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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
• • 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
• • 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

Definitions

• This disclosure relates to a polymerizable composition for optical materials, a polymerizable prepolymer composition for optical materials, a cured product, and a method for producing an optical material.
• a method for producing a resin used in an optical material for a plastic lens for example, there is a cast polymerization method in which a polymerizable composition containing a monomer is injected into a mold and cured by heating.
• a polymerizable composition is prepared and degassed, and then the polymerizable composition is injected into a mold (form), and after heat curing (polymerization reaction), the product is removed from the mold (demolding), and annealed to obtain an optical material (for example, a lens, a semi-finished blank, etc.).
• the polymerization reaction in order to improve the quality of the optical material, the polymerization reaction is generally carried out over a long period of time (e.g., about 20 to 48 hours) while gradually increasing the temperature of the polymerizable composition by heating. For this reason, it is known that a large proportion (e.g., about 90%) of the total time required for the production of the optical material is spent on the heat polymerization.
• Patent Document 1 it is described that the mold into which the polymerizable composition has been injected is gradually heated from 10°C to 120°C, and polymerized for 20 hours to obtain a molded product.
• the polymerizable compositions used in the methods described in Patent Documents 1 and 2 have a high rate of increase in viscosity after preparation, and there is room for improvement in pot life (working time).
• An object of one embodiment of the present disclosure is to provide a polymerizable composition and a polymerizable prepolymer composition that can shorten the production time of an optical material and have an excellent pot life.
• Another problem to be solved by one embodiment of the present disclosure is to provide a method for producing an optical material using the polymerizable composition or polymerizable prepolymer composition, and a cured product thereof.
• a composition comprising two or more different monomers for optical materials, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4, At least one of the two or more different monomers for optical materials is an isocyanate compound, A polymerizable composition for optical materials, having a viscosity of 10 mPa ⁇ s to 1000 mPa ⁇ s as measured with a Brookfield viscometer at 25° C. and 60 rpm.
• At least one of the two or more different monomers for optical materials is an isocyanate compound having an aromatic ring
• At least one of the two or more different monomers for optical materials is an isocyanate compound having no aromatic ring
• a prepolymer which is a polymer of the two or more different monomers for optical materials and has a polymerizable functional group.
• ⁇ 6> The polymerizable composition for optical materials according to any one of ⁇ 1> to ⁇ 5>, wherein at least one of the two or more different monomers for optical materials is an active hydrogen compound, and a total ratio of the isocyanate compound and the active hydrogen compound to the total of the two or more different monomers for optical materials is more than 70 mass%.
• ⁇ 7> The polymerizable composition for an optical material according to any one of ⁇ 1> to ⁇ 6>, wherein the number of moles of the functional group of the organic acid having a pKa value of less than 4 is smaller than the number of moles of the functional group of the basic polymerization catalyst.
• the polymerizable composition for an optical material according to any one of ⁇ 1> to ⁇ 7>, wherein the basic polymerization catalyst includes a basic polymerization catalyst having a pKa value of 4 to 8.
• a prepolymer which is a polymer of two or more different monomers for optical materials and has a polymerizable functional group, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4, At least one of the two or more different monomers for optical materials is an isocyanate compound, A polymerizable prepolymer composition for optical materials, having a viscosity of 10 mPa ⁇ s to 2000 mPa ⁇ s as measured with a Brookfield viscometer at 25° C.
• At least one of the two or more different monomers for optical materials is an isocyanate compound having an aromatic ring
• At least one of the two or more different monomers for optical materials is an isocyanate compound having no aromatic ring
• ⁇ 12> A cured product of the polymerizable composition for an optical material according to any one of ⁇ 1> to ⁇ 8> or the polymerizable prepolymer composition for an optical material according to any one of ⁇ 9> to ⁇ 11>.
• An optical material monomer composition comprising two or more different monomers for an optical material, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4, a preparation step of preparing a polymerizable composition for an optical material, wherein at least one of the two or more different monomers for an optical material is an isocyanate compound; a casting step of adjusting the viscosity of the polymerizable composition for an optical material to 10 mPa ⁇ s to 1000 mPa ⁇ s, as measured by a Brookfield viscometer at 25° C.
• a method for producing an optical material comprising the steps of: ⁇ 14> At least one of the two or more different monomers for optical materials is an isocyanate compound having an aromatic ring, The method for producing an optical material according to ⁇ 13>, wherein the content of the basic polymerization catalyst is 0.010 parts by mass to 0.50 parts by mass based on 100 parts by mass of the total of the two or more different monomers for an optical material.
• At least one of the two or more different monomers for optical materials is an isocyanate compound having no aromatic ring,
• the method for producing an optical material wherein at least one of the two or more different monomers for an optical material is an isocyanate compound.
• At least one of the two or more different monomers for optical materials is an isocyanate compound having an aromatic ring
• the method for producing an optical material according to ⁇ 16> wherein a total amount of the two or more different monomers for an optical material is 100 parts by mass, and an amount of the basic polymerization catalyst is 0.010 parts by mass to 0.50 parts by mass.
• At least one of the two or more different monomers for optical materials is an isocyanate compound having no aromatic ring, The method for producing an optical material according to ⁇ 16>, wherein a total amount of the two or more different monomers for an optical material is 100 parts by mass, and an amount of the basic polymerization catalyst is more than 0.05 parts by mass and not more than 2.0 parts by mass.
• a step of producing a polymerizable composition for an optical material in which at least the remainder of the two or more different monomers for an optical material is added to the mixture containing the prepolymer, thereby obtaining a polymerizable composition for an optical material containing the two or more different monomers for an optical material, the prepolymer, the basic polymerization catalyst, and an organic acid having a pKa value of less than 4; and a curing step of curing the two or more different kinds of monomers for an optical material in the polymerizable composition for an optical material to obtain an optical material that is a cured product of the polymerizable composition for an optical material.
• a cured product of two or more different monomers for optical materials wherein at least one of the two or more different monomers for optical materials is an isocyanate compound, and there is no striae having a length of 1.0 mm or more within a range of a radius of 15 mm from the center of the cured product,
• a cured product having an amine content of more than 0 mass% as measured by gas chromatography-mass spectrometry, and an organic acid content having a pKa value of less than 4 of more than 0 mass% as measured by gas chromatography-mass spectrometry.
• At least one of the two or more different monomers for optical materials is an isocyanate compound having an aromatic ring
• At least one of the two or more different monomers for optical materials is an isocyanate compound having no aromatic ring,
• a polymerizable composition and a polymerizable prepolymer composition that can shorten the production time of an optical material and have an excellent pot life. Furthermore, according to one embodiment of the present disclosure, there is provided a method for producing an optical material using the polymerizable composition or the polymerizable prepolymer composition, and a cured product thereof.
• a numerical range expressed using “to” means a range that includes the numerical values before and after "to” as the lower and upper limits.
• the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
• the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
• the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
• the term "process” refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.
• the polymerizable composition for an optical material of the present disclosure comprises two or more different monomers for an optical material, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4, at least one of the two or more different monomers for an optical material is an isocyanate compound, and has a viscosity of 10 mPa ⁇ s to 1000 mPa ⁇ s as measured with a B-type viscometer under conditions of 25° C. and 60 rpm.
• the polymerizable composition for an optical material will also be simply referred to as a "polymerizable composition.”
• the polymerizable composition of the present disclosure can shorten the production time of an optical material and has an excellent pot life. Specifically, by using a basic polymerization catalyst as the polymerization catalyst and by using a relatively large amount of the basic polymerization catalyst, the polymerization reaction during curing proceeds quickly, and the time required for producing the optical material as a cured product is shortened. On the other hand, the viscosity of the polymerizable composition after preparation is likely to increase, and the pot life tends to be short.
• the polymerizable composition of the present disclosure is prevented from increasing in viscosity after preparation by including an organic acid having a pKa value of less than 4.
• a salt formed between an organic acid having a pKa value of less than 4 and a basic polymerization catalyst is dissociated by heat, and the activity of the basic polymerization catalyst is expressed, so that the polymerization reaction proceeds rapidly.
• a polymerizable composition having an excellent pot life has excellent injectability into a mold, and therefore a cured product having excellent optical properties (eg, fewer striae) can be obtained.
• the polymerizable composition contains two or more different monomers for optical materials, and at least one of the monomers for optical materials is an isocyanate compound.
• the monomer for optical materials is not particularly limited as long as it is a monomer that can be used in the production of optical materials.
• it may be a monomer used to produce an optical material having any of the following properties:
• the optical material obtained by using the monomer for optical materials may have a total light transmittance of 10% or more.
• the total light transmittance of the optical material may be measured in accordance with JIS K 7361-1 (1997).
• the optical material obtained by using the monomer for optical materials may have a haze (i.e., total haze) of 10% or less, 1% or less, or 0.5% or less.
• the haze of the optical material is a value measured at 25°C using a haze measuring device (TC-HIII DPK, manufactured by Tokyo Denshoku Co., Ltd.) in accordance with JIS-K7105.
• the optical material obtained by using the monomer for optical material has a refractive index of 1.56 or more, preferably 1.58 or more.
• the optical material obtained by using the monomer for optical material may have a refractive index of 1.80 or less, or may have a refractive index of 1.75 or less.
• the refractive index of the optical material may be measured in accordance with JIS K7142 (2014).
• the shape of the optical material obtained using the optical material monomer is not particularly limited, and may be plate-like, cylindrical, rectangular, etc.
• Monomers for optical materials include compounds that have the property of polymerizing when a basic polymerization catalyst, which will be described later, is used. Specific examples include isocyanate compounds, polythiol compounds having two or more mercapto groups, hydroxythiol compounds containing one or more mercapto groups and one or more hydroxyl groups, polyol compounds containing two or more hydroxyl groups, amine compounds, etc.
• the monomer for an optical material preferably contains an active hydrogen compound together with an isocyanate compound.
• the monomer for the optical material preferably contains at least one active hydrogen compound selected from the group consisting of a polythiol compound having two or more mercapto groups, a hydroxythiol compound containing one or more mercapto groups and one or more hydroxyl groups, a polyol compound containing two or more hydroxyl groups, and an amine compound.
• isocyanate compound examples include an aliphatic isocyanate compound, an alicyclic isocyanate compound, an aromatic isocyanate compound, and a heterocyclic isocyanate compound. These isocyanate compounds may include a dimer, a trimer, and a prepolymer. Examples of these isocyanate compounds include the compounds exemplified in International Publication No. 2011/055540.
• the isocyanate compound may be a halogen-substituted (e.g., chlorine-substituted or bromine-substituted), alkyl-substituted, alkoxy-substituted, carbodiimide-modified, urea-modified or biuret-modified compound of the above-mentioned compounds; Prepolymer-type modified products of the above compounds with nitro-substituted compounds, polyhydric alcohols, etc. Dimerization or trimerization reaction products of the above compounds may also be used. These compounds may be used alone or in combination of two or more.
• halogen-substituted e.g., chlorine-substituted or bromine-substituted
• alkyl-substituted alkoxy-substituted
• carbodiimide-modified urea-modified or biuret-modified compound of the above-mentioned compounds
• an aliphatic isocyanate compound refers to an isocyanate compound that does not contain an aromatic structure, an alicyclic structure, or a heterocyclic structure.
• the alicyclic isocyanate compound refers to an isocyanate compound which contains an alicyclic structure, does not contain an aromatic structure, and may contain a heterocyclic structure.
• the aromatic isocyanate compound refers to an isocyanate compound which contains an aromatic structure and may contain any one or combination of an aliphatic structure, an alicyclic structure, and a heterocyclic structure.
• the heterocyclic isocyanate compound refers to an isocyanate compound which contains a heterocyclic structure and does not contain an alicyclic structure or an aromatic structure.
• a heterocyclic ring or heterocyclic structure having aromaticity is not considered to be an aromatic ring or aromatic structure.
• the two or more different optical material monomers preferably include at least one selected from an aliphatic isocyanate compound, an alicyclic isocyanate compound, an aromatic isocyanate compound, and a heterocyclic isocyanate compound.
• At least one of the monomers for the optical material may be an isocyanate compound having an aromatic ring.
• the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring, with a benzene ring being preferred.
• Specific examples of isocyanate compounds having an aromatic ring include aromatic isocyanate compounds, and more specific examples include isocyanate compounds in which an isocyanate group is directly bonded to an aromatic ring, and isocyanate compounds in which an isocyanate group is bonded to the benzyl position of an aromatic ring.
• An isocyanate compound having an aromatic ring is preferred in that the activity of the isocyanate group is higher and the polymerization reaction is more easily promoted than an isocyanate compound not having an aromatic ring.
• At least one of the monomers for the optical material may be an isocyanate compound having no aromatic ring.
• Specific examples of the isocyanate compound having no aromatic ring include alicyclic isocyanate compounds having no aromatic ring, heterocyclic isocyanate compounds, and aliphatic isocyanate compounds.
• An isocyanate compound having no aromatic ring is preferred in that the rate of polymerization reaction is not too fast compared to an isocyanate compound having an aromatic ring, and the polymerization reaction is easier to control.
• the monomer for an optical material may contain an isocyanate compound having an aromatic ring and an isocyanate compound having no aromatic ring.
• the ratio (A:B) of the isocyanate compound A having no aromatic ring to the isocyanate compound B having an aromatic ring is preferably within a range of 3:7 to 0:10, and more preferably within a range of 2:8 to 0:10.
• the optical material monomer contains an isocyanate compound that does not have an aromatic ring and an isocyanate compound that has an aromatic ring
• the number of moles of isocyanate groups in the isocyanate compound that does not have an aromatic ring is smaller than the number of moles of isocyanate groups in the isocyanate compound that has an aromatic ring.
• the isocyanate compound preferably includes at least one selected from isophorone diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,6-hexamethylene diisocyanate, and 1,5-pentamethylene diisocyanate, It is more preferable that the diisocyanate compound contains at least one selected from the group consisting of isophorone diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane,
• active hydrogen compounds examples include a polythiol compound having two or more mercapto groups, a hydroxythiol compound containing one or more mercapto groups and one or more hydroxyl groups, a polyol compound containing two or more hydroxyl groups, and an amine compound.
• active hydrogen compound oligomers of the above active hydrogen compounds and halogen-substituted products (for example, chlorine-substituted products, bromine-substituted products, etc.) of the above active hydrogen compounds may be used.
• the active hydrogen compounds may be used alone or in combination of two or more.
• polythiol compounds having two or more mercapto groups include the compounds exemplified in WO 2016/125736.
• the polythiol compound is preferably 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetraacetate, It is preferable that the mercapto tetrakis (3-mercaptopropionate), bis(mercaptoethyl)
• the monomer comprises at least one selected from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), and 2,5-bis(mercaptomethyl)-1,4-dithiane; It is more preferable that the monomer contains at least one selected from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-
• the active hydrogen compound also includes a polythiol compound having three or more mercapto groups.
• the polymerizable composition contains a polythiol compound having three or more mercapto groups as an active hydrogen compound, from the viewpoint of promoting the polymerization reaction, it preferably contains a compound in which at least one mercapto group among the three or more mercapto groups contained in the polythiol compound having three or more mercapto groups is substituted with a group represented by the following formula (N1) (also referred to as compound (N1)).
• the peak area of the compound (N1) is preferably 3.0 or less, and more preferably 1.5 or less, per 100 of the peak area of the polythiol compound having three or more mercapto groups.
• the peak area of the compound (N1) is preferably 0.01 or more relative to 100 of the peak area of the polythiol compound having three or more mercapto groups, from the viewpoint of promoting the polymerization reaction.
• the peak area by high performance liquid chromatography can be measured by the method described in paragraph 0146 of WO 2014/027665, etc.
• thiol compounds having a hydroxy group examples include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin bis(mercaptoacetate), 4-mercaptophenol, 2,3-dimercapto-1-propanol, pentaerythritol tris(3-mercaptopropionate), and pentaerythritol tris(thioglycolate).
• the polyol compound may be one or more aliphatic or alicyclic alcohols. Specific examples include linear or branched aliphatic alcohols, alicyclic alcohols, and alcohols obtained by adding at least one selected from the group consisting of ethylene oxide, propylene oxide, and ⁇ -caprolactone to these alcohols. More specific examples include the compounds exemplified in WO 2016/125736.
• the polyol compound is preferably at least one selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol.
• amine compound examples include ethylenediamine, 1,2- or 1,3-diaminopropane, 1,2-, 1,3- or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-, 1,3- or 1,4-diaminocyclohexane, o-, m- or p-diaminobenzene, 3,4- or 4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3' or primary polyamine compounds such as 4,4'-diaminodiphenyl
• the molar ratio of the sum of hydroxyl groups (OH groups) and mercapto groups (SH groups) in the active hydrogen compound to the isocyanate groups (NCO groups) in the isocyanate compound is preferably 1.2 or less, more preferably 1.15 or less, and even more preferably 1.1 or less.
• the total proportion of the isocyanate compound and the active hydrogen compound in the entire monomers for optical materials is preferably more than 70 mass%, more preferably 75 mass% or more, and even more preferably 80 mass% or more.
• the total proportion of the isocyanate compound and the active hydrogen compound in the entire monomer for an optical material may be 100% by mass, less than 100% by mass, 95% by mass or less, or 90% by mass or less.
• the polymerizable composition contains at least one basic polymerization catalyst.
• the basic polymerization catalyst may be used alone or in combination of two or more kinds.
• Examples of the basic polymerization catalyst include amine-based catalysts (including imidazole-based catalysts).
• Specific examples of the amine catalyst include triethylenediamine, N,N-dimethylethanolamine, triethylamine, N-ethylmorpholine, 2-methylpyrazine, pyridine, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, 2,4-lutidine, 3,4-lutidine, 2-methyl-5-ethylpyridine, 3,5-diethylpyridine, 2,3,5-collidine, 2,3-cyclopentenopyridine, 2,3-cyclohexenopyridine, 2,3-cycloheptenopyridine, 2- Examples of such amines include phenylpyridine, 4-phenylpyridine, 2-(4-methylphenyl)pyridine, 2,6-lutidine, 3,5-lutidine
• an amine catalyst is preferred.
• Preferred amine catalysts include tertiary amine catalysts such as 3,5-lutidine, 2,6-lutidine, 2,4,6-collidine, 2-ethylpyridine, 2,4-lutidine, 2-methyl-5-ethylpyridine, 2,3,5-collidine, triethylenediamine, N,N-dimethylethanolamine, triethylamine, and N-ethylmorpholine.
• the amine catalyst contains at least one selected from 3,5-lutidine, 2,6-lutidine, 2,4,6-collidine, 2-ethylpyridine, 2,4-lutidine, 2-methyl-5-ethylpyridine, 2,3,5-collidine, triethylenediamine, and N-ethylmorpholine.
• the basic polymerization catalyst contains a compound represented by the following general formula (2) and/or a compound represented by the following general formula (3).
• R 1 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a halogen atom, and a plurality of R 1s may be the same or different.
• Q represents a carbon atom or a nitrogen atom.
• m represents an integer of 0 to 5.
• R 2 , R 3 and R 4 each independently represent a linear alkyl group having 3 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an allyl group, or a hydrocarbon group containing a hydroxyl group.
• the pKa value of the basic polymerization catalyst is preferably 1 or more, more preferably 3 or more, and even more preferably 4 or more.
• the pKa value of the basic polymerization catalyst is preferably 9 or less, and more preferably 8 or less.
• the pKa value (acid dissociation index) can be measured, for example, by (a) the method described in The Journal of Physical Chemistry, vol. 68, number 6, page 1560 (1964), or (b) a method using an automatic potentiometric titrator (such as AT-610 (product name)) manufactured by Kyoto Electronics Manufacturing Co., Ltd. Alternatively, (c) the acid dissociation index described in Chemistry Handbook compiled by the Chemical Society of Japan (Revised 3rd Edition, June 25, 1984, published by Maruzen Co., Ltd.) can be used as the pKa value of the basic polymerization catalyst.
• the basic polymerization catalyst preferably contains at least one selected from basic polymerization catalysts having a pKa value of 4 to 8.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials is not particularly limited.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials may be selected from the range of 0.010 parts by mass to 2.0 parts by mass.
• a polymerizable composition having a content of the basic polymerization catalyst within the above range contains a larger amount of the polymerization catalyst than polymerizable compositions used in conventional methods for producing optical materials.
• reaction heat i.e., heat due to self-heating
• the polymerization reaction of the polymerizable composition rapidly increases the viscosity, suppressing thermal convection that is believed to be the cause of striae, thereby making it possible to obtain a high-quality optical material.
• the content of the basic polymerization catalyst may be determined depending on the type of isocyanate compound contained in the polymerizable composition. For example, the content of the basic polymerization catalyst may be determined depending on whether or not the isocyanate compound has an aromatic ring.
• the content of the basic polymerization catalyst per 100 parts by mass of the two or more different optical material monomers in total is preferably 0.010 parts by mass to 0.50 parts by mass.
• the polymerization reaction can be favorably promoted, and a high-quality optical material can be obtained in a short time.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials is preferably 0.020 parts by mass or more, and more preferably 0.030 parts by mass or more.
• the handleability when injecting the polymerizable composition into a mold can be improved, for example.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials is preferably 0.20 parts by mass or less, more preferably 0.10 parts by mass or less, and even more preferably 0.09 parts by mass or less.
• the content of the basic polymerization catalyst is more than 0.05 parts by mass and not more than 2.0 parts by mass per 100 parts by mass of the two or more different monomers for optical materials.
• the polymerization reaction can be favorably promoted, and therefore a high-quality optical material can be obtained in a short time.
• the polymerization reaction can be favorably promoted, and thus the releasability of the cured product when it is removed from the mold can be improved.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials is preferably 0.08 parts by mass or more, more preferably 0.10 parts by mass or more, more preferably 0.13 parts by mass or more, and even more preferably 0.15 parts by mass or more.
• the handleability when injecting the polymerizable composition into a mold can be improved, for example.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials is preferably 1.8 parts by mass or less, more preferably 1.5 parts by mass or less, even more preferably 1.0 part by mass or less, particularly preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less.
• the content of the basic polymerization catalyst in the polymerizable composition can be appropriately set depending on the type of basic polymerization catalyst, the type and amount of monomers used (isocyanate compounds, active hydrogen compounds, other components, etc.), and the desired shape of the molded product.
• the content of the basic polymerization catalyst described above is the content relative to 100 parts by mass of the monomer for an optical material including raw materials for the prepolymer.
• the range of the content of the basic polymerization catalyst described above may be appropriately changed depending on the types of the monomer for an optical material and the polymerization catalyst.
• the basic polymerization catalyst preferably satisfies the following condition 1.
• -Ea/R is -7100 or more and -2900 or less.
• Ea is the activation energy calculated by Arrhenius plot from the reaction rate constants of the two or more different monomers for optical materials at two or more different temperatures, and R is the gas constant (8.314 J/mol/K).
• the value of Ea is calculated by the following method.
• the polymerizable compositions of the present disclosure include at least one organic acid having a pKa value of less than four.
• the organic acid having a pKa value of less than 4 may be used alone or in combination of two or more kinds.
• the organic acid contained in the polymerizable composition that has a pKa value of less than 4 forms a salt with the basic polymerization catalyst and suppresses the activity of the basic polymerization catalyst. This suppresses the increase in viscosity that accompanies the polymerization reaction of the monomer after preparation of the polymerizable composition, improving the pot life.
• organic acids having a pKa value of less than 4 include 10-camphorsulfonic acid (pKa: 1.2), methanesulfonic acid (pKa: -2.6), ethanesulfonic acid (pKa: 1.8), propanesulfonic acid (pKa: 1.9), butanesulfonic acid (pKa: 1.9), paratoluenesulfonic acid (pKa: -2.8), vinylsulfonic acid (pKa: -2.7), benzenesulfonic acid (pKa: 0.7), formic acid (pKa: 3.8), and phthalic acid (pKa: 2.9).
• the organic acid may form a hydrate.
• the content of the organic acid having a pKa value of less than 4 contained in the polymerizable composition may be, for example, 0.001 part by mass or more per 100 parts by mass in total of the two or more different monomers for optical materials.
• the content of the organic acid having a pKa value of less than 4 is 0.001 part by mass or more relative to a total of 100 parts by mass of two or more different monomers for optical materials, an increase in viscosity of the polymerizable composition is effectively suppressed.
• the content of the organic acid having a pKa value of less than 4 per 100 parts by mass of the total of two or more different monomers for optical materials is preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more.
• the content of the organic acid having a pKa value of less than 4 contained in the polymerizable composition may be, for example, 1 part by mass or less per 100 parts by mass in total of two or more different monomers for optical materials.
• the content of the organic acid having a pKa value of less than 4 is 1 part by mass or less relative to a total of 100 parts by mass of two or more different monomers for optical materials, dissociation of the salt formed by the organic acid and the basic polymerization catalyst due to heat is promoted in the curing step, and the activity of the basic polymerization catalyst is easily expressed, thereby allowing the polymerization reaction to proceed quickly.
• the content of the organic acid having a pKa value of less than 4 per 100 parts by mass of the total of two or more different monomers for optical materials is preferably 0.50 parts by mass or less, and more preferably 0.1 parts by mass or less.
• the content of the organic acid having a pKa value of less than 4 described above is the content per 100 parts by mass of the monomer for optical materials, which includes the raw material for the prepolymer.
• the molar ratio (X/Y) of the organic acid (X) having a pKa value of less than 4 to the basic polymerization catalyst (Y) is preferably 0.1 to 2.0, more preferably 0.15 to 1.25, and even more preferably 0.2 to 1.2.
• the number of moles (x) of the functional groups of the organic acid having a pKa value of less than 4 in the polymerizable composition is less than the number of moles (y) of the functional groups of the basic polymerization catalyst (the molar ratio represented by x/y is less than 1.0).
• an excess amount of the basic polymerization catalyst is present in the polymerizable composition relative to the organic acid having a pKa value of less than 4.
• the polymerizable composition may include optional additives.
• Optional additives may include photochromic compounds, internal release agents, bluing agents, ultraviolet light absorbers, and the like.
• the photochromic compound is not particularly limited, and any compound that is conventionally known and can be used for photochromic lenses can be appropriately selected and used.
• any compound that is conventionally known and can be used for photochromic lenses can be appropriately selected and used.
• one or more of spiropyran compounds, spirooxazine compounds, fulgide compounds, naphthopyran compounds, bisimidazole compounds, etc. can be used depending on the desired coloring.
• the internal mold release agent may be an acidic phosphate ester.
• the acidic phosphate ester include a monophosphate ester and a diphosphate ester, and each of these may be used alone or in combination of two or more kinds.
• bluing agent examples include those that have an absorption band in the orange to yellow wavelength region of the visible light range and have the function of adjusting the hue of the optical material made of resin. More specifically, the bluing agent includes a substance that exhibits a blue to purple color.
• UV absorber examples include benzophenone-based ultraviolet absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, triazine-based ultraviolet absorbers such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and benzotriazole-based ultraviolet absorbers such as 2-(2H-benzotriazol-2-yl)-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol, and 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol.
• benzophenone-based ultraviolet absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone
• triazine-based ultraviolet absorbers such as 2-[4-[(2-hydroxy-3-dodecyloxypropy
• the polymerizable composition has a viscosity, measured with a Brookfield viscometer at 25° C. and 60 rpm, of 10 mPa ⁇ s or more, preferably 40 mPa ⁇ s or more, more preferably 70 mPa ⁇ s or more, even more preferably 80 mPa ⁇ s or more, particularly preferably 100 mPa ⁇ s or more, and even more preferably 120 mPa ⁇ s or more.
• the polymerizable composition has a viscosity, measured with a Brookfield viscometer under conditions of 25° C. and 60 rpm, of 1000 mPa ⁇ s or less, preferably 700 mPa ⁇ s or less, and more preferably 400 mPa ⁇ s or less.
• the viscosity of the polymerizable composition may be adjusted depending on the application of the resulting cured product.
• the edge i.e., the injection port
• the viscosity of the polymerizable composition is preferably 10 mPa ⁇ s to 100 mPa ⁇ s from the viewpoint of suppressing striae.
• the edge i.e., the injection port
• the viscosity of the polymerizable composition is preferably 10 mPa ⁇ s to 1000 mPa ⁇ s, and more preferably 100 mPa ⁇ s to 1000 mPa ⁇ s, from the viewpoint of suppressing striae.
• the viscosity of the polymerizable composition By increasing the viscosity of the polymerizable composition, thermal convection caused by the temperature difference between the inside and outside of the polymerizable composition when heat is applied from the outside can be suppressed, and striae caused by thermal convection can be reduced.
• the amount of catalyst is small as in conventional polymerizable compositions, the viscosity does not increase sufficiently during polymerization, so that the viscosity does not increase to a level sufficient to suppress thermal convection, and the temperature cannot be increased rapidly in a short period of time. Furthermore, the time required to complete the polymerization is also lengthened.
• the viscosity of the entire composition can be increased more quickly, which can suppress thermal convection caused by a sudden temperature rise while suppressing uneven polymerization, thereby allowing polymerization to proceed in a short period of time.
• the slope of the thickening rate of the polymerizable composition is preferably 0.005 or more, more preferably 0.007 or more, and even more preferably 0.01 or more. From the viewpoint of improving the pot life of the polymerizable composition, the slope of the thickening rate is preferably 0.04 or less, more preferably 0.035 or less, and even more preferably 0.03 or less.
• Y a*exp(b*X)
• the viscosity X of the polymerizable composition in the above formula is measured using a Brookfield viscometer at 25° C. and 60 rpm or 30 rpm.
• the time Y in the above formula is the time elapsed from a reference time (for example, the time when the polymerizable composition is prepared).
• the thixotropy ratio of the polymerizable composition is preferably 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less.
• the thixotropy ratio of the polymerizable composition is preferably 0.9 or more, more preferably 0.95 or more, and even more preferably 1.0 or more.
• the thixotropy ratio of the polymerizable composition is calculated by dividing the viscosity ⁇ 1 measured with a Brookfield viscometer at 25° C. and a rotation speed of 6 rpm by the viscosity ⁇ 2 measured at a rotation speed of 60 rpm.
• the thixotropy ratio of the polymerizable composition can be reduced, for example, by reducing the molecular weight of two or more types of monomers for optical materials, by suppressing the degree of polymerization of the prepolymer below a certain level, or by reducing the proportion of structures that impart elasticity in the monomer.
• the polymerizable composition preferably further contains a prepolymer which is a polymer of two or more different monomers for optical materials and has a polymerizable functional group.
• a prepolymer means a polymer that is a polymer of two or more different monomers for optical materials and has a polymerizable functional group.
• a cured product obtained by polymerizing a prepolymer and two or more different monomers for optical materials can be used as an optical material.
• the prepolymer examples include a polymer in which two types of monomers for optical materials among the monomers for optical materials are not polymerized at an equivalent ratio of 1:1, and a polymer in which two types of monomers for optical materials are polymerized at an unbalanced equivalent ratio among the monomers for optical materials.
• the polymerizable functional group refers to a functional group that can polymerize with another polymerizable functional group.
• Specific examples of the polymerizable functional group include functional groups having active hydrogen, such as an isocyanate group and a mercapto group, which will be described later.
• polymerization at an equivalent ratio of 1:1 means, for example, when polymerizing an isocyanate compound and a polythiol compound, polymerizing them in amounts such that the isocyanate group of the isocyanate compound and the mercapto group of the polythiol compound are polymerized in a molar ratio of 1:1.
• the polymerizable prepolymer composition for optical materials of the present disclosure comprises a prepolymer which is a polymer of two or more different monomers for optical materials and has a polymerizable functional group, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4, wherein at least one of the two or more different monomers for optical materials is an isocyanate compound, and the viscosity of the prepolymer measured with a B-type viscometer at 25° C. and 60 rpm is 10 mPa ⁇ s to 2000 mPa ⁇ s.
• the polymerizable prepolymer composition for optical materials may be simply referred to as a "polymerizable prepolymer composition.”
• the polymerizable prepolymer composition of the present disclosure can shorten the production time of an optical material and has an excellent pot life.
• Specific examples, preferred specific examples, preferred aspects, etc. of the monomer for an optical material, the basic polymerization catalyst, and the organic acid having a pKa value of less than 4 of the polymerizable prepolymer composition are the same as the specific examples, preferred specific examples, preferred aspects, etc. of the monomer for an optical material, the basic polymerization catalyst, and the organic acid having a pKa value of less than 4 described in the section of the polymerizable composition for optical material above.
• the definition of the prepolymer in the polymerizable prepolymer composition is the same as the definition of the prepolymer described in the section on the polymerizable composition above.
• Specific examples, preferred specific examples, preferred aspects, etc. of the physical properties such as viscosity of the polymerizable prepolymer composition are the same as the specific examples, preferred specific examples, preferred aspects, etc. of the physical properties described above in the section on the polymerizable composition for optical material.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials is not particularly limited.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials may be selected from the range of 0.002 parts by mass to 4.0 parts by mass.
• the content of the basic polymerization catalyst contained in the polymerizable prepolymer composition is preferably 0.002 parts by mass to 1 part by mass per 100 parts by mass of the total of the two or more different monomers for optical materials.
• the polymerization reaction can be favorably promoted, and therefore a high-quality optical material can be obtained in a short time.
• the polymerization reaction can be favorably promoted, and thus the releasability of the cured product when it is removed from the mold can be improved.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials is preferably 0.010 parts by mass or more, more preferably 0.050 parts by mass or more, and even more preferably 0.070 parts by mass or more.
• the handleability when injecting the polymerizable prepolymer composition into a mold can be improved, for example.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of the two or more different monomers for optical materials is preferably 0.50 parts by mass or less, more preferably 0.15 parts by mass or less, and even more preferably 0.10 parts by mass or less.
• the content of the basic polymerization catalyst contained in the polymerizable prepolymer composition is preferably 0.1 to 4.0 parts by mass per 100 parts by mass of the total of the two or more different monomers for optical materials.
• the polymerization reaction can be favorably promoted, and therefore a high-quality optical material can be obtained in a short time.
• the content of the polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials is preferably 0.15 parts by mass or more, and more preferably 0.20 parts by mass or more.
• the handleability when injecting the polymerizable prepolymer composition into a mold can be improved, for example.
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials is preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, and even more preferably 1.0 part by mass or less.
• the polymerizable prepolymer composition has a viscosity, as measured with a Brookfield viscometer at 25° C. and 60 rpm, of 10 mPa ⁇ s or more, preferably 40 mPa ⁇ s or more, more preferably 70 mPa ⁇ s or more, even more preferably 80 mPa ⁇ s or more, particularly preferably 100 mPa ⁇ s or more, and even more preferably 120 mPa ⁇ s or more.
• the method for measuring the viscosity of the polymerizable prepolymer composition is as described above.
• the slope of the thickening rate of the polymerizable prepolymer composition is preferably 0.005 or more, more preferably 0.007 or more, and even more preferably 0.01 or more.
• the slope of the thickening rate is preferably 0.04 or less, more preferably 0.035 or less, and even more preferably 0.03 or less.
• the method for measuring the slope of the thickening rate of the polymerizable prepolymer composition is as described above.
• the polymerizable prepolymer composition preferably has a thixotropy ratio of 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less.
• the polymerizable prepolymer composition can be quickly filled into a polymerization vessel such as a mold, and thermal convection during polymerization can be suppressed to more effectively prevent the occurrence of striae, etc.
• the thixotropy ratio of the polymerizable prepolymer composition is preferably 0.9 or more, more preferably 0.95 or more, and even more preferably 1.0 or more.
• the method for measuring the thixotropy ratio is as described above.
• the prepolymer of the polymerizable prepolymer composition contains an isocyanate group. That is, it is preferable that not all of the isocyanate groups in the prepolymer are polymerized, but only a portion of them are polymerized, and it is preferable that 70% or more of the isocyanate groups in the isocyanate compound used in the production of the polymerizable prepolymer composition remain unpolymerized.
• the viscosity of the polymerizable prepolymer composition can be kept low even when the viscosity of the other monomer for optical materials is high, making handling easy.
• the other monomer for optical materials contains one or more selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and pentaerythritol tetrakis(3-mercaptopropionate), it is preferable that the prepolymer contains an isocyanate group from the viewpoint of handleability.
• the polymerizable prepolymer composition be such that the prepolymer is substantially free of isocyanate groups.
• the phrase “the prepolymer is substantially free of isocyanate groups” means that almost all of the isocyanate groups have been polymerized.
• the prepolymer is substantially free of isocyanate groups means that the content of isocyanate groups in the prepolymer is below the detection limit when measured with an IR spectrometer.
• the stability of the polymerizable prepolymer composition can be improved since highly reactive isocyanate groups are substantially absent.
• the polymerizable prepolymer composition has a refractive index A of the polymerizable prepolymer composition minus a refractive index B of a prepolymer raw material composition which is a composition before the formation of a prepolymer and contains two or more different types of monomers for optical materials and a polymerization catalyst (also referred to as "refractive index A - refractive index B") that is greater than 0, more preferably 0.005 or greater, and even more preferably 0.01 or greater.
• the refractive index A is the refractive index of a polymerizable prepolymer composition after a prepolymer is obtained by polymerizing a monomer for an optical material with a polymerization catalyst
• the refractive index B is the refractive index of a prepolymer raw material composition before a prepolymer is obtained by polymerizing a monomer for an optical material with a polymerization catalyst.
• the refractive index A minus the refractive index B may be 0.04 or less, or may be 0.03 or less.
• the refractive index A minus the refractive index B is preferably 0.005 or more, more preferably 0.010 or more, and the refractive index A minus the refractive index B is preferably 0.040 or less, more preferably 0.030 or less.
• the refractive index A-refractive index B is preferably 0.005 or more, more preferably 0.010 or more, and the refractive index A-refractive index B is preferably 0.035 or less, more preferably 0.025 or less.
• the cured product of the present disclosure may contain an amine as a component derived from the polymerizable composition or polymerizable prepolymer composition.
• a cured product of a polymerizable composition or a polymerizable prepolymer composition that contains an amine-based catalyst as a basic polymerization catalyst may contain an amine.
• the amount of amine contained in the cured product is not particularly limited, and may be, for example, more than 0% by mass and 1% by mass or less.
• the amine content in the cured product is preferably 0.001 mass % or more, more preferably 0.005 mass % or more, and even more preferably 0.01 mass % or more.
• the amine content in the cured product is preferably 0.50% by mass or less, more preferably 0.20% by mass or less, and even more preferably 0.10% by mass or less.
• the amine content in the cured product is preferably 0.03 mass% or more, more preferably 0.05 mass% or more, and even more preferably 0.07 mass% or more.
• the amine content in the cured product is preferably 2.5 mass % or less, more preferably 2.0 mass % or less, and even more preferably 1.5 mass % or less.
• the amine content in the cured product is the amine content measured by gas chromatography mass spectrometry from a dichloromethane composition obtained by dispersing the cured product in dichloromethane and ultrasonically extracting it.
• the amine content in the cured product was measured as follows. 200 mg of the hardened material powdered with a metal file and 3 mL of dichloromethane were placed in a centrifuge tube (volume 10 mL) and subjected to ultrasonic extraction at room temperature for 10 minutes using an ultrasonic cleaner (Iuchi Corporation, US-4), and then centrifuged at 4000 rpm for 10 minutes using a centrifuge (KUBOTA Corporation, mini tabletop centrifuge 2410).
• the supernatant is collected, and the residue is dispersed again in 3 mL of dichloromethane, and the above-mentioned ultrasonic extraction and centrifugation are performed, and the supernatant is collected (hereinafter also referred to as "residue extraction").
• the above residue extraction is carried out two more times, and then dichloromethane is added to the resulting supernatant so that the total volume becomes 10 mL.
• GC-MS gas chromatography mass spectrometry
• a calibration curve of the obtained peak area value derived from the amine and the amine amount is prepared, and the amine content in the cured product is measured.
• the above amine refers to an amine compound contained in the polymerizable composition or polymerizable prepolymer composition as a basic polymerization catalyst, active hydrogen compound, etc.
• the cured product of the present disclosure may contain an organic acid having a pKa value of less than 4 as a component derived from the polymerizable composition or polymerizable prepolymer composition.
• the content of the organic acid having a pKa value of less than 4 in the cured product is not particularly limited, and may be, for example, more than 0 mass % and 1 mass % or less.
• the content of the organic acid having a pKa value of less than 4 in the cured product is preferably 1 mass % or less, more preferably 0.5 mass % or less, and even more preferably 0.1 mass % or less.
• the content of the organic acid having a pKa value of less than 4 in the cured product is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.03% by mass or more.
• the content of the organic acid having a pKa value of less than 4 in the cured product is preferably 5 mass % or less, more preferably 3 mass % or less, and even more preferably 1 mass % or less.
• the content of organic acids in the cured product with a pKa value of less than 4 is measured in the same manner as the content of amines described above.
• the devitrification index of the cured product is preferably less than 50, and more preferably less than 35.
• the devitrification degree of the cured product is measured by the following method. Light from a light source (e.g., Luminar Ace LA-150A manufactured by Hayashi Lepic Co., Ltd.) is transmitted through the cured product in a dark place. An image of the light transmitted through the cured product is captured into an image processing device (e.g., an image processing device manufactured by Ube Information Systems Co., Ltd.), and the captured image is subjected to shading processing. The degree of shading of the processed image is quantified for each pixel, and the value calculated as the average value of the numerical values of the degree of shading of each pixel is regarded as the devitrification degree.
• a light source e.g., Luminar Ace LA-150A manufactured by Hayashi Lepic Co., Ltd.
• an image processing device e.g., an image processing device manufactured by Ube Information Systems Co., Ltd.
• the cured product may be a cured product of two or more different optical monomers, at least one of which is an isocyanate compound, which is free of striae with a length of 1.0 mm or more within a radius of 15 mm from the center of the cured product, which has an amine content of more than 0 mass% as measured by gas chromatography-mass spectrometry, and which has an organic acid content of more than 0 mass% having a pKa value of less than 4 as measured by gas chromatography-mass spectrometry.
• an isocyanate compound which is free of striae with a length of 1.0 mm or more within a radius of 15 mm from the center of the cured product, which has an amine content of more than 0 mass% as measured by gas chromatography-mass spectrometry, and which has an organic acid content of more than 0 mass% having a pKa value of less than 4 as measured by gas chromatography-mass spectrometry.
• the content of amines as measured by gas chromatography-mass spectrometry may be 1% by mass or less, and the content of organic acids having a pKa value of less than 4 as measured by gas chromatography-mass spectrometry may be 1% by mass or less.
• the preferred range of the content of the amine or organic acid having a pKa value of less than 4 contained in the cured product is as described above.
• Methods for producing the optical material of the present disclosure include the following Production Method A and Production Method B.
• Production method A includes a preparation step of preparing a polymerizable composition containing two or more different monomers for optical materials, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4, where at least one of the two or more different monomers for optical materials is an isocyanate compound; a casting step of adjusting the viscosity of the polymerizable composition, as measured with a B-type viscometer under conditions of 25° C.
• manufacturing method A can maintain the quality of the resulting optical material and shorten the manufacturing time of the optical material.
• the manufacturing method A may include the above-mentioned preparation step, the above-mentioned casting step, and the above-mentioned curing step, in this order.
• striae refers to a state in which the refractive index of a specific portion is different from the normal refractive index of the surrounding area. It can also be expressed as a state in which a disadvantage occurs in the intended use of an optical material. In optical materials, striae is a type of defect.
• the content of the basic polymerization catalyst contained in the polymerizable composition may be determined according to the type of isocyanate compound contained in the polymerizable composition.
• the content of the basic polymerization catalyst may be determined according to the presence or absence of an aromatic ring in the isocyanate compound.
• the preferred range of the content of the basic polymerization catalyst contained in the polymerizable composition is the same as the preferred range of the content of the basic polymerization catalyst contained in the polymerizable composition described above.
• the production method A includes a preparation step of preparing a polymerizable composition containing two or more different monomers for optical materials, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4, wherein at least one of the two or more different monomers for optical materials is an isocyanate compound.
• the preparation step may be a step of simply preparing a polymerizable composition that has been produced in advance, or may be a step of producing a polymerizable composition.
• the polymerizable composition is not particularly limited as long as it contains two or more different types of monomers for optical materials, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4.
• the polymerizable composition may be a ready-made product, or may be prepared by mixing at least two or more different types of monomers for optical materials, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4.
• the mixing method is not particularly limited, and known methods can be applied.
• the temperature at which the components of the polymerizable composition are mixed is not particularly limited, but is preferably 30° C. or lower, and more preferably room temperature (25° C.) or lower. From the viewpoint of the pot life of the polymerizable composition, it may be preferable to set the temperature to a temperature lower than 25° C. When the solubility of the additives such as the internal mold release agent and each of the above components is not good, the above components may be heated in advance to dissolve the additives in each of the above components.
• the preparation step is preferably a step of preliminarily mixing a basic polymerization catalyst and an organic acid having a pKa value of less than 4 with a part of the two or more different monomers for optical materials, and then mixing the remaining part of the two or more different monomers for optical materials with the part of the two or more different monomers for optical materials to produce a polymerizable composition.
• polymerization of the parts of the two or more different monomers for optical materials and the parts of the remainders of the two or more different monomers for optical materials can be prevented from occurring until the mixture containing the parts of the two or more different monomers for optical materials, the basic polymerization catalyst, and the organic acid having a pKa value of less than 4 is mixed with the mixture not containing the basic polymerization catalyst and the organic acid having a pKa value of less than 4 and containing the parts of the remainders of the two or more different monomers for optical materials.
• the viscosity of the polymerizable composition is 10 mPa ⁇ s or more, preferably 40 mPa ⁇ s or more, more preferably 70 mPa ⁇ s or more, even more preferably 80 mPa ⁇ s or more, particularly preferably 100 mPa ⁇ s or more, and even more preferably 120 mPa ⁇ s or more.
• the viscosity of the polymerizable composition is 1000 mPa ⁇ s or less, preferably 700 mPa ⁇ s or less, and more preferably 400 mPa ⁇ s or less.
• the method for adjusting the viscosity of the polymerizable composition is not particularly limited.
• the viscosity of the polymerizable composition may be adjusted by adding a high-viscosity compound, heating, stirring, or the like.
• the polymerizable composition in the curing step of the production method A, the polymerizable composition can be cured by leaving the polymerizable composition to stand. Therefore, in the preparation method A, it is not always necessary to heat the polymerizable composition, but the polymerizable composition may be heated in order to promote the polymerization reaction.
• the environment in which the curing step is carried out is not particularly limited, and curing can be carried out by heating from the outside of the mold. From the viewpoint of polymerizing in a short time while improving optical quality such as striae, however, a step in which the polymerizable composition is allowed to stand in a closed space to be cured is preferred.
• a closed space By leaving the polymerizable composition in a closed space, it is possible to prevent the heat generated by the self-heating of the polymerizable composition from being released to the outside. This makes it possible to retain the heat generated by the self-heating in the closed space. As a result, it is possible to promote the polymerization reaction more efficiently and produce the optical material in a shorter time.
• An example of a closed space is an insulated environment.
• the insulating environment can be created, for example, using insulating materials. That is, by placing the polymerizable composition at rest in a heat-insulating container made of a heat-insulating material, heat can be retained inside the heat-insulating container, and heat conduction between the inside and outside can be suppressed.
• the thermal conductivity of the insulating material is preferably 0.50 W/mK or less, more preferably 0.10 W/mK or less, and even more preferably 0.05 W/mK or less.
• the density of the insulating material is preferably 10 kg/m 3 or more, more preferably 15 kg/m 3 or more, and even more preferably 20 kg/m 3 or more.
• the adiabatic reactor a constant temperature state (constant temperature reactor) within a range that does not interfere with the polymerization reaction due to the reaction heat of the polymerizable composition or does not excessively promote the polymerization reaction of the polymerizable composition by heating from the outside.
• This makes it possible to maintain the environment in the reaction tank in which the mold is placed at a constant temperature or at a constant temperature depending on the temperature rise caused by the self-heating of the monomer for optical material, thereby more effectively promoting the polymerization reaction.
• an adiabatic reactor or a constant temperature reactor as described above can be used as the adiabatic environment.
• adiabatic polymerization in an adiabatic environment using the adiabatic reaction vessel can be carried out by the following procedure.
• the inside surface of the vacuum vessel is covered with a material having heat insulating and heat retaining properties such as urethane foam or cork, and the mold into which the monomer has been injected is wrapped with a material such as a rag if necessary. Then, the mold into which the monomer has been injected is left to stand in the vacuum vessel.
• the curing step may be a step in which the polymerizable composition is cured by leaving the polymerizable composition at rest without being heated from the outside.
• the preparation method A it is not always necessary to heat the polymerizable composition.
• a device may be used, which may increase the economic burden. Since the manufacturing method A allows the optical material to be manufactured by a simple method, the economic burden can be reduced.
• the polymerizable composition is preferably left to stand for 2 hours or more, and more preferably left to stand for 5 hours or more.
• the curing process may include a microwave irradiation process in which the polymerizable composition is irradiated with microwaves for a predetermined period of time.
• One embodiment of the curing step includes the following steps a and b.
• Step a A polymerizable composition is injected (cast) into a mold (into a cavity of a mold).
• Step b The mold into which the polymerizable composition has been injected is allowed to stand in a closed space for a predetermined period of time to allow adiabatic polymerization.
• Step a First, the polymerizable composition is injected into a mold (casting die) held by a gasket or tape, etc. At this time, depending on the physical properties required for the resulting optical material, it is preferable to perform a degassing treatment under reduced pressure, a filtration treatment under pressure or reduced pressure, etc., as necessary.
• the polymerization conditions are not limited, but are preferably adjusted appropriately depending on the composition of the polymerizable composition, the type and amount of the catalyst used, the shape of the mold, and the like.
• the mold into which the polymerizable composition has been poured may be left to stand in an insulated environment for 2 to 4 hours to allow polymerization to occur.
• a heating step may be added after the adiabatic polymerization process in which the mold into which the polymerizable composition has been injected is left standing in an adiabatic environment for a certain period of time.
• the mold into which the polymerizable composition has been injected in parallel with the step of leaving the mold into which the polymerizable composition has been injected in an adiabatic environment (adiabatic polymerization), the mold into which the polymerizable composition has been injected may be heated continuously or intermittently at a temperature not exceeding the self-heat generated by the polymerizable composition in the adiabatic polymerization process, or the inside of the adiabatic reaction tank may be heated to maintain the environmental temperature inside the adiabatic reaction tank.
• Preparation method A may optionally include an annealing step of annealing the cured polymerizable composition.
• the temperature at which the annealing treatment is carried out is usually 50 to 150°C, preferably 90 to 140°C, and more preferably 100 to 130°C.
• the manufacturing method A may include other steps as necessary.
• Another example of the process is an injection process of injecting a polymerizable composition into a mold when an optical material is produced using a mold.
• the optical material produced by the manufacturing method A can be used for plastic lenses, prisms, optical fibers, information recording substrates, filters, light emitting diodes, and the like.
• the optical material according to the embodiment of the present disclosure can be suitably used for plastic lenses, and more suitably used for plastic lenses for glasses.
• the production method B includes a preparation step of preparing two or more different monomers for optical materials and a basic polymerization catalyst; a prepolymerization step of mixing a portion of the two or more different monomers for optical materials with at least a portion of the basic polymerization catalyst, and polymerizing at least a portion of the portion of the two or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer; an acid addition step of adding an organic acid having a pKa value of less than 4 to the mixture containing the prepolymer; Including, At least one of the two or more different monomers for optical materials is an isocyanate compound.
• Process B includes a preparation step, a prepolymerization step, and an acid addition step, which makes it possible to suppress striae in the resulting optical material and to shorten the manufacturing time of the optical material.
• the production method B further includes a polymerizable composition production step of adding at least the remainder of the two or more different monomers for optical materials to a mixture containing the prepolymer, thereby obtaining a polymerizable composition containing two or more different monomers for optical materials, a prepolymer, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4; a curing step of curing two or more different types of monomers for optical materials in the polymerizable composition to obtain an optical material, which is a cured product of the polymerizable composition; It is preferred that the compound contains
• the content of the basic polymerization catalyst relative to a total of 100 parts by mass of the two or more different monomers for optical materials is not particularly limited.
• the content of the basic polymerization catalyst may be 0.010 parts by mass to 2.0 parts by mass relative to a total of 100 parts by mass of the two or more different monomers for optical materials.
• a polymerizable composition having a content of the basic polymerization catalyst within the above range contains a larger amount of the basic polymerization catalyst than those produced by conventional methods for producing optical materials. Therefore, similarly to the case of Production Method A, a high-quality optical material with suppressed striae can be obtained in a shorter time than before.
• Manufacturing method B includes a preparation step, a prepolymerization step, a polymerizable composition production step, and a curing step, and thus can suppress convection within the mold in which the polymerization reaction takes place, and can suppress the occurrence of striae in the obtained cured product. Furthermore, since Production Method B includes a prepolymerization step, the storage stability of the mixture (for example, a polymerizable composition) can be maintained better than in a case where prepolymerization is not performed.
• a polymerization reaction in the mixture can be suppressed, i.e., a longer pot life can be ensured.
• an organic acid having a pKa value of less than 4 added to the mixture containing the prepolymer in the acid addition step, the activity of the basic polymerization catalyst is suppressed, and the pot life of the polymerizable composition is further improved.
• the production method B includes a preparation step of preparing two or more different types of monomers for optical materials and a basic polymerization catalyst.
• the amount of the basic polymerization catalyst in the preparation step may be determined according to the type of isocyanate compound contained in the two or more different types of monomers for optical materials.
• the content of the basic polymerization catalyst may be determined according to the presence or absence of an aromatic ring in the isocyanate compound.
• the amount of the basic polymerization catalyst may be 0.010 parts by mass to 0.50 parts by mass per 100 parts by mass of the two or more different optical material monomers in total.
• the polymerization reaction can be favorably promoted, and therefore a high-quality optical material with suppressed striae can be obtained in a short time.
• the basic polymerization catalyst is preferably used in an amount of 0.015 part by mass or more, and more preferably 0.030 part by mass or more, per 100 parts by mass of the two or more different monomers for optical materials.
• the range of the content of the basic polymerization catalyst described above may be changed as appropriate depending on the type of monomer for optical materials and the basic polymerization catalyst.
• the optical material monomers include m-xylylene diisocyanate (an isocyanate compound having an aromatic ring), 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and the basic polymerization catalyst includes 3,5-lutidine, it is preferable to use 0.015 parts by mass or more of the basic polymerization catalyst, and more preferably 0.020 parts by mass or more, per 100 parts by mass of two or more different optical material monomers.
• the optical material monomer contains m-xylylene diisocyanate and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
• the basic polymerization catalyst contains 3,5-lutidine
• the amount of the basic polymerization catalyst may be more than 0.05 parts by mass and not more than 2.0 parts by mass per 100 parts by mass of the two or more different monomers for optical materials in total.
• the polymerization reaction can be favorably promoted, and therefore a high-quality optical material with suppressed striae can be obtained in a short time.
• the amount of the basic polymerization catalyst is preferably 0.08 parts by mass or more, more preferably 0.10 parts by mass or more, even more preferably 0.13 parts by mass or more, and particularly preferably 0.17 parts by mass or more, relative to 100 parts by mass of the two or more different monomers for optical materials.
• the range of the content of the basic polymerization catalyst described above may be changed as appropriate depending on the type of monomer for optical materials and the basic polymerization catalyst.
• the optical material monomers include 2,5(6)-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane, pentaerythritol tetrakis(3-mercaptopropionate), and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
• the polymerization catalyst includes 3,5-lutidine
• the handleability when injecting the polymerizable composition into a mold can be improved.
• the amount of the basic polymerization catalyst is preferably 1.5 parts by mass or less based on 100 parts by mass of the two or more different monomers for optical materials.
• the amount of the basic polymerization catalyst may be 1.0 part by mass or less, 0.3 part by mass or less, or 0.15 part by mass or less relative to 100 parts by mass of the two or more different monomers for an optical material.
• the amount of basic polymerization catalyst can be appropriately set depending on the type of basic polymerization catalyst, the type and amount of monomers used (isocyanate compounds, active hydrogen compounds, other components, etc.), the desired shape of the molded product, etc.
• Production method B includes a prepolymerization step of mixing a portion of two or more different monomers for optical materials with at least a portion of a basic polymerization catalyst, and polymerizing at least a portion of the portion of the two or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing a prepolymer.
• the present inventors believed that one of the causes of the formation of striae in the obtained cured product is convection caused by non-uniform temperature distribution in the mold in which the polymerization reaction takes place. Therefore, the present inventors have focused on the fact that a part of the monomer for an optical material is polymerized in advance to produce a prepolymer, and the polymerizable composition contains the prepolymer, thereby increasing the viscosity of the polymerizable composition for an optical material, which makes it possible to suppress convection in the mold. Furthermore, manufacturing method B can prevent the self-heated heat from escaping to the outside, thereby making it difficult for a temperature difference to occur between the inside and the periphery of the mold. It is presumed that the combination of the above-mentioned aspects makes it possible for Process B to suppress striae in the resulting cured product.
• Process B makes it possible to obtain a prepolymer with excellent pot life.
• the embodiment of the "part of two or more different monomers for optical materials” is not particularly limited.
• a portion of two or more different types of monomers for optical materials may be a portion of each of two or more different types of monomers for optical materials.
• a part of two or more different types of monomers for optical materials may be one or all of a plurality of types of monomers for optical materials among the two or more different types of monomers for optical materials.
• the basic polymerization catalyst used in the prepolymerization step may be a part or the whole of the basic polymerization catalyst contained in the polymerizable composition.
• the aspect of the "part of the basic polymerization catalyst” is not particularly limited, as is the case with the "part of the two or more different monomers for an optical material".
• "a portion of a basic polymerization catalyst” may be a portion of the amount of a basic polymerization catalyst.
• the portion of the basic polymerization catalyst is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 15 to 50 parts by mass, out of 100 parts by mass of the basic polymerization catalyst.
• the portion of the two or more different optical material monomers is preferably 5 to 95 parts by mass out of 100 parts by mass of the two or more different optical material monomers, more preferably 20 to 80 parts by mass, and even more preferably 30 to 70 parts by mass.
• prepolymerization process is not limited to the following examples.
• the prepolymerization step of aspect a is a step of mixing some of the two or more different monomers for optical materials with the whole of the basic polymerization catalyst, and polymerizing at least a part of the some of the two or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing a prepolymer.
• the portion of the two or more different monomers for optical materials preferably comprises all of one of the two or more different monomers for optical materials and a portion of another monomer for optical materials other than the one monomer for optical materials.
• the prepolymerization step of aspect b is a step of mixing a portion of two or more different monomers for optical materials with a portion of a basic polymerization catalyst, and polymerizing at least a portion of the portions of the two or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing a prepolymer.
• the polymerizable composition production step described below is a step of adding at least the remainder of two or more different types of monomers for optical materials and the remainder of the basic polymerization catalyst to a mixture containing the prepolymer, thereby obtaining a polymerizable composition containing two or more different types of monomers for optical materials, the prepolymer, the basic polymerization catalyst, and an organic acid having a pKa value of less than 4.
• the two or more different monomers for optical materials contain an isocyanate compound, a portion of the two or more different monomers for optical materials contains a portion of an isocyanate compound, and the remainder of the two or more different monomers for optical materials contains a remainder of an isocyanate compound.
• Process B includes an acid addition step of adding an organic acid having a pKa value of less than 4 to a mixture containing the prepolymer.
• the amount of the organic acid having a pKa value of less than 4 added to the mixture containing the prepolymer there is no particular limitation on the amount of the organic acid having a pKa value of less than 4 added to the mixture containing the prepolymer.
• the content of the organic acid having a pKa value of less than 4 may be 0.001 part by mass to 1 part by mass relative to a total of 100 parts by mass of two or more different monomers for optical materials that are raw materials for the prepolymer.
• the content of the organic acid having a pKa value of less than 4 is 0.001 part by mass or more relative to a total of 100 parts by mass of the two or more different monomers for optical materials, an increase in viscosity of the polymerizable composition is effectively suppressed.
• the content of the organic acid having a pKa value of less than 4 relative to a total of 100 parts by mass of two or more different monomers for optical materials is preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more.
• the content of the organic acid having a pKa value of less than 4 is 1 part by mass or less relative to a total of 100 parts by mass of two or more different monomers for optical materials, dissociation of the salt formed by the organic acid and the basic polymerization catalyst due to heat is promoted in the curing step, and the activity of the basic polymerization catalyst is easily expressed, thereby allowing the polymerization reaction to proceed quickly.
• the content of the organic acid having a pKa value of less than 4 per 100 parts by mass of the total of two or more different monomers for optical materials is preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less.
• the temperature at which the mixture containing the prepolymer is prepared is not particularly limited as long as the prepolymer can be obtained by the polymerization reaction.
• the temperature may be 20° C. to 50° C., or 25° C. to 45° C.
• the stirring time during preparation of the mixture containing the prepolymer is not particularly limited as long as it is a stirring time that allows a prepolymer to be obtained by a polymerization reaction, and may be, for example, 30 minutes to 5 hours, or 1 hour to 5 hours.
• Preparation method B includes a polymerizable composition production step of adding at least the remainder of two or more different types of monomers for optical materials to a mixture containing a prepolymer, thereby obtaining a polymerizable composition containing two or more different types of monomers for optical materials, a prepolymer, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4.
• the polymerizable composition production step is a step of adding the remainder of at least two or more different types of monomers for optical materials to a mixture containing a prepolymer, thereby obtaining a polymerizable composition for optical materials containing two or more different types of monomers for optical materials, a prepolymer, a basic polymerization catalyst, and an organic acid having a pKa value of less than 4. This makes it possible to prevent polymerization between the prepolymer and the remainder of the two or more different monomers for optical materials from occurring until the mixture containing the prepolymer and the remainder of the two or more different monomers for optical materials are mixed together.
• the polymerizable composition production step at an appropriate time, it is possible to improve the handling properties when, for example, injecting the polymerizable composition into a mold.
• the addition may be carried out in a single time or in multiple times.
• the polymerizable composition was filtered through a 1 ⁇ m PTFE filter and injected at a rate of 10 g/sec into a mold having a cavity for producing a lens, which was composed of a 4-curve glass mold (upper mold) having a diameter of 78 mm and a 4-curve glass mold (lower mold) having a diameter of 78 mm.
• the mold into which the polymerizable composition was injected was placed in a polymerization oven, and the temperature was raised from 20° C. to 120° C. over 10 hours.
• the molded body in which the polymerizable composition had been cured was released from the mold, and further annealed at 120° C. for 2 hours to obtain a molded body (lens).
• Example 1-2 A molded body (lens) was obtained in the same manner as in Example 1-1, except that the production method of the mixture 1 containing the prepolymer was changed as follows. 1.50 parts by mass of Tinuvin 329 [ultraviolet absorber] manufactured by BASF and 46.80 parts by mass of m-xylylene diisocyanate [monomer a1 for optical materials] were mixed and stirred at 25 ° C for 1 hour to completely dissolve, and a mixed solution was obtained.
• Tinuvin 329 ultraviolet absorber
• m-xylylene diisocyanate monomer a1 for optical materials
• Molded bodies were obtained in the same manner as in Example 1-1, except that prepolymer-containing mixture 1 and prepolymer-containing mixture 2 were changed to those shown in Table 1. Specifically, the monomer for optical materials used in preparing the mixture 1 containing a prepolymer and the mixture 2 containing a prepolymer was changed from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane [monomer for optical materials b1] to a mixture of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane [monomer for optical materials b2], and the amount of each component was changed to the amount shown
• Molded bodies were obtained in the same manner as in Example 1-2, except that prepolymer-containing mixture 1 and prepolymer-containing mixture 2 were changed to those shown in Table 1. Specifically, the monomer for optical materials used in preparing the mixture 1 containing a prepolymer and the mixture 2 containing a prepolymer was changed from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane [monomer for optical materials b1] to a mixture of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane [monomer for optical materials b2], and the amount of each component was changed to the amount shown
• Comparative Example 1-1 A molded article (lens) was obtained in the same manner as in Example 1-1, except that ( ⁇ )-10-camphorsulfonic acid was not used in the preparation of the prepolymer-containing mixture 1.
• Comparative Examples 1-3 A molded article (lens) was obtained in the same manner as in Example 1-3, except that ( ⁇ )-10-camphorsulfonic acid was not used in the preparation of the prepolymer-containing mixture 1.
• Comparative Examples 1 to 4 A molded article (lens) was obtained in the same manner as in Example 1-3, except that in the preparation of the prepolymer-containing mixture 1, octylic acid was used instead of ( ⁇ )-10-camphorsulfonic acid.
• Example 2-1 0.10 parts by mass of MR internal release agent [internal release agent] manufactured by Mitsui Chemicals, 1.5 parts by mass of Tinuvin 329 [ultraviolet absorber] manufactured by BASF, and 43.07 parts by mass of a mixture of 2,5-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane [monomer a1 for optical materials] were mixed and stirred for 1 hour at 25 ° C. to obtain a mixed solution by completely dissolving.
• a polymerizable composition was obtained by mixing the prepolymer-containing mixture 1 and the prepolymer-containing mixture 2 at 20° C.
• the obtained polymerizable composition was transferred to a casting mold (i.e., a mold) while being mixed again in a static mixer.
• the viscosity of the polymerizable composition when it was delivered to the mold and cast was adjusted to a value shown in Table 1.
• the polymerizable composition was filtered through a 1 ⁇ m PTFE filter and injected at a rate of 10 g/sec into a mold having a cavity for producing a lens, which was composed of a 4-curve glass mold (upper mold) having a diameter of 78 mm and a 4-curve glass mold (lower mold) having a diameter of 78 mm.
• the mold into which the polymerizable composition was injected was placed in a polymerization oven, and the temperature was raised from 20° C. to 120° C. over 10 hours.
• the molded body in which the polymerizable composition had been cured was released from the mold, and further annealed at 120° C. for 2 hours to obtain a molded body (lens).
• Example 2-2 A molded body (lens) was obtained in the same manner as in Example 2-1, except that the production method of the prepolymer-containing mixture 1 was changed as follows. 0.1 parts by mass of MR internal release agent [internal release agent] manufactured by Mitsui Chemicals, 1.5 parts by mass of Tinuvin 329 [ultraviolet absorber] manufactured by BASF, and 48.07 parts by mass of a mixture of 2,5-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)-bicyclo-[2.2.1]-heptane [monomer a1 for optical materials] were mixed and stirred for 1 hour at 25 ° C.
• Comparative Example 2-1 A molded article (lens) was obtained in the same manner as in Example 2-1, except that ( ⁇ )-10-camphorsulfonic acid was not used in the preparation of the prepolymer-containing mixture 1.

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