prepared by a combination of the organic glass substrate 11 and the functional resin layer 15, and the photochromic characteristics and appearance were evaluated for these, and the adhesion was measured as strength evaluation.

<Light control (photochromic characteristics)>
For photochromic properties, the optical element was colored by UV irradiation and decolored by UV blocking, and the spectral average transmittance (colorability) in the colored state and the spectral average transmittance (return speed) 2 minutes after blocking were measured. . UV irradiation is FL4. BLB (black light fluorescent lamp manufactured by Toshiba Lighting & Technology Co., Ltd., ultraviolet output 0.25 W, ultraviolet radiation intensity 2.7 μW / cm ² ) was irradiated from a position 20 cm away from the optical axis of the optical element of the test specimen. 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 optical element.

・ 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 colorability was evaluated as follows by measuring the spectral average transmittance immediately after the optical element was irradiated with ultraviolet rays for 15 minutes. A: 20% or less, B: 20% to 30%, Δ: 30% to 50%, ×: 50% or more. As the spectral average transmittance increases, the colorability becomes worse. The return speed was evaluated as follows by irradiating the optical element with ultraviolet rays for 15 minutes, measuring the spectral average transmittance after 2 minutes from blocking irradiation. A: 70% or more, O: 50% or more and less than 70%, Δ: 30% or more and less than 50%, ×: less than 30%. The return speed becomes worse as the spectral average transmittance is smaller. The dimming property was evaluated as the dimming property, which is the worse of the coloring property and the return speed.

<Lens appearance>
The external appearance of the lens was confirmed by visual inspection. And the lens external appearance was evaluated as follows. ○: no abnormality, Δ: striae or white turbidity is observed, but there are no problems in use, ×: striae or white turbidity causes problems 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 1-31, Test Example 2-1 to Test Example 2-31, Test Example 3-1 to Test Example 3-31, Test Example 4-1 to Test Example 4-31, Test Examples 5-1 to 5-31 and Test Examples 6-1 to 6-31 are examples, and the best example is Test Example 1-31.

(Test Example 1-1 to Test Example 1-31)
Test Examples 1-1 to 1-31 are test examples in which the resin A (thiourethane resin) is used for the organic glass substrate 11. Although not shown in the table, Test Examples 1-13 to 1-16 are optical elements having polarization characteristics. The results of evaluation performance are listed in Table 2-1.

Test Example 1-1 to Test Example 1-12 are modified types of polyol compounds (polyalkylene glycol compound and phenol skeleton-containing polyalkylene glycol compound). In addition, the kind of the isocyanate compound and the thiol compound was changed as appropriate.

Test Example 1-1 is a test example in which PEG200 of polyalkylene glycol having an average molecular weight of slightly small as 200, polyoxyalkylene is polyoxyethylene, and average degree of polymerization (m + n) is 4 is used as the polyol compound. is there. Test Example 1-1 is slightly inferior in light control due to a small average degree of polymerization, slightly inferior in adhesiveness because of an average molecular weight of slightly small as 200, polyoxyalkylene is polyoxyethylene, and dispersibility of the photochromic agent is It was somewhat inferior, and white turbidity was observed in the functional resin layer 15.

Test Examples 1-2 and 1-3 are test examples using PEG400 or PEG1000 of polyalkylene glycol in which polyoxyalkylene is polyoxyethylene as the polyol compound. In Test Example 1-2, since the average degree of polymerization was small (m + n≈9), the light control was slightly inferior, but there was no problem in adhesion and lens appearance. In Test Example 1-3, although there is no problem in the light control and adhesion, the functional resin layer 15 is slightly cloudy because the polyoxyalkylene is polyoxyethylene and the dispersibility of the photochromic agent is slightly inferior. It was.

Test Example 1-4 and Test Example 1-5 are test examples using PPG400 or PPG1000 of a polyalkylene glycol whose polyoxyalkylene is polyoxypropylene as a polyol compound. In Test Example 1-4 and Test Example 1-5, there was no problem in adhesion and lens appearance, but in Test Example 1-4, the average degree of polymerization was small (m + n≈9), but the light control property was slightly inferior.

Test Examples 1-6 to 1-8 are test examples in which polyalkylene glycol PEPG1500, PEPG2000 or PEPG2500 in which polyoxyalkylene is a copolymer of polyoxyethylene and polyoxypropylene is used as a polyol compound. is there. In Test Example 1-6, there were no problems in light control, adhesion, and lens appearance. In Test Example 1-7 and Test Example 1-8, the ratio of EO / PO of polyoxyalkylene is EO / (EO + PO) = 20% by mass and the ratio of EO is small. White turbidity sometimes occurred.

Test Examples 1-9 and 1-10 are test examples using a phenol skeleton-containing polyalkylene glycol EPH400 or EPH700 whose polyoxyalkylene is polyoxyethylene as the polyol compound. In Test Example 1-9 and Test Example 1-10, a phenol skeleton-containing polyalkylene glycol was used as the polyol compound, so that distortion due to heat was reduced.

Test Example 1-11 is a test example in which a phenol skeleton-containing polyalkylene glycol PPH400 in which the polyoxyalkylene is polyoxypropylene is used as the polyol compound. In Test Example 1-11, although there was no problem in adhesion and lens appearance, the light control property was slightly inferior because of the small average degree of polymerization (m + n≈4).

Test Example 1-12 is a test example using a phenol skeleton-containing polyalkylene glycol EPPH800, in which the polyoxyalkylene is a copolymer of polyoxyethylene and polyoxypropylene, as the polyol compound. In Test Example 1-12, there were no problems in light control, adhesion, and lens appearance.

Test Examples 1-13 to 1-20 are test examples in which a polyalkylene glycol compound and a phenol skeleton-containing polyalkylene glycol compound are used in combination with a polyol compound. Test Example 1-15 resulted in slightly inferior light control, but the other test examples had no problems with light control, adhesion, and lens appearance. Since Test Examples 1-13 to 1-16 were provided with the polarizing film, they had polarization characteristics.

Test Examples 1-21 to 1-24 are test examples in which two types of polyalkylene glycol compounds were used in combination with a polyol compound and no thiol compound was used. These did not have any problems in light control and lens appearance, but because of the use of polyoxyethylene / polyoxypropylene-pentaerythritol-ether, which is a highly hydrophilic tetrafunctional polyol compound, it has good adhesion. Since the functional resin layer 15 is a urethane resin, the refractive index is inferior (lower) compared to other test examples.

Test Example 1-25 to Test Example 1-31 are PEPG1500, PEPG2000, PEPG2500, PEPG3500, PEPG10000, PEPG13000, which are polyalkylene glycols in which a polyoxyalkylene is a copolymer of polyoxyethylene and polyoxypropylene. This is a test example using PEPG 14000. In Test Example 1-25 and Test Example 1-28 to Test Example 1-31, there were no problems in light control, adhesion, and lens appearance. Test Examples 1-28 to 1-31 also contained NeoContrast as a functional drug, and the appearance of the optical element was improved. In Test Example 1-26 and Test Example 1-27, the ratio of EO to PO in polyoxyalkylene is EO / (EO + PO) = 20% by mass, and the ratio of EO is small. In some cases, white turbidity occurred in the conductive resin layer 15.

Although not shown in the table, in Test Example 1-13, a test was performed in which the thickness of the functional resin layer 15 was changed from 0.8 mm to 0.2 mm and 3.0 mm. The test example in which the thickness of the functional resin layer 15 was 0.2 mm was considered to be the lower limit value of the thickness from the viewpoint of workability because the functional resin could be injected but the work was difficult. On the other hand, in the test example in which the thickness of the functional resin layer 15 was 3.0 mm, the thickness of the functional resin layer 15 was uneven because of the thickness, and a slight occurrence of striae was confirmed.

(Test Example 2-1 to Test Example 2-31, Test Example 3-1 to Test Example 3-31, Test Example 4-1 to Test Example 4-31, Test Example 5-1 to Test Example 5-31, Test Example 6-1 to Test Example 6-31)
Test Examples 2-1 to 2-31 are test examples in which resin B (episulfide resin) is used for the organic glass substrate 11. The results of evaluation performance are listed in Table 2-2. Test examples 3-1 to 3-31 are test examples using the resin C ((meth) acrylic resin) for the organic glass substrate 11. The results of evaluation performance are shown in Table 2-3. Test Examples 4-1 to 4-31 are test examples in which resin D (nylon resin) is used for the organic glass substrate 11. The results of evaluation performance are shown in Table 2-4. Test Examples 5-1 to 5-31 are test examples in which resin E (polycarbonate resin) is used for the organic glass substrate 11. The results of evaluation performance are shown in Table 2-5. Test Examples 6-1 to 6-31 are test examples in which resin F (polyurea resin) is used for the organic glass substrate 11. The results of evaluation performance are shown in Table 2-6.

From the results of Test Example 2-1 to Test Example 2-31, Test Example 3-1 to Test Example 3-31, Test Example 4-1 to Test Example 4-31, and Test Example 5-1 to Test Example 5-31 The functional resin layer 15 of the embodiment can be used even when the organic glass substrate 11 is an episulfide resin, a (meth) acrylic resin, a nylon resin, a polycarbonate resin, or a polyurea resin. It could be confirmed.

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

Claims

In an optical element in which a functional resin layer is integrated on one side or both sides of an organic glass substrate that is a resin molded body,
The functional resin layer contains a functional agent, an isocyanate compound, and a polyol compound,
The polyol element contains a polyhydric alcohol polymer compound having an average molecular weight of 180 or more.
The optical element according to claim 1, wherein the polyhydric alcohol polymer compound contains a polyalkylene glycol compound.
2. The optical element according to claim 1, wherein the polyhydric alcohol polymer compound contains a phenol skeleton-containing polyalkylene glycol compound.
The optical element according to claim 1, wherein the polyhydric alcohol polymer compound contains a polyalkylene glycol compound and a phenol skeleton-containing polyalkylene glycol compound.
The optical element according to any one of claims 1 to 4, wherein the functional resin layer contains a thiol compound.
The optical element according to claim 5, wherein the functional drug contains a photochromic agent.
The optical element according to claim 5, further comprising a polarizing film between the organic glass substrate and the functional resin layer.
6. The optical element according to claim 5, wherein the functional resin layer has a thickness of 0.2 to 3.0 mm.