WO2021132559A1 - Composition polymérisable pour matériaux optiques, objet moulé à partir de ladite composition et application d'utilisation associée - Google Patents

Composition polymérisable pour matériaux optiques, objet moulé à partir de ladite composition et application d'utilisation associée Download PDF

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Publication number
WO2021132559A1
WO2021132559A1 PCT/JP2020/048717 JP2020048717W WO2021132559A1 WO 2021132559 A1 WO2021132559 A1 WO 2021132559A1 JP 2020048717 W JP2020048717 W JP 2020048717W WO 2021132559 A1 WO2021132559 A1 WO 2021132559A1
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Prior art keywords
compound
polymerizable composition
optical material
acid
polyol
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PCT/JP2020/048717
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English (en)
Japanese (ja)
Inventor
リベイロ，ニジェル
伸介 伊藤
河戸　伸雄
駿一 内藤
貴行 塙
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三井化学株式会社
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Priority claimed from JP2019235967A external-priority patent/JP2023011059A/ja
Priority claimed from JP2020031316A external-priority patent/JP2023011060A/ja
Application filed by 三井化学株式会社 filed Critical 三井化学株式会社
Publication of WO2021132559A1 publication Critical patent/WO2021132559A1/fr

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    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • G02C7/00—Optical parts
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses

Definitions

  • the present invention relates to a polymerizable composition for an optical material, a molded product obtained from the composition, and its use.
  • plastic lenses are lightweight, hard to break, and can be dyed, they are rapidly becoming widespread as optical materials for spectacle lenses, camera lenses, etc., and molded bodies for lenses using various plastic materials have been developed and used so far. ing.
  • Typical examples include an allyl resin obtained from diethylene glycol bisallyl carbonate or diallyl isophthalate, a (meth) acrylic resin obtained from (meth) acrylate, and a polythiourethane resin obtained from an isocyanate compound and a thiol compound. ..
  • Patent Document 1 discloses a polymerizable composition for an optical material, which comprises a compound having one or more mercapto groups, an aliphatic linear oligomer having a number average molecular weight of 200 or more, an isocyanate compound, and the like. .. The document describes that aliphatic linear oligomers such as polycaptolactone diols function as soft segments.
  • Patent Document 2 discloses a polymerizable composition for an optical material, which comprises a block copolymer, a photochromic compound, and a polythiol and polyiso (thio) cyanate compounds.
  • Patent Document 3 discloses a polymerizable composition for an optical material, which comprises a polyether polyol, a photochromic compound, and a polythiol and a polyiso (thio) cyanate compound.
  • Patent Document 4 describes that p-toluenesulfonic acid and the like have an effect of improving the pot life of polyurethane.
  • Patent Document 4 does not describe the use of polyols (polyether polyols, polyester polyols).
  • the present inventors can solve the above-mentioned problems by using a polyol compound, a polymerization-reactive compound other than the polyol compound, and an acid having a pKa of a predetermined value or an anhydride thereof in combination. And completed the present invention.
  • Composition [4] The polymerizable composition for an optical material according to any one of [1] to [3], which contains 200 ppm or more of an acid (b1).
  • R 1 represents an alkyl group of C1 to C5, a haloalkyl group of C1 to C5, and a substituted or unsubstituted phenyl group.
  • R 2 represents a hydrogen atom, an alkyl group of C1 ⁇ C5, a haloalkyl group of C1 ⁇ C5, a substituted or unsubstituted phenyl group.
  • X is a carbon atom and R 1 is a haloalkyl group of C1 to C5.
  • Q represents a divalent group derived from a diol, or a 3 to 30 valent group derived from a polyol having at least three primary alcohol groups, and m is 3 to 30.
  • An integer of 10 is indicated, n is an integer of 2 to 200, and the number of multiple ns existing may be the same or different.
  • Q indicates an integer of 2 to 30.
  • the polyiso (thio) cyanate compound is an aliphatic polyiso (thio) cyanate compound, an alicyclic polyiso (thio) cyanate compound, or an aromatic polyiso (thio) cyanate compound [1] to [12].
  • the polymerizable composition for an optical material according to any one of.
  • a primer coat layer is provided between the lens base material and the hard coat layer.
  • An optical material comprising the molded product according to any one of [17] to [19] or the laminate according to [20] or [21].
  • a plastic lens made of the molded product according to any one of [17] to [19] or the laminated body according to [19] or [20].
  • At least one polyol compound selected from (a) polyether polyol (a1) and polyester polyol (a2), (b1) an acid having a pKa of less than 0, and (c) a polyiso (thio) cyanate compound.
  • a method for producing a polymerizable composition for an optical material which comprises a polymerization-reactive compound (excluding polyol (a)) containing a bifunctional or higher active hydrogen compound.
  • a method for producing a polymerizable composition for an optical material which comprises. [25] At least one polyol compound selected from (a) polyether polyol (a1) and polyester polyol (a2), (b1) an acid having a pKa of less than 0, and (c) a polyiso (thio) cyanate compound.
  • a method for producing a polymerizable composition for an optical material which comprises a polymerization-reactive compound (excluding polyol (a)) containing a bifunctional or higher active hydrogen compound and (e) an internal release agent.
  • a polythiol compound is contained as the bifunctional or higher active hydrogen compound, and the compound is contained.
  • An acid (b1) having a pKa of less than 0 is mixed with the mixed solution obtained in the above step, and then a polythiol compound is mixed.
  • a method for producing a polymerizable composition for an optical material which comprises.
  • Example a1 It is a TEM photograph of the molded article prepared in Example a1. It is a TEM photograph of the molded article prepared in Example a2. It is a TEM photograph of the molded article prepared in Example a3. It is a TEM photograph of the molded article prepared in Example a4. It is a TEM photograph of the molded article prepared in Example a5. It is a TEM photograph of the molded article prepared in Example a6. It is a TEM photograph of the molded article prepared in the comparative example a1.
  • the polymerizable composition for an optical material of the present invention is At least one polyol compound (a) selected from the polyether polyol (a1) and the polyester polyol (a2), and At least one compound (b) selected from an acid (b1) having a pKa of less than 0 and an anhydride (b2) of an acid having a pKa of less than 0.
  • the polymerizable composition for an optical material of the present invention may further contain an internal mold release agent (d), a tin catalyst (e), a photochromic compound (f) and the like.
  • an internal mold release agent d
  • a tin catalyst e
  • a photochromic compound f
  • the components described in the following embodiments can be used.
  • the present invention will be described with reference to the first embodiment and the second embodiment.
  • the same components are designated by the same reference numerals, and the description thereof will be omitted as appropriate.
  • the polymerizable composition for an optical material of the present embodiment is At least one polyol compound (a) selected from the polyether polyol (a1) and the polyester polyol (a2), and Acids with a pKa of less than 0 (b1) and A polymerization-reactive compound (c) (excluding the polyol compound (a)) and.
  • a plastic lens is required to have excellent impact resistance in order to prevent cracking due to an impact such as dropping. Further, the plastic lens is also required to have excellent dyeability from the viewpoint of fashionability and the like.
  • Patent Documents 1 to 4 there is room for improvement in both impact resistance and dyeability. Further, the polymerizable composition obtained by mixing each component may have a high thickening rate after mixing, and there is room for improvement in handleability (pot life).
  • the polymerizable composition for optical materials of the present embodiment it is possible to obtain a molded product having excellent handleability (pot life), impact resistance and dyeability. Further, the polymerizable composition for an optical material of the present invention is excellent in handleability (pot life), is also excellent in transparency, heat resistance, impact resistance and dyeability, and is capable of generating optical strain (pulse). It is possible to obtain a molded product that is suppressed, has excellent light resistance, and has an excellent balance of these characteristics.
  • the polyol compound (a) of the present embodiment comprises at least one selected from the polyether polyol (a1) and the polyester polyol (a2).
  • the weight average molecular weight of the polyol compound (a) can be 2000 or more, preferably 5000 or more, and more preferably 10000 or more. Further, from the viewpoint of maintaining good transparency of the resin, it can be set to 20000 or less, preferably 15000 or less.
  • polyether polyol (a1) As the polyether polyol (a1), a known compound can be used as long as the effects of the present invention can be obtained.
  • the polyether polyol (a1) can contain a compound represented by the following general formula (a1).
  • R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom.
  • R 1 each other there are two or more may be the same or different, R 2 each other existing in plural numbers may be the same or different.
  • m represents an integer of 15 or more and 500 or less.
  • the compound represented by the general formula (a1) can have a weight average molecular weight of 2000 or more, preferably 5000 or more, and more preferably 10000 or more. Further, from the viewpoint of maintaining good transparency of the resin, it can be set to 20000 or less, preferably 15000 or less.
  • one or a combination of two or more selected from the compounds represented by the general formula (a1) can be used as the polyether polyol (a1).
  • a compound represented by the following general formula (a1-1) can be specifically used.
  • R 3 and R 4 represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom.
  • a + c is an integer of 2 or more and 499 or less, preferably 2 or more and 400 or less
  • b is an integer of 1 or more and 300 or less, preferably 1 or more and 100 or less.
  • a plurality of R 3 and R 4 may be the same or different.
  • Examples of such compounds include the Pluronic series manufactured by BASF.
  • the structure of the compound contained in Pluronic is shown in Non-Patent Document 1.
  • the terminal hydroxyl group of the compound represented by the general formula (a1) may react with the polymerizable compound (c) such as isocyanate.
  • the compound represented by the following general formula (a1-2) or the following general formula (a1-3) can be used as the compound represented by the general formula (a1-1).
  • a, b, and c each indicate the number of units, and each is an integer of 3 or more and 300 or less independently.
  • Examples of such compounds include the Pluronic series (manufactured by BASF).
  • a, b, and c each indicate the number of units, and each is an integer of 3 or more and 300 or less independently.
  • Examples of such compounds include the Pluronic R series (manufactured by BASF).
  • polyester polyol (a2) As the polyester polyol (a2), a known compound can be used as long as the effects of the present invention can be obtained.
  • the polyester polyol (a2) can contain a compound represented by the following general formula (a2).
  • Q represents a divalent group derived from a diol, or a 3 to 30 valent group derived from a polyol having at least three primary alcohol groups, and m is 3 to 10 Indicates an integer of, n indicates an integer of 2 to 200, and the number of n that exists may be the same or different. q indicates an integer of 2 to 30.
  • the oxygen atom directly connected to Q is an oxygen atom derived from a diol or an oxygen atom derived from a polyol.
  • diol examples include ethylene glycol, propylene glycol, neopentyl glycol, 1,2-propanediol, 1,4-butanediol, and 1,6-hexanediol.
  • polyol having at least three primary alcohol groups examples include trimethylolpropane, pentaerythritol, dipentaerythritol and the like.
  • a compound having a weight average molecular weight of 1000 or more, preferably 2000 or more, and more preferably 3000 or more can be used from the viewpoint of the effect of the present embodiment. Further, from the viewpoint of maintaining good transparency of the resin, it can be 10,000 or less, preferably 5,000 or less.
  • CAPA polycaprolactone polyol series manufactured by PERSTORP, PLACCEL series manufactured by DEICEL, and the like can be used. These alcohol compounds may be used alone or as a mixture of two or more.
  • polyether polyol (a1) represented by the general formula (a1) and the polyester polyol (a2) represented by the general formula (a2) can be used in combination.
  • the polymerizable composition for an optical material of the present embodiment has handleability (pot life) because thickening is suppressed by using an acid (b1) having a pKa of less than 0 together with the component (a) and the component (c). ), And a molded product having excellent impact resistance and dyeability can be obtained.
  • the acid (b1) having a pKa of less than 0 hydrochloric acid (pKa: -3.7), methanesulfonic acid (pKa: -2.6), and p-toluenesulfonic acid (pKa: -2. 8), vinyl sulfonic acid (pKa: -2.7) and the like can be mentioned, with hydrochloric acid, methane sulfonic acid, p-toluene sulfonic acid and vinyl sulfonic acid being preferable, and hydrochloric acid, methane sulfonic acid and vinyl sulfonic acid being more preferable. preferable.
  • the acid (b1) having a pKa of less than 0 can include at least one selected from these.
  • thickening is suppressed, so that a polymerizable composition for an optical material having excellent handleability (pot life) can be obtained, and the composition has more impact resistance and dyeability.
  • An excellent molded product can be obtained.
  • the polymerizable composition for an optical material of the present embodiment can contain an acid (b1) having a pKa of less than 0 from the viewpoint of the effect of the present embodiment at 200 ppm or more, preferably 300 ppm or more, and more preferably 500 ppm or more. ..
  • the upper limit is not particularly limited, but from the viewpoint of handleability of the polymerizable composition for optical materials, it can be 5000 ppm or less, preferably 3000 ppm or less, and more preferably 2000 ppm or less.
  • Polymerization-reactive compound (c) A polymerizable functional group capable of self-polymerization, copolymerization, or addition polymerization in the presence or absence of an initiator and an additive such as a catalyst added to the polymerization-reactive compound (c) as needed.
  • a polymerization-reactive compound having at least one of the above is included.
  • the polymerization-reactive compound (c) does not contain the polymer (a).
  • polymerization-reactive compound a known compound can be used as long as the effects of the present invention can be obtained.
  • a polyiso (thio) cyanate compound having two or more isocyanato groups or isothiocyanato groups, an epoxy group or a thioepoxy group.
  • the polymerization-reactive compound (c) contains the polyiso (thio) cyanate compound and the bifunctional or higher active hydrogen compound.
  • polyiso (thio) cyanate compound examples include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.
  • An aliphatic polyisocyanate compound such as lysine diisocyanatomethyl ester, lysine triisocyanate, xylylene diisocyanate; Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) ) Bicyclo- [2.2.1] -heptane, 3,8-bis (isocyanatomethyl) tricyclodecane, 3,9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) ) Alicyclic polyisocyanate compounds such as tricyclodecane, 4,9-bis (isocyanatomethyl) tricyclodecane; Aromatic polyisocyanate compounds such as tolylene di
  • bifunctional or higher active hydrogen compound examples include a poly (thio) all compound having two or more hydroxy groups or mercapto groups, a polyamine compound having two or more amino groups or secondary amino groups, and a poly having two or more carboxyl groups. Examples thereof include carboxylic acid compounds. Further, a compound having two or more active hydrogen groups selected from a hydroxy group, a mercapto group, an amino group, a second amino group, a carboxyl group and the like in one molecule can also be mentioned. Two or more active hydrogen groups may be the same or different.
  • polyol compound examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, methanolyl glycol, glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, butanetriol, 1,2-.
  • Methylglucoside pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, sreitol, ribitol, arabinitol, xylitol, aritol, manitol, zulcitol, iditol, glycol, inositol, hexanetriol, triglycerose, diglycerol, triethylene Glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5.2.1.
  • polythiol compounds examples include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, and diethylene glycol bis.
  • the polymerizable composition for an optical material of the present invention may further contain an internal mold release agent (d) for the purpose of improving the mold release property from the mold after molding.
  • the internal mold release agent (d) is not particularly limited, and conventionally known ones can be used, and examples thereof include acidic phosphoric acid esters. Examples of the acidic phosphoric acid ester include phosphoric acid monoester and phosphoric acid diester, which can be used alone or in combination of two or more.
  • ZelekUN manufactured by STEPAN
  • internal mold release agent for MR manufactured by Mitsui Chemicals
  • JP series manufactured by Johoku Chemical Industry Co., Ltd.
  • Phosphanol series manufactured by Toho Chemical Industry Co., Ltd.
  • Daihachi Chemical Industry Co., Ltd. AP DP series and the like manufactured by Kogyo Co., Ltd.
  • ZelekUN manufactured by STEPAN
  • an internal mold release agent for MR manufactured by Mitsui Chemicals Co., Ltd.
  • JP series manufactured by Johoku Chemical Industry Co., Ltd. are more preferable.
  • the amount of the internal mold release agent (d) used is not particularly limited, but is in the range of 0.0001 to 10 parts by weight with respect to 100 parts by weight of the polymerizable composition for optical materials.
  • the polymerizable composition for an optical material of the present embodiment may further contain a tin catalyst (e). ..
  • a tin catalyst (e) When the tin catalyst (e) is contained, the polymerizable composition for optical materials tends to thicken and the pot life tends to be shortened, but the polymerizable composition for optical materials of the present embodiment has an acid (b1) having a pKa of less than 0. ) Is included, so it is excellent in the effect of suppressing thickening, and the pot life can be improved while making the best use of the catalytic performance of the tin catalyst.
  • tin catalyst (e) examples include dibutyl tin dilaurate, dibutyl tin dichloride, dimethyl tin dichloride, and the like, and one or more of them can be used in combination.
  • the amount of the tin catalyst (e) used is not particularly limited, but is in the range of 0 to 10 parts by weight with respect to 100 parts by weight of the polymerization-reactive compound (c).
  • the polymerizable composition for an optical material of the present embodiment can further contain a photochromic compound (f).
  • Examples of the photochromic compound (f) include compounds whose absorption characteristics (absorption spectrum) change with respect to light of a specific wavelength.
  • Known photochromic compounds can be used, for example, naphthopyran, chromene, spiropyran, spiroxazine and thiospiropirane, benzopyran, stilbene, azobenzene, thioindigo, bisimidazole, spirodihydroindidine, quinine, perimidine spiro
  • Examples include compounds derived from compounds such as cyclohexadienone, viologen, flugide, flugimid, diarylethene, hydrazine, aniline, aryldisulfide, arylthiosulfonate, spiroperimidine, triarylmethane.
  • the component (d) added as needed, the component (e) or the component (f), ultraviolet absorption is absorbed. It may further contain an agent, a light stabilizer, a polymerization catalyst, a resin modifier and the like.
  • the polymerizable composition for an optical material of the present embodiment can be obtained by mixing the above components by a conventionally known method.
  • the polymerization-reactive compound (c) contains a polyiso (thio) cyanate compound and a bifunctional or higher functional hydrogen compound, the following from the viewpoint of handleability and obtaining a desired composition, the following Can be obtained by the method.
  • a polyiso (thio) cyanate compound, a polyol compound (a), and an acid (b1) having a pKa of less than 0 are mixed to prepare a mixed solution, and then a bifunctional or higher active hydrogen is added to the mixed solution.
  • a bifunctional or higher active hydrogen compounds may be added to the mixed solution all at once, or may be added gradually.
  • the polymerizable composition for an optical material of the present embodiment contains an internal mold release agent (d), and the polymerization reactive compound (c) is a polyiso (thio) cyanate compound and a bifunctional or higher functional hydrogen compound.
  • the polythiol compound When the polythiol compound is contained, it can be obtained by the following method from the viewpoint of handleability and obtaining a desired composition.
  • the internal mold release agent (d) and the polyiso (thio) cyanate compound are mixed, and then the polyol compound (a) is mixed. Then, an acid (b1) having a pKa of less than 0 is mixed with the obtained mixed solution, and then a polythiol compound is mixed.
  • the polyol compound (a) and the acid (b1) may be added to the mixed solution all at once, or may be added gradually.
  • a molded product can be obtained by curing the polymerizable composition for an optical material.
  • the molded product of the present embodiment contains a microphase-separated structure of the polyol compound (a). Since the molded product contains a microphase-separated structure, it is superior in impact resistance and dyeability.
  • the impact absorption and hydrophilicity are improved by including the micro-phase separation structure in the molded body, especially in the vicinity of the surface of the molded body. As a result, it is considered to be superior in impact resistance and dyeability.
  • the microphase-separated structure tends to be unevenly distributed near the surface of the molded product, and it is considered that the shock absorption and hydrophilicity are further improved.
  • the average particle size of the microphase-separated structure is 1 to 50 nm, preferably 2 to 30 nm, and more preferably 5 to 20 nm from the viewpoint of the effect of the present embodiment. The average particle size can be measured by cross-sectional TEM analysis.
  • the molded product of the present embodiment can be used as various optical materials by forming a desired shape and providing a coat layer, other members, or the like formed as needed.
  • the optical material examples include a plastic lens, a light emitting diode (LED), a prism, an optical fiber, an information recording substrate, a filter, and the like.
  • a plastic lens it is suitable as a plastic lens.
  • the plastic lens made of the molded product of the present embodiment will be described.
  • the plastic lens can be manufactured as follows.
  • the plastic lens of the present embodiment is usually produced by a casting polymerization method using the above-mentioned polymerizable composition for an optical material.
  • the method for producing a plastic lens of the present embodiment includes a step of forming a lens base material by cast polymerization of a polymerizable composition for an optical material.
  • the obtained composition of the present embodiment is injected into a cavity composed of a glass mold and a gasket or tape, and is polymerized and cured by heating or irradiating with radiation such as ultraviolet rays other than infrared rays.
  • a resin of the form and a plastic lens base material made of the resin are manufactured.
  • the polymerization-reactive compound (c) polymerizes to form a resin, and the polymer (a) forms a microphase-separated structure, and the resin, the microphase-separated structure, and the acid (b1) are combined.
  • a plastic lens base material made of the above can be obtained.
  • the polymerization conditions are not limited because they differ greatly depending on the polymerizable composition for optical materials, the type and amount of catalyst used, the shape of the mold, etc., but are not limited, but are approximately 1 to 150 ° C. It takes 50 hours.
  • the lens base material obtained by removing the mold from the mold may be reheated (annealed) as necessary for the purpose of completing polymerization or removing strain due to residual stress.
  • a laminated body may be provided in which a hard coat layer and an antireflection layer are provided in this order on a lens base material made of a molded product. From the viewpoint of impact resistance, it is also preferable to provide a primer coat layer between the lens base material and the hard coat layer.
  • the coating agent used for the primer layer examples include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, polyethylene and polypropylene.
  • a coating agent containing a polyolefin resin or a copolymer or a modified resin thereof, a resin such as a cellulose resin as the main component of the vehicle can be used.
  • the laminated body can be provided with a functional coat layer such as a dimming coat layer and an antistatic coat as other layers. Furthermore, various functions such as dyeing for fashionability, polishing of the surface and edges, and putting a polarizing film inside or sticking to the surface for the purpose of imparting polarization. Processing or the like that imparts sex may be performed.
  • a functional coat layer such as a dimming coat layer and an antistatic coat as other layers.
  • various functions such as dyeing for fashionability, polishing of the surface and edges, and putting a polarizing film inside or sticking to the surface for the purpose of imparting polarization. Processing or the like that imparts sex may be performed.
  • the surface of the obtained lens base material was subjected to corona treatment, ozone treatment, oxygen gas, nitrogen gas, or the like.
  • Physical or chemical treatments such as low temperature plasma treatment, glow discharge treatment, oxidation treatment with chemicals, flame treatment and the like can also be performed.
  • the plastic lens of the present embodiment made of the molded body or laminated body thus obtained can be used for various lens applications such as a glasses lens, a camera lens, a pickup lens, a fullnel lens, a prism lens, and a lenticular lens.
  • lens applications such as a glasses lens, a camera lens, a pickup lens, a fullnel lens, a prism lens, and a lenticular lens.
  • particularly preferable applications include spectacle lenses, camera lenses, and pickup lenses having a smooth surface.
  • the polymerizable composition for an optical material of the present embodiment is with a polyether polyol (a1), At least one compound (b) selected from an acid (b1) having a pKa of less than 0 and an anhydride (b2) of an acid having a pKa of less than 0.
  • the polymerizable composition for an optical material of the present invention is excellent in handleability (pot life) by containing these components.
  • Polyether polyol (a1) As the polyether polyol (a1), a known compound can be used as long as the effects of the present invention can be obtained.
  • polyether polyol (a1) comprises at least one segment of the polyether and is either polyester, polycarbonate, poly (meth) acrylate, polyamide, polyethyleneimine, polysiloxane, polysulfide, polyolefin, or polystyrene.
  • polyether polyol (a1) is a linear polyether block copolymer having at least two different segments.
  • the structure of the segment has a divalent organic group derived from ethylene glycolate, propylene glycolate, butylene glycolate and the like, and a divalent organic group derived from thiolates such as ethanedithiolate and propanedithiolate.
  • the segment structure can be mentioned.
  • the polyether block copolymer is a branched block copolymer such as a dendrimer, a star block copolymer, a graft block copolymer or the like.
  • Branched block copolymers may have at least three branched chains made from a combination of at least two different segments.
  • the structure of the branched chain portion includes, for example, a trivalent organic group derived from glycerol, trioxyethylamine, trioxyethyl (alkyl) ammonium salt, etc., and a tetravalent organic group derived from ethylenediamine, alkylammonium salt, etc.
  • Tetraoxyethylenediamine Tetraoxyethylenediamine, tetravalent organic group derived from oxy form of pentaerythritol, hexavalent organic group derived from oxy form of dipentaerythritol, etc., structure having trivalent or higher organic group Can be mentioned.
  • the polyether is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, and polybutylene glycol.
  • the polyester includes, but is not limited to, a composition obtained from the condensation of a dicarboxylic acid and a diol. Examples of the dicarboxylic acid include adipic acid, succinic acid and the like, or a combination thereof.
  • diol examples include ethylene-1,2-diol, butane-1,4-diol, hexane-1,6-diol, propane-1,2-diol, 3-methylpentane-1,5-diol, and 2-.
  • polyester examples include polycaprolactone, polybutyrolactone, polyvalerolactone, polylactic acid, polyglycolic acid, or a combination thereof.
  • the polycarbonate is not particularly limited, and examples thereof include a composition obtained by condensation of carbonate and diol.
  • diol examples include ethylene-1,2-diol, butane-1,4-diol, hexane-1,6-diol, propane-1,2-diol, 3-methylpentane-1,5-diol, and 2-.
  • Methylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, pentane-1,5-diol, heptane-1,7-diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene Glycol and the like, or a combination thereof can be mentioned.
  • the poly (meth) acrylate is not particularly limited, but is limited to methyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and benzyl.
  • (Meta) acrylate, phenyl (meth) acrylate and the like, or a combination thereof can be mentioned.
  • the polyamide is not particularly limited, and examples thereof include a composition obtained by condensation of a dicarboxylic acid and a diamine.
  • examples of the dicarboxylic acid include adipic acid, succinic acid and the like, or a combination thereof.
  • examples of the diamine include hexamethylenediamine and the like.
  • polyamide examples include lactam such as polycaprolactam.
  • polyethyleneimine chain which is a polymer chain examples include a polyethyleneimine chain, a polypropionyl aziridine chain, a polyacetyl aziridine chain, and a polyformyl aziridine chain.
  • polysiloxane chain which is a polymer chain
  • examples of the polysiloxane chain include a polydimethylsiloxane chain and a polymethylphenylsiloxane chain.
  • the polysulfide may contain a polyethylene sulfide chain or the like.
  • examples of the polyolefin include polyethylene, polypropylene and the like, or a combination thereof.
  • examples of the polystyrene include polystyrene, polystyrene sulfonate, and the like, or a combination thereof.
  • the polyether block copolymer of the present embodiment can preferably form micelles by microphase separation and provide a uniformly dispersed nano-sized structure.
  • the micellar structure may be contained in the cured polyurethane thermosetting resin or may be formed during the curing process.
  • the morphology of micelles depends on the nature, concentration, and temperature of the block copolymer and can include, for example, spherical, worm-like, and vesicular.
  • the micellar structure contributes to useful properties such as improved resin toughness, and is effective for functional molecules such as photochromic dyes while maintaining the glass transition temperature, mechanical and optical properties of poly (thio) urethane resins. Can be dispersed in.
  • the polyether polyol (a1) can contain the compound represented by the general formula (a1) in the first embodiment. Since the compound represented by the general formula (a1) is the same as that of the first embodiment, the description thereof will be omitted.
  • the compound (b) is at least one selected from an acid (b1) having a pKa of less than 0 and an anhydride (b2) of an acid having a pKa of less than 0.
  • the acid (b1) having a pKa of less than 0 the compound exemplified in the first embodiment can be used.
  • the anhydride (b2) of the acid having a pKa of less than 0 a known compound can be used as long as the effect of the present invention can be obtained, and the anhydride of the acid (b1) can be mentioned.
  • Examples of the compound (b) include a compound (b') represented by the following general formula (1), and one kind or a mixture of two or more kinds can be used. In this embodiment, it is preferable to include compound (b').
  • n represents 0 or 1.
  • R 1 represents an alkyl group of C1 to C5, a haloalkyl group of C1 to C5, and a substituted or unsubstituted phenyl group.
  • R 2 represents a hydrogen atom, an alkyl group of C1 ⁇ C5, a haloalkyl group of C1 ⁇ C5, a substituted or unsubstituted phenyl group.
  • Examples of the substituent of the substituted phenyl group include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, an alkyl group of C1 to C3, a haloalkyl group of C1 to C3, and the like.
  • the compound (b') contains at least one selected from methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic anhydride, and methanesulfonic acid anhydride.
  • the polymerizable composition for an optical material of the present embodiment contains the compound (b') in an amount of 10 ppm or more, preferably 50 ppm or more, more preferably 100 ppm or more, from the viewpoint of the effect of the present embodiment.
  • the compound (b') is a compound in which X is a carbon atom and R 1 is a haloalkyl group of C1 to C5 in the general formula (1), or X is a carbon atom and R. 1 is an alkyl group of C1, n is 0, and R 2 is free of acetic acid, which is a hydrogen atom.
  • Examples of the compound excluded from the compound (b') include trifluoroacetic anhydride and the like.
  • the above-mentioned acid (b1) having a pKa of less than 0 and the anhydride (b2) of the acid having a pKa of less than 0 can be mixed and used.
  • the mixing ratio (b1: b2) in that case is not particularly limited, but is 5:95 to 95: 5.
  • the compound (b) is more preferably the compound (b') represented by the general formula (1).
  • the polymerization-reactive compound (c) has a polymerizable functional group capable of self-polymerization, copolymerization, or addition polymerization in the presence or absence of an initiator and an additive such as a catalyst, which are added as necessary. A polymerization-reactive compound having at least one is included.
  • the polymerization-reactive compound (c) does not contain the polyether polyol (a1). Since the polymerization-reactive compound (c) in the present embodiment is the same as that in the first embodiment, the description thereof will be omitted.
  • the polymerizable composition for an optical material of the present invention may further contain an internal mold release agent (d) for the purpose of improving the mold release property from the mold after molding.
  • an internal mold release agent (d) for the purpose of improving the mold release property from the mold after molding.
  • the internal mold release agent (d) the same one as in the first embodiment can be used.
  • the polymerizable composition for an optical material of the present embodiment may further contain a tin catalyst (e). ..
  • the polymerizable composition for optical materials tends to thicken and the pot life tends to be shortened, but the polymerizable composition for optical materials of the present embodiment is anhydrous with an acid having a pKa of less than 0. Since it contains a substance (b2), it has an excellent effect of suppressing thickening, and can improve the pot life while making the best use of the catalytic performance of the tin catalyst.
  • tin catalyst (e) examples include dibutyl tin dilaurate, dibutyl tin dichloride, dimethyl tin dichloride, and the like, and one or more of them can be used in combination.
  • the amount of the tin catalyst (e) used is not particularly limited, but is in the range of 0 to 10 parts by weight with respect to 100 parts by weight of the polymerization-reactive compound (c).
  • the polymerizable composition for an optical material of the present embodiment can further contain a photochromic compound (f).
  • the same compound as in the first embodiment can be used.
  • the component (d) added as needed, the component (e) or the component (f), ultraviolet absorption is absorbed. It may further contain an agent, a light stabilizer, a polymerization catalyst, a resin modifier and the like.
  • the polymerizable composition for an optical material of the present embodiment can be obtained by mixing the above components by a conventionally known method.
  • a molded product can be obtained by curing the polymerizable composition for an optical material.
  • the molded product of the present embodiment can be used as various optical materials by forming a desired shape and providing a coat layer, other members, or the like formed as needed.
  • the optical material examples include a plastic lens, a light emitting diode (LED), a prism, an optical fiber, an information recording substrate, a filter, and the like.
  • a plastic lens it is suitable as a plastic lens.
  • the plastic lens made of the molded product of the present embodiment will be described.
  • the plastic lens can be manufactured as follows.
  • the plastic lens of the present embodiment is usually produced by a casting polymerization method using the above-mentioned polymerizable composition for an optical material.
  • the method for producing a plastic lens of the present embodiment includes a step of forming a lens base material by cast polymerization of a polymerizable composition for an optical material. Each step is the same as that of the first embodiment, and the description thereof will be omitted.
  • the plastic lens of the present embodiment made of the molded body or laminated body thus obtained can be used for various lens applications such as a glasses lens, a camera lens, a pickup lens, a fullnel lens, a prism lens, and a lenticular lens.
  • lens applications such as a glasses lens, a camera lens, a pickup lens, a fullnel lens, a prism lens, and a lenticular lens.
  • particularly preferable applications include spectacle lenses, camera lenses, and pickup lenses having a smooth surface.
  • Example A First, the evaluation method in Example A of the present invention is shown below. ⁇ Evaluation method> -Viscosity: After adjusting the polymerizable composition for an optical material of the present embodiment, stirring was continued at 15 ° C. for 5 hours in a nitrogen atmosphere, and then BROOKFIELD ENGINEERING LABS. INC. The viscosity of the composition was measured using a B-type viscometer (model: LVT) manufactured by the same company.
  • HAZE value Using a haze meter (model number: NDH 2000) manufactured by Nippon Denshoku Kogyo Co., Ltd., the HAZE value of a 2.5 mm thick flat plate resin was measured. If the HAZE value is less than 0.70, it can be used as a lens without any problem.
  • Refractive index (ne), Abbe number ( ⁇ e) Using Shimadzu's Purfrich refractometer KPR-30, wavelength 546.1 nm (mercury e-line), wavelength 480.0 nm (Cd F'line) and wavelength 643.9 nm. The refractive index (ne, nF', nC') at (CdC'line) was measured, and the refractive index (ne) and Abbe number ( ⁇ e) were determined, respectively.
  • Tg The glass transition temperature Tg was measured by the TMA penation method (50 g load, pin tip 0.5 mm ⁇ , heating rate 10 ° C./min).
  • -Relative density Measured by the Archimedes method.
  • a dyeing solution prepared by dissolving 40 g of a dye (BPI gray / Brain Power Inc.) in 1960 g of water is heated to 90 ° C., and a 9.0 mm ⁇ 50.0 mm ⁇ 1.4 mm test piece is immersed for 60 minutes. After that, the transmittance at each wavelength was measured with an ultraviolet-visible spectrophotometer.
  • Example a1 49.56 parts by weight of metaxylylene diisocyanate, 1.50 parts by weight of UV absorber (manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583), 0.30 parts by weight of internal mold release agent (manufactured by Johoku Chemical Co., Ltd .; trade name JP506H) Poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer (manufactured by Sigma Aldrich; trade name: Pluronic F-127) 1.98 weight The part was charged and reacted at 20 ° C. for 1 hour.
  • compositions comprising-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 48. 45 parts by weight were mixed and dissolved to prepare a uniform solution. After defoaming at 400 Pa, it was injected into the molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20 ° C.
  • Example a2 49.58 parts by weight of metaxylylene diisocyanate, 1.50 parts by weight of UV absorber (manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583), 0.30 parts by weight of internal mold release agent (manufactured by Johoku Chemical Co., Ltd .; trade name JP506H) Poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer (manufactured by Sigma Aldrich; trade name: Pluronic F-77) 1.98 weight The part was charged and reacted at 20 ° C. for 1 hour.
  • compositions comprising-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 48. 44 parts by weight were mixed and dissolved to prepare a uniform solution. After defoaming at 400 Pa, it was injected into the molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20 ° C.
  • Example a3 49.61 parts by weight of metaxylylene diisocyanate, 1.50 parts by weight of UV absorber (manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583), 0.30 parts by weight of internal mold release agent (manufactured by Johoku Chemical Co., Ltd .; trade name JP506H) Poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer (manufactured by Sigma Aldrich; trade name: Pluronic L-64) 1.98 weight The part was charged and reacted at 20 ° C. for 1 hour.
  • compositions comprising-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 48. 40 parts by weight were mixed and dissolved to prepare a uniform solution. After defoaming at 400 Pa, it was injected into the molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20 ° C.
  • Example a4 49.61 parts by weight of metaxylylene diisocyanate, 1.50 parts by weight of UV absorber (manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583), 0.30 parts by weight of internal mold release agent (manufactured by Johoku Chemical Co., Ltd .; trade name JP506H) Was mixed and dissolved to prepare a uniform solution, and then 1.98 parts by weight of polycaprolactone diol (manufactured by Perstop; trade name CAPA 2302A) having a weight average molecular weight of 3000 was charged and reacted at 20 ° C. for 1 hour.
  • UV absorber manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583
  • internal mold release agent manufactured by Johoku Chemical Co., Ltd .; trade name JP506H
  • compositions comprising-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 48. 41 parts by weight were mixed and dissolved to prepare a uniform solution. After defoaming at 400 Pa, it was injected into the molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20 ° C.
  • Example a5 39.60 parts by weight of metaxylylene diisocyanate, 1.50 parts by weight of UV absorber (manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583), 0.30 parts by weight of internal mold release agent (manufactured by Johoku Chemical Co., Ltd .; trade name JP506H) Was mixed and dissolved to prepare a uniform solution, and then 1.98 parts by weight of polycaprolactone diol (manufactured by Perstop; trade name CAPA 2403D) having a weight average molecular weight of 4000 was charged and reacted at 20 ° C. for 1 hour.
  • UV absorber manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583
  • internal mold release agent manufactured by Johoku Chemical Co., Ltd .; trade name JP506H
  • compositions comprising-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 48. 42 parts by weight were mixed and dissolved to prepare a uniform solution.
  • a uniform solution obtained by mixing and dissolving 0.0060 parts by weight of dimethyltin dichloride (manufactured by Honjo Chemical Co., Ltd .; trade name Nestin P) as a tin catalyst in 10.0 parts by weight of metaxylylene diisocyanate is added to the prepared solution and mixed. It was dissolved to give a homogeneous solution. After defoaming at 400 Pa, it was injected into the molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20 ° C. to 120 ° C. over 24 hours for polymerization. After the polymerization was completed, it was taken out from the oven and removed from the molding mold.
  • the releasability was good, and no peeling of the mold was observed.
  • the obtained molded product was further annealed at 120 ° C. for 2 hours. As a result of observing the nanodomains of the obtained molded product, it was observed from the TEM photograph that particles having a diameter of 5 to 20 nm were uniformly dispersed in the resin.
  • the composition and the evaluation results of the obtained molded product are shown in Table 1, and the TEM photograph is shown in FIG.
  • Example a6 39.61 parts by weight of metaxylylene diisocyanate, 1.50 parts by weight of UV absorber (manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583), 0.30 parts by weight of internal mold release agent (manufactured by Johoku Chemical Co., Ltd .; trade name JP506H) Was mixed and dissolved to prepare a uniform solution, and then 1.98 parts by weight of polycaprolactone diol (manufactured by Perstop; trade name CAPA 2302A) having a weight average molecular weight of 3000 was charged and reacted at 20 ° C. for 1 hour.
  • UV absorber manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583
  • internal mold release agent manufactured by Johoku Chemical Co., Ltd .; trade name JP506H
  • compositions comprising-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 48. 41 parts by weight were mixed and dissolved to prepare a uniform solution.
  • a uniform solution obtained by mixing and dissolving 0.0060 parts by weight of dimethyltin dichloride (manufactured by Honjo Chemical Co., Ltd .; trade name Nestin P) as a tin catalyst in 10.0 parts by weight of metaxylylene diisocyanate is added to the prepared solution and mixed. It was dissolved to give a homogeneous solution. After defoaming at 400 Pa, it was injected into the molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20 ° C. to 120 ° C. over 24 hours for polymerization. After the polymerization was completed, it was taken out from the oven and removed from the molding mold.
  • the releasability was good, and no peeling of the mold was observed.
  • the obtained molded product was further annealed at 120 ° C. for 2 hours. As a result of observing the nanodomains of the obtained molded product, it was observed from the TEM photograph that particles having a diameter of 5 to 8 nm were uniformly dispersed in the resin.
  • the composition and the evaluation results of the obtained molded product are shown in Table 1, and the TEM photograph is shown in FIG.
  • Example a7 Hydrogen chloride gas was blown into metaxylylene diisocyanate to dissolve it, and a solution having a hydrogen chloride concentration of 3000 ppm was prepared. To 33.3 parts by weight of this solution, 16.3 parts by weight of metaxylylene diisocyanate was added, 1.50 parts by weight of an ultraviolet absorber (manufactured by Kyodo Yakuhin Co., Ltd .; trade name: Biosorb 583), and an internal mold release agent (manufactured by Johoku Chemical Co., Ltd .; Product name JP506H) After mixing and dissolving 0.30 parts by weight to make a uniform solution, polyoxyethylene polyoxypropylene glycol having a weight average molecular weight of 13300 (manufactured by Sigma Aldrich; trade name Pluronic F-127) 1.98 parts by weight Was charged and reacted at 20 ° C.
  • an ultraviolet absorber manufactured by Kyodo Yakuhin Co., Ltd .; trade name: Biosorb 583
  • Example a8 49.56 parts by weight of metaxylylene diisocyanate, 1.50 parts by weight of UV absorber (manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583), 0.30 parts by weight of internal mold release agent (manufactured by Johoku Chemical Co., Ltd .; trade name JP506H)
  • UV absorber manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583
  • internal mold release agent manufactured by Johoku Chemical Co., Ltd .; trade name JP506H
  • To obtain a uniform solution 1.98 parts by weight of polyoxyethylene polyoxypropylene glycol (manufactured by Sigma Aldrich; trade name: Pluronic F-127) having a weight average molecular weight of 13300 was charged, and 1 at 20 ° C. Reacted for time.
  • compositions comprising-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 48. 45 parts by weight were mixed and dissolved to prepare a uniform solution. After defoaming at 400 Pa, it was injected into the molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20 ° C.
  • Example a9 49.56 parts by weight of metaxylylene diisocyanate, 1.50 parts by weight of UV absorber (manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583), 0.30 parts by weight of internal mold release agent (manufactured by Johoku Chemical Co., Ltd .; trade name JP506H)
  • UV absorber manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583
  • internal mold release agent manufactured by Johoku Chemical Co., Ltd .; trade name JP506H
  • polyoxyethylene polyoxypropylene glycol manufactured by Sigma Aldrich; trade name: Pluronic F-127 having a weight average molecular weight of 13300 was charged, and 1 at 20 ° C. Reacted for time.
  • Example a10 39.56 parts by weight of metaxylylene diisocyanate, 1.50 parts by weight of UV absorber (manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583), 0.30 parts by weight of internal mold release agent (manufactured by Johoku Chemical Co., Ltd .; trade name JP506H)
  • UV absorber manufactured by Kyodo Yakuhin Co., Ltd .; trade name Biosorb 583
  • internal mold release agent manufactured by Johoku Chemical Co., Ltd .; trade name JP506H
  • To obtain a uniform solution 1.98 parts by weight of polyoxyethylene polyoxypropylene glycol (manufactured by Sigma Aldrich; trade name: Pluronic F-127) having a weight average molecular weight of 13300 was charged, and 1 at 20 ° C. Reacted for time.
  • compositions comprising-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 48. 45 parts by weight were mixed and dissolved to prepare a uniform solution.
  • a uniform solution obtained by mixing and dissolving 0.0020 parts by weight of dimethyltin dichloride (manufactured by Honjo Chemical Co., Ltd .; trade name Nestin P) as a tin catalyst in 10.0 parts by weight of metaxylylene diisocyanate is added to the prepared solution and mixed. It was dissolved to give a homogeneous solution. After defoaming at 400 Pa, it was injected into the molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20 ° C. to 120 ° C. over 24 hours for polymerization. After the polymerization was completed, it was taken out from the oven and removed from the molding mold. The releasability was good, and no peeling of the mold was observed. The obtained molded product was further annealed at 120 ° C. for 2 hours. Table 1 shows the composition and the evaluation results of the obtained molded product.
  • the releasability was good, and no peeling of the mold was observed.
  • the obtained molded product was further annealed at 120 ° C. for 2 hours. As a result of observing the nanodomains of the obtained molded product, no particles were confirmed in the resin from the TEM photograph.
  • the composition and the evaluation results of the obtained molded product are shown in Table 1, and the TEM photograph is shown in FIG.
  • 0.10 parts by weight of formic acid was mixed and dissolved in the solution to make a uniform solution, and then 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-di.
  • Composition 48.45 weight containing mercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane The parts were mixed and dissolved to prepare a uniform solution. After defoaming at 400 Pa, it was injected into the molding mold. This was put into a polymerization oven, and the temperature was gradually raised from 20 ° C. to 120 ° C.
  • the obtained molded product was further annealed at 120 ° C. for 2 hours.
  • the obtained molded product had a heat resistance of 95 ° C. and was transparent, but many cracks were generated, so that the physical properties could not be evaluated.
  • P1 Poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer (Pluronic F-127 manufactured by Sigma Aldrich) having a weight average molecular weight of 13333.
  • P2 Poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer (Pluronic F-77 manufactured by Sigma Aldrich) having a weight average molecular weight of 6800.
  • P3 Poly (ethylene glycol) poly (propylene glycol) poly (ethylene glycol) block copolymer (Pluronic L-64 manufactured by Sigma Aldrich) having a weight average molecular weight of 2900.
  • P4 Poly (caprolactone) diol having a weight average molecular weight of 3000 (CAPA2302A manufactured by Polyester)
  • P5 Poly (caprolactone) diol having a weight average molecular weight of 4000 (CAPA2403D manufactured by Perstop)
  • the thiourethane urethane molded products of Examples a1 to a10 are excellent in impact resistance and dyeability as compared with Comparative Example a1 which is a thiourethane molded product containing no polyol compound (a) and acid (b1). It was excellent in balance with various physical properties as other optical materials.
  • the thiourethane urethane molded articles of Examples a1 to a10 have a gradual increase in the viscosity of the formulation as compared with the thiourethane urethane molded articles (Comparative Examples a2 to a4) in which an acid having a pKa of 0 or more is used as an additive. Therefore, it is excellent in handleability, can be handled smoothly in the process of manufacturing an optical material, and has an excellent appearance with less occurrence of optical distortion. Further, in the thiourethane urethane molded product to which formic acid was added (Comparative Example a2), a large amount of cracks were generated in the resin during the curing process, and the physical properties could not be evaluated.
  • Example a1 The laminate in which the hard coat layer and the antireflection layer are laminated on the thiourethane urethane molded body of Example a1 is compared with the laminate in which the hard coat layer and the antireflection layer are laminated on the thiourethane urethane molded body of Examples a2 to a10. As a result, it was superior in impact resistance, and the appearance was superior because no veins were confirmed in the molded body itself.
  • the laminate obtained by laminating the primer layer, the hard coat layer and the antireflection layer on the thiourethane urethane molded body of Example a1 and Example a10 is the thiourethane molded body of Comparative Example a1 and the primer layer, the hard coat layer and the antireflection layer. It was superior in impact resistance as compared with the laminated body in which the above was laminated.
  • the thiourethane urethane molded product obtained from the polymerizable composition for optical materials of the present invention is excellent in transparency, heat resistance, impact resistance and dyeability, and the occurrence of optical strain (pulse) is suppressed. It was excellent in light resistance and a good balance of these characteristics.
  • the thiourethane urethane molded product obtained from the polymerizable composition for optical materials of the present invention can be suitably used in various optical materials that require high transparency, especially in spectacle lenses.
  • Example B First, the evaluation method in Example B of the present invention is shown below.
  • -Fading speed t1 / 2 (fading half-life): After irradiating the molded product with light for 15 minutes in the same manner as above, the absorbance of the molded product sample at 550 nm recovers to an intermediate value before and after color development after the light irradiation is stopped. The time (s) required for the above was measured. This time was defined as the fading half-life. A molded product with a fast fading half-life is judged to have good dimming performance.
  • Example b1 2.0 parts by weight of polyol L64 (manufactured by Kaneka) as a polyether polyol (a), 0.2 parts by weight of acidic phosphate ester JP-506H (manufactured by Johoku Chemical Industry Co., Ltd.), and methanesulfonic acid as a compound (b). 0.01 part by weight of (manufactured by Tokyo Kasei Co., Ltd.) and 40.22 parts by weight of metaxylylene diisocyanate were mixed at room temperature.
  • polyol L64 manufactured by Kaneka
  • acidic phosphate ester JP-506H manufactured by Johoku Chemical Industry Co., Ltd.
  • methanesulfonic acid as a compound (b).
  • 0.01 part by weight of (manufactured by Tokyo Kasei Co., Ltd.) and 40.22 parts by weight of metaxylylene diisocyanate were mixed at room temperature.
  • a polymerizable composition was prepared by adding 10 parts by weight of metaxylylene diisocyanate in which 0.005 parts by weight of dimethyltin dichloride (manufactured by Tokyo Kasei) was dissolved. This polymerizable composition is stirred at 20 ° C., and the viscosity of the polymerizable composition after 1 hour, 3 hours, and 5 hours have passed immediately after the preparation of the polymerizable composition is measured using a B-type viscometer (manufactured by Brookfield). And measured. The measurement results are shown in Table-1.
  • Example b1 [Reference Example b1, Examples b2 to b13, Comparative Examples b1 to b10] The description in Example b1 except that the types and amounts of the polyether polyol (a) and the compound (b) and the amount of the tin catalyst (d) added were changed to the values shown in Tables 1 and 2. A polymerizable composition was prepared by the method and the viscosity was measured. The measurement results are shown in Table 4 and Table-5.
  • Example b14 0.078 parts by weight of Reveracol Wembley Gray (manufactured by Vivid) as a photochromic compound (f), 0.064 parts by weight of Reveracol Heath green (manufactured by Vivimed), and polyol L64 (manufactured by Kaneka) 2 as a polyether polyol (a). .0 parts by weight, 0.2 parts by weight of acidic phosphate ester JP-506H (manufactured by Johoku Chemical Industry Co., Ltd.), 0.05 parts by weight of methanesulfonic acid (manufactured by Tokyo Kasei) as compound (b), and metaxylylene.
  • a polymerizable composition by adding 10 parts by weight of methylxylylene diisocyanate in which 0.004 parts by weight of dimethyltin dichloride (manufactured by Tokyo Kasei Co., Ltd.) was dissolved, the polymerizable composition was stirred at 20 ° C. for 1 hour. did.
  • the polymerizable composition was filtered through a 1 ⁇ m PTFE membrane filter while depressurizing at a depressurization degree of 133 to 400 Pa using a vacuum pump, and degassing was performed with a vacuum pump for 40 minutes while stirring until the bubbles disappeared. ..
  • the polymerizable composition was poured into a glass mold having a thickness of 2 mm, and the temperature was raised from room temperature to 120 ° C. in an oven to cure the polymerizable composition to prepare a molded product.
  • the viscosity of the polymerizable composition did not increase rapidly during the preparation of the polymerizable composition, and the polymerizable composition could be injected into the glass mold.
  • the measurement results of the photochromic characteristics are shown in Table-6.
  • Example b15 A molded product was prepared by the method described in Example b14 and the photochromic characteristics were measured, except that the type and the amount of compound (b) added were changed to the values shown in Table 3. The measurement results are shown in Table-6.
  • PEG2000 Polyethylene glycol (weight average molecular weight 2000, manufactured by Sigma Aldrich)
  • PPG2000 Polypropylene glycol (weight average molecular weight 2000, manufactured by Sigma Aldrich)
  • Polyol L64 Block PEG / PPG (manufactured by Kaneka Corporation)
  • DMC Dimethyltin dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • MSA Methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), pKa: -2.6
  • MSANA Sodium methanesulfonate (manufactured by Wako Kagaku)
  • MSAA Methanesulfonic acid anhydride (manufactured by Wako Kagaku)
  • Phosphoric acid Phosphoric acid (manufactured by Wako Kagaku)
  • pKa 2.12 PTSA: p-toluenesulfonic acid (man

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Ophthalmology & Optometry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La composition polymérisable pour matériau optique selon la présente invention contient : au moins un composé polyol (a) choisi parmi (a1) des polyéthers polyols et (a2) des polyesters polyols ; au moins un composé (b) choisi parmi (b1) acides ayant un pKa inférieur à 0 et (b2) des anhydrides d'acides ayant un pKa inférieur à 0 ; et un composé réactif de polymérisation (c) (à l'exclusion du composé polyol (a)) comprenant un composé polyiso(thio)cyanate et un composé d'hydrogène actif ayant deux groupes fonctionnels ou plus.
PCT/JP2020/048717 2019-12-26 2020-12-25 Composition polymérisable pour matériaux optiques, objet moulé à partir de ladite composition et application d'utilisation associée WO2021132559A1 (fr)

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JP2019-235967 2019-12-26
JP2020-031316 2020-02-27
JP2020031316A JP2023011060A (ja) 2020-02-27 2020-02-27 光学材料用重合性組成物、当該組成物から得られる成形体およびその用途

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114921090A (zh) * 2022-06-08 2022-08-19 浙江海正生物材料股份有限公司 一种光学聚乳酸组合物、其制备方法及其用途
WO2024024918A1 (fr) * 2022-07-29 2024-02-01 三井化学株式会社 Composition polymérisable, résine, article moulé, matériau optique et lentille

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Publication number Priority date Publication date Assignee Title
JPH04359008A (ja) * 1991-06-06 1992-12-11 Mitsui Toatsu Chem Inc 反応性遅延方法
JP2001348415A (ja) * 2000-06-05 2001-12-18 Canon Inc ウレタンゴム組成物、クリーニングブレード、クリーニングブレードの製造方法
JP2002351277A (ja) * 2001-05-23 2002-12-06 Canon Inc クリーニングブレード用ウレタン組成物及びその製造方法
WO2017047744A1 (fr) * 2015-09-16 2017-03-23 三井化学株式会社 Corps moulé et composition polymérisable pour matériaux optiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04359008A (ja) * 1991-06-06 1992-12-11 Mitsui Toatsu Chem Inc 反応性遅延方法
JP2001348415A (ja) * 2000-06-05 2001-12-18 Canon Inc ウレタンゴム組成物、クリーニングブレード、クリーニングブレードの製造方法
JP2002351277A (ja) * 2001-05-23 2002-12-06 Canon Inc クリーニングブレード用ウレタン組成物及びその製造方法
WO2017047744A1 (fr) * 2015-09-16 2017-03-23 三井化学株式会社 Corps moulé et composition polymérisable pour matériaux optiques

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114921090A (zh) * 2022-06-08 2022-08-19 浙江海正生物材料股份有限公司 一种光学聚乳酸组合物、其制备方法及其用途
CN114921090B (zh) * 2022-06-08 2023-12-29 浙江海正生物材料股份有限公司 一种光学聚乳酸组合物、其制备方法及其用途
WO2024024918A1 (fr) * 2022-07-29 2024-02-01 三井化学株式会社 Composition polymérisable, résine, article moulé, matériau optique et lentille

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