[go: up one dir, main page]

WO2018037621A1 - Élément optique de modulation de lumière - Google Patents

Élément optique de modulation de lumière Download PDF

Info

Publication number
WO2018037621A1
WO2018037621A1 PCT/JP2017/016157 JP2017016157W WO2018037621A1 WO 2018037621 A1 WO2018037621 A1 WO 2018037621A1 JP 2017016157 W JP2017016157 W JP 2017016157W WO 2018037621 A1 WO2018037621 A1 WO 2018037621A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin layer
general formula
meth
organic glass
optical element
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/016157
Other languages
English (en)
Japanese (ja)
Inventor
忠史 鳥居
敬介 荻野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Itoh Optical Industrial Co Ltd
Original Assignee
Itoh Optical Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Itoh Optical Industrial Co Ltd filed Critical Itoh Optical Industrial Co Ltd
Publication of WO2018037621A1 publication Critical patent/WO2018037621A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C1/00—Assemblies of lenses with bridges or browbars
    • G02C1/04—Bridge or browbar secured to or integral with partial rims, e.g. with partially-flexible rim for holding lens

Definitions

  • 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. .
  • a photochromic agent 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 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).
  • a photochromic agent is dissolved in tetrahydrofuran to be uniformly dispersed in a synthetic resin so that the decoloring time can be reduced.
  • 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.
  • JP-A-8-216271 JP 2014-32273 A Japanese Patent Laid-Open No. 2014-156067
  • 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.
  • the functional resin layer may contain (poly) alkylene glycol di (meth) acrylate represented by the following general formula (2).
  • the light control optical element can obtain a uniform light control function. it can.
  • 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).
  • 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.
  • 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.
  • 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).
  • 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.
  • FIG. 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.
  • 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.
  • (meth) acrylate is a general term for acrylate and methacrylate.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • aliphatic or alicyclic polyisocyanates are desirable from the standpoint of yellowing resistance.
  • 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.
  • 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.
  • organic glass substrate 11 examples 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.
  • 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.
  • a synthetic resin for molding the organic glass substrate 11 is injected and cured, and the organic glass substrate 11 is polished as necessary.
  • 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).
  • 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.
  • 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).
  • an azobenzene photochromic agent 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.
  • 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.
  • 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.
  • R ⁇ alkyl radical
  • ROO. peroxy radicals
  • ROOH peroxides
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • R ⁇ 1 > in General formula (1) is a hydrogen group or a methyl group.
  • 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.
  • 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. .
  • 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.
  • 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 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.
  • R ⁇ 2 > in General formula (2) is a hydrogen group or a methyl group.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the peripheral gap between the first mold 13 and the second mold 17 is sealed with a taping 19 or the like.
  • 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.
  • 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. 2 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • the light control optical element 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.
  • 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
  • the lower side (ground side) penetrates the UV absorber. Increase the amount to make it difficult for the photochromic agent to turn dark.
  • the upper side of the spectacle lens that is exposed to sunlight has a dark color and thus has an anti-glare effect
  • 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.
  • 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.
  • BPAc polyalkylene glycol-modified bisphenol A di (meth) acrylate
  • BPAc polyalkylene glycol-modified bisphenol A di (meth) acrylate
  • m + n 30, acrylic, polyethylene glycol
  • ROAc (poly) alkylene glycol di (meth) acrylates
  • n viscosities, (meth) acrylic types, and polyalkylene glycol types are described below.
  • ROAc1 1, 3 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.
  • a functional resin for forming the functional resin layer 15 was prepared by filtration through a 1 ⁇ m filter.
  • 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
  • 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. .
  • ⁇ 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.
  • NXT polyurea resin manufactured by Tribex Corporation (ICRX NXT)
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ W / 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%, ⁇ : 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.
  • the amount of return was determined by obtaining a value (%) obtained by subtracting dimming property (%) from recoverability (%) and evaluated as follows.
  • ⁇ 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, ⁇ : Streaks are observed but there are no problems in use, ⁇ : Streaks and cracks are problematic in use.
  • 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), ⁇ : 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.
  • 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 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.
  • 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.
  • 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.
  • 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 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
  • 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.
  • 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.
  • 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.

Landscapes

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

Abstract

L'invention concerne un élément optique de modulation de lumière qui permet de raccourcir le temps de décoloration par l'intermédiaire d'une interaction avec une résine synthétique. Cet élément optique de modulation de lumière est utilisé en tant que matériau de verres de lunettes dans lequel une couche de résine fonctionnelle (15) est intégrée à un ou aux deux côtés d'un substrat de verre organique (11) fabriqué en résine moulée, la couche de résine fonctionnelle (15) renfermant un agent photochromique et un di(méth)acrylate A de bisphénol polyalkylène modifié par le glycol représenté par la formule générale (1). L'énergie de transition dans l'agent photochromique ayant subi une transition suite à l'irradiation avec de la lumière (ultraviolette) est facilement convertie en énergie thermique et reçue par le di(méth)acrylate A de bisphénol polyalkylène modifié par le glycol représenté par la formule générale (1) après l'arrêt de l'irradiation, ce qui permet de raccourcir le temps de décoloration.
PCT/JP2017/016157 2016-08-23 2017-04-24 Élément optique de modulation de lumière Ceased WO2018037621A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-162954 2016-08-23
JP2016162954 2016-08-23

Publications (1)

Publication Number Publication Date
WO2018037621A1 true WO2018037621A1 (fr) 2018-03-01

Family

ID=61246478

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/016157 Ceased WO2018037621A1 (fr) 2016-08-23 2017-04-24 Élément optique de modulation de lumière

Country Status (1)

Country Link
WO (1) WO2018037621A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025109980A1 (fr) * 2023-11-20 2025-05-30 三井化学株式会社 Élément optique et procédé de fabrication d'élément optique

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11511765A (ja) * 1994-12-12 1999-10-12 コーニング インコーポレイテッド 温度安定性および耐日光性のあるフォトクロミック製品
JP2001188206A (ja) * 1999-12-28 2001-07-10 Hoya Corp フォトクロミックレンズ
JP2011145513A (ja) * 2010-01-15 2011-07-28 Ito Kogaku Kogyo Kk 偏光素子
WO2012141306A1 (fr) * 2011-04-13 2012-10-18 Hoya株式会社 Lentille photochromique pour lunettes
WO2013129531A1 (fr) * 2012-02-29 2013-09-06 Hoya株式会社 Composition de revêtement et son procédé de fabrication, lentille en plastique et son procédé de fabrication.
WO2014125738A1 (fr) * 2013-02-15 2014-08-21 伊藤光学工業株式会社 Procédé de production de lentille de résine
WO2017029825A1 (fr) * 2015-08-20 2017-02-23 伊藤光学工業株式会社 Matériau pour lunettes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11511765A (ja) * 1994-12-12 1999-10-12 コーニング インコーポレイテッド 温度安定性および耐日光性のあるフォトクロミック製品
JP2001188206A (ja) * 1999-12-28 2001-07-10 Hoya Corp フォトクロミックレンズ
JP2011145513A (ja) * 2010-01-15 2011-07-28 Ito Kogaku Kogyo Kk 偏光素子
WO2012141306A1 (fr) * 2011-04-13 2012-10-18 Hoya株式会社 Lentille photochromique pour lunettes
WO2013129531A1 (fr) * 2012-02-29 2013-09-06 Hoya株式会社 Composition de revêtement et son procédé de fabrication, lentille en plastique et son procédé de fabrication.
WO2014125738A1 (fr) * 2013-02-15 2014-08-21 伊藤光学工業株式会社 Procédé de production de lentille de résine
WO2017029825A1 (fr) * 2015-08-20 2017-02-23 伊藤光学工業株式会社 Matériau pour lunettes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025109980A1 (fr) * 2023-11-20 2025-05-30 三井化学株式会社 Élément optique et procédé de fabrication d'élément optique

Similar Documents

Publication Publication Date Title
JP5824218B2 (ja) 防眩光学要素
KR101761828B1 (ko) 광학수지 조성물 및 이를 이용한 광학용 렌즈
US7035010B2 (en) Polarized lenses with variable transmission
JP5650963B2 (ja) 保護眼鏡用遮光レンズ
EP1243621B1 (fr) Matiere a base de plastique
US8084133B2 (en) Tintable film-forming compositions having high refractive indices and coated optical articles using same
WO2012165050A1 (fr) Élément optique antireflet
JP2008281973A (ja) 赤外線吸収性眼鏡用レンズおよびその製造方法
KR102074604B1 (ko) 광학 재료용 중합성 조성물의 제조 방법 및 광학 재료의 제조 방법
JP2014032273A (ja) フォトクロミックレンズ
CN108026277A (zh) 光学材料用聚合性组合物、光学材料、光学材料用聚合性组合物的制造方法及光学材料的制造方法
KR20170008679A (ko) 전자기파 차단용 광학 조성물 및 이로부터 광학 렌즈의 제조 방법
WO2018123077A1 (fr) Élément optique
JP7540625B2 (ja) 光学材料、光学材料用重合性組成物、プラスチックレンズ、アイウェア及び光学センサー
US8474973B2 (en) Infrared absorbing polarized eyeglass lens
EP3327488A1 (fr) Article d'optique comportant un colorant résistant à la photodégradation
WO2018037621A1 (fr) Élément optique de modulation de lumière
JP2012173675A (ja) レンズの製造方法
CN113692552B (zh) 光学材料
KR20210139235A (ko) 더 넓은 근적외선 커트 및 보다 양호한 미감을 위한 근적외선 염료의 혼합물을 포함하는 광학적 요소
WO2018124063A1 (fr) Élément optique et son procédé de production
JP7254168B2 (ja) 光学材料、光学材料用重合性組成物、プラスチックレンズ、アイウェア、赤外線センサー及び赤外線カメラ
WO2018008179A1 (fr) Matériau de lunettes
JP6692249B2 (ja) 眼鏡素材
EP3951481A1 (fr) Composition de revêtement pour articles optiques, verre de lunettes, lunettes, procédé de fabrication de verre de lunettes, article optique et procédé de fabrication d'article optique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17843111

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 17843111

Country of ref document: EP

Kind code of ref document: A1