Method for producing a polyallyl functionalized prepolymer composition, and method for producing an optical component using the prepolymer composition.

Abstract

The present invention comprises the steps of (a) preparing a reaction mixture and heating the reaction mixture to a temperature within a range of 12 to 3°C lower than the 10-hour half-life temperature of the aromatic peroxide compound, and measuring the kinematic viscosity at 25°C in accordance with ASTM D446 to 40 to 350 mm². 2 The present invention relates to a method for producing a polyallyl-functionalized prepolymer composition, comprising the steps of (b) forming a prepolymer composition having a reaction ratio in the range of / s (40 to 350 cSt), wherein the reaction mixture comprises at least one polyallyl-functionalized monomer and at least one aromatic peroxide compound as a free radical initiator, and the at least one aromatic peroxide compound is present in an amount of 0.5 to 3.0% by weight based on the total amount of the polyallyl-functionalized monomer. The present invention also relates to a method for producing an optical component using the prepolymer composition.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polyallyl-functionalized prepolymer composition, and to a method for producing an optical component using the prepolymer composition. [Background technology]

[0002] Polyallyl functional monomers are polymerized using free radical initiators to produce rigid polymers. Many of these polymers are substantially transparent to visible light, substantially colorless, have a refractive index of about 1.45 to about 1.6, and possess good mechanical resistance. For this reason, such monomers are widely used as precursors for optical components such as optical lenses, optical lens blanks, safety lenses, and transparent sheets of flat or curved surfaces. The light transmission properties can be modified by including dyes, light-absorbing compounds, pigments, etc., in the polymerizable composition containing the monomer before polymerization, or by dyeing the polymer after polymerization.

[0003] Polymerization reactions of polyallyl functional monomers are typically carried out using peroxide initiators, particularly dialkyl peroxycarbonates such as diisopropyl peroxycarbonate (IPP) or a mixture of IPP and di-s-butyl peroxycarbonate, which can yield rigid polymers with excellent optical properties, especially transparency and low coloration. Polymerization reactions of polyallyl functional monomers are typically carried out in the presence of a peroxide initiator, particularly a dialkyl peroxycarbonate such as diisopropyl peroxycarbonate (IPP) or a mixture of IPP and di-s-butyl peroxycarbonate, thereby yielding rigid polymers with excellent optical properties, especially transparency and low coloration.

[0004] However, dialkylperoxycarbonate initiators, particularly IPPs, are expensive, thermally unstable and prone to explosive decomposition, and have very strict transport and storage requirements. Even when diluted, for example with polyallyl functional monomers, the transport and storage temperature must be kept as low as approximately -20 to -10°C.

[0005] In the prior art, peroxide initiators that are stable at room temperature (ambient stable initiators (ASIs)) are also known and have the potential to overcome the aforementioned drawbacks of dialkylperoxycarbonate initiators. As used herein, “ambient stable initiator” means a free radical initiator compound that does not require storage under refrigerated conditions, that is, one that can be stored at temperatures in the range of 20°C to 36°C without substantial decomposition. In this specification, ASI initiators therefore have a “high” 10-hour half-life temperature, where “high” means a 10-hour half-life temperature of at least about 55°C.

[0006] However, certain ASI compounds, such as certain diacyl peroxides, alkyl peroxyesters, alkyl peroxyketals, and peroxy monocarbonates, have several drawbacks that have so far limited their practical use as polymerization initiators for polyallyl functional monomers.

[0007] For example, certain ASI compounds have low solubility in polyallyl functional monomers, resulting in insufficient curing of rigid polymers. Furthermore, rigid polymers obtained using ASI compounds such as diacyl peroxide (e.g., benzoyl peroxide) yellow significantly and exhibit poor UV resistance. In addition, compared to rigid polymer materials obtained using IPP as an initiator, materials polymerized with ASI compounds typically exhibit relatively high hardness and brittleness, as well as a high level of shrinkage. In this specification, "shrinkage (S)" refers to the following ratio:

number

[0008] D pol is the density of the final thermoset polymer at 23°C, and D mon is the density at 23°C of the polymerizable composition in liquid form containing monomers before polymerization. The term "% shrinkage" refers to the value obtained by multiplying the shrinkage by 100.

[0009] A high level of shrinkage is particularly problematic in casting processes commonly used for manufacturing ophthalmic lenses and ophthalmic lens blanks, in which a liquid monomer composition is introduced into a mold and then polymerized into a final thermoset polymer.

[0010] In fact, when polymerization is carried out using an ASI compound as an initiator, it is necessary to heat the liquid polymerizable composition to a relatively high initial temperature to initiate the curing cycle of the polymerization reaction. For example, in the case of benzoyl peroxide, which has a 10-hour half-life temperature of 73°C, the initial temperature is about 60°C, which is much higher than the approximate 40°C initial temperature for IPP, which has a 10-hour half-life temperature of 45°C. However, this initial heating step is accompanied by volume expansion of the polymerizable composition in the mold, resulting in a significant decrease in its density. Since the initial volume expansion when curing with an ASI compound is larger than that when curing the same polymerizable composition with IPP or a non-ASI initiator, the shrinkage observed in a rigid polymer cured with an ASI initiator is significantly higher than that in a rigid polymer cured with IPP or a non-ASI initiator.

[0011] Such a high level of shrinkage in the mold causes numerous defects in the rigid polymer, including dimensional changes, internal stress, and peeling of the material from the mold wall, leads to inadequate surface smoothness, and causes damage to the polymerized material or the mold. Due to these negative aspects, manufacturing processes using ASI initiators are characterized by low productivity.

[0012] Said drawbacks particularly affect the production of unpolished lens blanks with complex designs and shapes, such as unpolished lenses with a high radius of curvature (6-base or higher), and multifocal unpolished lens blanks (for example, unpolished lens blanks provided with bifocal correction on the front surface for simultaneously correcting myopia and presbyopia).

[0013] In fact, in bifocal blanks, since the mechanical stress caused by shrinkage differs between the two power portions of the lens blank, damage often occurs to the lens during demolding, resulting in the generation of fragments, dents, or overall breakage along the separation surface between the two power portions. The breakage problem is particularly prominent in the casting of flat-top bifocal lens blanks, that is, multifocal lens blanks in which the two power portions are separated by a flat separation surface.

[0014] In the prior art, it is known that shrinkage can be reduced by using a special formulation of polyallyl functional monomers. For example, the following formula (II), which is one of the most frequently used polyallyl functional monomers in the production of optical components

Chemical Formula

[0015] (wherein n is a positive integer, for example, in the range of 1 to 10). When diethylene glycol bis(allyl carbonate) represented by the above formula is used as the polyallyl functional monomer, shrinkage can be reduced by including one or more mono- or polyethylenically unsaturated compounds that are not poly(allyl carbonate) functional monomers in the formulation of the polymerizable composition.

[0016] Examples of these mono- or polyethylene-unsaturated compounds, so-called copolymer monomers or reaction diluents, include mono- or polyethylene-unsaturated compounds such as vinyl esters of versatic acid 9 and 10. These copolymer monomers may be liquid components with a lower density of polymerizable double bonds (number of double bonds per unit mass of the compound) than diethylene glycol bis(allyl carbonate) monomers. Compared to rigid polymers obtained from diethylene glycol bis(allyl carbonate) monomers that do not contain copolymer monomers, these copolymer monomers result in a lower degree of crosslinking of the final rigid polymer (i.e., term D in the above shrinkage equation). pol (The value of becomes lower), so the contraction becomes less.

[0017] Alternatively, in addition to the above effects, these copolymer monomers have a higher density (i.e., mass / volume ratio) than diethylene glycol bis(allyl carbonate) monomers, which increases the density of the cast polymerizable composition containing the polyallyl functional monomer and these copolymer monomers (i.e., D in the above shrinkage equation). mon The value of the term increases, and therefore the final shrinkage is lower. In this case, for example, as described in U.S. Patent No. 4,144,262, examples include compounds with high molar mass or polyfunctional structure (having three or more ethylenically unsaturated functional groups per molecule) that are used as a single monomer as an alternative to diethylene glycol bis(allyl carbonate) monomer.

[0018] Approaches to shrinkage reduction using copolymer monomers are described in International Publication No. 2004 / 090002, U.S. Patent Application Publication No. 2021 / 0263197, European Patent No. 3381951, and European Patent No. 0241997.

[0019] As an alternative approach, if the polyallyl functional monomer is diethylene glycol bis(allyl carbonate) represented by formula (II) above, the polymerizable composition may contain a relatively high concentration of oligomer species, i.e., species represented by formula (II) above where n is an integer of 2 or more. Compared to the linear species of diethylene glycol bis(allyl carbonate) monomer (species represented by formula (II) where n=1), these oligomer species have a lower density of polymerizable double bonds, resulting in a lower degree of crosslinking (i.e., the term D in the contraction equation). pol This results in a hard polymer (with a lower value), and therefore, lower shrinkage.

[0020] This approach to contraction reduction is described in International Publication No. 00 / 27794 and International Publication No. 2017 / 168325. [Overview of the project] [Problems that the invention aims to solve]

[0021] Furthermore, in conventional technology, a method for reducing shrinkage is known in which a liquid prepolymer composition is introduced into a mold and then polymerized to obtain the final thermosetting polymer.

[0022] Prepolymer compositions (hereinafter also referred to as "prepolymers") are typically produced by partially polymerizing polyallyl-functional monomers, thereby consuming some of the allyl groups. This partial polymerization (hereinafter also referred to as "prepolymerization") is stopped at a level where gelation is minimal, so that the prepolymer composition can be introduced into the mold as a liquid with a higher density than the initial polyallyl-functional monomer.

[0023] Prepolymerization reactions require precise control. Typically, prepolymerization reactions are controlled by adding a small amount of initiator so that only the desired portion of the allyl double bonds of the initial polyallyl functional monomer reacts to form a prepolymer composition. Furthermore, using a small amount of initiator ensures that the initiator is completely consumed by the end of the prepolymerization reaction, resulting in a liquid prepolymer composition that is stable at room temperature and has a suitable shelf life; that is, the liquid prepolymer composition can be stored for a considerable period of time without gelation before being used to manufacture rigid polymer products.

[0024] Furthermore, the prepolymerization reaction is controlled by adjusting the heat supplied to the reaction mixture of monomer and initiator in the reactor. In particular, once the desired viscosity for the prepolymer is achieved, the reaction mixture may need to be cooled to stop the reaction and prevent subsequent gelation that may be caused by the thermal inertia of the prepolymer mass (the so-called "bulk effect").

[0025] To produce rigid polymers, a liquid prepolymer composition is then polymerized by adding an initiator and subjecting it to a thermosetting cycle. This initiator may be the same as or different from the one used in the preparation of the prepolymer composition, and is added in an amount that substantially polymerizes the allyl double bonds of the prepolymer. However, when using an initiator with a low 10-hour half-life temperature (i.e., a non-ASI initiator such as IPP) in this thermosetting cycle, it must be used quickly after mixing with the monomer due to its short shelf life. If not used quickly, it must be refrigerated for later use, resulting in high energy consumption. This drawback imposes a burden on manufacturers to prepare polymerizable compositions in small batches.

[0026] To extend the shelf life of this composition, it is possible to increase the concentration of the initiator in the composition and perform casting at low temperatures, i.e., below 10°C. However, this procedure has the disadvantage of increasing the viscosity of the cooled prepolymer, which prolongs the mold filling process and reduces efficiency, thus limiting productivity, especially in the manufacture of lenses with complex designs and shapes.

[0027] In another prior art, a prepolymer composition can be prepared by solution polymerization. The monomer composition is dissolved in a substantially inert organic solvent in which the partially polymerized monomers are also soluble, and heated with a small amount of initiator. At the end of prepolymerization, the solvent is removed, for example, by evaporation or distillation, and after adding fresh initiator, the liquid prepolymer composition is polymerized to produce a rigid polymer.

[0028] U.S. Patent No. 4,623,708 discloses a method for preparing a prepolymer, in which the prepolymerization step includes adding a small amount of a free radical initiator, which may be the same as or different from the one used immediately before casting, and heating to a temperature higher than the one-hour half-life temperature of the initiator. In this method, most of the added initiator is consumed, and the prepolymerization produces the highest possible conversion while preventing overpolymerization.

[0029] U.S. Patent No. 6,057,411 describes a process for forming a polymerizable, liquid, substantially gel-free poly(allyl carbonate) group-functionalized prepolymer composition, comprising heating a neat composition consisting of at least one poly(allyl carbonate) functional monomer and a free radical initiator having a 10-hour half-life temperature of at least 85°C at a temperature from 5°C below the 10-hour half-life temperature of the free radical initiator to 150°C to form a reaction mixture with a viscosity at 25°C in the range of 25 to 10,000 cps, such that the utilization of ethylenically double bonds is at least 3%, and cooling the reaction mixture to a temperature at least 20°C below the 10-hour half-life temperature of the initiator over a period of less than 90 minutes.

[0030] In the above-mentioned prior art, the monomer and prepolymer compositions used to reduce shrinkage are costly because they involve the use of additional raw materials and complex preparation processes (i.e., providing copolymer monomers and special polyallyl monomers and prepolymer compositions).

[0031] In particular, the methods for producing these prepolymer compositions and their uses are impractical for several reasons. Firstly, in the prepolymerization process, it is difficult to obtain prepolymers with the desired properties reproducibly because numerous variables such as the amount of initiator added and the reaction temperature must be precisely controlled. Secondly, in order to produce the final polymer, a step of adding an initiator to the liquid prepolymer composition before casting is required, resulting in a short shelf life of the polymerizable composition, making the manufacturing process very complex and inefficient. Thirdly, when preparing prepolymers by solution polymerization, complete removal of the solvent is time-consuming and costly, and if the solvent is toxic or flammable, it also poses a risk.

[0032] Therefore, there is a need for new methods for preparing and using polyallyl functional monomers, particularly in the form of prepolymer compositions, that can overcome the shortcomings of conventional technologies. [Means for solving the problem]

[0033] The inventors have discovered a method for producing rigid allyl polymers having substantially equivalent mechanical and optical properties to rigid polymers obtained by curing with highly effective initiators such as IPP and other conventional peroxycarbonate initiators, using a room-temperature stable polymerization initiator.

[0034] This method involves preparing a liquid prepolymer composition by partial polymerization of a polyallyl-functionalized monomer with a selected group of room-temperature stable free radical initiators, wherein the free radical initiator is mixed with the polyallyl-functionalized monomer in an amount that is not completely consumed during the prepolymerization reaction, and the prepolymerization reaction is carried out by heating the resulting mixture at a temperature close to but lower than the 10-hour half-life temperature of the initiator (and therefore lower than the 1-hour half-life temperature) for a period of time sufficient to obtain a prepolymer composition with the desired viscosity.

[0035] Since a sufficient amount of initiator remains in the prepolymer composition, its ability to generate radical species can be utilized in the subsequent steps after thermal curing of this prepolymer composition, eliminating the need for an additional step of adding an additional initiator to the prepolymer composition before casting into the mold.

[0036] A free radical initiator that is stable at room temperature is an aromatic peroxide compound (e.g., benzoyl peroxide), which has high solubility in polyallyl functional monomers and can be added in an effective amount that can convert a liquid prepolymer composition into a rigid polymer in a conventional curing cycle, for example, in about 24 to 30 hours at a temperature of 80 to 120°C.

[0037] Furthermore, because the initiator is stable at room temperature, the shelf life of ready-to-cast liquid prepolymer compositions at room temperature (i.e., 25°C) is very long (about 1-2 weeks), and even longer (several months) with refrigerated storage (e.g., in the range of 0-4°C). This is especially much longer compared to liquid prepolymer compositions for casting containing IPP (1 hour at room temperature) or similar non-ASI initiators.

[0038] The prepolymer composition prepared by this method can very effectively control shrinkage during the polymerization process that forms the rigid polymer, and the observed shrinkage values ​​are substantially the same as those of rigid polymers obtained using an IPP initiator (approximately 12% or less).

[0039] Furthermore, these methods allow for the highly efficient and simple production of rigid polymers and optical components using room-temperature stable initiators such as benzoyl peroxide. They overcome the drawbacks associated with handling and using IPP and other non-ASI initiators, while possessing mechanical and optical properties equivalent to those of rigid polymers cured with IPP. Moreover, these methods effectively control material shrinkage, enabling improved manufacturing yields even in the production of lenses with complex designs and shapes, such as high-radius-curvature elemental lenses and bifocal elemental lenses, using ASI initiators.

[0040] These methods offer the additional advantage of reducing the negative effects associated with the use of relatively high amounts of aromatic peroxide initiators, such as changes in the refractive index of the lens, increased hardness and brittleness, inherent yellowing, and yellowing due to ultraviolet irradiation, because the total amount of aromatic peroxide initiator used to produce the final polymer after preparing the prepolymer is lower than the amount typically used when directly polymerizing a polyallyl functional monomer composition to produce the final polymer.

[0041] The effects of the present invention can be achieved by using a wide variety of polyallyl-functional monomers, although they are not particularly limited. However, these methods are particularly advantageous when the starting material to be prepolymerized is a low-viscosity and low-density polyallyl-functional monomer, because they can be obtained by a simpler and more cost-effective manufacturing process than monomers specially manufactured to have intrinsic reduced shrinkage properties.

[0042] Therefore, in a first embodiment, the present invention comprises the steps of (a) preparing a reaction mixture and heating the reaction mixture to a temperature within a range of 12 to 3°C lower than the 10-hour half-life temperature of the aromatic peroxide compound, and measuring the kinematic viscosity at 25°C in accordance with ASTM D446 to 40 to 350 mm². 2 The present invention relates to a method for producing a polyallyl-functionalized prepolymer composition, comprising the step (b) of forming a prepolymer composition having a concentration in the range of / s (40 to 350 cSt), wherein the reaction mixture comprises at least one polyallyl-functionalized monomer and at least one aromatic peroxide compound as a free radical initiator, and the amount of the at least one aromatic peroxide compound is 0.5 to 3.0% by weight based on the total amount of the polyallyl-functionalized monomer.

[0043] In a third embodiment, the present invention comprises the steps of (i) preparing a reaction mixture and heating the reaction mixture to a temperature range of 12 to 3°C lower than the 10-hour half-life temperature of the aromatic peroxide compound, wherein the kinematic viscosity at 25°C, as measured in accordance with ASTM D446, ​​is 40 to 350 mm². 2 (ii) A step of forming a prepolymer composition in the range of / s (40~350 cSt), (iii) A step of pouring the prepolymer composition into a mold, The present invention relates to a method for manufacturing an optical component, comprising the steps of (iv) curing the prepolymer composition in the mold to form an optical component, The reaction mixture comprises at least one polyallyl functional monomer and at least one aromatic peroxide compound as a free radical initiator, wherein the at least one aromatic peroxide compound is present in an amount of 0.5 to 3.0% by weight based on the total amount of the polyallyl functional monomer.

[0044] Further features of the present invention are described in the dependent claims accompanying this description.

[0045] The compositions of the present invention may include, substantially consist of, or consist solely of the essential and optional components described herein. In this specification, "consistently consist of" means that a composition or component may include additional components, provided that such additional components do not substantially alter the basic and novel properties of the claimed composition or method.

[0046] In this specification, the articles "a," "an," and "the" include one or more, and the singular includes the plural. This is done solely for convenience and to provide a general understanding of this disclosure.

[0047] In this specification and in the claims, numerical quantities, reaction conditions, etc., are interpreted as "approximately" in all contexts, except in the examples, or unless otherwise specified. [Modes for carrying out the invention]

[0048] Polyallyl functional monomers In preparing the prepolymer composition of the present invention, a reaction mixture is prepared containing at least one polyallyl-functional monomer and at least one aromatic peroxide compound as a free radical initiator. This mixture may contain two or more polyallyl-functional monomers.

[0049] The polyallyl functional monomer can be selected from a wide variety of liquid polyallyl compounds, and may include monomers and oligomers having at least two allyl groups as polymerizable functional groups.

[0050] The polyallyl functional monomer may, for example, comprise a compound containing two or more allyl groups such as diallyl ester, diallyl carbonate and diallyl phthalate.

[0051] In one embodiment, the polyallyl functional monomer comprises liquid polyallyl carbonate of a polyhydroxy organic substance. Examples of such monomers include polyallyl carbonates of linear or branched aliphatic polyols, polyallyl carbonates of cycloaliphatic-containing polyols, and polyallyl carbonates of aromatic-containing polyhydroxy compounds. These monomers are known and can be prepared according to conventionally known procedures.

[0052] In one embodiment, the polyallyl functional monomer is selected from the group consisting of: diethylene glycol bis(allyl carbonate), ethylene glycol bis(allyl carbonate), oligomers of diethylene glycol bis(allyl carbonate), oligomers of ethylene glycol bis(allyl carbonate), bisphenol A bis(allyl carbonate), diallyl phthalates such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and diallyl orthophthalate, and mixtures thereof.

[0053] The polyallyl functional monomer is liquid at room temperature, and has a kinematic viscosity measured at 25°C of 10 to 1000 mm 2 / s (10 to 1000 cSt).

[0054] In one embodiment, the polyallyl functional monomer preferably has a kinematic viscosity in the range of 10 to 300 mm 2 / s (10 to 300 cSt), more preferably 10 to 100 mm2 It is more preferable that the range is / s (10 to 100 cSt), and 10 to 40 mm 2 It is even more preferable that the range is / s (10 to 40 cSt).

[0055] In this specification, the kinematic viscosity of compounds comprising polyallyl-functional monomers or prepolymer compositions is measured using a KPG Ubbelodhe viscometer (capillary type 1C, 2C, or 3C) in accordance with ASTM D446.

[0056] Preferably, the polyallyl functional monomer has a density at 25°C in the range of 1.10 to 1.30 g / ml, and more preferably in the range of 1.11 to 1.20 g / ml.

[0057] Compound (A) containing two or more allyloxycarbonyl groups In one embodiment, the polyallyl functional monomer can be represented by a compound (A) containing two or more allyloxycarbonyl groups, as shown in formula (1) below. [ka]

[0058] Here, in the formula, n is an integer from 2 to 6, R1 represents a hydrogen atom or a methyl group, and multiple R1s may be the same or different, and X represents a divalent to hexavalent organic group a derived from a linear or branched aliphatic polyol having 3 to 12 carbon atoms which may have an oxygen atom, a divalent to hexavalent organic group b derived from an alicyclic polyol having 5 to 16 carbon atoms which may have an oxygen atom, or a divalent to hexavalent organic group c derived from an aromatic compound having 6 to 12 carbon atoms, and organic group a or organic group b forms an allyl carbonate group by bonding with an allyloxycarbonyl group via an oxygen atom derived from a hydroxyl group.

[0059] These polyols typically contain 2 to 6 hydroxyl groups in their molecule, preferably 2 to 4 hydroxyl groups.

[0060] Examples of aliphatic polyol a1 include diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, glycerol, trimethylolpropane, tris(hydroxyethyl) isocyanurate, pentaerythritol, and dipentaerythritol.

[0061] As for alicyclic polyol b1, 1,4-dimethylolcyclohexane, 4,8-bis(hydroxymethyl)-[5.2.1.0 2,6 Examples include tricyclodecane.

[0062] Examples of aromatic compound c1 include benzene, toluene, xylene, and naphthalene.

[0063] Specific examples of compounds containing two or more allyloxycarbonyl groups include allyl carbonate polymerizable compounds (A1), allyl ester polymerizable compounds (A2), and polymerizable compounds containing at least one of an allyl carbonate group and an allyl ester group (A3).

[0064] Compound (A) containing two or more allyloxycarbonyl groups may also contain its oligomer.

[0065] Compounds containing two or more allyloxycarbonyl groups are liquid at room temperature and have a kinematic viscosity of 10-1000 mmHg as measured at 25°C. 2 The concentration is / s (10~1000 cSt), and the oligomer content can be varied over a wide range, for example, from 0 to approximately 80% by weight.

[0066] In one embodiment, a compound containing two or more allyloxycarbonyl groups has a kinematic viscosity of 10 to 300 mm². 2 The range is / s (10~300 cSt), and 10~100 mm 2 The range is preferably / s (10 to 100 cSt), and 10 to 40 mm 2 The density is more preferably in the range of / s (10 to 40 cSt). The density of compounds containing two or more allyloxycarbonyl groups at 25°C is preferably in the range of 1.10 to 1.30 g / ml, and more preferably in the range of 1.11 to 1.20 g / ml.

[0067] Allyl carbonate polymerizable compound (A1) The allyl carbonate polymerizable compound (A1) can be represented by the following formula (2). [ka]

[0068] Here, in formula (2), X represents a divalent to hexavalent group derived from a linear or branched aliphatic polyol having 3 to 12 carbon atoms, or a divalent to hexavalent group derived from an alicyclic polyol having 5 to 16 carbon atoms, and n represents an integer from 2 to 6.

[0069] The allyl carbonate polymerizable compound (A1) of formula (2) may also contain its oligomer. The oligomer is a poly(allyl carbonate) in which two or more polyol molecules are linked via carbonate groups produced by a transesterification reaction between allyl carbonate and polyol generated during the manufacturing process.

[0070] Allyl carbonate polymerizable compounds are poly(allyl carbonate) compounds of linear or branched aliphatic polyols having 3 to 12 carbon atoms. Poly(allyl carbonate) compounds of alicyclic polyols having 5 to 16 carbon atoms in the molecule are also suitable. These polyols usually have 2 to 6 hydroxyl groups in the molecule, preferably 2 to 4 hydroxyl groups. Mixed poly(allyl carbonate) compounds, that is, compounds derived from at least two or more polyols and obtained by mechanically mixing each polyol poly(allyl carbonate) compound, or compounds obtained by a direct chemical reaction from a mixture of polyol and diallyl carbonate can also be used.

[0071] Finally, these poly(allyl carbonate) compounds may be in the form of monomers or mixtures of monomers and oligomers.

[0072] Generally, allyl carbonate polymerizable compounds are liquid at room temperature and have a kinematic viscosity of 10-1000 mmHg as measured at 25°C. 2 The concentration is / s (10~1000 cSt), and the oligomer content can be varied over a wide range, for example, from 0 to approximately 80% by weight.

[0073] In one embodiment, the allyl carbonate polymerizable compound has a kinematic viscosity in the range of 10 to 300 mm² / s (10 to 300 cSt), preferably in the range of 10 to 100 mm² / s (10 to 100 cSt), and 10 to 40 mm 2 The density is more preferably in the range of / s (10 to 40 cSt). The allyl carbonate polymerizable compound is preferably in the range of 1.10 to 1.30 g / ml at 25°C, and more preferably in the range of 1.11 to 1.20 g / ml.

[0074] Specific examples of polyols that form X in general formula (2) include diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane, and 4,8-bis(hydroxymethyl)-[5.2.1.0 2,6 Examples include tricyclodecane, glycerol, trimethylolpropane, tris(hydroxyethyl) isocyanurate, pentaerythritol, diglycerol, ditrimethylolpropane, and dipentaerythritol.

[0075] The polyol forming X in general formula (2) may be an extended polyol, such as a lactone-modified polyol or an alkyl oxide-modified polyol. An extended polyol refers to a reaction product having a hydroxyl group at its terminus, obtained by the reaction of a polyol with a suitable reactive substance, such as a lactone or an alkyl oxide.

[0076] Examples of lactone-modified polyols include ε-caprolactone-modified diethylene glycol, ε-caprolactone-modified dipropylene glycol, ε-caprolactone-modified triethylene glycol, ε-caprolactone-modified tetraethylene glycol, ε-caprolactone-modified pentaerythritol, and ε-caprolactone-modified trimethylolpropane.

[0077] Examples of alkyl oxide-modified polyols include ethylene oxide or propylene oxide-modified diethylene glycol, ethylene oxide or propylene oxide-modified dipropylene glycol, ethylene oxide or propylene oxide-modified triethylene glycol, ethylene oxide or propylene oxide-modified tetraethylene glycol, ethylene oxide or propylene oxide-modified pentaerythritol, and ethylene oxide or propylene oxide-modified trimethylolpropane.

[0078] Therefore, examples of allyl carbonate compounds include diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane, and 4,8-bis(hydroxymethyl)-[5.2.1.0 2,6 Examples include bis(allyl carbonate) compounds of at least one diol selected from tricyclodecane, tris(allyl carbonate) compounds of at least one triol selected from glycerol, trimethylolpropane, and tris(hydroxyethyl) isocyanurate, tetra(allyl carbonate) compounds of at least one tetraol selected from pentaerythritol, diglycerol, and ditrimethylolpropane, hexa(allyl carbonate) compounds of dipentaerythritol, and mixed poly(allyl carbonate) compounds of at least two compounds selected from diols, triols, tetraols, and dipentaerythritol.

[0079] "Bis(allyl carbonate) of a mixture of at least two diols" can be obtained, for example, as a mixture of the following monomer and oligomer components when the diols are diethylene glycol and neopentyl glycol. Monomer components: (1) Diethylene glycol bis(allyl carbonate); (2) Neopentyl glycol bis(allyl carbonate); Oligomer components:

[0080] (3) Oligomers containing only hydrocarbons (and ethers) derived from diethylene glycol (compounds in which two hydroxyl groups of a compound in which diethylene glycol is oligomerized linearly via carbonate bonds are replaced with allyl carbonate groups),

[0081] (4) Oligomers containing only hydrocarbons derived from neopentyl glycol (compounds having a structure in which two hydroxyl groups of a compound oligomerized linearly via carbonate bonds from neopentyl glycol are replaced by allyl carbonate groups),

[0082] (5) A complex oligomer containing both a hydrocarbon (and ether) derived from diethylene glycol and a hydrocarbon derived from neopentyl glycol within the same molecule (a compound having a structure in which two hydroxyl groups of a compound in which diethylene glycol and neopentyl glycol are oligomerized linearly in any sequence via carbonate bonds within the same molecule are substituted with allyl carbonate groups).

[0083] The following are preferred examples of allyl carbonate polymerizable compounds (A1) suitable for the purpose of the present invention.

[0084] (i) A mixture of diethylene glycol bis(allyl carbonate) and its oligomer, where diethylene glycol bis(allyl carbonate) can be defined by formula (I). [ka]

[0085] Furthermore, the oligomer of diethylene glycol bis(allyl carbonate) can be defined by formula (II). [ka]

[0086] Here, in equation (II), n is between 2 and 10.

[0087] Compound (I) can be prepared, for example, by reacting diethylene glycol bis(chloroformate) with allyl alcohol, as described in "Encyclopedia of Chemical Technology," Kirk-Othmer, Third Edition, Volume 2, pages 111-112. Mixtures of diethylene glycol bis(allyl carbonate) (formula (I)) and its oligomer (formula (II)) can be readily prepared, for example, by a transesterification reaction between diallyl carbonate and diethylene glycol in the presence of a basic catalyst, as described in EP 35304. These mixtures can typically contain up to about 80% by weight of the oligomer.

[0088] (ii) A mixture of a bis(allyl carbonate) compound of a mixed diol of diethylene glycol and neopentyl glycol, and its oligomer.

[0089] This bis(allyl carbonate) compound is similar to the bis(allyl carbonate) compound at point (i), but the diethylene glycol is replaced with a mixture of diethylene glycol and neopentyl glycol.

[0090] (iii) A mixture of poly(allyl carbonate) compounds of a mixed polyol of diethylene glycol and tris(hydroxyethyl) isocyanurate, and its oligomer.

[0091] This poly(allyl carbonate) compound can be obtained, for example, by a transesterification reaction of a mixture of diethylene glycol and tris(hydroxyethyl) isocyanurate with diallyl carbonate, as described in US 4,812,545.

[0092] (iv) A mixture of poly(allyl carbonate) compounds of a mixed polyol of diethylene glycol and trimethylolpropane, and its oligomer.

[0093] This poly(allyl carbonate) compound is identical to the poly(allyl carbonate) compound in point (iii) above, except that tris(hydroxyethyl) isocyanurate is replaced with trimethylolpropane.

[0094] (v) A mixture of poly(allyl carbonate) compounds of a mixed polyol of diethylene glycol and pentaerythritol, and its oligomer.

[0095] This poly(allyl carbonate) compound is identical to the poly(allyl carbonate) compound in point (iii) above, except that tris(hydroxyethyl) isocyanurate is replaced with pentaerythritol.

[0096] (vi) A mixture of poly(allyl carbonate) compounds of a mixed polyol of diethylene glycol, neopentyl glycol, and pentaerythritol, and its oligomer.

[0097] This poly(allyl carbonate) compound is identical to the poly(allyl carbonate) compound at point (v), but the diethylene glycol has been replaced with two diols: diethylene glycol and neopentyl glycol.

[0098] (vii) A poly(allyl carbonate) mixture comprising a mixture of a poly(allyl carbonate) compound of a mixed polyol of diethylene glycol, neopentyl glycol, and pentaerythritol and its oligomer, and a mixture of a diethylene glycol bis(allyl carbonate) compound and its oligomer.

[0099] In one embodiment, the polyallyl functional monomer includes or is a diethylene glycol bis(allyl carbonate) compound of general formula (II). [ka]

[0100] Here, in equation (II), n is between 1 and 10 (inclusive).

[0101] Preferably, the polyallyl functional monomer contains 70% by weight or more, preferably 80% by weight or more, of a diethylene glycol bis(allyl carbonate) compound (i.e., the monomer compound of formula (I) above) in which n is 1 in formula (II), and the weight percentage is based on the weight of the polyallyl functional monomer.

[0102] The relative concentrations (by weight) of the monomer species (n=1) and oligomer species (n=2-10) of formula (II) in polyallyl functional monomers can be determined by known methods. In particular, the concentration values ​​can be determined by performing HPLC or GPC analysis under conditions in which the peaks corresponding to the monomer species and each oligomer species are sufficiently separated, and calculating the % area of ​​the chromatographic peaks associated with each monomer species and oligomer species.

[0103] In one embodiment, the polyallyl functional monomer comprises or is a reaction product (RP) of a component comprising diallyl carbonate (A), one or more linear or branched aliphatic diols (B) having 3 to 10 carbon atoms in the molecule, and optionally a linear or branched aliphatic polyol (C) having 4 to 20 carbon atoms and 3 to 6 hydroxyl groups in the molecule. Here, the molar ratio A / (B+C) is in the range of 4 / 1 to 20 / 1, and the amount of the optional component (C) in the mixture (B+C) is 5% by weight or less relative to the weight of the mixture (B+C).

[0104] Preferably, the molar ratio A / (B+C) is in the range of 5 / 1 to 10 / 1, and the amount of (C) in the mixture (B+C) is 3% by weight or less relative to the weight of the mixture (B+C).

[0105] Diol (B) is a linear or branched aliphatic diol, preferably containing 3 to 10 carbon atoms in its molecule.

[0106] Suitable diols (B) include, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol, neopentyl glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, and 1,4-cyclohexanedimethanol.

[0107] Preferably, the diol (B) is selected from diethylene glycol, neopentyl glycol, and combinations thereof.

[0108] The polyol (C) is a linear or branched aliphatic polyol, preferably containing 4 to 20 carbon atoms and 3 to 6 hydroxyl groups in its molecule.

[0109] Suitable polyols (C) include, for example, pentaerythritol, trimethylolpropane, dipentaerythritol, ditrimethylolpropane, and tris(hydroxyethyl) isocyanurate.

[0110] Preferably, the polyol (C) is selected from pentaerythritol, trimethylolpropane, and combinations thereof.

[0111] Polyallyl functional monomers can be obtained as reaction products (RP) by reacting a diallyl carbonate (A) with a diol (B) or a mixture of diol (B) and a polyol (C) under transesterification conditions and in the presence of a basic catalyst, for example, as described in WO2004 / 090002.

[0112] The reaction product (RP) is a liquid at room temperature and has a kinematic viscosity of 10–1000 mmHg as measured at 25°C. 2 The value is / s (10~1000cSt).

[0113] In one embodiment, the reaction product (RP) has a kinematic viscosity of 10 to 300 mm at 25°C. 2 The range is / s (10~300 cSt), and 10~100 mm 2 The range is preferably / s (10 to 100 cSt), and 10 to 40 mm 2 The concentration is more preferably in the range of / s (10 to 40 cSt). The reaction product RP is preferably in the range of 1.10 to 1.30 g / ml, and more preferably in the range of 1.11 to 1.20 g / ml, at 25°C.

[0114] The reaction product (RP) is typically obtained as a mixture of allyl carbonate species of components (B) and (C) (if present) in the form of monomers and oligomers, as well as in the form of allyl carbonate of mixed oligomers of components (B) and (C), the relative amounts of these allyl carbonate species depend primarily on the ratio of the selected reagents (A), (B), and (C).

[0115] (Allyl ester polymerizable compound (A2) and polymerizable compound (A3)) Examples of allyl ester polymerizable compounds (A2) include diallyl phthalate represented by general formula (3) and its oligomer, and allyl ester compounds represented by general formula (4) and their oligomers obtained by the transesterification reaction of a mixture of diallyl phthalate and polyol. Examples of polymerizable compounds (A3) include polymerizable compounds represented by general formula (5) and their oligomers, which include at least one of an allyl ester group and an allyl carbonate group.

[0116] Polymerizable compounds represented by general formula (5) include allyl ester compounds, allyl carbonate compounds, and mixtures of compounds having allyl ester groups and allyl carbonate groups, obtained by transesterification reactions of mixtures of dialkyl phthalates, allyl alcohols, diallyl carbonates, and polyols.

[0117] In this embodiment, the compounds of general formulas (3) to (5) include positional isomers. [ka]

[0118] The diallyl phthalate represented by general formula (3) is at least one selected from diallyl isophthalate, diallyl terephthalate, and diallyl orthophthalate. [ka]

[0119] In formula (4), X represents a divalent group derived from a linear or branched aliphatic diol having 2 to 8 carbon atoms, or a trivalent to hexavalent group derived from a linear or branched aliphatic polyol having 3 to 10 carbon atoms and 3 to 6 hydroxyl groups, and n is an integer from 2 to 6. [ka]

[0120] In formula (5), X represents a divalent group derived from a linear or branched aliphatic diol having 2 to 8 carbon atoms, or a trivalent to hexavalent group derived from a linear or branched aliphatic polyol having 3 to 10 carbon atoms and 3 to 6 hydroxyl groups, m and n represent integers from 0 to 6, and the sum of m and n is an integer from 2 to 6.

[0121] Specific examples of polyols (aliphatic diols, aliphatic polyols) that form X in formulas (4) and (5) include ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, and diols of 1,4-dimethylolcyclohexane, triols of glycerol and trimethylolpropane, tris(hydroxyethyl) isocyanurate, pentaerythritol, diglycerol, ditrimethylolpropane, and polyols of dipentaerythritol.

[0122] The compounds of formulas (4) and (5) may contain their oligomers. The oligomer in formula (4) is produced by a transesterification reaction between an allyl ester compound produced during the manufacturing process and a polyol. The oligomer in formula (5) is produced by a transesterification reaction between an allyl ester compound or allyl carbonate compound produced during the manufacturing process and a polyol.

[0123] Therefore, allyl ester polymerizable compound (A2) or polymerizable compound (A3) is, for example, Diallyl phthalate compounds selected from diallyl isophthalate, diallyl terephthalate, and diallyl orthophthalate; Diallyl ester compounds and their oligomers obtained by transesterification reaction of the aforementioned diallyl phthalate compound with a mixture of at least one diol selected from ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-dimethylolcyclohexane, etc.; Polyallyl ester compounds and their oligomers obtained by a transesterification reaction of diallyl phthalate with a mixture of at least one polyol selected from glycerol and trimethylolpropane triols, tris(hydroxyethyl) isocyanurate, pentaerythritol, diglycerol, ditrimethylolpropane, dipentaerythritol, etc.; and Dimethyl isophthalate, dimethyl terephthalate, dimethyl orthophthalate, diethyl isophthalate, diethyl terephthalate, diethyl orthophthalate, dipropyl isophthalate, dipropyl terephthalate, and dipropyl orthophthalate; at least one C1-C3 dialkyl phthalate selected from these; allyl alcohol; diallyl carbonate; and allyl ester compounds, allyl carbonate compounds, compounds having an allyl carbonate group and an allyl ester group, and their oligomers obtained by transesterification reaction with the above diols or polyols; It contains at least one compound selected from the following.

[0124] More specifically, allyl ester polymerizable compound (A2) or polymerizable compound (A3) is, (i) A mixture of diallyl terephthalate and a diethylene glycol bis(allyl carbonate) compound, comprising a mixture containing 30% by weight of the diethylene glycol bis(allyl carbonate) compound relative to diallyl terephthalate, and its oligomer, (ii) Allyl ester compounds obtained by transesterification of a mixture of diallyl terephthalate and propylene glycol, (iii) A mixture of the allyl ester compound of (ii) and a diethylene glycol bis(allyl carbonate) compound, comprising a mixture containing 20% ​​by weight of the allyl ester compound (including the diethylene glycol bis(allyl carbonate) compound) and its oligomer, (iv) Allyl ester compounds, allyl carbonate compounds, and mixtures of compounds having an allyl ester group and an allyl carbonate group obtained by the transesterification reaction of a mixture of dimethyl terephthalate, allyl alcohol, diallyl carbonate, and diethylene glycol, A mixture of the mixture obtained in (v)(iv) and a diethylene glycol bis(allyl carbonate) compound, wherein the mixture contains 10% by weight of the mixture (containing the diethylene glycol bis(allyl carbonate) compound) and its oligomer, Preferably, it includes at least one selected from the following.

[0125] Suitable examples of allyl ester polymerizable compounds (A2) or polymerizable compounds (A3) suitable for the purpose of the present invention include allyl ester compounds, allyl carbonate compounds, and mixtures of compounds having an allyl ester group and an allyl carbonate group, obtained by a transesterification reaction of a mixture of dimethyl terephthalate, allyl alcohol, diallyl carbonate, and diethylene glycol.

[0126] The above allyl ester polymerizable compound (A2) or polymerizable compound (A3) can be defined by formulas (III) to (V), in which diallyl terephthalate of formula (III) is the main component, and each includes oligomers obtained by transesterification reaction with polyols. [ka]

[0127] According to the present invention, a compound (A) containing two or more allyloxycarbonyl groups can be selected as a mixture of an allyl ester polymerizable compound (A2) and / or a polymerizable compound (A3), an allyl carbonate polymerizable compound (A1), and their respective oligomers.

[0128] Polymerizable copolymer monomers The reaction mixture may also contain polymerizable ethylenically unsaturated compounds (as monomers or oligomers) with the polyallyl functional monomers described above. Here, these optional ethylenically unsaturated compounds are also referred to as "copolymerization monomers."Suitable copolymer monomers include, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, chloromethylstyrene, and divinylbenzene, as well as alkyl mono(meth)acrylates such as methyl(meth)acrylate, n-butyl(meth)acrylate, n-hexyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, methoxydiethylene glycol(meth)acrylate, methoxypolyethylene glycol(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, stearyl(meth)acrylate, lauryl(meth)acrylate, phenyl(meth)acrylate, glycidyl(meth)acrylate, benzyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 3-phenoxy-2-hydroxypropyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate. Acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, 2,2-bis Examples include di(meth)acrylates such as [4-((meth)acryloxyethoxy)phenyl]propane, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, and 2,2-bis[4-((meth)-acryloxypolyethoxy)phenyl]propane; tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate and tetramethylolmethane tri(meth)acrylate; and tetra(meth)acrylates such as tetramethylolmethane tetra(meth)acrylate. These copolymer monomers may be used individually or in combination of two or more.In the above explanation, "(meth)acrylate" means "methacrylate" or "acrylate," and "(meth)acryloxy" means "methacryloxy" or "acryloxy."

[0129] The total amount of copolymer monomers in the reaction mixture of the present invention may be 1 to 80% by weight, preferably 1 to 50% by weight, more preferably 2 to 20% by weight, and particularly preferably 3 to 10% by weight, based on the total amount of the reaction mixture.

[0130] In one preferred embodiment, the reaction mixture does not contain ethylenically unsaturated compounds, that is, no polymerizable copolymer monomers are added to the reaction mixture, and the only polymerizable compound present in the reaction mixture is a polyallyl functional monomer.

[0131] In one preferred embodiment, the reaction mixture comprises a polyallyl functional monomer which is a diethylene glycol bis(allyl carbonate) compound represented by general formula (II) and n is an integer between 1 and 10, and the reaction mixture does not contain an ethylenically unsaturated compound as a copolymer monomer, and the only polymerizable compound present in the reaction mixture is the diethylene glycol bis(allyl carbonate) compound of general formula (II).

[0132] In one embodiment, the reaction mixture comprises a polyallyl functional monomer which is the reaction product (RP) of a component comprising diallyl carbonate (A), one or more aliphatic diols (B), and optionally an aliphatic polyol (C), wherein the reaction mixture does not contain an ethylenically unsaturated compound as a copolymer monomer, and the only polymerizable compound present in the reaction mixture is the reaction product (RP) of components A, B, and any C.

[0133] Free radical polymerization initiator The radical initiator is an aromatic peroxide compound. A preferred aromatic peroxide compound has the following general formula (F1). [ka]

[0134] Here, X is hydrogen, C1~C 12 The initiator is selected from alkoxy groups, chlorine, and bromine. In one embodiment, X is selected from hydrogen, a C1-C4 alkoxy group, or bromine. Suitable aromatic peroxide initiators include, for example, benzoyl peroxide (BPO), bis(p-methoxybenzoyl) peroxide, bis(p-ethoxybenzoyl) peroxide, bis(p-propoxybenzoyl) peroxide, bis(p-isopropoxybenzoyl) peroxide, bis(p-butoxybenzoyl) peroxide, and bis(p-chlorobenzoyl) peroxide. A particularly preferred initiator is benzoyl peroxide [CAS 94-36-0].

[0135] The half-life of a free radical initiator at any given temperature represents the time it takes for half of the initiator's activity to be lost. This half-life temperature is determined by studying the decomposition kinetics of the initiator. The 10-hour half-life temperature of an initiator is the temperature at which half of the original initiator decomposes in 10 hours.

[0136] The half-life temperature is determined by periodically sampling solutions of peroxides maintained at several selected constant temperatures, measuring the decomposition rate of the peroxides in the aromatic solvent monochlorobenzene, and determining the amount of undecomposed peroxide in the sampled solutions using conventional iodine titration techniques. Such half-life measurement techniques are well known to those skilled in the art. Suitable techniques for determining such half-life temperatures in the same solvent by differential scanning calorimetry are also well known to those skilled in the art and can be used as an alternative to iodine titration. These two techniques provide equivalent results for the same solvent within the expected standard experimental deviation of the procedure. It is well known to those skilled in the art that the half-life temperature depends on the solvent in which the measurement is performed, and in order to improve the accuracy of comparing the half-life temperatures of one peroxide with those of another, it is necessary to identify the solvent in which the half-life is determined.

[0137] The aromatic peroxide initiator used in the present invention has a 10-hour half-life temperature of 55°C or higher, preferably 60°C or higher. For example, the 10-hour half-life temperature of the initiator is in the range of 55 to 100°C, preferably 60 to 95°C, and more preferably 60 to 85°C. In one embodiment, the 10-hour half-life temperature of the initiator is in the range of 60 to 80°C. A particularly preferred aromatic peroxide is benzoyl peroxide, which has a 10-hour half-life temperature of 73°C.

[0138] In one embodiment, the reaction mixture contains only one aromatic peroxide compound as a radical polymerization initiator. However, if necessary, a combination of two or more aromatic peroxide compounds with the same or different 10-hour half-life temperatures may be used.

[0139] The total amount of a single free radical initiator or combination of initiators in the reaction mixture is in the range of 0.5 to 3.0% by weight, preferably 1.0 to 2.0% by weight, and more preferably 1.3 to 1.8% by weight, relative to the weight of the polyallyl functional monomer to be prepolymerized (the above weight percentages refer to the amount of initiator excluding solid or liquid diluent components). Initiators exceeding 3.0% by weight have the disadvantage of generating excessive heat, increasing the likelihood of cracks and optical defects in the rigid polymer. They also increase the undesirable degree of yellowing and hardness in spectacle lenses.

[0140] Aromatic peroxide initiators are typically commercially available in the form of compositions containing diluents (phlegmatizers) such as alkylbenzoate diluents, phthalate diluents, or cresol diluents, and / or stabilizers, or water as a stabilizer. It has also been observed that the use of initiators containing phthalate and cresol diluents can result in optical components with defects known as "dots," which are particularly noticeable in coated lenses. Furthermore, phthalate and cresol diluents have relatively low solubility in polyallyl functional monomers and their prepolymers, which tends to result in higher haze in optical components.

[0141] Furthermore, the use of water-containing peroxides may have some drawbacks in the manufacturing process if the water content in the prepolymer composition before casting exceeds a certain concentration. For example, residual water exceeding 0.5% by weight relative to the weight of the prepolymer composition may cause premature delamination of optical components from the mold or non-uniform conversion of polyallyl functional monomers in different molds during the curing cycle. However, in one embodiment, it is preferable to use water-containing peroxides because water can be more easily removed from the prepolymer composition before casting, for example, by degassing or purging with an inert gas.

[0142] A particularly preferred initiator is benzoyl peroxide containing water, which is commercially available as a moistened powder. Preferably, the water content is 50% by weight or less, and more preferably 25% by weight or less, relative to the weight of the aromatic peroxide containing water (e.g., benzoyl peroxide).

[0143] In one embodiment, the step of preparing the reaction mixture includes adding an aromatic peroxide compound, preferably benzoyl peroxide, in a form containing water.

[0144] Other ingredients The reaction mixture and prepolymer composition may contain further additive compounds such as internal demolding agents, UV and / or HEV light absorbers, resin modifiers (e.g., chain extenders, crosslinking agents, light stabilizers), antioxidants, fillers, adhesion enhancers, and bleaching agents.

[0145] As internal demolding agents, for example, acidic phosphate esters or non-reactive silicone oils can be used. Examples of acidic phosphate esters include monophosphate esters and diphosphate esters, which can be used individually or in combination of two or more.

[0146] Examples of resin modifiers include olefin compounds containing episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids and their anhydrides, and (meth)acrylate compounds.

[0147] Suitable bleaching agents include, for example, those based on inorganic pigments or organic dyes dispersed in an allyl resin, as disclosed in the applicant's name in International Publication Nos. 2021 / 095774 and International Publication Nos. 2022 / 224928.

[0148] Examples of UV and / or HEV light absorbers include benzotriazoles, benzophenones, triazines, and oxalanilides.

[0149] These additional compounds may be introduced into either or both the reaction mixture and / or the prepolymer composition, in the latter case, before casting to the mold.

[0150] In one embodiment, the reaction mixture and the prepolymer composition are solvent-free, i.e., they do not contain any inert organic solvents that need to be removed from the prepolymer composition at the end of the prepolymerization reaction.

[0151] Preparation of prepolymer compositions According to the present invention, a prepolymer composition is prepared by heating a reaction mixture containing at least one polyallyl functional monomer, at least one radical polymerization initiator, and an optional component.

[0152] The mixing of components and the prepolymerization reaction can be carried out in a stainless steel reactor or the like, equipped with heating and cooling means for adjusting the temperature of the reaction mixture.

[0153] The prepolymerization reaction is carried out by heating the reaction mixture at a temperature in the range of 12 to 3°C lower than the 10-hour half-life temperature of the aromatic peroxide compound. Preferably, the reaction mixture is heated at a temperature in the range of 10 to 5°C lower than the 10-hour half-life temperature of the aromatic peroxide compound. For example, when benzoyl peroxide (with a 10-hour half-life temperature of 73°C) is used as the initiator, the temperature of the prepolymerization reaction can be selected in the range of 61 to 70°C, for example, 63 to 70°C or 65 to 68°C.

[0154] While maintaining the above temperature, the reaction mixture is preferably degassed to remove substantially all of the oxygen and water it contains. Degassing can be carried out by any suitable means, for example, by reducing the reaction mixture under reduced pressure (e.g., 50 mbar or less) or by sparging with a non-reactive gas such as nitrogen, helium, or argon.

[0155] In one embodiment, at the end of the prepolymerization reaction, the prepolymer composition contains 0.5% by weight or less of water relative to the weight of the prepolymer composition.

[0156] While maintaining the above temperature, the reaction mixture may be left to stand or stirred.

[0157] As the reaction mixture is heated and polymerization proceeds, its viscosity increases. The viscosity of the reaction mixture, measured at 25°C, is 40-350 mmHg. 2 The mixture is heated until a prepolymer composition with a viscosity in the range of / s (40-350 cSt) is formed. Preferably, the reaction mixture is heated until the viscosity of the formed prepolymer composition, measured at 25°C, is 60-200 mm². 2 / s (range of 60-200 cSt), more preferably 70-120 mm 2 The mixture is heated to a temperature in the range of 70-120 cSt / s. At the end of the prepolymerization reaction, the prepolymer composition is liquid and substantially gel-free. Being liquid means that the prepolymer composition is suitable for casting into a mold.

[0158] The duration of the prepolymerization reaction depends largely on the prepolymerization temperature, the type of polyallyl functional monomer, and the desired degree of viscosity increase. Generally, the duration of the prepolymerization reaction ranges from 0.5 to 15 hours, and in most cases, it is between 1 and 10 hours.

[0159] Thus, a combination of two or more aromatic peroxide compounds having the same or different 10-hour half-life temperatures can also be used. In this case, if the 10-hour half-life temperatures are the same, a temperature 12-13°C lower than the 10-hour half-life temperature, or within the preferred range indicated above, is selected according to the principle of the present invention described above. If the 10-hour half-life temperatures of the two or more initiators are different, it is preferable to select a temperature 12-13°C lower than the lowest 10-hour half-life temperature among the initiators in the combination, or within the preferred range indicated above.

[0160] In one preferred embodiment, the reaction mixture and its prepolymer composition contain only one aromatic peroxide compound as an initiator.

[0161] Once the prepolymer composition is formed, that is, after the reaction mixture reaches the desired viscosity, the prepolymer composition may be cast into a mold or stored at room temperature, for example.

[0162] In one embodiment, the manufacturing method therefore includes a step of cooling the prepolymer composition so that the polymerization reaction does not proceed further. This has the advantage of avoiding an undesirable viscosity increase before or during the casting process, for example, when preparing large batches of prepolymers.

[0163] In one embodiment, the process includes cooling the prepolymer composition to a temperature at least 20°C lower than the 10-hour half-life temperature of the initiator. For example, when benzoyl peroxide is used as the initiator, the prepolymer composition can be cooled to 53°C or below.

[0164] Cooling can be carried out for a period of less than 90 minutes, preferably less than 60 minutes, and more preferably less than 30 minutes.

[0165] The prepolymer composition is relatively stable at normal room temperature. Although it contains some of the initially added initiator that was not consumed during the prepolymerization reaction, its storage and working shelf life is very long. The storage shelf life can be, for example, about 20 weeks or more, depending on the amount of initiator used and the degree of viscosity increase achieved at the end of the prepolymerization reaction.

[0166] The prepolymer composition can be polymerized into a thermosetting state, i.e., a rigid polymer, by conventionally known techniques for polymerizing compositions containing polyallyl functional monomers.

[0167] In one embodiment, the prepolymer composition is placed in a mold, such as a glass mold, and polymerized to form a molded article such as a lens element or a lens. This procedure is particularly advantageous in the preparation of spectacle lens elements and spectacle lenses.

[0168] According to the present invention, it is not necessary to further introduce a free radical initiator before casting the prepolymer composition. However, if necessary, a prepolymer composition can also be prepared that includes the prepolymer composition and further optional components (e.g., a UV absorber and a bluing agent).

[0169] Immediately after the prepolymerization reaction is complete, for example, at the end of the cooling step to a temperature at least 20°C lower than the 10-hour half-life temperature of the initiator, the prepolymerization composition may be cast. For example, in the case of benzoyl peroxide, prepolymerization may be interrupted at about 50°C or below, and the prepolymerization composition may be cast into the mold at that temperature. Alternatively, the prepolymerization composition may be cooled to room temperature or refrigerated (for example, at a temperature in the range of 0-6°C) and stored for later use.

[0170] The cast prepolymer composition can be polymerized by heating in the mold, which can be done, for example, in an oven or a water bath.

[0171] As the curing cycle, i.e., the temperature-time profile used to polymerize the prepolymer composition into a rigid polymer, conventionally known curing cycles, such as those commonly used for curing allyl polymers in IPP, can be used.

[0172] Typically, to achieve full polymerization of optical components, polymerization is carried out at a temperature of 80-120°C for 10-48 hours. Full polymerization is considered achieved when the liquid prepolymer composition is determined to have transformed into a mold-releaseable rigid polymer.

[0173] After obtaining the rigid polymer, it is common to cool it before demolding. Preferably, the rigid polymer in the mold is cooled to a temperature in the range of 40 to 80°C, more preferably in the range of 50 to 70°C. For this purpose, the mold containing the polymerized optical material may be left at room temperature outside the heating device.

[0174] The demolded optical material may be post-cured, i.e., heated at a temperature above the maximum temperature of the curing cycle but below the temperature at which thermal degradation of the material occurs. Post-curing can neutralize any radical species of polymerization initiator that may remain in the optical component and remove internal stress from the optical component.

[0175] When a bleach containing a tetraazaporphyrin (TAP) dye is added to a polymerizable composition to correct the yellowing of optical components (for example, due to the presence of a UV-absorbing compound or an initiator), the post-cure can also be used to enhance the efficiency of the TAP dye, as described in WO2022224928A1.

[0176] Post-curing is often performed at temperatures between 90 and 130°C.

[0177] Polymerization of the prepolymer composition can be carried out using conventionally known apparatus, such as a convection oven or a water bath. The mold is a conventional mold, for example, consisting of two mold pieces and a sealing material that forms a cavity defining the shape and dimensions of the final optical material of the mold. The mold pieces can be made of glass, metal, or plastic.

[0178] The optical material of the present invention can be used in a variety of applications, and in particular, it can be used in eyeglass lenses, protective mask lenses, optical filters, etc. Here, an eyeglass lens is a lens designed to be fitted into an eyeglass frame to protect the eye and / or correct vision. The eyeglass lens may be either a non-corrective eyeglass lens (also called a plano or afocal lens) or a corrective eyeglass lens. The corrective lens may be a monofocal, bifocal, trifocal, or progressive lens.

[0179] The optical material may have one or more functional coatings selected from the group consisting of abrasion-resistant coatings, anti-reflective coatings, anti-fouling coatings, anti-static coatings, anti-fog coatings, polarizing coatings, colored coatings, and light-color-changing coatings.

[0180] The present invention will be described in more detail below with reference to examples, but these are merely illustrative and do not limit the scope of the invention in any way. [Examples]

[0181] Characterization Method The optical materials were evaluated using the following methods.

[0182] Density / specific gravity: The densities of polyallyl functional monomers and different prepolymerized resins were measured using a volumetric glass pycnometer (25 ml) immersed in a water bath adjusted to 23°C, with the resin volume adjusted to reach the meniscus. Density rho(g / cm³) 3 ) is defined as the weight of the filled monomer / 25.

[0183] Polymer density / specific gravity (ASTM D-792): The density of the above polymer was measured by the drainage method in accordance with ASTM D-792. The scale used for measuring the lift gain was Model E42 ex Gibertini SRL.

[0184] Kinematic viscosity (ASTM D-446): In accordance with ASTM D-446, viscosity at 25°C was measured using a KPG Ubbelodhe viscometer, capillary type 1C, for polyallyl functional monomers and capillary type 2C / 3C for prepolymer compositions.

[0185] Shrinkage rate: The shrinkage rate was calculated using the following formula.

number

[0186] Yellowing index (YI) (ASTM D-1925): The degree of yellowing (YI) was measured for optical materials in the form of a 4 mm planar lens using a GretagMacbeth 1500 Plus spectrophotometer, taking into account a standard light source C and a 2-degree field of view (2-degree observer). YI is defined by the following formula: YI = (100 / Y)(1.277X - 1.06Z).

[0187] Total light transmittance and haze value: The total light transmittance and haze values ​​of a 2 mm thick flat plate of optical material were measured using a BYK-Gardner Haze-Gard Plus digital haze meter in accordance with ASTM D 1003.

[0188] Light transmittance at a given wavelength: The transmittance of a 2 mm thick flat optical material at a given wavelength was measured using an Agilent Cary 60 UV-Visible spectrophotometer. "UV cut" and "HEV cut" refer to the highest wavelengths in the UV region (280nm to 380nm) and HEV region (380nm to 500nm), respectively, at which the light transmittance of the optical material, as measured in accordance with ASTM D 1003, is less than 1%.

[0189] Coloring test of 2mm plano lenses: A neutral 2mm planar lens was used with a colorimeter bath (model COLORADO Electronic ex ORGANIZZAZIONE GF) and BPI TM The ability to adsorb dye onto the surface was measured by immersion (dip) staining in a gray solution at 93°C for 15 minutes. After rinsing with deionized water, the lens transmittance was measured by measuring the total light transmittance as described above. In addition, the uniformity / non-uniformity of the colored lenses was visually evaluated by holding them up to a backlit visor (Model Professional 20 - 5000K ex LUPO DAYLIGHT).

[0190] Refractive index nD20: The refractive index was measured at 20°C using an ATAGO ABBE refractometer model NAR-3T.

[0191] Mechanical properties - Rockwell hardness M The Rockwell hardness M (ASTM D-785) of optical materials was evaluated using a 5 mm thick flat plate.

[0192] material The following compounds were used in the examples.

[0193] Polyallyl functional monomers A polyallyl functional monomer was prepared by reacting diallyl carbonate (component A), having a molar ratio A / (B+C) of 7.2 and a ratio C / (B+C) of 2.29% by weight, with diethylene glycol (component B) as a diol and pentaerythritol (component C) as a polyol. A three-necked jacketed flask equipped with a thermometer, a magnetic stirrer, and a distillation column with 10 perforated plates with a diameter of 30 mm was filled with the following compounds: - Pentaerythritol (PE): 5g (approximately 0.04 moles) -Diethylene glycol (DEG): 213g (approximately 2.01 moles) - Diallyl carbonate (DAC): 2100g (approximately 14.80 moles) - 1.0 ml of sodium methylate in a 20% by weight solution in methanol.

[0194] The reaction was carried out for 3 hours at a temperature of 85-120°C and a decreasing pressure of 200-130 mbar, with distillation performed during the production of allyl alcohol (total 242g, approximately 285ml, purity >99%). After cooling, the reaction mixture was washed with 500 ml each of deionized water in two separate portions.

[0195] Excess DAC was distilled at a pressure of approximately 1 mbar by raising the temperature to 130°C, and the resulting product was filtered through a 0.45 μm membrane filter.

[0196] 512 g of a liquid product with the following characteristics was obtained. -Viscosity (25C): 17mm 2 / s(17cSt), -Density (20C): 1.152g / ml, -Refractive index nD20: 1.453, -APHA color depth: 1.

[0197] The above polyallyl functional monomers were obtained as monomers and oligomers of bis(allyl carbonate)diethylene glycol, monomers and oligomers of pentaerythritol tetra(allyl carbonate), and mixtures of the above diol and polyol poly(allyl carbonate).

[0198] The amount of the diethylene glycol bis(allyl carbonate) compound, where n=1 in formula (II), relative to the weight of the monomer and oligomer mixture was approximately 83% by weight. This amount was determined by HPLC analysis of the reaction product under the following conditions: temperature = 25°C, reaction product sample for analysis in the form of a 10% by weight acetonitrile solution, injection sample = 5 microliters, eluent: acetonitrile / water (45 / 55 vol%) mixture, UV detector.

[0199] UV absorber -BP6 (2,2'-dihydroxy-4,4'-dimethoxybenzophenone, manufactured by MFCI) - Addivant Lowilite 20: 2-hydroxy-4-methoxybenzophenone.

[0200] Peroxide radical polymerization initiator -LuperoxA75 (ARKEMA's registered trademark): Granular wet powder of water-stabilized benzoyl peroxide (25% by weight of water) -PERKADOX CH50-L (Nouryon): Granular wet powder of phthalate-stabilized benzoyl peroxide (50% by weight of alkyl phthalate) -NOURYON's Trigonox ADC-NS30 (registered trademark), a commercially available product, contains approximately 70% by weight of diethylene glycol bis(allyl carbonate) and 30% by weight of a mixture of isopropyl peroxydicarbonate, sec-butyl peroxydicarbonate, and isopropyl / sec-butyl peroxydicarbonate.

[0201] TAP dye (bleach) As a bleaching agent, we used commercially available FDG-005 (a Pd-containing TAP compound with a main absorption peak at 583 nm) manufactured by Yamada Chemical Co., Ltd. FDG-005 was used in the form of a masterbatch, i.e., pre-dispersed in a polyallyl functional monomer at a concentration of 0.05% by weight.

[0202] UV & Blue Light Blocking MB TM (Bleach) A bleaching masterbatch based on a proprietary composition of pigment dispersed in polyallyl functional monomers provided by Acomon Inc. (approximately 2.0% by weight of pigment in the polyallyl functional monomer, based on the weight of monomer).

[0203] Prepolymerization process A three-necked jacketed flask equipped with a magnetic stirrer and thermocouple was filled with polyallyl functional monomers. Optionally, at this stage, any additives such as light stabilizers, UV absorbers, antioxidants, and bleaching agents were also introduced into the flask.

[0204] The monomer (or composition containing any additives) is heated under reduced pressure (P) while being vigorously stirred. abs Prepolymerization temperature (T) <50 mbar p ) was heated until it reached the end. p After reaching a certain pressure, nitrogen gas was flowed into the flask to return it to atmospheric pressure. Then, a BPO initiator was introduced into the flask. The pressure was reduced again (<50 mbar), and mixing was continued until the polymerization reaction achieved the desired viscosity. The thickening of the prepolymer composition was measured in successive samples of the reaction mixture taken from the reaction flask at predetermined intervals. The prepolymer composition was drained from the flask and cast directly into a glass mold (i.e., without cooling).

[0205] Examples 1. Preparation of prepolymer composition A prepolymer composition was prepared by mixing 100 parts by weight (pbw) of polyallyl functional monomer with a BPO initiator, or Trigonox ADC-NS30 (a dicarbonate peroxide initiator for comparison), and any additive in the proportions shown in Table 1.

[0206] The shelf life of each prepolymer composition was evaluated by measuring the viscosity trend at different prepolymerization temperatures and time periods. Here, the shelf life at a given temperature refers to the time period during which the prepolymer composition can be maintained at that temperature until its viscosity increases to a point where it becomes practically unusable for mold filling.

[0207] [Table 1]

[0208] In Comparative Example CC1, polyallyl functional monomers were prepolymerized according to a conventionally known curing procedure using a dicarbonate peroxide initiator. Temperature T p At 80°C, add a small amount of initiator (0.1 parts by weight) to the monomer and pressurize under reduced pressure (P abs Degassed at <50 mbar for 3 hours. Temperature T at 80°C. p The temperature was selected to be higher than the half-life temperature of the initiator (66°C for ADC NS-30). A small amount of initiator and a relatively high T p This allowed us to obtain a prepolymer composition having the desired increase in viscosity (and consequently, an increase in density), and also provided a good shelf life due to the complete consumption of the initiator compound.

[0209] A polymerizable composition for casting was obtained by mixing a large amount of the same initiator into the prepared prepolymer composition CC1 (Comparative Example CC2). However, as shown in Table 1, the readily castable composition CC2 had a significantly shorter shelf life at room temperature compared to CC1 (approximately 1 hour at 25°C). Such a short shelf life makes low-temperature storage practically essential when manufacturing optical components with these compositions (a shelf life of more than 6 months at 4°C).

[0210] As shown in Table 1, the prepolymer compositions (PP1-PP3) of the present invention are readily castable compositions with good processability and a very good shelf life. Samples PP1-PP3 exhibit effective thickening to ensure a shrinkage level comparable to that achieved by curing with a carbonate peroxide initiator, while not rapidly increasing in thickness over time. This allows for proper casting even in the presence of the entire initiator.

[0211] 2. Preparation of optical components EX2 and EX3, and comparative EX1* and EX1-PP* The readily castable polymerizable compositions (EX2 and EX3) according to the present invention were converted into rigid polymers. For comparison, a non-prepolymerized polyallyl functional monomer was cured with the conventionally known dicarbonate peroxide ADC NS-30 to prepare a rigid polymer (EX1).

[0212] Compositions EX2 and EX3 were prepared by filling a jacketed stainless steel reactor equipped with a mechanical stirrer, thermocouple, and bottom drain line for mold filling with polyallyl functional monomers, initiators, and additives. The prepolymerization process was carried out under the conditions described for prepolymer PP3 in point 1 above, with the reaction mixture being mixed and degassed at 65°C for 3 hours (P abs (<50 mbar) was used (the final viscosity at 25°C was 90 mm²). 2 / s(90cSt)). At the end of the reaction period, the prepolymer composition was cooled to 50°C. Then, nitrogen gas (P abs The pressure was replaced with 1.2 bar. Before casting, the prepolymer composition was filtered through a stainless steel disc holder containing a 0.45 μm PTFE membrane (47 mm diameter) placed on the discharge line and used for filling the glass mold.

[0213] Comparative composition EX1 was 2 hours (P abs Prepared in the same manner as EX2 and EX3, except that the mixture was mixed and degassed at room temperature (<50 mbar).

[0214] Polymerization to form a rigid polymer was carried out by heating a mold containing the polymerizable composition in a forced-air circulating oven according to one of the curing cycles described in Tables 2 and 3.

[0215] [Table 2]

[0216] [Table 3]

[0217] At the end of the curing cycle, the mold was removed from the oven and allowed to cool. Demolding was performed at a temperature in the range of 50-70°C. Subsequently, the polymer was post-cured in a forced-air circulating oven under the following conditions. -1 hour, 100℃ EX1 -2 hours, 120°C for EX2 and EX3

[0218] For the measurement of total transmittance, haze%, and staining test (T% after coloring and uniformity of dye uptake), polymerizable compositions EX1 to EX3 were cast into 2 mm thick plano-lens shaped glass molds and cured. Furthermore, for the measurement of YI and Rockwell hardness, they were cast as 5 mm thick flat sheets.

[0219] The characteristic evaluation data listed in Tables 4 and 5 were measured for post-cured lenses. Furthermore, to more rigorously evaluate the manufacturing yield of the compositions of the present invention, lenses with complex designs and shapes were also prepared. The lenses prepared for each cast test are as follows:

[0220] -10 semi-finished blanks, with base curves of 6 and 8 (5 pieces each), center thickness 10mm. -5 double-focus lens, with an additional power of +2.00, and a flat segment line with a base curve of 6, front and rear type.

[0221] Process yield was evaluated, regardless of design type, as the ratio of the number of discarded cast products having defects (i.e., cracks, flow lines or defective segments of multifocal lenses) to the total number of cast products.

[0222]

Table 4

[0223] The data in Table 4 show that using BPO according to the prepolymerization method of the present invention (EX2 and EX3) makes it possible to obtain optical components having mechanical and optical properties as good as those of composition EX1 polymerized using dicarbonate peroxide ADC NS-30 initiator, and furthermore, shows that the difference in refractive index remains limited. EX2 has a slightly higher yellowness than comparative material EX1, but this can be easily corrected by adding a small amount of a TAP-based bleaching agent without adversely affecting other properties.

[0224] Furthermore, both EX2 and EX3 exhibit the same T% and tinting aspect as comparative material EX1 (the dye adsorption capacity of two lenses can be considered identical if the difference in the total T% value of the lenses is within ±5 units).

[0225] Furthermore, EX2 and EX3 exhibit excellent production efficiency due to the control of shrinkage obtained by the prepolymerization method of the present invention. In fact, compared to curing of polyallyl-functional monomers with a standard dicarbonate peroxide ADC NS-30 initiator, no early release, cracks or flow lines were observed in all prepared semi-finished blanks, and furthermore, all multifocal lenses were successfully cast without defective segment lines.

[0226] This is the same as that obtained by prepolymerizing polyallyl functional monomers with dicarbonate peroxide ADC NS-30 initiator, as shown in Comparative Example EX1-PP* in Table 4. However, the prepolymer composition of the present invention is a readily castable composition with improved shelf life and does not require the addition of an additional initiator before casting, representing a significant improvement.

[0227] 3. Preparation of optical components EX5, EX7, EX9 and comparative EX4*, EX6*, EX8* Polymerizable compositions according to the present invention (EX5, EX7, EX9) were prepared by prepolymerizing polyallyl functional monomers under the conditions described above for the prepolymer PP3. UV absorber compounds and bluing agents were added to the prepolymerized compositions to obtain final lenses with different cutoff ratios. For comparison, compositions containing non-prepolymerized polyallyl functional monomers and optional components were cured with dicarbonate peroxide ADC NS 30 initiator (comparative EX4*, EX6*, EX8*).

[0228] The composition of each composition, along with the characterization data, is listed in Table 5. The curing and post-curing conditions are as described in point 2 above.

[0229] [Table 5]

[0230] The polymerizable compositions EX4-EX9 refer to alternative UV and HEV compositions containing a higher dose of the UV absorber BP6 introduced in powder form. The higher dose of UV absorber does not affect the outcome of the prepolymerization reaction, and the resulting prepolymer composition has a viscosity in the desired range of 70-110 mm at 25°C. 2 The viscosity increased within the range of / s (70-110 cSt).

[0231] The data in Table 5 demonstrates that the prepolymerization method of the present invention can be advantageously used in preparing optical components having similar optical and mechanical properties to high-quality lenses obtained from non-prepolymerized monomers cured with dicarbonate peroxide ADC NS-30 initiator.

[0232] For 400nm and 410nm cutoff optical components (EX6-EX9), it was observed that regardless of the type of initiator used, higher doses of UV absorber required to achieve the desired cutoff ratio increased the yellowness of the optical components. However, the yellowness could be kept to an acceptable level by appropriately adding a bluing agent.

[0233] Furthermore, the optical components of the present invention are also characterized by exhibiting superior properties compared to comparative materials when using high doses of UV absorbers, i.e., in optical components with higher cutoff values. In fact, stable hardness values ​​were observed in the lenses of the present invention (EX5, EX7, and EX9), while a decreasing trend was observed in the comparative lens (EX4*, EX6*, and EX8*). In addition, in the material of the present invention (EX9), the addition of a high UV absorber did not affect color adsorption and final color uniformity, whereas in the lens cured with TX ADC NS30 (EX8), it was observed that lower hardness not only increased the dye penetration rate but also resulted in uniformity defects.

[0234] Finally, the comparative composition tended to exhibit cracks, streamlines, and frequent defective segments during demolding of the bifocal lenses. In contrast, the composition of the present invention showed superior casting results due to reduced polymerization shrinkage.

Claims

1. Step (a) of preparing the reaction mixture, The reaction mixture is heated to a temperature 12 to 3°C lower than the 10-hour half-life temperature of the aromatic peroxide compound, and the kinematic viscosity at 25°C, measured according to ASTM D446, ​​is 40 to 350 mm². ２ (b) A step of forming a prepolymer composition in the range of / s (40 to 350 cSt), A method for producing a polyallyl functionalized prepolymer composition, comprising: The reaction mixture described above is At least one polyallyl functional monomer, As a free radical initiator, at least one aromatic peroxide compound, including, A method for producing a polyallyl-functionalized prepolymer composition, wherein at least one of the aromatic peroxide compounds is contained in an amount of 0.5 to 3.0% by weight, based on the total amount of the polyallyl-functionalized monomer.

2. The method according to claim 1, wherein in step (b), the reaction mixture is heated at a temperature in the range of 10°C to 5°C lower than the 10-hour half-life temperature of the aromatic peroxide compound.

3. The aforementioned prepolymer composition has a viscosity of 60 to 200 mm at 25°C. ２ / s (in the range of 60 to 200 cSt), preferably 70 to 120 mm ２ The method according to claim 1 or 2, wherein the value is in the range of / s (70 to 120 cSt).

4. The method according to any one of claims 1 to 3, wherein at least one of the aromatic peroxide compounds includes a compound represented by the following general formula (F1). 【Chemistry 1】 (In equation (F1), X is hydrogen, C １ ~C １２ (Selected from alkoxy groups, chlorine, and bromine.)

5. The method according to claim 4, wherein at least one of the aromatic peroxide compounds is benzoyl peroxide.

6. The method according to any one of claims 1 to 5, wherein step (b) includes a step of degassing the reaction mixture.

7. In step (a), the viscosity of the at least one polyallyl functional monomer at 25°C is 10 to 300 mm. ２ / s (10 to 300 cSt) range, preferably 10 to 100 mm ２ / s (10-100 cSt), more preferably 10-40 mm ２ The method according to any one of claims 1 to 6, wherein the value is in the range of / s (10 to 40 cSt).

8. The method according to any one of claims 1 to 7, comprising cooling the prepolymer composition to a temperature at least 20°C lower than the 10-hour half-life temperature of the aromatic peroxide compound.

9. The method according to any one of claims 1 to 8, wherein the at least one polyallyl functional monomer comprises a compound containing two or more allyloxycarbonyl groups represented by the following formula (1). 【Chemistry 2】 (In formula (1), n is an integer of 2 to 6, R １ represents a hydrogen atom or a methyl group, and when a plurality of R １ are present, they may be the same or different; X is a divalent to hexavalent organic group (a) derived from a linear or branched aliphatic polyol having 3 to 12 carbon atoms which may optionally contain an oxygen atom, a divalent to hexavalent organic group (b) derived from an alicyclic polyol having 5 to 16 carbon atoms which may optionally contain an oxygen atom, or a divalent to hexavalent organic group (c) derived from an aromatic compound having 6 to 12 carbon atoms; the organic group (a) or the organic group (b) forms an allyl carbonate group by bonding to an allyloxycarbonyl group via an oxygen atom derived from a hydroxyl group.)

10. The method according to any one of claims 1 to 9, wherein at least one of the polyallyl functional monomers comprises a diethylene glycol bis(allyl carbonate) compound represented by general formula (II). 【Transformation 3】 (In equation (II), n is an integer between 1 and 10, inclusive.)

11. The method according to claim 10, wherein the diethylene glycol bis(allyl carbonate) compound of general formula (II) contains 70% by weight or more, preferably 80% by weight or more, of the diethylene glycol bis(allyl carbonate) compound of general formula (II) having n = 1, based on the total weight of the diethylene glycol bis(allyl carbonate) compound of general formula (II) having n = 1 or more and 10 or less.

12. At least one of the polyallyl functional monomers, diallyl carbonate (A) and, A linear or branched aliphatic diol (B) containing 3 to 10 carbon atoms in its molecule, Optionally, a linear or branched aliphatic polyol (C) containing 4 to 20 carbon atoms and 3 to 6 hydroxyl groups in its molecule, The reaction product (RP) comprises the components including, The method according to any one of claims 1 to 9, wherein the molar ratio A / (B+C) of each component is in the range of 4 / 1 to 20 / 1, and the amount of any component (C) in the mixture (B+C) is 5% by weight or less, preferably 3% by weight or less, relative to the total weight of the mixture (B+C).

13. At least one of the polyallyl functional monomers, diallyl carbonate (A) and, A linear or branched aliphatic diol (B) containing 3 to 10 carbon atoms in its molecule, A linear or branched aliphatic polyol (C) containing 4 to 20 carbon atoms and 3 to 6 hydroxyl groups in its molecule, The reaction product (RP) comprises the components including, The method according to any one of claims 1 to 9, wherein the molar ratio A / (B+C) of each component is in the range of 4 / 1 to 20 / 1, preferably in the range of 5 / 1 to 15 / 1, and the amount of component (C) in the mixture (B+C) is 5% by weight or less, preferably 3% by weight or less, relative to the total weight of the mixture (B+C).

14. The method according to any one of claims 10 to 11, wherein the reaction mixture does not contain an ethylenically unsaturated compound other than a diethylene glycol bis(allyl carbonate) compound of general formula (II) where n is 1 or more and 10 or less.

15. The reaction mixture does not contain an ethylenically unsaturated compound other than the reaction product (RP) listed below. The reaction product (RP) is diallyl carbonate (A) and, A linear or branched aliphatic diol (B) containing 3 to 10 carbon atoms in its molecule, A reaction product (RP) of a component comprising an optional linear or branched aliphatic polyol (C) having 4 to 20 carbon atoms and 3 to 6 hydroxyl groups in its molecule, The method according to any one of claims 12 to 13, wherein the molar ratio A / (B+C) of each component is in the range of 4 / 1 to 20 / 1, and the amount of any component (C) in the mixture (B+C) is 5% by weight or less of the total weight of the mixture (B+C).

16. Step (i) of preparing the reaction mixture, The reaction mixture is heated to a temperature range 12 to 3°C lower than the 10-hour half-life temperature of the aromatic peroxide compound, and the kinematic viscosity at 25°C, as measured according to ASTM D446, ​​is 40 to 350 mmHg. ２ (ii) A step of forming a prepolymer composition in the range of / s (40 to 350 cSt), The steps include: (iii) pouring the prepolymer composition into a mold, (iv) A step of curing the prepolymer composition within the mold to form an optical component, A method for manufacturing optical components, including, The reaction mixture At least one polyallyl functional monomer, As a free radical initiator, at least one aromatic peroxide compound, Includes, A method for producing an optical component, comprising at least one of the aromatic peroxide compounds in an amount of 0.5 to 3.0% by weight based on the total amount of the polyallyl functional monomer.

17. The method according to claim 16, wherein no additional free radical initiators other than at least one aromatic peroxide are added before the prepolymer composition is injected into the mold.

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