Polymerizable composition for optical material, polymerizable prepolymer composition for optical material, cured product, and method for producing optical material

Abstract

The polymerizable composition for optical materials of the present disclosure contains 2 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 aforementioned 2 or more different monomers for optical materials being an isocyanate compound, and the viscosity measured using a B-type viscometer at 25°C at 60 rpm being 10 mPa-s to 1000 mPa-s.

Description

Technical Field

[0001] This disclosure relates to polymeric compositions for optical materials, polymeric prepolymer compositions for optical materials, cured products, and methods for manufacturing optical materials. Background Technology

[0002] As a method for manufacturing resins that can be used in optical materials for plastic lenses, for example, casting polymerization involves injecting a polymeric composition containing monomers into a mold (casting) and then heating and curing it.

[0003] In the casting polymerization method, after preparing and degassing the polymerizable composition, the polymerizable composition is injected into a mold (casting mold), heated and cured (polymerization reaction), the product is removed from the mold (demolding), and annealed, thereby obtaining optical materials (e.g., lenses, semi-finished blanks, etc.).

[0004] In casting polymerization, to improve the quality of optical materials, the polymerization reaction is typically carried out over a relatively long period (e.g., about 20 to 48 hours) while the temperature of the polymerizable composition is gradually increased by heating. Therefore, it is known that a large proportion (e.g., about 90%) of the total time required for manufacturing optical materials is spent on heating polymerization.

[0005] According to the embodiments of Patent Document 1, the mold into which the polymerizable composition is injected is gradually heated to 10°C to 120°C, and the polymer is obtained by polymerization over 20 hours.

[0006] In addition, according to the embodiments of Patent Document 2, the mold into which the polymeric composition is injected is heated little by little from 25°C to 120°C over 16 hours, and heated at 120°C for 4 hours to obtain the molded body.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2014 / 027427

[0010] Patent Document 2: International Publication No. 2014 / 133111 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] Regarding the polymeric compositions used in the methods described in Patent Documents 1 and 2, the viscosity increases rapidly after preparation, and there is room for improvement in terms of pot life (usable time).

[0013] One embodiment of this disclosure aims to address the problem of providing polymeric compositions and polymeric prepolymer compositions that can shorten the manufacturing time of optical materials and have excellent service life.

[0014] In addition, one embodiment of this disclosure aims to solve the problem of providing a method for manufacturing optical materials using the above-described polymeric composition or polymeric prepolymer composition, and a cured product.

[0015] Methods for solving problems

[0016] <1> A polymeric composition for optical materials, comprising two or more different monomers for optical materials, a basic polymerization catalyst, and an organic acid with a pKa value less than 4.

[0017] At least one of the aforementioned two or more different monomers for optical materials is an isocyanate compound.

[0018] The viscosity measured using a type B viscometer at 25°C and 60 rpm ranged from 10 mPa·s to 1000 mPa·s.

[0019] <2> The polymeric composition for optical materials as described in <1>, wherein at least one of the aforementioned two or more different monomers for optical materials is an isocyanate compound having an aromatic ring.

[0020] The content of the aforementioned alkaline polymerization catalyst is 0.010 to 0.50 parts by mass relative to a total of 100 parts by mass of the aforementioned two or more different optical material monomers.

[0021] <3> The polymeric composition for optical materials as described in <1>, wherein at least one of the aforementioned two or more different monomers for optical materials is an isocyanate compound without an aromatic ring.

[0022] The content of the aforementioned alkaline polymerization catalyst is greater than 0.05 parts by mass and less than 2.0 parts by mass relative to a total of 100 parts by mass of the aforementioned two or more different optical material monomers.

[0023] <4> The polymeric composition for optical materials as described in any one of <1> to <3> further comprises a polymer as one of the aforementioned two or more different monomers for optical materials and a prepolymer having polymeric functional groups.

[0024] <5> The polymeric composition for optical materials as described in any one of <1> to <4>, wherein the aforementioned two or more different monomers for optical materials further comprise at least one active hydrogen compound, said active hydrogen compound being selected from the group consisting of polythiols having two or more thiols, hydroxythiols containing one or more thiols and one or more hydroxyl groups, polyols containing two or more hydroxyl groups, and amine compounds.

[0025] <6> The polymeric composition for optical materials as described in any one of <1> to <5>, wherein at least one of the aforementioned two or more different optical material monomers is an active hydrogen compound, and the combined proportion of the isocyanate compound and the active hydrogen compound in the total of the aforementioned two or more different optical material monomers is greater than 70% by mass.

[0026] <7> The polymeric composition for optical materials as described in any one of <1> to <6>, wherein the number of moles of the functional groups of the aforementioned organic acid with a pKa value less than 4 is less than the number of moles of the functional groups of the aforementioned basic polymerization catalyst.

[0027] <8> The polymerizable composition for optical materials as described in any one of <1> to <7>, wherein the aforementioned basic polymerization catalyst comprises a basic polymerization catalyst with a pKa value of 4 to 8.

[0028] <9> A polymeric prepolymer composition for optical materials, comprising: a polymer of two or more different monomers for optical materials and a prepolymer having polymeric functional groups; an alkaline polymerization catalyst; and an organic acid with a pKa value less than 4.

[0029] At least one of the aforementioned two or more different monomers for optical materials is an isocyanate compound.

[0030] The viscosity measured using a type B viscometer at 25°C and 60 rpm ranged from 10 mPa·s to 2000 mPa·s.

[0031] <10> The polymeric prepolymer composition for optical materials as described in <9>, wherein at least one of the aforementioned two or more different monomers for optical materials is an isocyanate compound having an aromatic ring.

[0032] The content of the aforementioned alkaline polymerization catalyst is 0.002 to 1 part by mass relative to a total of 100 parts by mass of the aforementioned prepolymer.

[0033] <11> The polymeric prepolymer composition for optical materials as described in <9>, wherein at least one of the aforementioned two or more different monomers for optical materials is an isocyanate compound without an aromatic ring.

[0034] The content of the aforementioned alkaline polymerization catalyst is 0.1 to 4.0 parts by mass relative to a total of 100 parts by mass of the aforementioned prepolymer.

[0035] Cured form of the polymeric composition for optical materials described in any one of <12>, <1> to <8>, or the polymeric prepolymer composition for optical materials described in any one of <9> to <11>.

[0036] <13> A method for manufacturing optical materials, comprising:

[0037] The preparation step involves preparing a polymerizable composition for optical materials, wherein the polymerizable composition comprises two or more different monomers for optical materials, an alkaline polymerization catalyst, and an organic acid with a pKa value less than 4.

[0038] At least one of the aforementioned two or more different optical material monomers is an isocyanate compound;

[0039] In the casting process, the viscosity of the aforementioned polymeric composition for optical materials, measured using a type B viscometer at 25°C and 60 rpm, is adjusted to 10 mPa·s to 1000 mPa·s, and the aforementioned polymeric composition for optical materials is cast into a mold; and

[0040] The curing process involves polymerizing two or more different optical material monomers in the aforementioned optical material polymeric composition in the aforementioned mold, thereby curing the aforementioned optical material polymeric composition.

[0041] <14> The method for manufacturing optical materials as described in <13>, wherein at least one of the aforementioned two or more different optical material monomers is an isocyanate compound having an aromatic ring.

[0042] The content of the aforementioned alkaline polymerization catalyst is 0.010 to 0.50 parts by mass relative to a total of 100 parts by mass of the aforementioned two or more different optical material monomers.

[0043] <15> The method for manufacturing optical materials as described in <13>, wherein at least one of the aforementioned two or more different optical material monomers is an isocyanate compound without an aromatic ring.

[0044] The content of the aforementioned alkaline polymerization catalyst is greater than 0.05 parts by mass and less than 2.0 parts by mass relative to a total of 100 parts by mass of the aforementioned two or more different optical material monomers.

[0045] <16> A method for manufacturing optical materials, comprising:

[0046] Preparation process: Prepare two or more different monomers for optical materials and alkaline polymerization catalysts;

[0047] The prepolymerization process involves mixing a portion of the monomers of the aforementioned two or more different optical materials with at least a portion of the aforementioned alkaline polymerization catalyst, and polymerizing at least a portion of the monomers of the aforementioned two or more different optical materials to obtain a prepolymer, thereby obtaining a mixture containing the aforementioned prepolymer; and

[0048] In the acid addition step, an organic acid with a pKa value less than 4 is added to the mixture containing the aforementioned prepolymer.

[0049] At least one of the aforementioned two or more different optical material monomers is an isocyanate compound.

[0050] <17> The method for manufacturing optical materials as described in <16>, wherein at least one of the aforementioned two or more different optical material monomers is an isocyanate compound having an aromatic ring.

[0051] The total amount of the aforementioned two or more different optical material monomers is 100 parts by mass, and the amount of the aforementioned alkaline polymerization catalyst is 0.010 to 0.50 parts by mass.

[0052] <18> The method for manufacturing optical materials as described in <16>, wherein at least one of the aforementioned two or more different optical material monomers is an isocyanate compound without an aromatic ring.

[0053] The total amount of the aforementioned two or more different optical material monomers is 100 parts by mass, and the amount of the aforementioned alkaline polymerization catalyst is greater than 0.05 parts by mass and less than 2.0 parts by mass.

[0054] <19> A method for manufacturing an optical material as described in any one of <16> to <19>, further comprising:

[0055] A manufacturing process for a polymeric composition for optical materials involves adding the remainder of at least two different monomers for optical materials to a mixture comprising the aforementioned prepolymer, thereby obtaining a polymeric composition for optical materials containing the aforementioned two or more different monomers for optical materials, the aforementioned prepolymer, the aforementioned alkaline polymerization catalyst, and an organic acid with a pKa value less than 4; and

[0056] The curing process involves curing two or more different optical material monomers in the aforementioned polymeric composition for optical materials to obtain an optical material as a cured product of the aforementioned polymeric composition for optical materials.

[0057] <20> A cured product comprising two or more different optical material monomers, wherein at least one of the aforementioned two or more different optical material monomers is an isocyanate compound, and there are no ripples longer than 1.0 mm within a radius of 15 mm from the center of the cured product.

[0058] The content of amines determined by gas chromatography-mass spectrometry is greater than 0 by mass, and the content of organic acids with pKa values ​​less than 4 determined by gas chromatography-mass spectrometry is greater than 0 by mass.

[0059] <21> The cured product as described in <20>, wherein at least one of the aforementioned two or more different optical material monomers is an isocyanate compound having an aromatic ring.

[0060] The content of the aforementioned amine is 0.001% by mass or more and 0.50% by mass or less, and the content of the aforementioned organic acids with a pKa value less than 4 is 0.001% by mass or more and 1% by mass or less.

[0061] <22> The cured product as described in <20>, wherein at least one of the aforementioned two or more different optical material monomers is an isocyanate compound without an aromatic ring.

[0062] The content of the aforementioned amine is 0.03% by mass or more and 2.5% by mass, and the content of the aforementioned organic acids with a pKa value less than 4 is 0.01% by mass or more and 5% by mass.

[0063] The effects of the invention

[0064] According to one embodiment of this disclosure, polymeric compositions and polymeric prepolymer compositions that can shorten the manufacturing time of optical materials and have excellent service life can be provided.

[0065] In addition, according to one embodiment of this disclosure, a method for manufacturing optical materials using the above-described polymeric composition or polymeric prepolymer composition and a cured product can be provided. Detailed Implementation

[0066] In this public document, the range of values ​​indicated by “~” refers to the range of values ​​recorded before and after “~” as the lower and upper limits.

[0067] In this disclosure, when a composition contains multiple substances belonging to each component, unless otherwise specified, the amount of each component in the composition refers to the total amount of the multiple substances present in the composition.

[0068] In the numerical ranges described in stages in this disclosure, the upper or lower limit of one numerical range can be replaced with the upper or lower limit of other numerical ranges described in stages. Furthermore, the upper or lower limit of a numerical range described in this disclosure can be replaced with the values ​​shown in the embodiments.

[0069] In this disclosure, the term "process" refers not only to a single process, but also to any process that can be clearly distinguished from other processes, as long as it achieves the desired purpose of the process.

[0070] Polymer Compositions for Optical Materials

[0071] The polymeric composition for optical materials disclosed herein comprises two or more different monomers for optical materials, an alkaline polymerization catalyst, and an organic acid with a pKa value less than 4. At least one of the aforementioned two or more different monomers for optical materials is an isocyanate compound, and the viscosity measured using a type B viscometer at 25°C and 60 rpm is 10 mPa·s to 1000 mPa·s.

[0072] Hereinafter, polymeric compositions for optical materials will be referred to simply as "polymeric compositions".

[0073] The polymeric compositions disclosed herein can shorten the manufacturing time of optical materials and have excellent pot life.

[0074] Specifically, by using an alkaline polymerization catalyst as the polymerization catalyst and in a relatively high amount, the polymerization reaction proceeds rapidly during curing, shortening the manufacturing time of the cured optical material. However, on the other hand, there is a tendency for the viscosity of the polymerizable composition to increase and for its pot life to be short after preparation.

[0075] The polymerizable composition disclosed herein suppresses viscosity increase after preparation by containing an organic acid with a pKa value less than 4. This is believed to be because the organic acid with a pKa value less than 4 forms a salt with the basic polymerization catalyst, thereby inhibiting the activity of the basic polymerization catalyst.

[0076] It should be noted that during the curing process of the polymerizable composition, the salt formed by the organic acid with a pKa value less than 4 and the basic polymerization catalyst is dissociated by heat, and the activity of the basic polymerization catalyst is exhibited, so the polymerization reaction proceeds rapidly.

[0077] Furthermore, the polymerizable composition with excellent pot life has excellent injection properties into the mold, thus yielding a cured product with excellent optical properties (such as fewer ripples).

[0078] (Monomers for optical materials)

[0079] The polymeric composition contains two or more different optical material monomers, at least one of which is an isocyanate compound.

[0080] As a monomer for optical materials, any monomer used in the manufacture of optical materials is acceptable; there are no special limitations.

[0081] For example, it can be a monomer used to manufacture optical materials having any of the following properties.

[0082] The total light transmittance of optical materials obtained using monomers can be above 10%. The total light transmittance of the aforementioned optical materials can be measured according to JIS K 7361-1 (1997).

[0083] The haze (i.e., total haze) of optical materials obtained using monomers can be less than 10%, less than 1%, or less than 0.5%. The haze of the optical material is the value measured according to JIS-K7105 at 25°C using a haze measuring machine [(available) Tokyo Denshoku Co., Ltd., TC-HIIIDPK].

[0084] The refractive index of the optical material obtained using the optical material monomer is 1.56 or higher, preferably 1.58 or higher. The refractive index of the optical material obtained using the optical material monomer can be 1.80 or lower, or 1.75 or lower. The refractive index of the optical material can be measured according to JIS K7142 (2014).

[0085] The shape of optical materials obtained from monomers is not particularly limited and can be plate-shaped, cylindrical, cuboid, etc.

[0086] As monomers for optical materials, examples include compounds that exhibit the property of polymerization when using the alkaline polymerization catalyst described later. Specifically, examples include isocyanate compounds, polythiols having two or more thiol groups, hydroxythiols containing one or more thiol groups and one or more hydroxyl groups, polyols containing two or more hydroxyl groups, and amine compounds.

[0087] The monomers used in optical materials preferably contain isocyanate compounds and active hydrogen compounds.

[0088] The monomer for optical materials preferably contains at least one active hydrogen compound, wherein the active hydrogen compound is selected from the group consisting of polythiols having two or more thiols, hydroxythiols containing one or more thiols and one or more hydroxyl groups, polyols containing two or more hydroxyl groups, and amine compounds.

[0089] [Isocyanate compounds]

[0090] Examples of isocyanate compounds include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, and heterocyclic isocyanate compounds. These isocyanate compounds may include dimers, trimers, and prepolymers. Examples of such isocyanate compounds include compounds exemplified in International Publication No. 2011 / 055540.

[0091] In addition, as isocyanate compounds, the following can also be used: halogen-substituted compounds (e.g., chlorinated, bromine-substituted compounds, etc.), alkyl-substituted compounds, alkoxy-substituted compounds, carbodiimide-modified compounds, urea-modified compounds, or biuret-modified compounds.

[0092] The prepolymer-type modified compounds formed by the above-mentioned compounds with nitro-substituted products, polyols, etc., and the dimerization or trimerization reaction products of the above-mentioned compounds, etc.

[0093] These compounds can be used alone or in combination of two or more.

[0094] In this publication, aliphatic isocyanate compounds refer to isocyanate compounds that do not contain aromatic, alicyclic, or heterocyclic structures.

[0095] Alicyclic isocyanate compounds are isocyanate compounds that contain an alicyclic structure, do not contain an aromatic structure, and may contain a heterocyclic structure.

[0096] Aromatic isocyanate compounds refer to isocyanate compounds that contain an aromatic structure and may contain any one or a combination of aliphatic, alicyclic, and heterocyclic structures.

[0097] Heterocyclic isocyanate compounds are isocyanate compounds that contain heterocyclic structures but do not contain alicyclic or aromatic structures.

[0098] In this disclosure, aromatic heterocycles or heterocyclic structures are not aromatic rings or aromatic structures.

[0099] The monomers used for two or more different optical materials preferably include at least one selected from aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds and heterocyclic isocyanate compounds.

[0100] At least one of the monomers used in optical materials may be an isocyanate compound having an aromatic ring.

[0101] Examples of aromatic rings include benzene rings, naphthalene rings, and anthracene rings, with benzene rings being the preferred choice.

[0102] As isocyanate compounds having an aromatic ring, examples include aromatic isocyanate compounds, and more specifically, isocyanate compounds in which the isocyanate group is directly bonded to the aromatic ring, and isocyanate compounds in which the isocyanate group is bonded to the benzyl position of the aromatic ring.

[0103] Compared with isocyanate compounds without aromatic rings, isocyanate compounds with aromatic rings have highly reactive isocyanate groups that readily promote polymerization reactions, making them preferred from this perspective.

[0104] At least one of the monomers used in optical materials may be an isocyanate compound that does not have an aromatic ring.

[0105] As isocyanate compounds that do not have an aromatic ring, examples include alicyclic isocyanate compounds, heterocyclic isocyanate compounds, and aliphatic isocyanate compounds that do not have an aromatic ring.

[0106] Compared to isocyanate compounds with aromatic rings, isocyanate compounds without aromatic rings have a slower polymerization rate and are easier to control, making them a preferred choice from this perspective.

[0107] Monomers for optical materials may include isocyanate compounds with aromatic rings and isocyanate compounds without aromatic rings.

[0108] When the monomer for optical materials comprises an isocyanate compound without an aromatic ring and an isocyanate compound with an aromatic ring, from the viewpoint of controlling the polymerization reaction, the ratio (A:B) of the isocyanate compound A without an aromatic ring to the isocyanate compound B with an aromatic ring, in terms of the molar ratio of isocyanate groups, is preferably in the range of 3:7 to 0:10, more preferably in the range of 2:8 to 0:10.

[0109] When the monomer for optical materials comprises an isocyanate compound without an aromatic ring and an isocyanate compound with an aromatic ring, the molar number of isocyanate groups in the isocyanate compound without an aromatic ring is preferably less than the molar number of isocyanate groups in the isocyanate compound with an aromatic ring.

[0110] From the viewpoint of maintaining the quality of optical materials and shortening the manufacturing time of optical materials, the isocyanate compound preferably includes at least one selected from isophorone diisocyanate, 2,5-bis(isocyanate-methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate-methyl)bicyclo-[2.2.1]-heptane, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, 1,4-bis(isocyanate-methyl)cyclohexane, 1,6-hexamethylene diisocyanate, and 1,5-pentamethylene diisocyanate.

[0111] More preferably, it comprises at least one selected from isophorone diisocyanate, 2,5-bis(isocyanate-methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate-methyl)bicyclo-[2.2.1]-heptane, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, dicyclohexylmethane diisocyanate, and 1,3-bis(isocyanate-methyl)cyclohexane.

[0112] [Active hydrogen compounds]

[0113] Examples of active hydrogen compounds include polythiols with two or more thiol groups, hydroxythiols containing one or more thiol groups and one or more hydroxyl groups, polyols containing two or more hydroxyl groups, and amine compounds.

[0114] As active hydrogen compounds, oligomers of the above-mentioned active hydrogen compounds and halogen-substituted derivatives of the above-mentioned active hydrogen compounds (e.g., chlorine-substituted derivatives, bromine-substituted derivatives, etc.) can be used.

[0115] Active hydrogen compounds can be used alone or in combination of two or more.

[0116] (Polythiol compounds with two or more thiol groups)

[0117] Examples of polythiols having two or more thiol groups include compounds exemplified in International Publication No. 2016 / 125736.

[0118] From the viewpoint of maintaining the quality of optical materials and shortening their manufacturing time, the polythiol compound preferably comprises a compound 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, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane. At least one of the following: 9-trithiaundecane, pentaerythritol tetra(3-mercaptopropionate), bis(mercaptoethyl) sulfide, pentaerythritol tetra(2-mercaptoacetate), 2,5-bis(mercaptomethyl)-1,4-dithiacyclohexane, 1,1,3,3-tetra(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclobutane.

[0119] More preferably, it 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 tetra(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), and 2,5-bis(mercaptomethyl)-1,4-dithiacyclohexane.

[0120] Further preferably, it 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, and pentaerythritol tetra(3-mercaptopropionate).

[0121] (Polythiol compounds with 3 or more thiol groups)

[0122] As active hydrogen compounds, polythiols with three or more thiol groups can also be cited.

[0123] When a polymerizable composition contains a polythiol compound having three or more thiol groups as an active hydrogen compound, from the viewpoint of promoting the polymerization reaction, it is preferable to contain a compound (also called compound (N1) in which at least one of the three or more thiol groups contained in the aforementioned polythiol compound having three or more thiol groups is replaced with a group represented by the following formula (N1).

[0124] [Chemical Formula 1]

[0125]

[0126] In equation (N1), * represents the bonding position.

[0127] When the polymerizable composition contains a polythiol compound having three or more thiol groups as an active hydrogen compound, from the viewpoint of easily adjusting the polymerization reaction, when determining the peak area using high performance liquid chromatography, the peak area of ​​compound (N1) is preferably 3.0 or less, more preferably 1.5 or less, relative to the peak area 100 of the polythiol compound having three or more thiol groups.

[0128] When determining the peak area using high performance liquid chromatography, from the viewpoint of promoting polymerization, the peak area of ​​compound (N1) is preferably 0.01 or higher, relative to the peak area of ​​100 for polythiol compounds having 3 or more thiol groups.

[0129] Peak area based on high performance liquid chromatography can be determined using the method described in paragraph 0146 of International Publication No. 2014 / 027665.

[0130] (Hydroxythiol compounds containing one or more thiol groups and one or more hydroxyl groups)

[0131] Examples of thiol compounds containing hydroxyl groups include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol bis(mercaptoacetate), 4-mercaptophenol, 2,3-dimercapto-1-propanol, pentaerythritol tris(3-mercaptopropionate), pentaerythritol tris(mercaptoacetate), etc.

[0132] (Polyol compounds containing two or more hydroxyl groups)

[0133] As polyol compounds, one or more aliphatic or alicyclic alcohols can be mentioned. Specifically, examples include straight-chain or branched aliphatic alcohols, alicyclic alcohols, and alcohols obtained by adding at least one alcohol selected from the group consisting of ethylene oxide, propylene oxide, and ε-caprolactone to these alcohols. More specifically, examples include compounds exemplified in International Publication No. 2016 / 125736.

[0134] The polyol compound is preferably selected from at least one of 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.

[0135] (amine compounds)

[0136] Examples of amine compounds 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, and 4,4'-diaminodiphenylmethane. Primary polyamine compounds including diphenyl sulfide, 3,3' or 4,4'-diaminodiphenyl sulfone, 2,7-diaminofluorene, 1,5-, 1,8- or 2,3-diaminonaphthalene, 2,3-, 2,6- or 3,4-diaminopyridine, 2,4- or 2,6-diaminotoluene, meta- or p-phenylenediamine, isophorone diamine, diaminomethylbicycloheptane, 1,3- or 1,4-diaminomethylcyclohexane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, etc.

[0137] Diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di(2-ethylhexyl)amine, methylhexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N-ethylaniline, dinaphthylamine, 1-methylpiperazine, morpholine, and other monofunctional secondary amine compounds;

[0138] N,N'-Dimethylethylenediamine, N,N'-Dimethyl-1,2-diaminopropane, N,N'-Dimethyl-1,3-diaminopropane, N,N'-Dimethyl-1,2-diaminobutane, N,N'-Dimethyl-1,3-diaminobutane, N,N'-Dimethyl-1,4-diaminobutane, N,N'-Dimethyl-1,5-diaminopentane, N,N'-Dimethyl-1,6-diaminohexane, N,N'-Dimethyl-1,7-diaminoheptane, N,N'-Diethylethylenediamine, N,N'-Diethyl-1,2-diaminopropane, N,N'-Diethyl-1,3-diaminopropane, N,N' -Diethyl-1,2-diaminobutane, N,N'-diethyl-1,3-diaminobutane, N,N'-diethyl-1,4-diaminobutane, N,N'-diethyl-1,5-diaminopentane, N,N'-diethyl-1,6-diaminohexane, N,N'-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, homopiperazine, 1,1-di(4-piperidinyl)methane, 1,2-di(4-piperidinyl)ethane, 1,3-di(4-piperidinyl)propane, 1,4-di(4-piperidinyl)butane, tetramethylguanidine, and other secondary polyamine compounds; etc.

[0139] From the perspective of improving the heat resistance and refractive index of the cured product, the active hydrogen compound preferably contains a polythiol compound having two or more thiol groups.

[0140] The content of polythiols having two or more thiol groups is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, relative to the total mass of the active hydrogen compounds.

[0141] As an active hydrogen compound, the total content of 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, and pentaerythritol tetra(3-mercaptopropionate) relative to the total mass of the active hydrogen compound is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0142] In the polymerizable composition, the molar ratio (NCO group / (OH group + SH group)) of the sum of hydroxyl (OH group) and mercapto (SH group) groups in the active hydrogen compound relative to the isocyanate group (NCO group) in the isocyanate compound is preferably 0.8 or more, more preferably 0.85 or more, and even more preferably 0.9 or more.

[0143] In the polymerizable composition, the molar ratio (NCO group / (OH group + SH group)) of the sum of hydroxyl (OH group) and mercapto (SH group) groups in the active hydrogen compound relative to the isocyanate group (NCO group) in the isocyanate compound is preferably 1.2 or less, more preferably 1.15 or less, and even more preferably 1.1 or less.

[0144] When the polymerizable composition contains isocyanate compounds and active hydrogen compounds as monomers for optical materials, the total proportion of isocyanate compounds and active hydrogen compounds in the total monomers for optical materials is preferably greater than 70% by mass, more preferably 75% by mass or more, and even more preferably 80% by mass or more.

[0145] The total percentage of isocyanate compounds and active hydrogen compounds in the monomers used in optical materials can be 100% by mass, less than 100% by mass, less than 95% by mass, or less than 90% by mass.

[0146] <Alkaline Polymerization Catalyst>

[0147] The polymerizable composition contains at least one basic polymerization catalyst.

[0148] Alkaline polymerization catalysts can be used in combination, either by using only one type or by using two or more types in combination.

[0149] Examples of basic polymerization catalysts include amine catalysts (including imidazole catalysts).

[0150] As amine catalysts, specific examples include triethylenediamine, N,N-dimethylethanolamine, triethylamine, N-ethylmorpholine, 2-methylpyrazine, pyridine, α-methylpyridine, β-methylpyridine, γ-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, 2,4-dimethylpyridine, 3,4-dimethylpyridine, 2-methyl-5-ethylpyridine, 3,5-diethylpyridine, 2,3,5-trimethylpyridine, 2,3-cyclopentenopyridine, 2,3-cyclohexenopyridine, and 2... 3-Cycloheptenopyridine, 2-phenylpyridine, 4-phenylpyridine, 2-(4-methylphenyl)pyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, 3-chloropyridine, N,N-diethylaniline, N,N-dimethylaniline, hexamethylenetetramine, quinoline, isoquinoline, N,N-dimethyl-p-toluidine, N,N-dimethylpiperazine, quinalidine, 4-methylmorpholine, triallylamine, trioctylamine, 1-phenylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, etc.

[0151] Amine-based catalysts are preferred as alkaline polymerization catalysts.

[0152] Preferred amine catalysts include tertiary amine catalysts such as 3,5-dimethylpyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, 2-ethylpyridine, 2,4-dimethylpyridine, 2-methyl-5-ethylpyridine, 2,3,5-trimethylpyridine, triethylenediamine, N,N-dimethylethanolamine, triethylamine, and N-ethylmorpholine.

[0153] From the viewpoint of promoting polymerization reaction during the curing process, the amine catalyst preferably contains at least one selected from 3,5-dimethylpyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, 2-ethylpyridine, 2,4-dimethylpyridine, 2-methyl-5-ethylpyridine, 2,3,5-trimethylpyridine, triethylenediamine, and N-ethylmorpholine.

[0154] The basic polymerization catalyst also preferably contains compounds represented by general formula (2) below and / or compounds represented by general formula (3) below.

[0155] [Chemical Formula 2]

[0156]

[0157] In general formula (2), R1 represents a straight-chain alkyl group with 1 to 20 carbon atoms, a branched alkyl group with 3 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, or a halogen atom. Multiple R1s can be the same or different. Q represents a carbon atom or a nitrogen atom. m represents an integer from 0 to 5.

[0158] [Chemical Formula 3]

[0159]

[0160] In general formula (3), R2, R3 and R4 each independently represent a straight-chain alkyl group with 3 to 20 carbon atoms, a branched alkyl group with 3 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an allyl group, or a hydrocarbon group containing a hydroxyl group.

[0161] The pKa value of the alkaline polymerization catalyst is preferably 1 or higher, more preferably 3 or higher, and even more preferably 4 or higher.

[0162] The pKa value of the alkaline polymerization catalyst is preferably 9 or less, and more preferably 8 or less.

[0163] The pKa value (acid dissociation index) can be determined, for example, by the method described in (a) *The Journal of Physical Chemistry*, vol. 68, number 6, page 1560 (1964), or by the method using an automatic potentiometric titration apparatus (AT-610, etc.) manufactured by Kyoto Electronics Industry Co., Ltd. Alternatively, the acid dissociation index described in (c) *The Chemical Handbook* (revised 3rd edition, published June 25, 1959 by Maruzen Co., Ltd.) compiled by the Chemical Society of Japan can be used as the pKa value of basic polymerization catalysts.

[0164] The alkaline polymerization catalyst preferably includes at least one alkaline polymerization catalyst selected from those with a pKa value of 4 to 8.

[0165] In the polymerizable compositions disclosed herein, there is no particular limitation on 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.

[0166] For example, the content of the alkaline polymerization catalyst relative to a total of 100 parts by mass of monomers for two or more different optical materials can be selected from a range of 0.010 parts by mass to 2.0 parts by mass.

[0167] Compared to polymeric compositions used in conventional optical material manufacturing methods, polymeric compositions with an alkaline polymerization catalyst content within the aforementioned range contain a greater amount of polymerization catalyst.

[0168] Therefore, when the optical material in the polymerizable composition is polymerized with monomers during the curing process, the heat of reaction of the polymerizable composition (i.e., heat generated due to self-heating) can be generated in a short time. As a result, the polymerization reaction can be well promoted.

[0169] Furthermore, the rapid increase in viscosity due to the polymerization reaction of the polymeric composition suppresses the thermal convection that is presumably the cause of the corrugations. As a result, high-quality optical materials can be obtained.

[0170] The content of basic polymerization catalyst can be determined based on the type of isocyanate compound contained in the polymerizable composition. For example, the content of basic polymerization catalyst can be determined based on the presence or absence of an aromatic ring in the isocyanate compound.

[0171] When at least one of the two or more different optical material monomers is an isocyanate compound with an aromatic ring, the content of the basic polymerization catalyst relative to a total of 100 parts by mass of the two or more different optical material monomers is preferably 0.010 to 0.50 parts by mass.

[0172] By using an alkaline polymerization catalyst containing an isocyanate compound with an aromatic ring at a content of 0.010 parts by mass or more, the polymerization reaction can be effectively promoted, enabling the production of high-quality optical materials in a short time. Furthermore, by effectively promoting the polymerization reaction, the demolding properties when removing the cured material from the mold can be improved.

[0173] From the above perspective, the content of the alkaline 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.

[0174] By using an alkaline polymerization catalyst with an isocyanate compound having an aromatic ring in a content of 0.50 parts by mass or less, for example, it is possible to improve the operability of injecting the polymerizable composition into a mold.

[0175] From the above perspective, the content of the alkaline 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.

[0176] When at least one of the two or more different monomers for optical materials is an isocyanate compound without an aromatic ring, the content of the aforementioned basic polymerization catalyst relative to a total of 100 parts by mass of the two or more different monomers for optical materials is preferably greater than 0.05 parts by mass and less than 2.0 parts by mass.

[0177] By using an alkaline polymerization catalyst with an isocyanate compound that does not have an aromatic ring in a content greater than 0.05 parts by mass, the polymerization reaction can be well promoted, thus enabling the production of high-quality optical materials in a short time. Furthermore, by effectively promoting the polymerization reaction, the demolding properties when removing the cured material from the mold can be improved.

[0178] From the above perspective, the content of the alkaline 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, 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.

[0179] By using an alkaline polymerization catalyst with an isocyanate compound that does not have an aromatic ring in a content of 2.0 parts by mass or less, for example, it is possible to improve the operability of injecting the polymerizable composition into a mold.

[0180] From the above perspective, the content of the alkaline 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 parts by mass or less, particularly preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less.

[0181] In this disclosure, the content of the basic polymerization catalyst in the polymerizable composition can be appropriately set by 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 article.

[0182] When the polymeric composition contains a prepolymer of a polymer that is a monomer for optical materials, the content of the alkaline polymerization catalyst described above is the content of 100 parts by mass of the monomer for optical materials containing the prepolymer.

[0183] The range of the content of the alkaline polymerization catalyst mentioned above can be appropriately changed according to the type of monomer used in optical materials and the type of polymerization catalyst.

[0184] The alkaline polymerization catalyst preferably satisfies the following condition 1.

[0185] [Condition 1]

[0186] -Ea / R is above -7100 and below -2900.

[0187] (Ea is the activation energy calculated from the reaction rate constants of the aforementioned two or more different optical materials at two or more different temperatures using monomers, and R is the gas constant (8.314 J / mol / K).)

[0188] By ensuring that the alkaline polymerization catalyst meets condition 1, deviations in the polymerization rate of the polymerizable composition can be suppressed. As a result, optical strain and the generation of ridges are suppressed, leading to the production of optical materials with excellent appearance.

[0189] The value of Ea is calculated using the following method.

[0190] The value of Ea can be calculated by performing the following steps:

[0191] In the property acquisition process, a composition 1 containing a polymerization reactive compound and a specified amount of polymerization catalyst is heated to obtain property values ​​1a of the functional groups of the polymerization reactive compound before heating and property values ​​1b of the residual functional groups after heating for a specified time, under conditions of holding at various temperatures.

[0192] The residual functional group ratio calculation process calculates the residual functional group ratio 1 at various temperatures mentioned above from the physical property value 1a and physical property value 1b.

[0193] The reaction rate constant calculation procedure, based on the residual functional group ratio 1 and the reaction rate formula, calculates the reaction rate constant 1 at various aforementioned temperatures; and

[0194] The fitting process involves calculating the activation energy Ea1 and the frequency factor A1 from the reaction rate constant 1 at various aforementioned temperatures using an Arrhenius curve.

[0195] Use the calculated Ea to determine whether the polymerization catalyst satisfies condition 1.

[0196] The specific methods for calculating the Ea value and determining whether the polymerization catalyst meets condition 1 are the same as those described in International Publication No. 2020 / 256057.

[0197] <Organic acids with pKa values ​​less than 4>

[0198] The polymerizable compositions disclosed herein contain at least one organic acid with a pKa value less than 4.

[0199] Organic acids with a pKa value less than 4 can be used alone or in combination of two or more.

[0200] Organic acids with pKa values ​​less than 4 in the polymerizable composition form salts with the basic polymerization catalyst, inhibiting the activity of the catalyst. Therefore, the viscosity increase associated with the polymerization of monomers after the preparation of the polymerizable composition is suppressed, and the pot life is improved.

[0201] Examples of organic acids with pKa values ​​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), p-toluenesulfonic 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).

[0202] Organic acids can form hydrates.

[0203] For example, the content of organic acids with a pKa value of less than 4 in the polymeric composition may be 0.001 parts by mass or more, relative to a total of 100 parts by mass of monomers for two or more different optical materials.

[0204] When the content of organic acids with pKa values ​​less than 4 is 0.001 parts by mass or more relative to a total of 100 parts by mass of monomers for two or more different optical materials, the increase in viscosity of the polymerizable composition is effectively suppressed.

[0205] From the above perspective, the content of organic acids with pKa values ​​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.

[0206] For example, relative to a total of 100 parts by mass of monomers for two or more different optical materials, the content of organic acids with a pKa value of less than 4 in the polymeric composition may be less than 1 part by mass.

[0207] When the content of organic acids with pKa values ​​less than 4 is less than 1 part by mass relative to the total of 100 parts by mass of monomers used in two or more different optical materials, the thermal dissociation of the salt formed by the organic acid and the basic polymerization catalyst is promoted during the curing process, and the activity of the basic polymerization catalyst is readily exhibited. As a result, the polymerization reaction can proceed rapidly.

[0208] From the above perspective, the content of organic acids with pKa values ​​less than 4 relative to a total of 100 parts by mass of two or more different monomers for optical materials is preferably 0.50 parts by mass or less, more preferably 0.1 parts by mass or less.

[0209] When the polymeric composition contains a prepolymer of a polymer that is a monomer for optical materials, the content of the organic acid with a pKa value of less than 4 is the content relative to 100 parts by mass of the monomer for optical materials containing the prepolymer.

[0210] The molar ratio (X / Y) of an organic acid (X) with a pKa value less than 4 to an alkaline 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.

[0211] From the viewpoint of ensuring good activity of the basic polymerization catalyst, the molar number (x) of functional groups of organic acids with pKa values ​​less than 4 in the polymerizable composition is preferably less than the molar number (y) of functional groups of the basic polymerization catalyst (the molar ratio expressed as x / y is less than 1.0). That is, it is preferable that an excess of basic polymerization catalyst exists in the polymerizable composition relative to the organic acids with pKa values ​​less than 4.

[0212] (Other additives)

[0213] Polymerizable compositions may contain any additives.

[0214] Examples of any additive include photochromic compounds, internal mold release agents, bluing agents, and ultraviolet absorbers.

[0215] (Photochromic compounds)

[0216] Photochromic compounds are compounds whose molecular structure changes reversibly when exposed to light of a specific wavelength, and whose light absorption properties (absorption spectra) change accordingly.

[0217] As photochromic compounds, examples can be found that compounds whose absorption characteristics (absorption spectrum) change with respect to a specific wavelength of light.

[0218] There are no particular limitations on the photochromic compound used; any photochromic compound can be appropriately selected from those previously known compounds that can be used in photochromic lenses. For example, one or more of the following compounds can be used, depending on the desired coloring: spiropyran compounds, spiroxazine compounds, fumonisin compounds, naphthopyran compounds, and diimidazole compounds.

[0219] (Internal release agent)

[0220] Acidic phosphate esters can be used as internal mold release agents. Examples of acidic phosphate esters include monophosphate esters and diphosphate esters, and two or more types can be used individually or in combination.

[0221] (Blueing agent)

[0222] Examples of bluing agents include substances that have absorption bands in the orange to yellow wavelength region of the visible light spectrum and that function to adjust the hue of optical materials formed from resins. More specifically, bluing agents include substances that exhibit a blue to violet hue.

[0223] (UV absorber)

[0224] Examples of UV absorbers include benzophenone-based UV absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, triazine-based UV absorbers such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, benzotriazole-based UV 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.

[0225] (Viscosity)

[0226] In terms of the polymerizable composition, from the viewpoint of suppressing ripples in the cured product, the viscosity measured by a type B viscometer at 25°C and 60 rpm 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.

[0227] In terms of polymerizable compositions, from the viewpoint of maintaining operability when molding optical materials into the desired shape, the viscosity measured by a Type B viscometer at 25°C and 60 rpm is 1000 mPa·s or less, preferably 700 mPa·s or less, and more preferably 400 mPa·s or less.

[0228] The viscosity of the polymeric composition can be adjusted according to the intended use of the resulting cured product.

[0229] For example, when a cured material is obtained using a mold for a convex lens, the end face (i.e., the injection port) is narrow (e.g., 1 mm to 3 mm). Therefore, from the viewpoint of suppressing ripples, the viscosity of the polymeric composition is preferably 10 mPa·s to 100 mPa·s.

[0230] On the other hand, when a cured product is obtained using a conventional lens mold other than a convex lens, the end face (i.e., the injection port) is wide (e.g., 5 mm to 15 mm). Therefore, from the viewpoint of suppressing ripples, the viscosity of the polymeric composition is preferably 10 mPa·s to 1000 mPa·s, more preferably 100 mPa·s to 1000 mPa·s.

[0231] By increasing the viscosity of the polymeric composition, heat convection caused by the temperature difference between the inside and outside of the polymeric composition can be suppressed when heat is applied from the outside, and ripples caused by heat convection can be reduced.

[0232] If the amount of catalyst is low, as in conventional polymerizable compositions, the viscosity-increasing rate during polymerization is insufficient. Therefore, the viscosity will not increase to a level that can suppress thermal convection, and the temperature cannot rise rapidly in a short time. In addition, the time required until polymerization is complete is also longer.

[0233] On the other hand, by considering the reactivity of isocyanate compounds with aromatic rings as described in this disclosure, the amount of catalyst can be increased to an optimal range, thereby enabling a faster increase in the overall viscosity of the aforementioned composition. Consequently, polymerization unevenness can be suppressed while thermal convection caused by a rapid temperature rise can be inhibited, allowing polymerization to proceed in a short time.

[0234] (Tackification rate)

[0235] From the viewpoint of shortening the curing time of the polymeric composition, the slope of the tackification rate of the polymeric composition is preferably 0.005 or more, more preferably 0.007 or more, and even more preferably 0.01 or more.

[0236] 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.

[0237] The slope of the viscosity-increasing rate of the polymeric composition is calculated by plotting the viscosity change over time at 25°C with the horizontal axis (=X) set to time (hr) and the vertical axis (=Y) set to the viscosity of the polymeric composition (mPa·s). The value of b is then fitted using the following formula, where a is the intercept.

[0238] Y = a * exp(b * X)

[0239] The viscosity X of the polymeric composition in the above formula was measured using a type B viscometer at 25°C and 60 rpm or 30 rpm.

[0240] In the above formula, time Y is set as the elapsed time from a reference time (e.g., the time of preparation of the polymeric composition).

[0241] (Thixotropic ratio)

[0242] The thixotropic 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.

[0243] When the thixotropic ratio of the polymerizable composition is 1.3 or less, it can be rapidly filled into polymerization containers such as molds, and the heat convection during polymerization can be suppressed, thereby effectively preventing the formation of ripples and the like. As a result, the quality of the obtained optical material can be well maintained.

[0244] The thixotropic 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.

[0245] The thixotropic ratio of the polymeric composition is calculated by dividing the viscosity η1, measured by a type B viscometer at 25°C and 6 rpm, by the viscosity η2, measured at 60 rpm.

[0246] The thixotropic ratio of a polymeric composition can be reduced, for example, by reducing the molecular weight of two or more monomers used in optical materials; suppressing the degree of polymerization of the prepolymer to below a certain value; or by reducing the proportion of structures that provide elasticity in the monomers.

[0247] The polymeric composition preferably further comprises polymers that are monomers for two or more different optical materials, and prepolymers having polymeric functional groups.

[0248] In this publication, a prepolymer is defined as a polymer that is a monomer for two or more different optical materials and has polymerizable functional groups.

[0249] The cured product obtained by polymerizing the prepolymer with two or more different optical materials using monomers can be used as an optical material.

[0250] Examples of prepolymers include: polymers in which two types of optical material monomers are not polymerized in a 1:1 equivalence ratio; and polymers in which two types of optical material monomers are polymerized in an unbalanced equivalence ratio.

[0251] In this disclosure, a polymerizable functional group refers to a functional group capable of polymerizing with other polymerizable functional groups. Specifically, examples of polymerizable functional groups include isocyanate groups, mercapto groups, and other functional groups with active hydrogen, which will be described later.

[0252] In this disclosure, polymerization in a 1:1 equivalent ratio, for example, when polymerization is carried out using isocyanate compounds and polythiols, means polymerization is carried out in a molar ratio of 1:1 between the isocyanate groups of the isocyanate compound and the mercapto groups of the polythiols compound.

[0253] Polymer prepolymer compositions for optical materials

[0254] The polymeric prepolymer composition for optical materials disclosed herein comprises: a polymer having polymeric functional groups as two or more different monomers for optical materials; an alkaline polymerization catalyst; and an organic acid with a pKa value less than 4.

[0255] At least one of the aforementioned two or more different optical material monomers is an isocyanate compound, and its viscosity, measured using a type B viscometer at 25°C and 60 rpm, is 10 mPa·s to 2000 mPa·s.

[0256] Hereinafter, the polymeric prepolymer composition for optical materials will also be referred to as "polymeric prepolymer composition".

[0257] The polymeric prepolymer compositions disclosed herein can shorten the manufacturing time of optical materials and have excellent pot life.

[0258] The specific examples, preferred examples, and preferred methods of the monomer for optical materials, the basic polymerization catalyst, and the organic acid with a pKa value less than 4 in the polymerizable prepolymer composition are the same as those described in the above-mentioned polymerizable composition for optical materials.

[0259] The definition of prepolymer in polymeric prepolymer compositions is the same as that of prepolymer described in the section on polymeric compositions above.

[0260] The specific examples, preferred examples, and preferred methods of the physical properties such as viscosity of the polymeric prepolymer composition are the same as those described in the item "Polymeric Composition for Optical Materials" above.

[0261] In the polymeric prepolymer compositions disclosed herein, there is no particular limitation on the content of the alkaline polymerization catalyst relative to a total of 100 parts by mass of two or more different monomers for optical materials.

[0262] For example, the content of the alkaline polymerization catalyst relative to a total of 100 parts by mass of monomers for two or more different optical materials can be selected from a range of 0.002 parts by mass to 4.0 parts by mass.

[0263] The content of the basic polymerization catalyst can be determined based on the type of isocyanate compound contained in the polymerizable prepolymer composition. For example, the content of the basic polymerization catalyst can be determined based on the presence or absence of an aromatic ring in the isocyanate compound.

[0264] When at least one of the two or more different optical material monomers is an isocyanate compound having an aromatic ring, the content of the basic polymerization catalyst contained in the polymerizable prepolymer composition is preferably 0.002 to 1 part by mass relative to a total of 100 parts by mass of the two or more different optical material monomers.

[0265] By using an alkaline polymerization catalyst containing an isocyanate compound with an aromatic ring at a content of 0.002 parts by mass or more, the polymerization reaction can be effectively promoted, thus enabling the production of high-quality optical materials in a short time. Furthermore, by effectively promoting the polymerization reaction, the demolding properties when removing the cured material from the mold can be improved.

[0266] From the above perspective, the content of the alkaline 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.

[0267] By using an alkaline polymerization catalyst with an isocyanate compound having an aromatic ring in a content of less than 1 part by mass, for example, it is possible to improve the operability of injecting the polymeric prepolymer composition into a mold.

[0268] From the above perspective, the content of the alkaline polymerization catalyst relative to a total of 100 parts by mass of the aforementioned two or more different optical material monomers 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.

[0269] When at least one of the two or more different optical material monomers is an isocyanate compound without an aromatic ring, the content of the basic polymerization catalyst contained in the polymerizable prepolymer composition is preferably 0.1 to 4.0 parts by mass relative to a total of 100 parts by mass of the two or more different optical material monomers.

[0270] By using an alkaline polymerization catalyst containing 0.1 parts by mass or more of an isocyanate compound that does not have an aromatic ring, the polymerization reaction can be effectively promoted, thus enabling the production of high-quality optical materials in a short time. Furthermore, by effectively promoting the polymerization reaction, the demolding properties when removing the cured material from the mold can be improved.

[0271] From the above perspective, the content of the aforementioned 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.

[0272] By using an alkaline polymerization catalyst with an isocyanate compound that does not have an aromatic ring in a content of 4.0 parts by mass or less, for example, it is possible to improve the operability of injecting the polymeric prepolymer composition into a mold.

[0273] From the above perspective, the content of the alkaline 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 parts by mass or less.

[0274] (Viscosity)

[0275] In terms of polymerizable prepolymer compositions, from the viewpoint of suppressing ripples in the cured product, the viscosity measured using a type B viscometer at 25°C and 60 rpm 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.

[0276] The method for determining the viscosity of polymeric prepolymer compositions is as described above.

[0277] (Tackification rate)

[0278] From the viewpoint of shortening the curing time of the polymeric prepolymer composition, the slope of the tackification rate of the polymeric prepolymer composition is preferably 0.005 or more, more preferably 0.007 or more, and even more preferably 0.01 or more.

[0279] From the viewpoint of improving the pot life of the polymerizable prepolymer 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.

[0280] The method for determining the slope of the thickening rate of the polymeric prepolymer composition is as described above.

[0281] (Thixotropic ratio)

[0282] The thixotropic ratio of the polymeric prepolymer composition is preferably 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less.

[0283] By setting the thixotropic ratio of the polymeric prepolymer composition to 1.3 or less, the polymeric prepolymer composition can be rapidly filled into polymerization containers such as molds, and thermal convection during polymerization can be suppressed, thereby further preventing the formation of ripples and the like. As a result, the formation of ripples and the like can be suppressed in the obtained optical material, maintaining good quality.

[0284] The thixotropic ratio of the polymeric 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 determining the thixotropic ratio is as described above.

[0285] From an operational point of view, prepolymer compositions that are polymerizable sometimes preferably contain isocyanate groups.

[0286] That is, it is preferable that not all isocyanate groups in the prepolymer are polymerized, but only a portion are polymerized, and preferably more than 70% of the isocyanate groups in the isocyanate compound used in the manufacture of the polymerizable prepolymer composition remain unpolymerized.

[0287] By including isocyanate groups in the prepolymer, that is, by including more isocyanate compounds than other optical material monomers that can be polymerized with isocyanate compounds, the viscosity of the polymerizable prepolymer composition can be kept at a low level when the viscosity of the aforementioned other optical material monomers is high, making operation easier.

[0288] In particular, when one or more monomers 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 tetra(3-mercaptopropionate) are used as monomers for the aforementioned other optical materials, from an operational point of view, the prepolymer preferably contains an isocyanate group.

[0289] With regard to polymerizable prepolymer compositions, it is also preferred that the prepolymer is substantially free of isocyanate groups.

[0290] In this publication, the phrase "prepolymer substantially free of isocyanate groups" refers to a state in which approximately all isocyanate groups are polymerized.

[0291] Specifically, the statement that "the prepolymer is substantially free of isocyanate groups" means that when measured using an IR spectrometer, the content of isocyanate groups in the prepolymer is below the detection limit.

[0292] When the prepolymer does not contain isocyanate groups, the highly reactive isocyanate groups are essentially absent, thus improving the stability of the polymerizable prepolymer composition.

[0293] For the polymerizable prepolymer composition, the value obtained by subtracting the refractive index B of the prepolymer raw material composition (which is a composition prior to the formation of the prepolymer and is a composition containing two or more different monomers for optical materials and a polymerization catalyst) from the refractive index A of the polymerizable prepolymer composition (also referred to as "refractive index A - refractive index B") is preferably greater than 0, more preferably 0.005 or more, and even more preferably 0.01 or more.

[0294] Refractive index A is the refractive index of the polymerizable prepolymer composition after the optical material is polymerized with monomers and a polymerization catalyst to obtain a prepolymer, and refractive index B is the refractive index of the prepolymer raw material composition before the optical material is polymerized with monomers and a polymerization catalyst to obtain a prepolymer.

[0295] By keeping the refractive indices A and B within the aforementioned range, the viscosity of the polymeric prepolymer composition can be easily adjusted to the specified range. Furthermore, the quality (refractive index, appearance, etc.) of the cured polymeric prepolymer composition is easily stabilized.

[0296] The refractive index A and refractive index B can be below 0.04 or below 0.03.

[0297] When the prepolymer contains isocyanate groups, the refractive index A-refractive index B is preferably 0.005 or more, more preferably 0.010 or more. Furthermore, the refractive index A-refractive index B is preferably 0.040 or less, more preferably 0.030 or less.

[0298] When the prepolymer is substantially free of isocyanate groups, the refractive index A-refractive index B is preferably 0.005 or more, more preferably 0.010 or more. Furthermore, the refractive index A-refractive index B is preferably 0.035 or less, more preferably 0.025 or less.

[0299] The viscosity of the polymeric prepolymer composition is preferably not easily changed over time (i.e., stable). The viscosity stability of the polymeric prepolymer composition means that, when the polymeric prepolymer composition is stored at 20°C for 24 hours, the viscosity change before and after storage is less than 10%.

[0300] As a viscosity-stable polymeric prepolymer composition, examples include polymeric prepolymer compositions that do not contain polymeric functional groups that readily undergo polymerization reactions with the polymeric functional groups contained in the prepolymer.

[0301] "Solidified Object"

[0302] The cured product of this disclosure is a cured product of the above-mentioned polymeric composition or polymeric prepolymer composition.

[0303] The cured product of this disclosure may contain amines as a component derived from a polymeric composition or a polymeric prepolymer composition. For example, a cured product of a polymeric composition or a polymeric prepolymer composition containing an amine catalyst as a basic polymerization catalyst may contain amines. There are no particular limitations on the content of amines contained in the cured product; for example, it may be greater than 0% by mass and less than 1% by mass.

[0304] When a polymeric composition or polymeric prepolymer composition contains an isocyanate compound having an aromatic ring as a monomer for optical materials and contains an amine catalyst as an alkaline polymerization catalyst, from the viewpoint of reducing ripples in the cured product, the amine content in the cured product is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more.

[0305] From the viewpoint of improving the workability of the polymerizable composition, 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.

[0306] When a polymeric composition or polymeric prepolymer composition contains an isocyanate compound without an aromatic ring as a monomer for optical materials and contains an amine catalyst as an alkaline polymerization catalyst, from the viewpoint of reducing ripples in the cured product, the amine content in the cured product is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.07% by mass or more.

[0307] From the viewpoint of improving the workability of the polymerizable composition, the amine content in the cured product is preferably 2.5% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.5% by mass or less.

[0308] In this disclosure, the amine content in the solidified product is determined by gas chromatography-mass spectrometry of a dichloromethane composition obtained by dispersing the solidified product in dichloromethane and extracting it by ultrasonication.

[0309] The method for determining the amine content in the solidified product is as follows.

[0310] 200 mg of the solidified material, which was formed into powder with a metal file, and 3 mL of dichloromethane were placed into a centrifuge tube (volume 10 mL). The mixture was ultrasonically extracted for 10 minutes at room temperature using an ultrasonic cleaner (IUCHI, US-4). The mixture was then centrifuged at 4000 rpm for 10 minutes using a centrifuge (KUBOTA, benchtop mini centrifuge 2410).

[0311] Collect the supernatant, redisperse the residue in 3 mL of dichloromethane, perform the above ultrasonic extraction and centrifugation, and collect the supernatant (hereinafter also referred to as "residue extraction").

[0312] After performing the above residue extraction twice more, dichloromethane was added to the obtained supernatant to make the total volume 10 mL.

[0313] The obtained 10 mL supernatant was filtered and analyzed using gas chromatography-mass spectrometry (GC-MS) (GC-MS apparatus: Agilent Technologies, 6890GC / 5973NMSD, column: CP-Sil 8CB for Amine (0.25 mm ID × 30 m F.T = 0.25 μm)) to obtain the peak area values ​​derived from the amine. A standard curve was constructed based on the obtained peak area values ​​derived from the amine and the amine content, and the amine content in the solidified product was determined.

[0314] It should be noted that the amines mentioned above refer to amine compounds contained in polymeric compositions or polymeric prepolymer compositions as basic polymerization catalysts, active hydrogen compounds, etc.

[0315] The cured product of this disclosure may contain an organic acid with a pKa value less than 4 as a component derived from a polymeric composition or a polymeric prepolymer composition.

[0316] There are no particular restrictions on the content of organic acids with pKa values ​​less than 4 in the solidified product; for example, it can be greater than 0% by mass and less than 1% by mass.

[0317] When a polymeric composition or polymeric prepolymer composition contains an isocyanate compound having an aromatic ring as a monomer for optical materials, from the viewpoint of improving the pot life of the polymeric composition or polymeric prepolymer composition and reducing ripples in the cured product, the content of organic acids with a pKa value of less than 4 in the cured product is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more.

[0318] From the viewpoint of shortening the curing time of the polymerizable composition, the content of organic acids with a pKa value of less than 4 in the cured product is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.

[0319] When the polymeric composition or polymeric prepolymer composition contains an isocyanate compound without an aromatic ring as a monomer for optical materials, from the viewpoint of improving the pot life of the polymeric composition or polymeric prepolymer composition and reducing ripples in the cured product, the content of organic acids with 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.

[0320] From the viewpoint of shortening the curing time of the polymerizable composition, the content of organic acids with a pKa value of less than 4 in the cured product is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0321] In this disclosure, the content of organic acids with pKa values ​​less than 4 in the cured product is determined in the same manner as the content of amines described above.

[0322] Especially in optical applications where light transmittance is required, the devitrification of the cured material is preferably less than 50, more preferably less than 35.

[0323] The devitrification of the cured material was determined using the following method.

[0324] In a dark environment, light from a light source (e.g., a Luminar Ace LA-150A manufactured by Hayashi-Repic Co., Ltd.) is passed through a cured material. An image of the light passing through the cured material is acquired and sent to an image processing device (e.g., an image processing device manufactured by UbeInformationSystems, Inc.), where the acquired image undergoes shading processing. The shading level of the processed image is quantified for each pixel, and the value calculated as the average of the shading levels for each pixel is used as the opacity.

[0325] For the cured material, it is preferable that there are no corrugations with a length of 1.0 mm or more within a radius of 15 mm from the center of the cured material, and more preferably that there are no corrugations with a length of 1.0 mm or more within and outside a radius of 15 mm from the center of the cured material.

[0326] More specifically, the cured product may also be a cured product of two or more different optical monomers, wherein at least one of the aforementioned two or more different optical monomers is an isocyanate compound, there are no ridges longer than 1.0 mm within a radius of 15 mm from the center of the cured product, and the content of amines determined by gas chromatography-mass spectrometry is greater than 0% by mass, and the content of organic acids with pKa values ​​less than 4 determined by gas chromatography-mass spectrometry is greater than 0% by mass.

[0327] The content of amines determined by gas chromatography-mass spectrometry can be less than 1% by mass, and the content of organic acids with a pKa value less than 4 determined by gas chromatography-mass spectrometry can be less than 1% by mass.

[0328] The preferred range for the content of amines or organic acids with a pKa value less than 4 in the cured product is as described above.

[0329] The details and preferred methods of two or more different monomers for optical materials and isocyanate compounds having aromatic rings are as described above.

[0330] In the cured products of this disclosure, two or more different optical material monomers may include isocyanate compounds having aromatic rings and isocyanate compounds not having aromatic rings.

[0331] When two or more different monomers for optical materials contain isocyanate compounds without aromatic rings and isocyanate compounds with aromatic rings, from the viewpoint of controlling the polymerization reaction, the ratio of the isocyanate compound without aromatic rings to the isocyanate compound with aromatic rings, in terms of the molar ratio of isocyanate groups, is preferably in the range of 3:7 to 0:10, more preferably in the range of 2:8 to 0:10.

[0332] Manufacturing Methods of Optical Materials

[0333] The manufacturing method of the optical material disclosed herein includes the following methods A and B.

[0334] <Method A>

[0335] Method A includes: a preparation step, preparing a polymerizable composition comprising two or more different optical material monomers, an alkaline polymerization catalyst, and an organic acid with a pKa value less than 4, wherein at least one of the two or more different optical material monomers is an isocyanate compound; a casting step, adjusting the viscosity of the polymerizable composition, measured using a type B viscometer at 25°C and 60 rpm, to 10 mPa·s to 1000 mPa·s, and casting the aforementioned optical material polymerizable composition into a mold; and a curing step, curing the aforementioned polymerizable composition by polymerizing the aforementioned two or more different optical material monomers in the aforementioned polymerizable composition in the aforementioned mold.

[0336] Method A, by including the above-described preparation process, casting process, and curing process, can maintain the quality of the obtained optical material and shorten the manufacturing time of the optical material.

[0337] Method A may include the above-mentioned preparation process, the above-mentioned casting process, and the above-mentioned curing process in sequence.

[0338] In the polymerizable composition prepared in the preparation step, there is no particular limitation on the content of the basic polymerization catalyst relative to the total of 100 parts by mass of two or more different optical material monomers. For example, the content of the basic polymerization catalyst can be from 0.010 parts by mass to 2.0 parts by mass relative to the total of 100 parts by mass of two or more different optical material monomers.

[0339] Compared with conventional methods for manufacturing optical materials, polymerizable compositions with an alkaline polymerization catalyst content within the aforementioned range contain a greater amount of alkaline polymerization catalyst.

[0340] Therefore, when the optical material in the polymeric composition is polymerized with monomers during the curing process, the heat of reaction of the polymeric composition (i.e., heat generated due to self-heating) can be generated in a short time.

[0341] The aforementioned heat of reaction can be used to promote the polymerization reaction of monomers for optical materials in polymerizable compositions, thus enabling the production of high-quality optical materials in a shorter time than ever before.

[0342] In conventional methods, the polymerization reaction is mainly caused by heating the polymerizable composition. However, in preparation method A, heating of the polymerizable composition is not necessarily required.

[0343] Furthermore, Method A utilizes the self-heating of the polymerizable composition, thus enabling polymerization without excessive reliance on external heat supply. Therefore, while increasing the viscosity of the polymerizable composition described later, it is possible to suppress thermal inhomogeneity and heat convection within the polymerizable composition, thereby suppressing the formation of ripples.

[0344] It should be noted that, in this disclosure, the term "ripple" refers to a condition where the refractive index of a specific portion differs from the surrounding normal refractive index. Alternatively, it can be described as a condition that detracts from the intended use of an optical material. In optical materials, a ripple is a type of defect.

[0345] The content of basic polymerization catalyst in a polymerizable composition can be determined based on the type of isocyanate compound contained in the polymerizable composition. For example, the content of basic polymerization catalyst can be determined based on the presence or absence of an aromatic ring in the isocyanate compound.

[0346] The preferred range of the content of the basic polymerization catalyst in the polymerizable composition is the same as the preferred range of the content of the basic polymerization catalyst in the polymerizable composition described above.

[0347] <Preparation Process>

[0348] Method A includes a preparation step of preparing a polymerizable composition, wherein the polymerizable composition comprises two or more different monomers for optical materials, an alkaline polymerization catalyst, and an organic acid with a pKa value of less than 4, and at least one of the aforementioned two or more different monomers for optical materials is an isocyanate compound.

[0349] The preparation process can be either a process of preparing a pre-manufactured polymeric composition or a process of manufacturing the polymeric composition.

[0350] In the preparation process, the polymerizable composition may contain two or more different monomers for optical materials, an alkaline polymerization catalyst, and an organic acid with a pKa value of less than 4, without any particular limitation.

[0351] As a polymerizable composition, existing products can be used, or at least two different optical materials can be prepared by mixing monomers, a basic polymerization catalyst, and an organic acid with a pKa value less than 4. There are no particular limitations on the mixing method; known methods can be applied.

[0352] There is no particular limitation on the temperature at which the components of the polymeric composition are mixed, but it is preferably below 30°C, and more preferably below room temperature (25°C).

[0353] From the viewpoint of the pot life of the polymerizable composition, it is sometimes preferable to set a temperature lower than 25°C. In cases where additives such as internal release agents have poor solubility with the aforementioned components, the components can be preheated to dissolve the additives in them.

[0354] When mixing the above components, it is preferable to do so under a dry, inactive gas to prevent moisture from entering the polymerizable composition.

[0355] The aforementioned preparation process is preferably the following process: premixing an alkaline polymerization catalyst and an organic acid with a pKa value of less than 4 in a portion of the aforementioned two or more different monomers for optical materials, and then mixing the remaining portion of the two or more different monomers for optical materials to produce a polymerizable composition.

[0356] In this case, polymerization of the portion of the two or more different optical material monomers and the remaining portion of the two or more different optical material monomers can be prevented until the mixture containing a portion of two or more different optical material monomers, an alkaline polymerization catalyst, and an organic acid with a pKa value less than 4, and the mixture containing the remaining portion of two or more different optical material monomers without an alkaline polymerization catalyst and an organic acid with a pKa value less than 4.

[0357] Therefore, by performing the preparation steps in the above order, the start time of polymerization can be adjusted. This, for example, improves the operability when injecting the polymerizable composition into the mold.

[0358] The mixing of the remaining portions of two or more different optical material monomers with a mixture containing a portion of two or more different optical material monomers, an alkaline polymerization catalyst, and an organic acid with a pKa value less than 4 can be carried out in a single operation or in multiple operations.

[0359] As specific methods of preparation, the following methods can be cited as examples.

[0360] First, a portion of the monomer for optical materials and an additive (such as an internal release agent) are added to prepare a mixture. This mixture is stirred at 25°C for 1 hour to ensure complete dissolution of all components. Then, a portion of the remaining monomer for optical materials is added, and the mixture is stirred to form a homogeneous solution. This solution is then degassed to obtain the first mixture.

[0361] Next, the remaining portion of the optical material monomer, the alkaline polymerization catalyst, and an organic acid with a pKa value less than 4 were stirred at 25°C for 30 minutes to completely dissolve them, resulting in the second mixture.

[0362] Then, the first mixture is mixed with the second mixture to obtain a polymerizable composition.

[0363] <Casting Process>

[0364] Method A includes a casting process: the viscosity of the polymeric composition, measured using a type B viscometer at 25°C and 60 rpm, is adjusted to 10 mPa·s to 1000 mPa·s and then cast into a mold.

[0365] By adjusting the viscosity of the polymeric composition to the above-mentioned range for casting, ripples in the resulting optical material can be effectively suppressed.

[0366] From the above perspective, the viscosity of the polymeric 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.

[0367] From the viewpoint of maintaining operability in shaping optical materials into the desired form, the viscosity of the polymeric composition is 1000 mPa·s or less, preferably 700 mPa·s or less, and more preferably 400 mPa·s or less.

[0368] There are no particular limitations on the method for adjusting the viscosity of polymerizable compositions.

[0369] For example, the viscosity of a polymeric composition can be adjusted by adding high-viscosity compounds, heating, stirring, etc.

[0370] <Curing Process>

[0371] Method A includes a curing step of polymerizing two or more different optical materials in the aforementioned polymeric composition in a mold with monomers, thereby curing the aforementioned polymeric composition.

[0372] Method A, which includes a curing process, enables the polymerization of a polymeric composition, thereby enabling the manufacture of optical materials.

[0373] In conventional methods, the polymeric composition is heated to induce a polymerization reaction. However, in Method A, the polymeric composition is able to promote the polymerization reaction of the monomers for optical materials in the polymeric composition by increasing the heat of reaction associated with the polymerization reaction (i.e., heat generated due to self-heating).

[0374] That is, in the curing process of method A, the polymeric composition can be cured by allowing it to stand.

[0375] Therefore, in method A, heating of the polymerizable composition is not necessarily required, but it may be necessary to heat the polymerizable composition in order to promote the polymerization reaction.

[0376] There are no particular restrictions on the environment in which the curing process is carried out, and curing can also be achieved by heating from outside the mold. However, from the viewpoint of improving the optical quality of the corrugations and polymerizing in a short time, it is preferable to cure the polymerizable composition by letting it stand in a closed space.

[0377] By placing the polymerizable composition in a confined space, heat generated by the self-heating of the composition can be prevented from escaping to the outside. This allows the heat generated by self-heating to be retained within the confined space. Consequently, the polymerization reaction can be promoted more effectively, enabling the manufacture of optical materials in a shorter time.

[0378] As an enclosed space, an insulated environment can be cited as an example.

[0379] An insulated environment refers to an environment that retains heat internally and inhibits heat conduction between the interior and exterior. An environment that inhibits heat conduction between the interior and exterior is one in which the heat conduction between the interior and exterior of the enclosed space is sufficient to allow the polymeric composition to solidify when the polymeric composition is left to stand in an enclosed space.

[0380] Thermal insulation environments can be created, for example, using thermal insulation materials.

[0381] That is, by placing the polymeric composition in an insulated container formed of insulating material, heat can be retained inside the insulated container, thus inhibiting heat conduction between the inside and outside.

[0382] The thermal conductivity of the insulation material is preferably below 0.50 W / mK, more preferably below 0.10 W / mK, and even more preferably below 0.05 W / mK.

[0383] The density of the thermal insulation material is preferably 10 kg / m³. 3 The above, preferably 15 kg / m 3 The above is further optimized to 20 kg / m 3 above.

[0384] In the "heat insulation" or "heat insulation environment" of Method A, the heating for making the heat insulation reaction tank a constant temperature state (constant temperature reaction tank) is preferably carried out within a range that does not hinder the polymerization reaction based on the heat of reaction of the polymerizable composition, or does not excessively promote the polymerization reaction of the polymerizable composition due to external heating.

[0385] Therefore, based on the heating state formed by the self-heating of the monomers through optical materials, the environment inside the reaction tank with the mold placed in place can be kept at a constant temperature or a heat-preserving state, thus promoting the polymerization reaction more effectively.

[0386] As an insulated environment, for example, an insulated reaction tank or a constant temperature reaction tank as described above can be used.

[0387] For example, when a mold containing monomers is placed in a vacuum container that serves as an insulated reaction tank, insulated polymerization in an insulated environment using an insulated reaction tank (constant temperature reaction tank) can be carried out through the following steps.

[0388] The inner surface of the vacuum container is covered with heat-insulating components such as polyurethane foam and cork. The mold containing the monomer is then wrapped with fabric or other materials as needed. The mold containing the monomer is then left to stand inside the vacuum container.

[0389] The curing process can also be a process of curing the polymeric composition by allowing it to stand without external heating.

[0390] As mentioned above, heating of the polymerizable composition is not necessarily required in method A.

[0391] External heating is sometimes required, which can increase the economic burden. Method A, on the other hand, allows for the manufacture of optical materials using a simpler method, thus reducing the economic burden.

[0392] The aforementioned curing process is preferably a process in which the polymeric composition is cured by allowing it to stand for 2 to 10 hours.

[0393] According to conventional methods, polymerization typically occurs by gradually increasing the temperature while the reaction takes place over several hours to tens of hours (e.g., about 20 to 48 hours).

[0394] If the polymerization reaction time is short, the polymeric composition will not be fully cured, thus failing to obtain optical materials or resulting in a reduction in the quality of the optical materials.

[0395] However, according to method A, the quality of the obtained optical material can be maintained, and the optical material can be manufactured in a short time. Specifically, the optical material can be manufactured by letting the polymeric composition stand for less than 10 hours.

[0396] From the above perspective, it is more preferable to let the polymeric composition stand for 8 hours or less during the curing process.

[0397] Furthermore, from the viewpoint of obtaining well-cured optical materials through polymerization, it is preferable to let the polymeric composition stand for 2 hours or more, and more preferably for 5 hours or more.

[0398] In the curing process, a microwave irradiation process can also be set up to irradiate the polymeric composition with microwaves for a specified time, as needed.

[0399] As a method of curing process, examples include the following steps a and b.

[0400] Step a: Inject (cast) the polymeric composition into the mold (mold cavity).

[0401] Step b: The mold containing the polymerizable composition is placed in a closed space for a specified time to carry out heat-insulated polymerization.

[0402] (Process a)

[0403] First, the polymeric composition is injected into a molding die (mold) held in place by a liner or tape. Then, depending on the required properties of the resulting optical material, degassing under reduced pressure, filtration under pressure, or other methods are preferably performed as needed.

[0404] (Process b)

[0405] There are no limitations on the polymerization conditions, but they are preferably adjusted appropriately according to the composition of the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc.

[0406] The polymerization can be carried out by letting the mold containing the polymerizable composition stand in an insulated environment for 2 to 4 hours.

[0407] In step b, if necessary, after the heat-insulated polymerization process in which the mold containing the polymerizable composition is placed in an insulated environment for a certain period of time, a heating step can be added.

[0408] In step b, as needed, the mold containing the polymeric composition may be heated continuously or intermittently, in parallel with the step of placing the mold containing the polymeric composition in an insulated environment (insulated polymerization), at a temperature not exceeding the self-heating temperature emitted by the polymeric composition during the insulated polymerization process, or the insulated reaction tank may be heated to maintain the ambient temperature inside the insulated reaction tank.

[0409] <Annealing process>

[0410] Method A may, as needed, include an annealing process for annealing the cured polymeric composition.

[0411] The annealing temperature is typically between 50 and 150°C, preferably between 90 and 140°C, and more preferably between 100 and 130°C.

[0412] <Other Processes>

[0413] Other processes can be added to method A as needed.

[0414] As another process, for example, in the case of manufacturing optical materials using molds, there is the injection process of injecting a polymeric composition into a mold.

[0415] <Applications of Optical Materials>

[0416] The optical materials used in method A can be used for plastic lenses, edges, optical fibers, information recording substrates, filters, light-emitting diodes, etc.

[0417] The optical materials described above in the embodiments of this disclosure are suitable for use in plastic lenses, and are more suitable for use in plastic lenses for eyeglasses.

[0418] <Method B>

[0419] Method B includes:

[0420] Preparation process: Prepare two or more different monomers for optical materials and alkaline polymerization catalysts;

[0421] The prepolymerization process involves mixing a portion of the monomers of the aforementioned two or more different optical materials with at least a portion of the aforementioned alkaline polymerization catalyst, and polymerizing at least a portion of the monomers of the aforementioned two or more different optical materials to obtain a prepolymer, thereby obtaining a mixture containing the aforementioned prepolymer; and

[0422] In the acid addition step, an organic acid with a pKa value less than 4 is added to the mixture containing the aforementioned prepolymer.

[0423] At least one of the aforementioned two or more different optical material monomers is an isocyanate compound.

[0424] Method B, through a preparation process, a prepolymerization process, and an acid addition process, can suppress ripples in the obtained optical material and shorten the manufacturing time of the optical material.

[0425] In addition to the above-mentioned processes, preferred method B also includes:

[0426] The manufacturing process of the polymerizable composition involves adding the remainder of at least two different optical material monomers to a mixture comprising the aforementioned prepolymer, thereby obtaining a polymerizable composition containing two or more different optical material monomers, a prepolymer, an alkaline polymerization catalyst, and an organic acid with a pKa value less than 4; and

[0427] The curing process involves curing two or more different optical materials in a polymeric composition with monomers to obtain an optical material that is a cured product of the polymeric composition.

[0428] Method B further includes a polymer composition manufacturing process and a curing process, which enables better suppression of ridges in the obtained optical material and a shorter manufacturing time for the optical material.

[0429] In the preparation process, there is no particular limitation on the content of the alkaline polymerization catalyst relative to the total of 100 parts by mass of the monomers for two or more different optical materials. For example, the content of the alkaline polymerization catalyst can be from 0.010 parts by mass to 2.0 parts by mass relative to the total of 100 parts by mass of the monomers for two or more different optical materials.

[0430] Compared with conventional methods for manufacturing optical materials, polymerizable compositions with an alkaline polymerization catalyst content within the aforementioned range contain a greater amount of alkaline polymerization catalyst.

[0431] Therefore, similar to the case of manufacturing method A, it is possible to obtain high-quality optical materials with suppressed wave lines in a shorter time than before.

[0432] Similar to method A, in method B, heating of the polymeric composition for optical materials is not necessarily required.

[0433] Method B, through a preparation step, a prepolymerization step, a polymerizable composition manufacturing step, and a curing step, can suppress convection within the mold where the polymerization reaction takes place and can suppress the generation of ripples in the resulting cured product.

[0434] In addition, by including a prepolymerization step, method B can better maintain the storage stability of the mixture (e.g., polymeric composition) compared to the case without prepolymerization.

[0435] For example, when a mixture containing prepolymer is stored for a certain period of time, the polymerization reaction within the mixture can be suppressed. That is, a longer service life can be ensured.

[0436] Furthermore, by adding an organic acid with a pKa value less than 4 to the mixture containing the prepolymer during the acid addition process, the activity of the basic polymerization catalyst is suppressed, thereby further improving the pot life of the polymerizable composition.

[0437] <Preparation Process>

[0438] Method B includes the preparation steps of preparing two or more different monomers for optical materials and alkaline polymerization catalysts.

[0439] The amount of basic polymerization catalyst in the preparation process can be determined based on the types of isocyanate compounds contained in two or more different monomers used for optical materials. For example, the content of basic polymerization catalyst can be determined based on the presence or absence of aromatic rings in the isocyanate compounds.

[0440] When at least one of the two or more different optical material monomers is an isocyanate compound with an aromatic ring, the amount of basic polymerization catalyst may be 0.010 to 0.50 parts by mass relative to a total of 100 parts by mass of the two or more different optical material monomers.

[0441] By using 0.010 parts by mass or more of an alkaline polymerization catalyst compared to 100 parts by mass of monomers used for two or more different optical materials, the polymerization reaction can be well promoted, thus enabling the production of high-quality optical materials with suppressed ripples in a short time. Furthermore, by effectively promoting the polymerization reaction, the demolding properties when removing the cured material from the mold can be improved.

[0442] From the above perspective, relative to 100 parts by mass of monomers for two or more different optical materials, the alkaline polymerization catalyst is preferably used at 0.015 parts by mass or more, and more preferably at 0.030 parts by mass or more.

[0443] The range of the content of the alkaline polymerization catalyst mentioned above can be appropriately changed according to the type of monomer used in optical materials and the type of alkaline polymerization catalyst.

[0444] For example, when the monomers for optical materials include isophthalene 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-dimethylpyridine, the basic polymerization catalyst is preferably used at 0.015 parts by mass or more, more preferably at 0.020 parts by mass or more, relative to 100 parts by mass of the two or more different monomers for optical materials.

[0445] For example, when the monomers for optical materials include isophthalene diisocyanate and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and the basic polymerization catalyst includes 3,5-dimethylpyridine, the basic polymerization catalyst is preferably used at 0.010 parts by mass or more, more preferably at 0.015 parts by mass or more, relative to 100 parts by mass of the two or more different monomers for optical materials.

[0446] By using less than 0.50 parts by mass of an alkaline polymerization catalyst relative to 100 parts by mass of monomers for two or more different optical materials, for example, it is possible to improve the operability when injecting the polymeric composition into a mold.

[0447] From the above perspective, relative to 100 parts by mass of monomers for two or more different optical materials, the amount of alkaline polymerization catalyst is preferably 0.09 parts by mass or less, more preferably 0.07 parts by mass or less, and even more preferably 0.05 parts by mass or less.

[0448] When at least one of two or more different optical material monomers is an isocyanate compound without an aromatic ring, the amount of alkaline polymerization catalyst may be greater than 0.05 parts by mass and less than 2.0 parts by mass relative to a total of 100 parts by mass of the two or more different optical material monomers.

[0449] By using more than 0.05 parts by mass of an alkaline polymerization catalyst compared to 100 parts by mass of monomers used for two or more different optical materials, the polymerization reaction can be effectively promoted, thus enabling the production of high-quality optical materials with suppressed ripples in a short time. Furthermore, by effectively promoting the polymerization reaction, the demolding properties when removing the cured material from the mold can be improved.

[0450] From the above perspective, relative to 100 parts by mass of monomers for two or more different optical materials, the amount of alkaline 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.

[0451] The range of the content of the alkaline polymerization catalyst mentioned above can be appropriately changed according to the type of monomer used in optical materials and the type of alkaline polymerization catalyst.

[0452] For example, when the monomers for optical materials contain 2,5(6)-bis(isocyanate methyl)-bicyclo-[2.2.1]-heptane, pentaerythritol tetra(3-mercaptopropionate), and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and the polymerization catalyst contains 3,5-dimethylpyridine, the polymerization catalyst is preferably used at 0.10 parts by mass or more, more preferably at 0.17 parts by mass or more, relative to 100 parts by mass of the two or more different monomers for optical materials.

[0453] By using an alkaline polymerization catalyst that is less than 2.0 parts by mass relative to 100 parts by mass of monomers for two or more different optical materials, for example, the operability of injecting the polymeric composition into a mold can be improved.

[0454] From the above perspective, the amount of alkaline polymerization catalyst is preferably 1.5 parts by mass or less relative to 100 parts by mass of monomers for two or more different optical materials.

[0455] In addition, depending on the type of monomers for optical materials and alkaline polymerization catalysts, the alkaline polymerization catalyst can be less than 1.0 parts by mass, less than 0.3 parts by mass, or less than 0.15 parts by mass relative to 100 parts by mass of two or more different monomers for optical materials.

[0456] The amount of alkaline polymerization catalyst can be appropriately set by the type of alkaline polymerization catalyst, the type and amount of monomers used (isocyanate compounds, active hydrogen compounds, other components, etc.), and the desired shape of the molded body.

[0457] <Prepolymerization Process>

[0458] Method B includes a prepolymerization step, which involves mixing two or more different optical materials with a portion of a monomer and at least a portion of an alkaline polymerization catalyst, and polymerizing the two or more different optical materials with at least a portion of the monomer to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer.

[0459] The inventors of this application believe that convection caused by uneven temperature distribution within the mold where the polymerization reaction takes place is one of the reasons for the formation of ripples in the resulting cured product.

[0460] Therefore, the inventors of this application have focused on increasing the viscosity of the polymeric composition for optical materials by prepolymerizing a portion of the monomers used in the optical material and including the prepolymer in the polymeric composition. This, in turn, suppresses convection within the mold.

[0461] In addition, regarding manufacturing method B, by preventing the self-heating from dissipating to the outside, it is possible to prevent the temperature difference between the inside and outside of the mold from occurring.

[0462] Based on the above points, it is speculated that method B can suppress the ripples in the resulting cured material.

[0463] According to method B, a prepolymer with excellent pot life can be obtained.

[0464] There are no particular limitations on the way it is used as "part of two or more different optical material monomers".

[0465] For example, "a portion of two or more different optical material monomers" can be a portion of each of two or more different optical material monomers.

[0466] In addition, "a portion of two or more different optical material monomers" can refer to all of one or more of the two or more different optical material monomers.

[0467] The alkaline polymerization catalyst used in the prepolymerization process can be part of or all of the alkaline polymerization catalyst contained in the polymerizable composition.

[0468] When a portion of the alkaline polymerization catalyst contained in the polymerizable composition is used in the prepolymerization process, the manner in which "a portion of the alkaline polymerization catalyst" is used is not particularly limited, similar to "a portion of two or more different monomers for optical materials".

[0469] For example, "a portion of the basic polymerization catalyst" can be the amount of a portion of the basic polymerization catalyst.

[0470] When used as part of an alkaline polymerization catalyst, from the viewpoint of ensuring a long service life, the part of the alkaline polymerization catalyst is preferably 5 to 80 parts by mass of 100 parts by mass of the alkaline polymerization catalyst, more preferably 10 to 60 parts by mass, and even more preferably 15 to 50 parts by mass.

[0471] From the viewpoint of ensuring a long service life, the portion of the monomers for two or more different optical materials is preferably 5 to 95 parts by mass out of 100 parts by mass of the monomers for two or more different optical materials, more preferably 20 to 80 parts by mass, and even more preferably 30 to 70 parts by mass.

[0472] The following are examples of specific methods for the prepolymerization process, but the prepolymerization process in method B is not limited to the following methods.

[0473] (Method a)

[0474] The prepolymerization process of method a is as follows: mixing a portion of two or more different optical materials with a monomer and all of an alkaline polymerization catalyst, and polymerizing at least a portion of the two or more different optical materials with a monomer to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer.

[0475] In method a, a portion of the two or more different optical material monomers preferably consists of all of one of the two or more different optical material monomers and a portion of the other optical material monomers besides the one optical material monomer.

[0476] (Method b)

[0477] The prepolymerization process of method b is as follows: mixing a portion of monomers of two or more different optical materials with a portion of alkaline polymerization catalyst, and polymerizing at least a portion of the portion of monomers of the two or more different optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer.

[0478] In the case of the prepolymerization step in method B, the polymerizable composition manufacturing step described later is the following step: by adding at least two different monomers for optical materials and the remaining portion of an alkaline polymerization catalyst to a mixture containing the prepolymer, a polymerizable composition containing two or more different monomers for optical materials, a prepolymer, an alkaline polymerization catalyst, and an organic acid with a pKa value of less than 4 is obtained.

[0479] In method b, preferably, two or more different optical material monomers contain isocyanate compounds, a portion of the two or more different optical material monomers contains a portion of isocyanate compounds, and the remaining portion of the two or more different optical material monomers contains the remaining portion of isocyanate compounds.

[0480] <Acid Addition Process>

[0481] Method B includes an acid addition step of adding an organic acid with a pKa value less than 4 to a mixture containing the prepolymer.

[0482] There is no particular limitation on the amount of organic acid with a pKa value less than 4 added to the mixture containing the prepolymer. For example, the content of organic acid with a pKa value less than 4 may be 0.001 to 1 part by mass relative to a total of 100 parts by mass of two or more different optical material monomers that are the raw materials for the prepolymer.

[0483] By ensuring that the content of organic acids with a pKa value of less than 4 is 0.001 parts by mass or more relative to a total of 100 parts by mass of monomers for two or more different optical materials, the viscosity increase of the polymerizable composition can be effectively suppressed.

[0484] From the above perspective, the content of organic acids with pKa values ​​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.

[0485] When the content of organic acids with pKa values ​​less than 4 is less than 1 part by mass relative to the total of 100 parts by mass of monomers used in two or more different optical materials, the salt formed by the organic acid and the basic polymerization catalyst is promoted to dissociate under heat during the curing process, and the basic polymerization catalyst is easily activated. As a result, the polymerization reaction can proceed rapidly.

[0486] From the above perspective, the content of organic acids with pKa values ​​less than 4 is preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, relative to a total of 100 parts by mass of two or more different monomers for optical materials.

[0487] The molar ratio (X / Y) of an organic acid (X) with a pKa value less than 4 to an alkaline 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.

[0488] From the viewpoint of well exhibiting the activity of the basic polymerization catalyst, the number of moles (x) of functional groups of organic acids with pKa values ​​less than 4 in the mixture containing the prepolymer is preferably less than the number of moles (y) of functional groups of the basic polymerization catalyst (the molar ratio represented by x / y is less than 1.0).

[0489] <Viscosity Adjustment Process>

[0490] Regarding method B, it is preferable to include a viscosity adjustment step, which adjusts the viscosity of the mixture containing the prepolymer to 30 mPa·s to 2000 mPa·s, after the prepolymerization step and before the polymerizable composition manufacturing step.

[0491] By ensuring that the viscosity of the mixture containing the prepolymer is within the aforementioned range, from the viewpoint of suppressing ripples in the obtained optical material, it is possible to keep the viscosity of the polymeric composition manufactured in the polymeric composition manufacturing process within an appropriate range. As a result, ripples in the obtained optical material can be suppressed.

[0492] From the above perspective, the viscosity of the mixture containing the prepolymer is preferably 40 mPa·s to 2000 mPa·s, more preferably 50 mPa·s to 1800 mPa·s.

[0493] The above viscosity was measured using a type B viscometer at 25°C and 60 rpm (revolutions per minute).

[0494] There are no particular limitations on the method for adjusting the viscosity of mixtures containing prepolymers.

[0495] For example, the viscosity of a mixture containing a prepolymer can be adjusted by adding high-viscosity compounds, heating, stirring, or other methods.

[0496] The temperature at which the mixture containing the prepolymer is prepared is not particularly limited, as long as it is a temperature at which the prepolymer can be obtained through the polymerization reaction. For example, it can be 20°C to 50°C, or 25°C to 45°C.

[0497] The stirring time used when preparing a mixture containing a prepolymer is not particularly limited, as long as it allows the prepolymer to be obtained through a polymerization reaction. For example, it can be 30 minutes to 5 hours, or 1 hour to 5 hours.

[0498] As a method for preparing a mixture containing a prepolymer, specifically, the following method can be used: the mixture containing a prepolymer is prepared by stirring at 40°C for 3 hours, thereby adjusting the viscosity.

[0499] <Production Process of Polymer Composition>

[0500] Method B includes the following manufacturing steps for a polymeric composition: by adding the remainder of at least two different monomers for optical materials to a mixture containing a prepolymer, a polymeric composition containing at least two different monomers for optical materials, a prepolymer, an alkaline polymerization catalyst, and an organic acid with a pKa value less than 4 is obtained.

[0501] The manufacturing process of the polymeric composition is as follows: by adding the remainder of at least two different monomers for optical materials to a mixture containing a prepolymer, a polymeric composition for optical materials containing at least two different monomers for optical materials, a prepolymer, an alkaline polymerization catalyst, and an organic acid with a pKa value less than 4 is obtained.

[0502] Therefore, polymerization of the prepolymer with the remaining portions of two or more different optical material monomers can be prevented until the mixture containing the prepolymer is mixed with the remaining portions of two or more different optical material monomers.

[0503] Therefore, by performing the manufacturing process of the polymeric composition at the appropriate time, for example, the operability of injecting the polymeric composition into the mold can be improved.

[0504] In the manufacturing process of polymeric compositions, when the remaining portions of at least two different monomers for optical materials are added to a mixture containing prepolymers, the addition can be carried out in a single step or in multiple steps.

[0505] It should be noted that the so-called "remaining portion of two or more different optical material monomers" refers to the remaining portion of two or more different optical material monomers relative to "a portion of two or more different optical material monomers" in the prepolymerization process.

[0506] "The remaining portion of two or more different optical material monomers" can also be an optical material monomer that has functional groups that can polymerize with the polymerizable functional groups of the prepolymer, and the amount of the aforementioned functional groups that can polymerize with the polymerizable functional groups of the prepolymer is the amount (i.e., equivalent) that can substantially polymerize with all the polymerizable functional groups of the prepolymer.

[0507] From the viewpoint of improving the optical uniformity of the polymerizable composition, the remaining portion of two or more different optical material monomers preferably includes monomers of the same kind as the optical material monomers constituting the prepolymer.

[0508] The temperature at which the above-mentioned components are mixed is not particularly limited, but is preferably 30°C or below, and more preferably room temperature (25°C or below).

[0509] The temperature at which the components are mixed is sometimes preferably set to be lower than 25°C. However, if the additives such as internal release agents do not dissolve well in the components, the components may be preheated to dissolve the additives in the components.

[0510] The following are specific methods for manufacturing polymeric compositions.

[0511] First, an organic acid with a pKa value less than 4 and other additives (such as an internal release agent) are added to the mixture containing the prepolymer to prepare a mixture. The mixture is stirred at 25°C for 1 hour to ensure that all components are completely dissolved, and then degassed to obtain the first mixture.

[0512] In addition, the remaining portion of the monomer for optical materials and the remaining portion of the alkaline polymerization catalyst added as needed are stirred at 25°C for 30 minutes to completely dissolve them, thus obtaining the second mixture.

[0513] Then, the first mixture and the second mixture are mixed, stirred, and degassed to obtain a polymerizable composition.

[0514] <Liquid feeding process>

[0515] For method B, a liquid feeding step of feeding the polymeric composition to a casting mold may be included after the polymeric composition manufacturing step and before the curing step.

[0516] The liquid delivery process can be a process in which the polymeric composition is remixed in a static mixer while being delivered to a casting mold.

[0517] The liquid delivery process can also involve simultaneously remixing the polymeric composition using a dynamic mixer and then delivering the polymeric composition to a casting mold. By remixing the polymeric composition while simultaneously delivering it to the mold, uneven distribution of the polymeric composition can be eliminated during delivery. Therefore, ripples in the resulting cured product can be suppressed.

[0518] <Curing Process>

[0519] Method B includes a curing step of obtaining an optical material as a cured product of a polymeric composition by curing two or more different optical materials in the polymeric composition with monomers.

[0520] The specific method and preferred method of the curing process in Method B are the same as those described in the "Curing Process" section of Method A above.

[0521] <Second Prepolymerization Process>

[0522] Regarding method B, in addition to the steps mentioned above, it may also include:

[0523] The second prepolymerization step involves mixing the remaining portions of monomers for two or more different optical materials with the remaining portions of an alkaline polymerization catalyst, and polymerizing at least a portion of the remaining portions of the monomers for two or more different optical materials to obtain a second prepolymer, thereby obtaining a mixture containing the second prepolymer.

[0524] A polymerizable composition manufacturing process involves adding the aforementioned mixture containing a second prepolymer to a mixture containing a prepolymer obtained from a prepolymerization process, thereby obtaining a polymerizable composition containing the aforementioned prepolymer, the aforementioned second prepolymer, an alkaline polymerization catalyst, and an organic acid with a pKa value less than 4; and

[0525] The curing process involves curing the aforementioned prepolymer and the aforementioned second prepolymer in the aforementioned polymeric composition to obtain an optical material that is a cured product of the aforementioned polymeric composition.

[0526] Regarding method B, by including the above-described composition, it is possible to obtain a mixture containing a prepolymer obtained by the prepolymerization process and a mixture containing a second prepolymer obtained by the second prepolymerization process.

[0527] Therefore, the viscosity of the mixture containing the prepolymer can be made close to that of the mixture containing the second prepolymer, thus making it easier to mix the two.

[0528] In the second prepolymerization step, the specific and preferred methods for using two or more different optical material monomers and alkaline polymerization catalysts are the same as those in the prepolymerization step.

[0529] In the case where preparation method B includes the second prepolymerization step, in the polymerizable composition manufacturing step, the aforementioned mixture containing the second prepolymer is added to the mixture containing the prepolymer obtained from the prepolymerization step, thereby obtaining a polymerizable composition containing the aforementioned prepolymer, the aforementioned second prepolymer, an alkaline polymerization catalyst, and an organic acid with a pKa value of less than 4.

[0530] In the manufacturing process of the polymeric composition, the specific and preferred methods of including the mixture of prepolymers are the same as those in the above-described manufacturing process of the polymeric composition.

[0531] In the case where method B includes the second prepolymerization step, the curing step is a step of obtaining an optical material as a cured product of the polymeric composition by curing the aforementioned prepolymer and the aforementioned second prepolymer in the polymeric composition.

[0532] In the above curing process, the specific method and preferred method of the prepolymer are the same as those in the above-mentioned curing process.

[0533] <Annealing process>

[0534] Method B may include, as needed, an annealing process for annealing the cured polymeric composition.

[0535] The specific method and preferred method of the annealing process in method B are the same as those in method A.

[0536] <Other Processes>

[0537] Method B can be configured with other steps as needed.

[0538] The specific methods and preferred methods of other processes in manufacturing method B are the same as those of other processes in manufacturing method A.

[0539] <Applications of Optical Materials>

[0540] The specific and preferred methods of using the optical material in method B are the same as those of using the optical material in method A.

[0541] Example

[0542] The following are embodiments of this disclosure, but this disclosure is not limited to these embodiments. It should be noted that, unless otherwise specified, "parts" refers to quantities.

[0543] [Example 1-1]

[0544] 1.50 parts by weight of Tinuvin 329 [UV absorber] manufactured by BASF and 43.80 parts by weight of isophthalene diisocyanate [monomer a1 for optical materials] were mixed and stirred at 25°C for 1 hour until completely dissolved to obtain a mixture. 10.56 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane [monomer b1 for optical materials] were added to this mixture and stirred at 25°C for 5 minutes to obtain a homogeneous solution. 0.028 parts by weight of 3,5-dimethylpyridine [basic polymerization catalyst, pKa = 6.15] were added to the obtained solution and stirred at 40°C for 1 hour, thereby polymerizing the optical material monomer to obtain a mixture containing a prepolymer.

[0545] A mixture was prepared by mixing 3.00 parts by weight of isophthalene diisocyanate [monomer a1 for optical materials], 0.1 parts by weight of JP-506H [release agent] manufactured by Jōhoku Chemical Industry Co., Ltd., and 0.029 parts by weight of (±)-10-camphorsulfonic acid [organic acid, pKa value = 1.17]. This mixture was then mixed with the aforementioned mixture containing the prepolymer and degassed at 400 Pa and 25°C for 1 hour to obtain mixture 1 containing the prepolymer.

[0546] The viscosity and refractive index of mixture 1 containing the prepolymer are shown in Table 1.

[0547] 5.20 parts by mass of isophthalene diisocyanate [monomer a1 for optical materials] and 37.44 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane [monomer b1 for optical materials] were mixed and stirred at 25°C for 5 minutes to obtain a homogeneous solution. 0.01 parts by mass of 3,5-dimethylpyridine [basic polymerization catalyst, pKa = 6.15] were added to the obtained homogeneous solution, and the mixture was stirred at 40°C for 1 hour to polymerize the monomers for optical materials. Then, degassing was carried out at 400 Pa and 25°C for 1 hour to obtain mixture 2 containing the prepolymer.

[0548] The viscosity of mixture 2 containing the prepolymer is shown in Table 1.

[0549] Mixture 1 containing prepolymer and mixture 2 containing prepolymer are mixed at 20°C to obtain a polymerizable composition. The obtained polymerizable composition is fed into a casting mold (i.e., mold) while being remixed in a static mixer.

[0550] The viscosity (also known as casting viscosity) of the polymeric composition when the liquid is fed into the mold and cast is adjusted to the values ​​shown in Table 1.

[0551] During liquid delivery, the polymerizable composition is filtered through a 1μm PTFE filter while being injected into the mold cavity of the mold at a rate of 10g / second. The mold consists of a 4-curve glass mold (upper mold) with a diameter of 78mm and a 4-curve glass mold (lower mold) with a diameter of 78mm, and has a mold cavity for lens making.

[0552] The mold containing the polymerizable composition is placed in a polymerization oven and heated from 20°C to 120°C over 10 hours. The molded body, after the polymerizable composition has solidified, is demolded from the mold and further annealed at 120°C for 2 hours to obtain the molded body (lens).

[0553] [Examples 1-2]

[0554] Except for the following changes to the preparation method of mixture 1 containing the prepolymer, the molded body (lens) is obtained using the same method as in Example 1-1.

[0555] 1.50 parts by weight of Tinuvin 329 [UV absorber] manufactured by BASF and 46.80 parts by weight of isophthalene diisocyanate [monomer a1 for optical materials] were mixed and stirred at 25°C for 1 hour until completely dissolved to obtain a mixture. 10.56 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane [monomer b1 for optical materials] were added to this mixture and stirred at 25°C for 5 minutes to obtain a homogeneous solution. 0.028 parts by weight of 3,5-dimethylpyridine [basic polymerization catalyst] were added to the obtained homogeneous solution and stirred at 40°C for 1 hour, thereby polymerizing the monomer for optical materials to obtain a mixture containing a prepolymer.

[0556] 0.1 parts by weight of JP-506H [release agent] manufactured by Jōhoku Chemical Industry Co., Ltd. and 0.007 parts by weight of methanesulfonic acid [organic acid, pKa value = -2.6] were mixed with the aforementioned mixture containing the prepolymer and degassed at 400 Pa and 25 °C for 1 hour to obtain mixture 1 containing the prepolymer.

[0557] The viscosity and refractive index of mixture 1 containing the prepolymer are shown in Table 1.

[0558] [Examples 1-3]

[0559] The basic polymerization catalyst was changed from 3,5-dimethylpyridine to 2,6-dimethylpyridine [basic polymerization catalyst, pKa value = 6.6], and the amount of organic acid added was changed to 0.025 parts by mass. Otherwise, the molded body (lens) was obtained using the same method as in Example 1-1.

[0560] [Examples 1-4]

[0561] Except for changing the mixture 1 containing prepolymer and the mixture 2 containing prepolymer to the substances shown in Table 1, the molded articles (lenses) were obtained using the same method as in Examples 1-1.

[0562] Specifically, the optical material monomers used in the preparation of mixture 1 containing prepolymers and mixture 2 containing prepolymers are changed from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane [optical material monomer 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 [optical material monomer b2], and the amounts of each component are changed to those shown in Table 1.

[0563] [Examples 1-5]

[0564] Except for changing the mixture 1 containing the prepolymer and the mixture 2 containing the prepolymer to the substances shown in Table 1, the molded body (lens) was obtained using the same method as in Examples 1-2.

[0565] Specifically, the optical material monomers used in the preparation of mixture 1 containing prepolymers and mixture 2 containing prepolymers are changed from 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane [optical material monomer 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 [optical material monomer b2], and the amounts of each component are changed to those shown in Table 1.

[0566] [Comparative Example 1-1]

[0567] Except that (±)-10-camphorsulfonic acid is not used in the preparation of mixture 1 containing the prepolymer, the molded body (lens) is obtained using the same method as in Examples 1-1.

[0568] [Comparative Examples 1-2]

[0569] Except that octanoic acid [organic acid, pKa value = 4.90] was used instead of (±)-10-camphorsulfonic acid in the preparation of mixture 1 containing the prepolymer, the molded body (lens) was obtained using the same method as in Examples 1-1.

[0570] [Comparative Examples 1-3]

[0571] Except that (±)-10-camphorsulfonic acid is not used in the preparation of mixture 1 containing the prepolymer, the molded articles (lenses) are obtained using the same method as in Examples 1-3.

[0572] [Comparative Examples 1-4]

[0573] Except that octanoic acid was used instead of (±)-10-camphorsulfonic acid in the preparation of mixture 1 containing the prepolymer, the molded articles (lenses) were obtained using the same method as in Examples 1-3.

[0574] [Example 2-1]

[0575] 0.10 parts by weight of an internal release agent for MR (Mitsui Chemicals Co., Ltd.), 1.5 parts by weight of Tinuvin 329 (BASF Co., Ltd.) (UV absorber), and 43.07 parts by weight of a mixture of 2,5-bis(isocyanate methyl)-bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanate methyl)-bicyclo-[2.2.1]-heptane (solvent a1 for optical materials) were mixed and stirred at 25°C for 1 hour until completely dissolved to obtain a mixture. 3.47 parts by weight of pentaerythritol tetra(3-mercaptopropionate) (solvent b2 for optical materials) and 3.70 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (solvent b1 for optical materials) were added to this mixture and stirred at 25°C for 5 minutes to obtain a homogeneous solution. 0.13 parts by mass of 3,5-dimethylpyridine [basic polymerization catalyst, pKa value = 6.15] were added to the obtained homogeneous solution, and the mixture was stirred at 40°C for 3 hours to polymerize the optical material with monomers, thereby obtaining a mixture containing prepolymer.

[0576] A mixture of 5.00 parts by mass of a mixture of 2,5-bis(isocyanate-methyl)-bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanate-methyl)-bicyclo-[2.2.1]-heptane [monomer a1 for optical materials] and 0.165 parts by mass of (±)-10-camphorsulfonic acid [organic acid, pKa value = 1.17] was prepared to form a mixture. This mixture was then mixed with the aforementioned mixture containing the prepolymer and degassed at 400 Pa and 25 °C for 1 hour to obtain mixture 1 containing the prepolymer.

[0577] The viscosity and refractive index of mixture 1 containing the prepolymer are shown in Table 1.

[0578] 2.53 parts by mass of a mixture of 2,5-bis(isocyanate-methyl)-bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanate-methyl)-bicyclo-[2.2.1]-heptane [monomer a1 for optical materials], 20.43 parts by mass of pentaerythritol tetra(3-mercaptopropionate) [monomer b2 for optical materials], and 21.80 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane [monomer b1 for optical materials] were mixed and stirred at 25°C for 5 minutes to obtain a homogeneous solution. 0.02 parts by mass of 3,5-dimethylpyridine [basic polymerization catalyst, pKa = 6.15] were added to the obtained homogeneous solution, and the mixture was stirred at 40°C for 3 hours to polymerize the monomers for optical materials. Then, degassing was carried out at 400 Pa and 25°C for 1 hour to obtain mixture 2 containing the prepolymer.

[0579] The viscosity and refractive index of mixture 2 containing the prepolymer are shown in Table 1.

[0580] Mixture 1 containing prepolymer and mixture 2 containing prepolymer are mixed at 20°C to obtain a polymerizable composition. The obtained polymerizable composition is fed into a casting mold (i.e., mold) while being remixed in a static mixer.

[0581] The viscosity (also known as casting viscosity) of the polymeric composition when the liquid is fed into the mold and cast is adjusted to the values ​​shown in Table 1.

[0582] During liquid delivery, the polymerizable composition is filtered through a 1μm PTFE filter while being injected into the mold cavity of the mold at a rate of 10g / second. The mold consists of a 4-bend glass mold (upper mold) with a diameter of 78mm and a 4-bend glass mold (lower mold) with a diameter of 78mm, and has a mold cavity for lens making.

[0583] The mold containing the polymerizable composition is placed in a polymerization oven and heated from 20°C to 120°C over 10 hours. The molded body, after the polymerizable composition has solidified, is demolded from the mold and further annealed at 120°C for 2 hours to obtain the molded body (lens).

[0584] [Example 2-2]

[0585] Except for the following changes to the preparation method of mixture 1 containing the prepolymer, the molded body (lens) is obtained using the same method as in Example 2-1.

[0586] 0.1 parts by weight of an internal release agent for MR (Mitsui Chemicals Co., Ltd.), 1.5 parts by weight of Tinuvin 329 (BASF Co., Ltd.) (UV absorber), and 48.07 parts by weight of a mixture of 2,5-bis(isocyanate methyl)-bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanate methyl)-bicyclo-[2.2.1]-heptane (solvent a1 for optical materials) were mixed and stirred at 25°C for 1 hour until completely dissolved to obtain a mixture. 3.47 parts by weight of pentaerythritol tetra(3-mercaptopropionate) (solvent b2 for optical materials) and 3.70 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (solvent b1 for optical materials) were added to this mixture and stirred at 25°C for 5 minutes to obtain a homogeneous solution. 0.13 parts by weight of 3,5-dimethylpyridine [basic polymerization catalyst] were added to the obtained homogeneous solution, and the mixture was stirred at 40°C for 3 hours to polymerize the optical material with monomers, thereby obtaining a mixture containing prepolymer.

[0587] 0.06 parts by mass of methanesulfonic acid [organic acid, pKa value = -2.6] were mixed with the aforementioned mixture containing the prepolymer and degassed at 400 Pa and 25 °C for 1 hour to obtain mixture 1 containing the prepolymer.

[0588] The viscosity and refractive index of mixture 1 containing the prepolymer are shown in Table 1.

[0589] [Comparative Example 2-1]

[0590] Except that (±)-10-camphorsulfonic acid is not used in the preparation of mixture 1 containing the prepolymer, the molded body (lens) is obtained using the same method as in Example 2-1.

[0591] [Comparative Example 2-2]

[0592] Except that octanoic acid [organic acid, pKa value = 4.90] was used instead of (±)-10-camphorsulfonic acid in the preparation of mixture 1 containing the prepolymer, the molded body (lens) was obtained using the same method as in Example 2-1.

[0593] 〔evaluate〕

[0594] The polymeric compositions and molded articles obtained in each embodiment or comparative example were evaluated as follows. The results are shown in Tables 1 and 2.

[0595] (Viscosity of the mixture containing prepolymer)

[0596] The mixture containing the prepolymer was stirred at 25°C and 60 rpm, and the viscosity was measured using a Type B viscometer (Spindle No. 2: Brookfield).

[0597] (Refractive index of the mixture containing the prepolymer)

[0598] The refractive index of the mixture containing the prepolymer at 20°C was measured using a refractometer (RA-600: Kyoto Electronics Industry Co., Ltd.).

[0599] (Viscosity of the polymeric composition)

[0600] The polymeric composition was stirred at 25°C and 60 rpm, and the viscosity was measured using a Type B viscometer (Spindle No. 2: Brookfield).

[0601] (Slope of viscosity increase rate)

[0602] Plot the viscosity change over time using the x-axis (=X) as time (hr) and the y-axis (=Y) as the viscosity of the polymerizable composition (mPa·s), and fit the result using the following formula. The value of 'b' in the formula is taken as the slope of the viscosity-increasing rate. The viscosity of the polymerizable composition was measured using a Type B viscometer (Spindle No. 2: Brookfield) at 25°C and 30 rpm.

[0603] Y = a * exp(b * X)

[0604] The smaller the slope of the viscosity-increasing rate, the slower the viscosity increases and the longer the pot life.

[0605] (Applicable period)

[0606] The state of the polymerizable composition was evaluated 30 minutes after mixing mixture 1 containing prepolymer and mixture 2 containing prepolymer using the following benchmarks.

[0607] A: It can be cast 30 minutes after mixing.

[0608] B: The viscosity increases 30 minutes after mixing, making it impossible to cast.

[0609] (Waves)

[0610] The molded body was projected using an ultra-high pressure mercury lamp (light source type OPM-252HEG: manufactured by Ushio Electric Co., Ltd.), and the transmitted image was observed visually. The evaluation was carried out according to the following criteria.

[0611] A: No ribs were observed. Specifically, no ribs longer than 1.0 mm were observed visually within and outside a radius of 15 mm from the center of the molded body.

[0612] B: Although ripples are observed, they are generally acceptable as a finished product. Specifically, although ripples with a length of 1.0 mm or more are visually observed outside a radius of 15 mm from the center of the molded body, ripples with a length of 1.0 mm or more are not visually observed within a radius of 15 mm from the center of the molded body, and this is generally acceptable as a finished product.

[0613] C: The observation of ripples is unacceptable as a finished product. Specifically, ripples with a length of 1.0 mm or more are visually observed within and outside a radius of 15 mm from the center of the molded body.

[0614] [Table 1]

[0615]

[0616] [Table 2]

[0617]

[0618] As shown in Tables 1 and 2, for the polymerizable compositions of the examples using an alkaline polymerization catalyst and an organic acid with a pKa value less than 4, the increase in viscosity was suppressed and the pot life was good compared to the polymerizable compositions of the comparative examples that did not use an organic acid or used an organic acid with a pKa value greater than 4. Furthermore, no ripples were observed in the molded articles (cured products) obtained using the polymerizable compositions of the examples.

[0619] The entire disclosure of Japanese Patent Application Nos. 2023-135607 and 2023-135613 is incorporated herein by reference.

[0620] All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the same extent as the specific and separately described cases.

Claims

1. A polymeric composition for optical materials, comprising two or more different monomers for optical materials, a basic polymerization catalyst, and an organic acid with a pKa value less than 4. The organic acid with a pKa value less than 4 has fewer molar numbers of functional groups than the basic polymerization catalyst. The two or more different monomers used in optical materials comprise isocyanate compounds and active hydrogen compounds, wherein the active hydrogen compounds comprise polythiol compounds. The content of the organic acid with a pKa value less than 4 is 0.001 to 1 part by mass relative to a total of 100 parts by mass of the two or more different monomers used in optical materials. The viscosity measured using a type B viscometer at 25°C and 60 rpm ranged from 10 mPa·s to 1000 mPa·s.

2. A polymeric composition for optical materials, comprising two or more different monomers for optical materials, a basic polymerization catalyst, and an organic acid with a pKa value less than 4. The alkaline polymerization catalyst comprises an alkaline polymerization catalyst with a pKa value of 4 to 8. The two or more different monomers used in optical materials comprise isocyanate compounds and active hydrogen compounds, wherein the active hydrogen compounds comprise polythiol compounds. The content of the organic acid with a pKa value less than 4 is 0.001 to 1 part by mass relative to a total of 100 parts by mass of the two or more different monomers used in optical materials. The viscosity measured using a type B viscometer at 25°C and 60 rpm ranged from 10 mPa·s to 1000 mPa·s.

3. The polymerizable composition for optical materials according to claim 1 or 2, wherein, At least one of the two or more different monomers used in optical materials is an isocyanate compound with an aromatic ring. The content of the alkaline polymerization catalyst is 0.010 to 0.50 parts by mass relative to a total of 100 parts by mass of the two or more different optical material monomers.

4. The polymerizable composition for optical materials according to claim 1 or 2, wherein At least one of the two or more different monomers used in optical materials is an isocyanate compound without an aromatic ring. The content of the alkaline polymerization catalyst is greater than 0.05 parts by mass and less than 2.0 parts by mass relative to a total of 100 parts by mass of the two or more different optical material monomers.

5. The polymeric composition for optical materials as claimed in claim 1 or 2, further comprising polymers as the two or more different monomers for optical materials, and a prepolymer having polymeric functional groups.

6. The polymerizable composition for optical materials according to claim 1 or 2, wherein The two or more different optical material monomers further comprise at least one active hydrogen compound, wherein the active hydrogen compound is selected from the group consisting of polythiols having two or more thiol groups, hydroxythiols containing one or more thiol groups and one or more hydroxyl groups, polyols containing two or more hydroxyl groups, and amine compounds.

7. The polymeric composition for optical materials as described in claim 1 or 2, wherein, The combined proportion of isocyanate compounds and active hydrogen compounds in the total of the two or more different optical material monomers is greater than 70% by mass.

8. A polymeric prepolymer composition for optical materials, comprising: a polymer of two or more different monomers for optical materials and a prepolymer having polymeric functional groups; a basic polymerization catalyst; and an organic acid with a pKa value less than 4. The two or more different monomers used in optical materials comprise isocyanate compounds and active hydrogen compounds, wherein the active hydrogen compounds comprise polythiol compounds. The content of the organic acid with a pKa value less than 4 is 0.001 to 1 part by mass relative to a total of 100 parts by mass of the two or more different monomers used in optical materials. The viscosity measured using a type B viscometer at 25℃ and 60 rpm ranged from 10 mPa·s to 2000 mPa·s. At least one of the two or more different monomers used in optical materials is an isocyanate compound with an aromatic ring. The content of the alkaline polymerization catalyst is 0.002 to 1 part by mass relative to a total of 100 parts by mass of the prepolymer.

9. A polymeric prepolymer composition for optical materials, comprising: a polymer having polymeric functional groups as two or more different monomers for optical materials; a basic polymerization catalyst; and an organic acid with a pKa value less than 4. The two or more different monomers used in optical materials comprise isocyanate compounds and active hydrogen compounds, wherein the active hydrogen compounds comprise polythiol compounds. The content of the organic acid with a pKa value less than 4 is 0.001 to 1 part by mass relative to a total of 100 parts by mass of the two or more different monomers used in optical materials. The viscosity measured using a type B viscometer at 25℃ and 60 rpm ranged from 10 mPa·s to 2000 mPa·s. At least one of the two or more different monomers used in optical materials is an isocyanate compound without an aromatic ring. The content of the alkaline polymerization catalyst is 0.1 to 4.0 parts by mass relative to a total of 100 parts by mass of the prepolymer.

10. The cured product of the polymeric composition for optical materials according to claim 1 or 2.

11. The cured product of the polymeric prepolymer composition for optical materials according to claim 8 or 9.

12. A method for manufacturing optical materials, comprising: Preparation process: Prepare two or more different monomers for optical materials and alkaline polymerization catalysts; In a prepolymerization process, a portion of the monomers for two or more different optical materials is mixed with at least a portion of the alkaline polymerization catalyst, and at least a portion of the monomers for the two or more different optical materials is polymerized to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer; and In the acid addition step, an organic acid with a pKa value less than 4 is added to the mixture containing the prepolymer. The two or more different monomers used in optical materials comprise isocyanate compounds and active hydrogen compounds, wherein the active hydrogen compounds comprise polythiol compounds. The content of the organic acid with a pKa value less than 4 is 0.001 to 1 part by mass relative to a total of 100 parts by mass of the two or more different monomers used in optical materials.

13. The method for manufacturing the optical material as described in claim 12, wherein, At least one of the two or more different monomers used in optical materials is an isocyanate compound with an aromatic ring. The total amount of the two or more different optical material monomers in the preparation process is 100 parts by mass, and the amount of the alkaline polymerization catalyst is 0.010 parts by mass to 0.50 parts by mass.

14. The method for manufacturing the optical material as described in claim 12, wherein, At least one of the two or more different monomers used in optical materials is an isocyanate compound without an aromatic ring. The total amount of the two or more different optical material monomers in the preparation process is 100 parts by mass, and the amount of the alkaline polymerization catalyst is greater than 0.05 parts by mass and less than 2.0 parts by mass.

15. The method for manufacturing the optical material as described in claim 12, further comprising: A manufacturing process for a polymeric composition for optical materials involves adding the remainder of at least two different monomers for optical materials to a mixture comprising the prepolymer, thereby obtaining a polymeric composition for optical materials containing the two or more different monomers for optical materials, the prepolymer, the alkaline polymerization catalyst, and an organic acid with a pKa value less than 4. and The curing process involves curing two or more different optical material monomers in the polymeric composition for optical materials to obtain an optical material as a cured product of the polymeric composition for optical materials.

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