Classifications

• • 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
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
• • 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
  • G02B1/041—Lenses
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
  • C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
  • C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
• • 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
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
  • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
  • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts
  • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes

Definitions

• the present disclosure relates to polythiol compositions and their applications.
• Plastic lenses which are lenses containing resin, are lighter than inorganic lenses, are less likely to crack, and can be dyed.
• various studies have been made so far on lenses containing thiourethane resin (see, for example, Patent Documents 1 to 3).
• Patent Document 1 JP-A-63-46213
• Patent Document 2 JP-A-2-270859
• Patent Document 3 JP-A-7-252207
• a thiourethane resin is usually produced using a polythiol composition and a polyisocyanate compound as raw materials. There are cases where the thiourethane resin is required to further improve the dyeability.
• An object of one aspect of the present disclosure is to provide a polythiol composition capable of producing a thiourethane resin with excellent dyeability and its application.
• Means for solving the above problems include the following aspects. ⁇ 1> A polythiol composition containing a polythiol compound, Containing compound C2 having a retention time of 16.0 to 19.0 minutes in high performance liquid chromatography measurement under the following measurement conditions A, The peak area of the compound C2 in the high performance liquid chromatography measurement is 1.000 or more relative to the total peak area 100 of the peak area of the compound C2 and the peak area of the main component in the polythiol composition. Polythiol composition. -Measurement conditions A- As a column, Kanto Chemical Co., Ltd.
• ⁇ 6> The polythiol composition according to ⁇ 5>, wherein the compound C4 is a polythiol compound having a molecular weight of 380.
• ⁇ 7> The polythiol composition according to any one of ⁇ 1> to ⁇ 6>, wherein the main component is a polythiol compound (XA) containing three or more mercapto groups.
• the polythiol compound (XA) is a polythiol component A1 that is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, or 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane is at least one polythiol component A2 selected from the group consisting of The polythiol composition according to ⁇ 7>.
• the polythiol compound (XA) is polythiol component A1, wherein the polythiol compound (XA) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.
• a polyiso (thio) cyanate compound The polythiol composition according to any one of ⁇ 1> to ⁇ 9>, A polymerizable composition for optical materials containing ⁇ 11>
• the polyiso(thio)cyanate compound includes pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanate), natomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and including at least one selected from the group consisting of phenylene diisocyanates, The polymerizable composition for optical materials
• the polymerizable composition for optical materials according to ⁇ 10> or ⁇ 11> which contains a polyiso(thio)cyanate composition containing the polyiso(thio)cyanate compound.
• the polyiso(thio)cyanate composition is xylylene diisocyanate and at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); including When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of the compound (N1) in gas chromatography measurement under the following GC conditions 1 is relative to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N2) in gas chromatography measurement under the following GC conditions 2 is relative to the peak area 1 of xylylene diisocyanate. is 0.05 ppm or more
• the peak area of the compound (N3) in gas chromatography measurement under the following GC conditions 1 is relative to the peak area 1 of xylylene diisocyanate. is 0.10 ppm or more
• ⁇ 14> A resin that is a cured product of the polymerizable composition for optical materials according to any one of ⁇ 10> to ⁇ 13>.
• ⁇ 15> A molded article containing the resin according to ⁇ 14>.
• ⁇ 16> An optical material containing the resin according to ⁇ 14>.
• ⁇ 17> A lens containing the resin according to ⁇ 14>.
• a polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound A method for producing a polymerizable composition for an optical material, comprising mixing the polythiol composition according to any one of ⁇ 1> to ⁇ 9>.
• the polyiso(thio)cyanate composition is xylylene diisocyanate and at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); including When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of the compound (N1) in gas chromatography measurement under the following GC conditions 1 is relative to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N2) in gas chromatography measurement under the following GC conditions 2 is relative to the peak area 1 of xylylene diisocyanate. is 0.05 ppm or more
• the peak area of the compound (N3) in gas chromatography measurement under the following GC conditions 1 is relative to the peak area 1 of xylylene diisocyanate. is 0.10 ppm or more
• a composition set used for producing a polymerizable composition for optical materials A polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound;
• the polythiol composition according to any one of ⁇ 1> to ⁇ 9>, A composition set, comprising: ⁇ 21>
• the polyiso(thio)cyanate composition is xylylene diisocyanate and at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); including
• the polyiso(thio)cyanate composition contains the compound (N1), the peak area of the compound (N1) in gas chromatography measurement under the following GC conditions 1 is relative to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N2) in gas chromatography measurement under the following GC conditions 2 is relative to the peak area 1 of xylylene diisocyanate. is 0.05 ppm or more
• the peak area of the compound (N3) in gas chromatography measurement under the following GC conditions 1 is relative to the peak area 1 of xylylene diisocyanate. is 0.10 ppm or more
• a polythiol composition capable of producing a thiourethane resin with excellent dyeability and its application are provided.
• a numerical range represented using “to” means a range including the numerical values described before and after “to” as lower and upper limits.
• the term “step” includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. .
• the amount of each component contained in the composition is the total amount of the multiple substances present in the composition unless otherwise specified.
• the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. .
• the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
• the polythiol compositions of the present disclosure are A polythiol composition containing a polythiol compound, Containing compound C2 having a retention time of 16.0 to 19.0 minutes in high-performance liquid chromatography measurement (hereinafter also simply referred to as "high-performance liquid chromatography measurement") under measurement conditions A below,
• the peak area of compound C2 in high performance liquid chromatography measurement is 1.000 or more relative to the total peak area of 100 of the peak area of compound C2 and the peak area of the main component in the polythiol composition.
• a polythiol composition is 1.000 or more relative to the total peak area of 100 of the peak area of compound C2 and the peak area of the main component in the polythiol composition.
• thiourethane resins By using the polythiol composition of the present disclosure as one of raw materials for thiourethane resins, thiourethane resins with excellent dyeability can be produced.
• polythiol composition means a composition containing at least one polythiol compound.
• the polythiol compound contained in the polythiol composition is also referred to as "polythiol component.”
• the polythiol composition may contain components other than the polythiol compound as impurities.
• the polythiol composition preferably contains at least one polythiol compound as a main component.
• the polythiol composition contains at least one polythiol compound as a main component
• the total content of at least one polythiol compound relative to the total amount of the polythiol composition is 50% or more. do.
• the total content of at least one polythiol compound relative to the total amount of the polythiol composition is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.
• the expression that the composition “includes a certain component (hereinafter referred to as “component X”) as a main component” refers to the content of component X (when component X consists of two or more compounds means that the total content of two or more compounds) is 50% or more of the total amount of the composition.
• the content of component X, which is the main component is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more, relative to the total amount of the composition.
• % in the explanation of the term “contained as a main component” is the component relative to the total area of all peaks of the composition (e.g., polythiol composition) determined by high-performance liquid chromatography under the above measurement conditions A. It means the ratio (area %) of the total area of all peaks of X (eg, at least one polythiol compound).
• polythiol compositions include polythiol compositions containing known polythiol compounds.
• the polythiol compound is not particularly limited as long as it contains two or more thiol groups (also known as mercapto groups).
• thiol groups also known as mercapto groups.
• the polythiol compound refer to the above-mentioned known documents (that is, JP-A-63-46213, JP-A-2-270859, JP-A-7-252207, WO 2008/047626, etc.) as appropriate. can.
• the polythiol composition of the present disclosure contains compound C2.
• Compound C2 is a compound having a retention time of 16.0 to 19.0 minutes in high performance liquid chromatography measurement under measurement conditions A.
• the polythiol composition of the present disclosure may contain only one type of compound C2, or may contain two or more types.
• Compound C2 may or may not be a polythiol compound, but is preferably a polythiol compound.
• Compound C2 is an effective component for improving the dyeability of the thiourethane resin produced using the polythiol composition.
• the peak area of compound C2 with respect to the total peak area of 100 of the peak area of compound C2 and the peak area of the main component in the polythiol composition in high performance liquid chromatography measurement (hereinafter simply “compound C2 When the peak area) is 1.000 or more, the effect of improving the dyeability of the produced thiourethane resin is exhibited.
• the lower limit of the peak area of compound C2 is preferably 1.250, more preferably 1.500, and still more preferably 1.600 from the viewpoint of further improving the dyeability of the thiourethane resin produced. , more preferably 2.500, more preferably 3.100, still more preferably 4.000, still more preferably 7.000, still more preferably 8.000.
• the upper limit of the peak area of compound C2 is preferably 20.000, more preferably 15.000, and still more preferably 13.000, from the viewpoint of reducing the yellowness index (YI) of the thiourethane resin to be produced. Yes, more preferably 9.000, more preferably 6.000.
• the molecular weight of compound C2 is 320, for example.
• the molecular weight referred to here is a value measured by high performance liquid chromatography mass spectrometry under measurement condition B below.
• Measurement condition B As a column, using YMC-Pack (registered trademark) C18RS (particle diameter S: 3 ⁇ m, column shape: ⁇ 4.6 mm ⁇ 250 mm) manufactured by YMC Co., Ltd.
• Examples of compound C2 include polythiol compounds with a molecular weight of 320.
• Compound C2, which is a polythiol compound with a molecular weight of 320 includes , for example, a compound represented by the molecular formula C9H20S6 .
• Examples of compound C2, which is a compound represented by the molecular formula C 9 H 20 S 6 include compounds represented by the following formula (C2-1).
• each of l, m, and n is 0 or 1, and the sum of l, m, and n is 1.
• the compound represented by formula (C2-1) may be a mixture of two or more compounds with different combinations of l, m, and n.
• Compound C2 when it is a polythiol compound preferably contains at least one selected from the group consisting of the following compound (C2-1a), the following compound (C2-1b), and the following compound (C2-1c).
• Compound (C2-1a) is a compound represented by formula (C2-1), wherein n is 1, l and m are both 0, Compound (C2-1b) is a compound represented by formula (C2-1), l is 1, n and m are both 0, Compound (C2-1b) is a compound represented by formula (C2-1) in which m is 1 and l and m are both 0.
• Compound C3 The polythiol composition of the present disclosure preferably further contains compound C3. Thereby, the dyeability of the produced thiourethane resin is further improved.
• Compound C3 is a compound having a retention time of 32.0 to 35.0 minutes in high performance liquid chromatography measurement under measurement conditions A.
• the number of compounds C3 contained may be one, or two or more.
• Compound C3 may or may not be a polythiol compound, but is preferably a polythiol compound.
• peak area of compound C3 with respect to the total peak area of 100 of the peak area of compound C3 and the peak area of the main component in the polythiol composition in the high-performance liquid chromatography measurement under the measurement conditions A (hereinafter, simply "peak area of compound C3" ) is preferably 0.050 or more. Thereby, the dyeability of the produced thiourethane resin is further improved.
• the lower limit of the peak area of compound C3 is more preferably 0.100 or more, still more preferably 0.150 or more, still more preferably 0.150 or more, from the viewpoint of further improving the dyeability of the produced thiourethane resin. 600, more preferably 1.000, still more preferably 1.500, still more preferably 2.000.
• the upper limit of the peak area of compound C3 is preferably 5.000, more preferably 4.000, still more preferably 3.500, from the viewpoint of reducing the yellowness index (YI) of the thiourethane resin to be produced. Yes, more preferably 2.500, more preferably 2.000, still more preferably 1.500.
• the molecular weight of compound C3 is 426, for example.
• the molecular weight referred to here is a value measured by high-performance liquid chromatography mass spectrometry under measurement conditions B described above.
• Examples of compound C3 include a polythiol compound having a molecular weight of 426.
• Compound C3, which is a polythiol compound with a molecular weight of 426 includes, for example, a compound represented by the molecular formula C 12 H 26 S 8 .
• As the compound C3, which is a compound represented by the molecular formula C 12 H 26 S 8 for example, from the compound represented by the following formula (C3-1), the following formula (C3-2), or the following formula (C3-3) At least one selected from the group consisting of
• each of p, q, r, and s is 0 or 1, and the sum of p, q, r, and s is 1.
• Compound C4 The polythiol composition of the present disclosure preferably further contains compound C4. Thereby, the dyeability of the produced thiourethane resin is further improved.
• Compound C4 is a compound having a retention time of 21.5 to 25.0 minutes in high performance liquid chromatography measurement under measurement conditions A. When the polythiol composition of the present disclosure contains compound C4, only one type of compound C4 may be contained, or two or more types may be contained.
• Compound C4 may or may not be a polythiol compound, but is preferably a polythiol compound.
• peak area of compound C4 with respect to the total peak area of 100 of the peak area of compound C4 and the peak area of the main component in the polythiol composition in the high-performance liquid chromatography measurement under the above measurement conditions A (hereinafter simply "peak area of compound C4" ) is preferably 0.030 or more. Thereby, the dyeability of the produced thiourethane resin is further improved.
• the lower limit of the peak area of compound C4 is preferably 0.040, more preferably 0.500, and still more preferably 0.600, from the viewpoint of further improving the dyeability of the thiourethane resin produced. .
• the upper limit of the peak area of compound C4 is preferably 1.300, more preferably 1.200, still more preferably 1.100, from the viewpoint of reducing the yellowness index (YI) of the thiourethane resin to be produced. be.
• the molecular weight of compound C4 is 380, for example.
• the molecular weight referred to here is a value measured by high-performance liquid chromatography mass spectrometry under measurement conditions B described above.
• Examples of compound C4 include a polythiol compound having a molecular weight of 380.
• Compound C4, which is a polythiol compound with a molecular weight of 380 includes, for example, a compound represented by the molecular formula C11H24S7 .
• Examples of the compound C4, which is a compound represented by the molecular formula C 11 H 24 S 7 include at least one selected from the group consisting of compounds represented by the following formula (C4-1).
• each of l, m, and n is 0, 1, or 2, and the sum of l, m, and n is 2.
• the compound represented by formula (C4-1) may be a mixture of two or more compounds with different combinations of l, m, and n.
• the main component in the polythiol composition of the present disclosure is preferably a polythiol compound, preferably a polythiol compound (XA) containing three or more mercapto groups.
• the polythiol compound (XA) is a polythiol compound containing three or more mercapto groups.
• the compound C2 described above is a "polythiol compound containing three or more mercapto groups"
• the compound C2 is not included in the scope of the polythiol compound (XA).
• the polythiol composition of the present disclosure contains compound C3, and the aforementioned compound C3 is a "polythiol compound containing three or more mercapto groups", the scope of the polythiol compound (XA) includes: Compound C3 shall not be included.
• the polythiol compound (XA) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and It is preferably at least one selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane.
• the polythiol compound (XA) is a polythiol component A1 that is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, or 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and
• the polythiol component A2 is preferably at least one selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, More preferably, it is the polythiol component A1.
• polythiol component A1 ie, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
• the polythiol component A1 is the following compound (A1).
• the polythiol component A1 has a retention time between 12.0 minutes and 13.0 minutes
• the polythiol component A2 has a retention time between 22.0 minutes and 26.0 minutes. .
• the polythiol composition of the present disclosure may contain at least one component other than the main component (eg, other polythiol compounds, components other than polythiol compounds, etc.).
• Other polythiol compounds include, for example, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate).
• polymerizable composition for optical material The polymerizable composition for optical materials of the present disclosure (hereinafter also simply referred to as "polymerizable composition”) is A polyiso (thio) cyanate compound, the aforementioned polythiol composition of the present disclosure; contains
• the polymerizable composition of the present disclosure contains the polythiol composition of the present disclosure described above, it exhibits the same effects as the polythiol composition of the present disclosure.
• polyiso (thio) cyanate compound The polyiso(thio)cyanate compound is not particularly limited as long as it is a compound having at least two iso(thio)cyanate groups in one molecule.
• Specific examples of polyiso (thio) cyanate compounds include: Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate , aliphatic polyisocyanate compounds such as xylylene diisocyanate; isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, dicyclohexy
• Polyiso(thio)cyanate compounds include halogen-substituted products such as chlorine-substituted products and bromine-substituted products thereof, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-type modified products with polyhydric alcohols, and carbodiimides. Modified products, urea modified products, buret modified products, dimerization or trimerization reaction products, etc. can also be used.
• Polyiso (thio) cyanate compounds are It preferably contains a polyisocyanate compound, pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1] - containing at least one selected from heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and phenylene diisocyanate is preferred.
• a polyisocyanate compound pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis
• the mixing ratio of the polythiol composition and the polyiso(thio)cyanate compound is not particularly limited.
• the molar ratio of the mercapto group of the polythiol compound and the iso(thio)cyanate group of the polyiso(thio)cyanate compound contained in the polythiol composition is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and preferably 0.8 to 1.3 More preferred.
• the mixing ratio is within the above range, it tends to be possible to satisfy various performances such as refractive index and heat resistance required for a plastic lens or the like in a well-balanced manner.
• the polymerizable composition of the present disclosure may contain a polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound. That is, the polymerizable composition of the present disclosure is A polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound; the aforementioned polythiol composition of the present disclosure; may contain.
• the polyiso (thio) cyanate compound in the polyiso (thio) cyanate composition contained may be only one type, Two or more types may be used.
• the contained polyiso(thio)cyanate composition preferably contains xylylene diisocyanate.
• the stability of the polyiso(thio)cyanate composition and the transparency of the resin formed using the polyiso(thio)cyanate composition are more excellent (that is, clouding and/or yellowing are further suppressed).
• a polyiso(thio)cyanate composition containing xylylene diisocyanate is also referred to as an XDI composition.
• the XDI composition preferably contains xylylene diisocyanate as the main component.
• the XDI composition preferably contains at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3).
• Preferred embodiments of the XDI composition are shown below from the viewpoint of the stability of the polyiso(thio)cyanate composition and the transparency of the resin formed using the polyiso(thio)cyanate composition.
• the peak area of the compound (N1) in the gas chromatography measurement under the following GC condition 1 is 0.20 ppm or more with respect to the peak area 1 of xylylene diisocyanate. is preferred.
• -GC condition 1- Filler; DB-1 (film thickness) 1.5 ⁇ m Column; inner diameter 0.53 mm ⁇ length 60 m (manufactured by Agilent) Oven temperature: from 130°C to 220°C at a rate of 3°C/min, after reaching 220°C, the temperature was raised to 300°C at a rate of 10°C/min.
• the peak area of the compound (N1) is more preferably 5.0 ppm or more, still more preferably 50 ppm or more, still more preferably 100 ppm or more relative to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N1) is preferably 4000 ppm or less, more preferably 3000 ppm or less, still more preferably 2000 ppm or less, still more preferably 1500 ppm or less, and still more preferably 1000 ppm or less relative to the peak area 1 of xylylene diisocyanate. .
• the peak area of the compound (N1) can be measured according to the method described in paragraph 0377 of Japanese Patent No. 6373536.
• the peak area of the compound (N2) in gas chromatography measurement under the following GC conditions 2 is 0.05 ppm or more with respect to the peak area 1 of xylylene diisocyanate. is preferred.
• -GC condition 2- Column: HP-50+, inner diameter 0.25 mm ⁇ length 30 m ⁇ film thickness 0.25 ⁇ m (manufactured by Hewlett-Packard) Oven temperature; raised from 50°C to 280°C at a rate of 10°C/min, and held for 6 minutes after reaching 280°C.
• the peak area of the compound (N2) is more preferably 0.1 ppm or more, still more preferably 0.3 ppm or more, still more preferably 0.6 ppm or more relative to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N2) is preferably 200 ppm or less, more preferably 150 ppm or less, still more preferably 100 ppm or less, still more preferably 80 ppm or less, still more preferably 70 ppm or less, relative to the peak area 1 of xylylene diisocyanate. It is preferably 60 ppm or less.
• the peak area of the compound (N2) can be measured according to the method described in paragraphs 0375 and 0376 of Japanese Patent No. 6373536.
• the peak area of the compound (N3) in the gas chromatography measurement under the above-mentioned GC condition 1 is 0.10 ppm or more with respect to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N3) is more preferably 0.1 ppm or more, still more preferably 3.0 ppm or more, still more preferably 5.0 ppm or more relative to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N3) is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 300 ppm or less, still more preferably 100 ppm or less, and still more preferably 75 ppm or less relative to the peak area 1 of xylylene diisocyanate. .
• the peak area of the compound (N3) can be measured according to the method described in paragraph 0377 of Japanese Patent No. 6373536.
• the acid content of the XDI composition is preferably 3000 ppm or less, more preferably 2000 ppm or less, more preferably 1000 ppm or less, more preferably 100 ppm or less, more preferably 50 ppm or less, more preferably 30 ppm or less, more preferably less than 15 ppm. .
• the lower limit of the acid content of the XDI composition is not particularly limited, the lower limit is, for example, 1 ppm.
• the acid content of the XDI composition can be measured according to the method described in paragraph 0091 of WO2021/256417.
• the XDI composition may contain a stabilizer.
• the polymerizable composition of the present disclosure may contain components other than the polythiol composition and the polyiso(thio)cyanate compound.
• Other ingredients include polymerization catalysts, internal release agents, resin modifiers, chain extenders, cross-linking agents, radical scavengers, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, adhesion Blue ink agents such as property improvers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, and inorganic pigments are included.
• polymerization catalysts include tertiary amine compounds, inorganic or organic acid salts thereof, metal compounds, quaternary ammonium salts, organic sulfonic acids, and the like.
• An acidic phosphate ester can be used as the internal release agent.
• acidic phosphates include phosphate monoesters and phosphate diesters, each of which can be used alone or in combination of two or more.
• resin modifiers include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids and their anhydrides, olefin compounds including (meth)acrylate compounds, and the like.
• the polymerizable composition of the present disclosure can be obtained by mixing the above components.
• the method for producing the polymerizable composition of the present disclosure is not particularly limited, and includes, for example, the production method according to one embodiment below.
• a composition set according to one embodiment below may be used to produce the polymerizable composition of the present disclosure.
• a method for producing a polymerizable composition for an optical material according to an embodiment of the present disclosure includes a polyiso (thio) cyanate composition containing a polyiso (thio) cyanate compound and the polythiol composition of the present disclosure described above. Including process. According to the method for producing a polymerizable composition for an optical material according to the above embodiment, it is easy to produce the above-described polymerizable composition of the present disclosure.
• the polyiso (thio) cyanate composition is xylylene diisocyanate and at least one selected from the group consisting of the aforementioned compound (N1), the aforementioned compound (N2), and the aforementioned compound (N3); is preferably included.
• the peak area of the compound (N1) in the gas chromatography measurement under the above-mentioned GC condition 1 is 0 with respect to the peak area of xylylene diisocyanate 1 .20 ppm or more
• the peak area of the compound (N2) in the gas chromatography measurement under the above-mentioned GC condition 2 is 0 with respect to the peak area of xylylene diisocyanate 1 .05 ppm or more
• the peak area of the compound (N3) in the gas chromatography measurement under the above-mentioned GC condition 1 is 0 with respect to the peak area of xylylene diisocyanate 1 .10 ppm or more is more preferable.
• the method for producing the polymerizable composition for optical materials according to the above embodiment may include other steps than the mixing step, if necessary.
• Other steps include a step of mixing the mixture obtained by the mixing step with other components other than the polythiol composition and the polyiso(thio)cyanate compound in the polymerizable composition of the present disclosure. .
• These other ingredients may also be mixed with the polyiso(thio)cyanate composition and xylylene diisocyanate in the mixing step.
• composition set includes A composition set used for producing a polymerizable composition for optical materials, A polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound; the polythiol composition of the present disclosure described above; including. According to the composition set according to the above embodiment, it is easy to produce the above-described polymerizable composition of the present disclosure. For example, according to the composition set according to the above embodiment, the mixing step in the method for producing the polymerizable composition for optical materials according to the above embodiment can be carried out.
• the polyiso (thio) cyanate composition is xylylene diisocyanate and at least one selected from the group consisting of the aforementioned compound (N1), the aforementioned compound (N2), and the aforementioned compound (N3); is preferably included.
• the peak area of the compound (N1) in the gas chromatography measurement under the above-mentioned GC condition 1 is 0 with respect to the peak area of xylylene diisocyanate 1 .20 ppm or more
• the peak area of the compound (N2) in the gas chromatography measurement under the above-mentioned GC condition 2 is 0 with respect to the peak area of xylylene diisocyanate 1 .05 ppm or more
• the peak area of the compound (N3) in the gas chromatography measurement under the above-mentioned GC condition 1 is 0 with respect to the peak area of xylylene diisocyanate 1 .10 ppm or more is more preferable.
• the resin of the present disclosure is a cured product of the polymerizable composition of the present disclosure described above.
• the resin of the present disclosure is obtained by curing the polymerizable composition of the present disclosure described above.
• Curing of the polymerizable composition can be performed by polymerizing the monomers (specifically, the polythiol composition and the polyiso(thio)cyanate compound; hereinafter the same) in the polymerizable composition.
• the polymerizable composition may be subjected to treatment such as filtration and degassing.
• Polymerization conditions e.g., polymerization temperature, polymerization time, etc.
• Polymerization temperature include -50°C to 150°C, 10°C to 150°C, and the like.
• the polymerization time is, for example, 1 hour to 200 hours, 1 hour to 80 hours, and the like.
• a polymer obtained by polymerization of monomers may be subjected to a treatment such as annealing to obtain the resin.
• Annealing temperatures include 50° C. to 150° C., 90° C. to 140° C., 100° C. to 130° C., and the like.
• the molded article of the present disclosure contains the resin of the present disclosure.
• the molded article of the present disclosure is obtained by curing the polymerizable composition of the present disclosure, similarly to the resin of the present disclosure. Preferred conditions for curing the polymerizable composition, ie, polymerization of the monomers in the polymerizable composition, are as described above.
• Cast polymerization is an example of a preferred method for producing the molded article of the present disclosure.
• the polymerizable composition is injected between molding molds held by gaskets, tapes, or the like. At this time, if necessary, defoaming treatment, filtration treatment, or the like may be performed.
• the composition is cured between the molding molds to obtain a cured product.
• the cured product is removed from the molding mold to obtain a molded body containing the resin.
• Polymerization of the above monomers may be carried out by heating the polymerizable composition. This heating can be performed, for example, by using a heating device having a mechanism for heating the object to be heated in an oven, in water, or the like.
• the optical material of the present disclosure contains the resin of the present disclosure.
• the optical material of the present disclosure like the resin of the present disclosure, is obtained by curing the polymerizable composition of the present disclosure. Preferred conditions for curing the polymerizable composition, ie, polymerization of the monomers in the polymerizable composition, are as described above.
• Optical materials include lenses (eg, eyeglass lenses, camera lenses, polarized lenses), light emitting diodes (LEDs), and the like.
• lenses eg, eyeglass lenses, camera lenses, polarized lenses
• LEDs light emitting diodes
• the optical material of the present disclosure may include a coating layer formed on one side or both sides of the resin of the present disclosure (or a molded article containing the resin of the present disclosure).
• coating layers include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, an antifouling layer, and a water repellent layer.
• Each of these coating layers may be formed independently, or may be formed by stacking a plurality of coating layers. When the coating layer is formed on both sides, the same coating layer may be formed on each side, or different coating layers may be formed on each side.
• the components of the coating layer can be appropriately selected depending on the purpose.
• Components of the coating layer include, for example, resins (e.g., urethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, Pigments, antistatic agents and the like can be mentioned.
• composition (A1-1) containing polythiol component A1 as a main component was produced. Details are shown below.
• a reactor was charged with 124.6 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of degassed water.
• 101.5 parts by mass of a 32% by mass sodium hydroxide aqueous solution was added dropwise at 12°C to 35°C over 40 minutes, and then 73.6 parts by mass of epichlorohydrin was added at 29°C to 36°C for 4 hours. It was added dropwise over 5 hours, followed by stirring for 40 minutes.
• a hydrolysis reaction was carried out by charging parts by mass at 31° C. to 41° C. over 44 minutes and then stirring at 54° C. to 62° C. for 3 hours.
• a toluene solution of a polythiol composition containing polythiol component A1 (ie, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane) as a main component was obtained.
• This toluene solution was acid washed with 162.8 parts by mass of 35.5% by mass hydrochloric acid at 35° C. to 43° C. for 1 hour.
• the acid-washed toluene solution was washed twice with 174.1 parts by mass of degassed water at 35° C.
• composition (A1-2) Containing Polythiol Component A1 as Main Component A composition (A1-2) containing polythiol component A1 as a main component was produced.
• the hydroxylation used in the step of producing 1,3-bis(2-hydroxyethylthio)-2-propanol By reducing the amount of sodium used, the residual amount of 2-mercaptoethanol was increased.
• the reaction by-products for the polythiol component A1 that is, the compound (A1) below
• Compound C2 that is, at least one selected from the group consisting of the following compound (C2-1a), the following compound (C2-1b), and the following compound (C2-1c)), which is a substance, is more easily generated.
• composition (A1-2) Details of the production of the composition (A1-2) are shown below.
• a reactor was charged with 124.8 parts by mass of 2-mercaptoethanol and 22.5 parts by mass of degassed water.
• 99.0 parts by mass of a 30.8% by mass sodium hydroxide aqueous solution was added dropwise at 12°C to 35°C over 40 minutes, and then 74.0 parts by mass of epichlorohydrin was added to 29°C to 36°C.
• the mixture was added dropwise over 4.5 hours, followed by stirring for 40 minutes.
• 1,3-bis(2-hydroxyethylthio)-2-propanol was produced in the reactor. This formation was confirmed by NMR data.
• a toluene solution of a polythiol composition containing polythiol component A1 ie, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
• polythiol component A1 ie, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
• This toluene solution was acid-washed with 147.8 parts by mass of 35.5% by mass hydrochloric acid at 35° C. to 43° C. for 1 hour.
• the acid-washed toluene solution was washed twice with 147.8 parts by mass of degassed water at 35° C. to 45° C. for 30 minutes.
• the toluene solution was washed with 147.8 parts by mass of 0.1% by mass ammonia water for 30 minutes.
• the toluene solution after washing with ammonia water was washed twice with 147.8 parts by mass of degassed water at 35° C. to 45° C. for 30 minutes.
• it is filtered under reduced pressure with a 3.0 ⁇ m PTFE type membrane filter to obtain a composition (A1-2) (199 .7 parts by mass) was obtained.
• Examples 1 to 6 ⁇ Production of polythiol composition> The composition (A1-1) and the composition (A1-2) are mixed at a mixing mass ratio [composition (A1-1)/composition (A1-2)] of 99/1. Thus, a polythiol composition of Example 1 containing polythiol component A1 as a main component and compound C2 and compound C3 as reaction by-products, respectively, was obtained.
• the polythiol composition of Example 2 was prepared in the same manner as the polythiol composition of Example 1, except that the mixing mass ratio [composition (A1-1)/composition (A1-2)] was changed to 75/25. got
• the polythiol composition of Example 3 was prepared in the same manner as the polythiol composition of Example 1, except that the mixing mass ratio [composition (A1-1)/composition (A1-2)] was changed to 60/40. got
• the polythiol composition of Example 4 was prepared in the same manner as the polythiol composition of Example 1, except that the mixing mass ratio [composition (A1-1)/composition (A1-2)] was changed to 40/60. got
• the polythiol composition of Example 5 was prepared in the same manner as the polythiol composition of Example 1, except that the mixing mass ratio [composition (A1-1)/composition (A1-2)] was changed to 20/80. got
• the polythiol composition of Example 6 was prepared in the same manner as the polythiol composition of Example 1, except that the mixing mass ratio [composition (A1-1)/composition (A1-2)] was changed to 0/100. got
• Compound C2 is a compound having a retention time of 16.0 minutes to 19.0 minutes in high performance liquid chromatography measurement under measurement conditions A
• Compound C3 is a compound having a retention time of 32.0 minutes to 35.0 minutes in high performance liquid chromatography measurement under measurement conditions A
• Compound C4 is a compound having a retention time of 21.5 minutes to 25.0 minutes in high performance liquid chromatography measurement under measurement conditions A
• the peak area of compound C2 is the peak area of compound C2 relative to the total peak area 1 of the peak area of compound C2 and the peak area of the main component (that is, polythiol component A1) in the polythiol composition
• the peak area of compound C3 is the peak area of compound C3 with respect to the total peak area 1 of the peak area of compound C3 and the peak area of the main component (that is, polythiol component A1) in the polythiol composition.
• the peak area of compound C4 is the peak area of compound C4 with respect to the total peak area 1 of the peak area of compound C4 and the peak area of the main component (that is, polythiol component A1) in the polythiol composition.
• Table 1 shows the results.
• XDI composition X1 52 parts by mass as the XDI composition described above, which is one aspect of the polyiso(thio)cyanate composition; dibutyltin dichloride (0.01 parts by mass) as a curing catalyst; Zelec UN (trade name, manufactured by Stepan; acidic phosphate ester) (0.10 parts by mass) as a release agent, Biosorb 583 (manufactured by Kyodo Pharmaceutical Co., Ltd.; UV absorber) (1.5 parts by mass) as a UV absorber, were mixed and dissolved at 20°C.
• the obtained mixed solution and 48 parts by mass of the polythiol composition of any one of Examples 1 to 5 were mixed to obtain a polymerizable composition which is a mixed homogeneous solution.
• the polymerizable composition was defoamed at 600 Pa for 1 hour.
• the polymerizable composition was filtered through a 1 ⁇ m Teflon (registered trademark) filter, the filtrate was injected between a pair of glass molds fixed with tape, and then the pair of glass molds were placed in an oven.
• the internal temperature was set at 10°C. Next, the temperature inside the oven was raised from 10° C. to 120° C. over 38 hours.
• the monomers (polyisocyanate compound and polythiol composition) in the polymerizable composition are polymerized to form a resin-containing molding (that is, a cured product of the polymerizable composition) between a pair of glass molds.
• a resin-containing molding that is, a cured product of the polymerizable composition
• the resin molding the molding containing resin
• XDI composition X1 gas chromatography measurement was performed under each of the above-described GC conditions 1 and GC conditions 2.
• the peak area of the compound (N1) is 0.20 ppm or more (specifically 600 ppm) with respect to the peak area 1 of xylylene diisocyanate
• the peak area of the compound (N2) is 0.05 ppm or more (specifically 18 ppm) with respect to the peak area 1 of xylylene diisocyanate
• the peak area of compound (N3) was 0.10 ppm or more (specifically 100 ppm) with respect to the peak area 1 of xylylene diisocyanate.
• the yellowness index (YI) of a 9 mm-thick plate-shaped resin molding was measured using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc. The smaller the yellowness index (YI) of the resin molding, the better the hue of the resin molding.
• the dyeability of the resin molded body was evaluated by dyeing a flat resin molded body having a thickness of 9 mm and measuring the light transmittance of the dyed resin molded body. The lower the light transmittance of the dyed resin molded article, the more excellent the dyeability of the resin molded article. Details are shown below.
• a flat resin molded article having a thickness of 9 mm was immersed in the resulting dye dispersion at 90° C. for 30 minutes to dye the resin molded article.
• the light transmittance (%) at 350 nm to 800 nm of the dyed resin molding was measured, and the light transmittance (%) at 567 nm was obtained from the measurement results.
• Table 1 shows the results. As described above, the lower the light transmittance (%) at 567 nm, the more excellent the dyeability of the resin molding.
• Table 1 it contains compound C2 having a retention time of 16.0 to 19.0 minutes in high performance liquid chromatography measurement under measurement condition A, and the peak area of compound C2 in the high performance liquid chromatography measurement. is 1.000 or more with respect to the total peak area 100 of the peak area of the compound C2 and the peak area of the main component in the polythiol composition. An excellent resin molding was obtained.

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• 2023
  • 2023-01-26 JP JP2023576990A patent/JP7727763B2/ja active Active
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