KR101922168B1 - Polymerizable composition for plastic lens - Google Patents

Abstract

According to an embodiment of the present invention, the present invention relates to a polymerizable composition for plastic lenses. Since the polymerizable composition for plastic lenses contains a boron-based compound as a reaction rate regulator, it is possible to control the polymerization rate by controlling strong activities of a halogen tin-based catalyst, thereby securing stable operation times. In addition, the composition is preliminarily polymerized in a mold at a low temperature of 5-20°C for a specific period of time, specifically, for 1-20 hours, thereby stabilizing the polymerization rate and appropriately controlling the viscosity of the composition while improving workability. Further, since bubbles formation can be prevented, and the transparency of the resin can be improved, thereby being useful in the production of various plastic lenses such as spectacle lenses and camera lenses.

Description

[0001] POLYMERIZABLE COMPOSITION FOR PLASTIC LENS [0002]

An embodiment relates to a polymerizable composition for a plastic lens, and a polythiourethane-based plastic lens obtained from the polymerizable composition.

Plastic materials of various resins are widely used as optical materials such as eyeglass lenses and camera lenses because they are lightweight and easily breakable and excellent in dyeability compared with optical materials made of inorganic materials such as glass. In recent years, higher performance of optical materials is required, and specifically high transparency, high refractive index, low specific gravity, high heat resistance, and high impact resistance are required. BACKGROUND ART Polythiourethane-based compounds are widely used as optical materials due to their excellent optical properties and mechanical properties.

Generally, a polythiourethane-based compound is produced by casting polymerization in which a polymerizable composition is injected into a mold and heat-cured. At this time, the polymerization reaction is carried out over several hours to several hours while slowly raising the temperature from a low temperature to a high temperature. Here, securing a sufficient time until the mold, that is, a sufficient pot life is very important for improving workability. Further, in order to sufficiently draw the resin properties, it is necessary to complete the polymerization. In order to complete the polymerization, a method of using a catalyst having a strong polymerization activity or increasing the amount of the catalyst may be mentioned. In order to obtain stable polymerizability, it is important to secure a stable pot life even in a different lot. If the pot life varies from lot to lot, polymerization deviations may occur, which may affect the quality stability of the resin.

A commonly used halogen tin catalyst is most widely used because it most closely matches the conditions described above. In addition, a method of using an amine-based catalyst is also known. For example, Korean Patent No. 10-1207128 discloses a method of polymerizing an amine-based hydrochloride using a catalyst.

Korean Patent No. 10-1207128

However, when the halogen-based catalyst is used, the activity of the catalyst during polymerization is strong and it is difficult to appropriately control the reaction rate. To solve this problem, attempts have been made to use an amine-based catalyst. However, when an amine-based catalyst is used, the blue-based dye must be mixed in a relatively large amount due to the problem of finely shading, (Korean Patent No. 10-1207128).

Thus, embodiments are directed to controlling the reactivity of a halogen tin-based catalyst using a polymerizable composition comprising a boron based compound and properly controlling the polymerization rate and viscosity to provide more stable pot life and improve workability. Furthermore, a polymerizable composition for a plastic lens having high transparency, which is an advantage of a glass lens, and a polythiourethane-based plastic lens obtained therefrom.

Embodiments provide a polymerizable composition comprising a polyiso (thio) cyanate compound, at least one sulfide bond, or at least one bifunctional thiol compound having at least one ester linkage, a boron based compound, and a catalyst.

Another embodiment is a polymerizable composition comprising a polyiso (thio) cyanate compound, at least one sulfide bond, or at least one bifunctional thiol compound having at least one ester bond, a reaction rate modifier, and a catalyst, ≪ / RTI >

[Equation 1]

ln Y = b x DELTA X

In the above formula, ln Y is ln Y _X - ln Y ₀ where Y ₀ is the initial viscosity (cps) of the polymerizable composition at a temperature between 5 ° C and 20 ° C and Y _X is the time at which the polymerizable composition has elapsed X hours at a temperature between 5 ° C and 20 ° C (Cps), DELTA X is from 1 hour to 10 hours, and b is from 0.1 hour- ¹ to 0.3 hour- ¹ .

Another embodiment provides a process for preparing a polymerizable composition comprising providing a polymerizable composition comprising a polyiso (thio) cyanate compound, at least one sulfide bond or at least one bifunctional thiol compound having at least one ester bond, a boron based compound, and a catalyst, At a temperature of 5 占 폚 to 20 占 폚, and curing the prepolymerized composition. The present invention also provides a method for producing a polythiourethane-based plastic lens.

Another embodiment is a poly (arylene ether) composition comprising a polyisocyanate compound, at least one sulfide bond, or at least one bifunctional thiol compound having at least one ester bond, a boron compound, and a catalyst, A plastic lens comprising a thiourethane resin is provided.

The polymerizable composition for a plastic lens according to an embodiment can control the polymerization rate by controlling the strong activity of the halogen tin-based catalyst by including the boron compound as a reaction rate regulator, so that a more stable pot life can be provided. In addition, the composition can be preliminarily polymerized in a mold at a low temperature of 5 to 20 ° C for a certain period of time, specifically, for 1 to 20 hours, thereby stabilizing the polymerization rate and appropriately controlling the viscosity of the composition. In addition, since bubbles can be prevented from occurring and the transparency of the resin can be improved, it can be usefully used in the production of various plastic lenses such as spectacle lenses and camera lenses.

1 to 6 show changes in viscosity (Y) with time (X) at 10 DEG C using a non-contact viscometer in the polymerizable compositions of Examples 1 to 4 and Comparative Examples 1 and 2, Graph.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of the present invention will be described in detail. The embodiments are not limited to what is described below, but may be modified into various forms as long as the gist of the invention is not changed.

As used herein, " comprising "means that other elements may be included unless otherwise specified.

In addition, all numbers and expressions indicating amounts of ingredients, reaction conditions, and the like described in this specification are to be understood as being modified in all instances by the term "about" unless otherwise specified.

One embodiment provides a polymerizable composition comprising a polyiso (thio) cyanate compound, at least one sulfide bond, or at least one bifunctional thiol compound having at least one ester linkage, a boron based compound, and a catalyst.

The boron compound can stabilize the polymerization rate by controlling the reactivity of the initial catalyst. Specifically, the activity of the catalyst at the initial stage of the polymerization is inhibited, and the polymerization rate is suppressed, thereby making it possible to secure a sufficient pot life in polymerization of the polymerizable composition. More specifically, the boron-based compound can suppress the polymerization rate of the polymerizable composition at a low temperature of 5 ° C to 20 ° C at the initial stage of the polymerization, and then, at a high temperature such as 80 ° C to 200 ° C The polymerization rate of the polymerizable composition is not suppressed at the temperature.

The boron based compound may be selected from the group consisting of boronic acid, boronate ester, alkyl boronate, borate ester, alkyl borate, Can be selected. Specifically, the boron compound may be a borate ester, an alkyl borate, or a mixture thereof.

More specifically, the boron based compound may be a compound represented by the following Formula 1:

[Chemical Formula 1]

Wherein R 1, R 2, and R 3 are each independently H, C _1-6 alkyl, C _5-8 cycloalkyl, C _6-12 alkylcycloalkyl, C _7-12 aralkyl, or phenyl.

More specifically, the boron-based compound is a compound consisting of trimethylborate, triethylborate, tripropylborate, triisopropylborate, tributylborate, tri-tert-butylborate, triphenylborate, tripentylborate, , And more specifically trimethyl borate, triethyl borate, tributyl borate, or mixtures thereof.

The polyiso (thio) cyanate compound is not particularly limited as long as it is a compound having at least two iso (thio) cyanate groups in one molecule.

Examples thereof include hexamethylene diisocyanate, 1,5-pentane diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene- Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanate Aliphatic polyisocyanate compounds such as natomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanato methyl ester, and lysine triisocyanate; (Isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, 2,5-bis (isocyanatomethyl) ) -Bicyclo [2.2.1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, 3,8-bis (isocyanatomethyl) tricyclodecane, Bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) tricyclodecane, bis Cyclohexane) methane, 1,3-bis (isocyanatomethyl) cyclohexane, and 1,4-bis (isocyanatomethyl) cyclohexane; 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, tolylene diisocyanate, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, ethyl Diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4 ', 4'-diisocyanate, isopentylene diisocyanate, Diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatomethyl) benzene, bis (isocyanatomethyl) benzene, (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-bis (isocyanatopropyl) benzene, m-xylylene diisocyanate, , A polyisocyanate compound containing an aromatic ring such as bis (isocyanatomethyl) naphthalene, bis (isocyanatomethylphenyl) ether, bis (isocyanatoethyl) phthalate and 2,5-di (isocyanatomethyl) ; Bis (isocyanatomethyl) sulfide, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (Isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) (Isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2,3- Methylthio) propane, 1,2,3-tris (isocyanatoethylthio) propane, 3,5-dithia-1,2,6,7-heptane tetraisocyanate, 2,6- , 5-dithia-1,7-heptane diisocyanate, 2,5-diisocyanate methylthiophene, and 4-isocyanatoethylthio-2,6-dithia-1,8-octane diisocyanate. A sulfated aliphatic polyisocyanate compound; Aromatic sulfide-based polyisocyanate compounds such as 2-isocyanatophenyl-4-isocyanatophenylsulfide, bis (4-isocyanatophenyl) sulfide and bis (4-isocyanatomethylphenyl) sulfide; Bis (3-methyl-5-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis Aromatic disulfide-based polyisocyanates such as bis (4-methyl-5-isocyanatophenyl) disulfide, bis (4-methoxy-3-isocyanatophenyl) compound; Diisocyanatotetrahydrothiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocynatomethyltetrahydrothiophene, 2,5-diisocyanato- Dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) Ditiorane, 4,5-diisocyanatomethyl-2-methyl-1,3-dithiolane, and other aliphatic alicyclic polyisocyanate compounds; Aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanatoethane and 1,6-diisothiocyanatohexane; Alicyclic polyisothiocyanate compounds such as cyclohexane diisothiocyanate; 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisobutyl Methylenebis (phenylisothiocyanate), 4,4'-methylenebis (2-methylphenylisothiocyanate), 4,4'-methylenebis (3- Methylphenyl isothiocyanate), 4,4'-diisothiocyanatobenzophenone, 4,4'-diisothiocyanato-3,3'-dimethylbenzophenone, bis (4-isothiocyanatophenyl) Aromatic polyisothiocyanate compounds such as ether; Carbonyl polyesters such as 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate and (2,2-pyridine) -4,4-dicarbonyldiisothiocyanate; Isothiocyanate compounds; Aliphatic polyisothiocyanate compounds such as thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), and dithiobis (2-isothiocyanatoethane); (2-isothiocyanato) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonyl (4-isothiocyanatobenzene), dithiobis And 4-isothiocyanatobenzene); aromatic polyisothiocyanate compounds such as 4,4'-bis Sulfo alicyclic polyisothiocyanate compounds such as 2,5-diisothiocyanatothiophene and 2,5-diisothiocyanato-1,4-dithiane; Isothiocyanatohexane, 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1- 1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocyanatophenyl-4- Sulfide, and a compound containing an isothiocyanato group such as 2-isocyanatoethyl-2-isothiocyanatoethyl disulfide and an isothiocyanato group.

Specific examples thereof include hexamethylene diisocyanate, 1,5-pentane diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) Bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, bis (4-isocyanatocyclohexyl) methane, 1,3-bis Bis (isocyanatomethyl) benzene, m-xylylene diisocyanate, 1,3-diisocyanatobenzene, tolylene diisocyanate, 2 (isocyanatomethyl) , 4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-methylenebis (phenylisocyanate), and the like.

Further, it is also possible to use a chlorine substituent, a bromine substituent or other halogen substituent of the polyisocyanate (thio) cyanate compound, an alkyl substituent, an alkoxy substituent, a nitro substituent, a prepolymer type modified product with a polyhydric alcohol, a carbodiimide- Modified products, biuret-modified products, dimerization or trimerization reaction products can also be used. At this time, the respective compounds may be used alone or in combination of two or more.

Wherein the bifunctional or more thiol compound having at least one sulfide bond is at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl- Mercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 5,7-dimercaptomethyl 1,1-dimercapto-3,6,9-trithiandecane, bis (mercaptoethyl) sulfide, 2,5-bis (mercaptomethyl) (Mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiaeethane, pentaerythritol tetrakis (3-mercaptopropionate), or a mixture thereof.

Specifically, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9- Undecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto- 6,9-trithiane undecane, or a mixture thereof.

The bifunctional or more thiol compound having at least one ester bond may be at least one selected from the group consisting of trimethylpropane tri (3-mercaptoacetate), trimethylpropane tri (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate) , Pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptoacetate), dipentaerythritol hexa (3-mercaptopropionate), or a mixture thereof have.

Specifically, it may be pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate) or a mixture thereof.

The catalyst may be a halogen tin catalyst.

Wherein the halogen tin catalyst is selected from the group consisting of phenyl tin trichloride, diphenyl tin dichloride, triphenyl tin chloride, tricyclohexyltin chloride, methyl tin trichloride, dimethyl tin dichloride, dibutyl tin dichloride, trimethyl tin chloride, And a mixture of two or more selected from the group consisting of trichloride, tributyltin chloride, ditert-butyltin dichloride, butyltin chloride dihydroxide, tributyltin bromide, tributyltin iodide, trimethyltin bromide, triethyltin bromide, Can be selected from the group. Specifically, it may be dimethyltin dichloride, dibutyltin dichloride or a mixture thereof.

The halogen tin-based catalyst may be contained in an amount of 0.001 to 0.5 parts by weight, 0.005 to 0.1 parts by weight, or 0.01 to 0.08 parts by weight based on 100 parts by weight of the sum of the polyisocyanate (thio) cyanate compound and the thiol compound. Further, the boron-based compound may be included in an amount of 5 to 150 parts by weight, or 10 to 90 parts by weight based on 100 parts by weight of the catalyst. When the catalyst and the boron compound are included in the above range, the reactivity and the rate can be appropriately controlled. For example, if the reactivity of the polymerizable composition is high, it is preferable to increase the amount of the boron compound.

The polymerizable composition may satisfy the following formula (1): " (1) "

 [Equation 1]

ln Y = b x DELTA X

In the above formula, ln Y is ln Y _X - ln Y ₀ where Y ₀ is the initial viscosity (cps) of the polymerizable composition at a temperature of 5 ° C to 20 ° C and Y _X is the initial viscosity of the polymerizable composition at a temperature of 5 ° C to 20 ° C in X hours (Cps), DELTA X is from 1 hour to 10 hours, and b is from 0.1 hour- ¹ to 0.3 hour- ¹ .

Specifically, the b is 0.1 hours ^{to 1} to 0.3 hours ^{to 1} or 0.15 hours ^-1 to 0.25 hours ^{- 1.} Within this range, the polymerizable composition may have an initial viscosity of from 5 to 20 캜, or from 20 to 100 cps, or from 30 to 80 cps, at a temperature of 10 캜 after mixing. When the polymerizable composition has a viscosity within the above range, the reactivity at the time of polymerization is maintained, so that the generation of bubbles is prevented, and the unevenness of hardening such as malleability after curing can be prevented.

Another embodiment is a polymerizable composition comprising a polyiso (thio) cyanate compound, at least one sulfide bond, or at least one bifunctional thiol compound having at least one ester bond, a reaction rate modifier, and a catalyst, Lt; / RTI >

The reaction rate controlling agent is not limited as long as it can control the catalyst reactivity and / or control the polymerization rate of the polymerizable composition to secure a sufficient pot life.

For example, the reaction rate modifier may be a boron-based compound as described above. The reaction rate regulator suppresses the polymerization rate of the polymerizable composition at a temperature in the early low temperature range of the polymerization, for example, from 5 to 20 ° C, and then, at a high temperature range during the subsequent curing process, The polymerization rate of the polymerizable composition can be suppressed at a temperature of 200 캜.

In addition, the respective structures of the polymerizable composition, specifically, the polyiso (thio) cyanate compound, the thiol compound, and the catalyst are the same as described above.

The polymerizable composition may further contain an additive such as an internal mold release agent, a heat stabilizer, an ultraviolet absorber, and a blueing agent depending on the purpose.

Examples of the internal release agent include a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group or a phosphate ester group; A silicone-based nonionic surfactant having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts such as trimethylcetylammonium salt, trimethylstearylammonium salt, dimethylethylcetylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, diethylcyclohexadecylammonium salt and the like; And acidic phosphate esters may be used singly or in combination of two or more.

Examples of the thermal stabilizer include a metal fatty acid salt, phosphorus, lead, and an organosilicate.

Examples of the ultraviolet absorber include benzophenone, benzotriazole, salicylate, cyanoacrylate, oxanilide, and the like.

The bluing agent has an absorption band in the wavelength range from orange to yellow in the visible light region and has a function of adjusting the color of the optical material made of the resin. Specifically, the bluing agent may include a material that exhibits blue to violet, but is not particularly limited. Examples of the bluing agent include dyes, fluorescent whitening agents, fluorescent pigments, and inorganic pigments, but they can be appropriately selected in accordance with physical properties and resin color required for the produced optical component. These bluing agents may be used alone or in combination of two or more.

The bluing agent is preferably a dye in view of the solubility in the polymerizable composition and the transparency of the resulting optical material. Specifically, the dye may be a dye having a maximum absorption wavelength of 520 to 600 nm, and more particularly, a dye having a maximum absorption wavelength of 540 to 580 nm. Further, in view of the structure of the compound, the dye is preferably an anthraquinone dye. The method of adding the bluing agent is not particularly limited and may be added to the monomer system in advance. Specifically, the method of adding the bluing agent may be a method of dissolving the monomer in a monomer, or a method of preparing a master solution containing a high concentration of a bluing agent and diluting the monomer solution or other additives using the master solution and adding You can use branching methods.

Another embodiment provides a process for preparing a polymerizable composition comprising providing a polymerizable composition comprising a polyiso (thio) cyanate compound, at least one sulfide bond or at least one bifunctional thiol compound having at least one ester bond, a boron based compound, and a catalyst, At a temperature of 5 占 폚 to 20 占 폚, and curing the prepolymerized composition. The present invention also provides a method for producing a polythiourethane-based plastic lens.

The polymerizable composition as described above may be preliminarily polymerized in a mold at a low temperature of 5 to 20 占 폚 and then cured by heating to prepare a polythiourethane compound. Specifically, the polymerizable composition is degassed under reduced pressure, and then injected into a lens mold (mold). Such degassing and mold injection can be carried out at a low temperature of, for example, 0 to 30 占 폚, 5 to 20 占 폚, or about 10 占 폚. After injection into the mold, prepolymerization is carried out under the same temperature condition (low temperature) to stabilize the polymerization rate. Specifically, the prepolymerization is carried out at 0 to 30 ° C, 5 to 20 ° C, or about 10 ° C for 1 to 20 hours, 1 to 15 hours, or 1 to 10 hours, . At this time, since the polymerization rate of the polymerizable composition is suppressed in the above-mentioned temperature range and can be polymerized for a sufficient pot life, it is possible to prevent a convection phenomenon caused by a rapid polymerization reaction, .

After the prepolymerization, the polymerization is carried out by a conventional method. For example, polymerization can be carried out by gradually heating the composition from a room temperature to a high temperature. The temperature of the polymerization reaction may be, for example, 20 to 200 캜, or 20 to 150 캜, specifically 25 to 120 캜, or 80 to 200 캜.

Then, the polythiourethane-based plastic lens is separated from the mold.

The polythiourethane-based plastic lens can be manufactured into various shapes by changing the mold of the mold used in the production. Specifically, it may be in the form of a spectacle lens, a camera lens, or the like.

The plastic lens may be subjected to surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, anti-reflection treatment, anti-reflection treatment, anti- A dyeing treatment, a dimming treatment, and the like.

By such a method, a plastic lens formed by the above-described method can be provided. That is, a polyiso (thio) cyanate compound according to another embodiment; A bifunctional or more thiol compound having at least one sulfide bond or at least one ester bond; Boron compounds; And a polythiourethane resin in which a polymerizable composition comprising a catalyst is cured to form a plastic lens.

As described above, the polymerizable composition for a plastic lens according to the embodiment contains the boric acid ester compound represented by the formula (1), thereby controlling the polymerization activity of the halogen tin catalyst to control the polymerization rate, You can get housekeeping time. In addition, the composition can be preliminarily polymerized in a mold at a low temperature of 5 to 20 ° C for a certain period of time, specifically, for 1 to 20 hours, thereby stabilizing the polymerization rate and appropriately controlling the viscosity of the composition. In addition, since bubbles can be prevented from occurring and the transparency of the resin can be improved, it can be usefully used in the production of various plastic lenses such as spectacle lenses and camera lenses.

The above contents will be described in more detail by the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the examples.

[ Example ]

Example  1: For plastic lenses Polymerizable  Preparation of composition

, 50.7 parts by weight of m-xylylene diisocyanate (m-XDI), 0.05 part by weight of dibutyltin dichloride (DBTDC) as a polymerization catalyst, 0.02 part by weight of tributylborate and 0.2 part by weight of Zelec® UN 0.1 part by weight of a release agent, Stepan) was mixed and dissolved at 20 占 폚. Here, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6 , 9-trithiane undecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane were homogeneously mixed To prepare a polymerizable composition.

Example  2 to 4 and Comparative Example  1 to 3: Polymerizable  Preparation of composition

A polymerizable composition for a plastic lens was produced in the same manner as in Example 1 except that the kind and content of the compound were changed as shown in Table 1 below.

[ Evaluation example  : Property check]

The properties of the polymerizable compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were measured as described below. The measurement results are shown in Table 1 below.

(1) Polymerization rate

The viscosity (cps) of the compositions of Examples 1 to 4 and Comparative Examples 1 to 3 was measured at 10 ° C using a non-contact viscometer (EMS-1000, Kyoto Electronics Co., Ltd.). In this case, the X-axis is time-series and the Y-axis is viscosity, and is logarithmically expressed as shown in the following Equation 1, which is shown graphically in FIGS. 1 to 4:

[Equation 1]

ln Y = b x DELTA X.

(2) Evaluation of transparency Presence or absence of cloudiness )

The compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were degassed at a reduced pressure of 10 Pa and 600 Pa for 1 hour and then filtered through a Teflon filter of 3 占 퐉. The filtered polymerizable composition was injected into a glass mold template assembled by tape. The mold was stabilized at 10 ° C for 5 hours, then heated to 25 ° C to 120 ° C at a rate of 5 ° C / minute and polymerized at 120 ° C for 18 hours. Then, the cured resin in the glass mold mold was further cured at 130 캜 for 4 hours, and then the molded body (plastic lens) was released from the glass mold mold. The obtained lens was evaluated for transparency by confirming the presence or absence of white turbidity as follows. Specifically, the lens was irradiated to a projector from a cow to visually observe whether the lens was blurred or opaque. When the lens was cloudy or had no opaque material, it was evaluated as O (no cloudiness) and when it was evaluated as X (with cloudiness).

(3) Evaluation of releasability

A lens was obtained in the same manner as in Evaluation Example (2) (evaluation of transparency), except that a convex molding die assembled with a glass mold having an outer diameter of 84 mm * height of 17 mm and an outer diameter of 84 mm * 11 mm was used. When 10 or more sets of the mold were broken and the mold was naturally cooled to room temperature after completion of the polymerization, there was no breakage or disruption of the mold. Or a case where there was a cleavage was evaluated as x.

(4) Bubble presence evaluation

The lenses obtained in the evaluation example (2) were observed with a naked eye through a microscope at a magnification of 100, and when the bubbles were 0, S, 1 to 10, A, 11 to 30 and B Respectively.

(5) Evaluation of reactivity

The lens obtained in the evaluation example (2) was analyzed by ATR type FT-IR. When it was confirmed that the characteristic peak of -NCO at 2260 cm ^-1 completely disappeared, the lens was marked with.

A-1: 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto- , 6,9-trithiandecane, and a mixture of tetrafunctional polythiol compounds including 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane

A-2: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane

A-3: Pentaerythritol tetrakis (3-mercaptopropionate)

DBTDC: Dibutyltin dichloride

Referring to Table 1 and FIGS. 1 to 6, the compositions of Examples 1 to 3 were improved in terms of polymerization rate, transparency, releasability, bubble presence, reactivity, etc. in comparison with the compositions of Comparative Examples 1 to 3 . In particular, from the viewpoint of the polymerization rate, the compositions of Examples 1 to 4 were found to have a gentler slope than that of the compositions of Comparative Examples 1 and 2, and it was found that the viscosity increased while maintaining an appropriate speed for a long time. On the other hand, the compositions of Comparative Examples 1 and 2 show that the viscosity of the composition of Examples 1 to 4 is increased rapidly with time and the reaction is terminated within a short time of about 10 hours. Furthermore, even when the amount of the halogen-tin-based catalyst was increased (Example 4), it was confirmed that the polymerization rate was controlled to an appropriate level by the boron compound and the surface of the lens was transparent. Therefore, it is expected that the plastic lens manufactured in the embodiment can be usefully used because it is easy to work and a plastic lens with high transparency can be obtained.

Claims (16)

Polyiso (thio) cyanate compounds;
A bifunctional or more thiol compound having at least one sulfide bond or at least one ester bond;
Boron compounds; And
Catalyst,
Wherein the boron-based compound is a compound represented by the following Formula 1:
[Chemical Formula 1]

In this formula,
R 1, R 2, and R 3 are each independently H, C _1-6 alkyl, C _5-8 cycloalkyl, C _6-12 alkylcycloalkyl, C _7-12 aralkyl, or phenyl. delete delete The method according to claim 1,
Wherein the catalyst is a halogen tin-based catalyst. 5. The method of claim 4,
Wherein the halogen tin catalyst is selected from the group consisting of phenyl tin trichloride, diphenyl tin dichloride, triphenyl tin chloride, tricyclohexyltin chloride, methyl tin trichloride, dimethyl tin dichloride, dibutyl tin dichloride, trimethyl tin chloride, And a mixture of two or more selected from the group consisting of trichloride, tributyltin chloride, ditert-butyltin dichloride, butyltin chloride dihydroxide, tributyltin bromide, tributyltin iodide, trimethyltin bromide, triethyltin bromide, ≪ / RTI > group. 5. The method of claim 4,
Wherein the halogen tin catalyst is contained in an amount of 0.001 to 0.5 parts by weight based on 100 parts by weight of the total of the polyiso (thio) cyanate compound and the thiol compound. The method according to claim 1,
Wherein the boron compound is selected from the group consisting of trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, tri-tert-butyl borate, triphenyl borate, tripentyl borate, Polymerizable composition. The method according to claim 1,
Wherein the boron-based compound is contained in an amount of 5 to 150 parts by weight based on 100 parts by weight of the catalyst. The method according to claim 1,
Wherein the polymerizable composition satisfies the following formula (1): < EMI ID =
[Equation 1]
ln Y = b x DELTA X
In this formula,
ln Y is ln Y _X - ln Y is ₀ ,
Y ₀ is the initial viscosity (cps) of the polymerizable composition at a temperature of 5 ° C to 20 ° C,
Y _X is the viscosity (cps) of the polymerizable composition after elapse of X hours at a temperature of 5 캜 to 20 캜,
DELTA X is from 1 hour to 10 hours,
b is from 0.1 hour- ¹ to 0.3 hour- ¹ . The method according to claim 1,
Wherein the polymerizable composition has an initial viscosity of from 20 to 100 cps at a temperature of from 5 캜 to 20 캜. Polyiso (thio) cyanate compounds;
A bifunctional or more thiol compound having at least one sulfide bond or at least one ester bond;
A reaction rate modifier comprising a boron compound represented by the following formula (1); And
Catalyst,
A polymerizable composition which satisfies the following formula (1):
[Equation 1]
ln Y = b x DELTA X
In this formula,
ln Y is ln Y _X - ln Y ₀ ,
Y ₀ is the initial viscosity (cps) of the polymerizable composition at a temperature of 5 ° C to 20 ° C,
Y _X is the viscosity (cps) of the polymerizable composition after elapse of X hours at a temperature of 5 캜 to 20 캜,
DELTA X is from 1 hour to 10 hours,
b is from 0.1 hour- ¹ to 0.3 hour- ¹ ,
[Chemical Formula 1]

In this formula,
R 1, R 2, and R 3 are each independently H, C _1-6 alkyl, C _5-8 cycloalkyl, C _6-12 alkylcycloalkyl, C _7-12 aralkyl, or phenyl. 12. The method of claim 11,
Wherein the rate controlling agent suppresses the polymerization rate of the polymerizable composition at a temperature of from 5 캜 to 20 캜 and does not inhibit the polymerization rate of the polymerizable composition at a temperature of from 80 캜 to 200 캜. Providing a polymerizable composition comprising a polyiso (thio) cyanate compound, a bifunctional or higher thiol compound having at least one sulfide bond or at least one ester bond, a boron compound, and a catalyst;
Pre-polymerizing the composition at a temperature of from 5 캜 to 20 캜; And
And curing the prepolymerized composition,
Wherein the boron compound is a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

In this formula,
R 1, R 2, and R 3 are each independently H, C _1-6 alkyl, C _5-8 cycloalkyl, C _6-12 alkylcycloalkyl, C _7-12 aralkyl, or phenyl. delete 14. The method of claim 13,
Wherein after the prepolymerization, the polymerizable composition satisfies the following formula (1): " (1) "
[Equation 1]
ln Y = b x DELTA X
In this formula,
ln Y is ln Y _X - ln Y is ₀ ,
Y ₀ is the initial viscosity (cps) of the polymerizable composition at a temperature of 5 ° C to 20 ° C,
Y _X is the viscosity (cps) of the polymerizable composition after elapse of X hours at a temperature of 5 캜 to 20 캜,
DELTA X is from 1 hour to 10 hours,
b is from 0.1 hour- ¹ to 0.3 hour- ¹ . Polyiso (thio) cyanate compounds; A bifunctional or more thiol compound having at least one sulfide bond or at least one ester bond; A boron-based compound represented by Formula 1 below; And a plasticizer comprising a polythiourethane resin formed by curing a polymerizable composition comprising a catalyst:
[Chemical Formula 1]

In this formula,
R 1, R 2, and R 3 are each independently H, C _1-6 alkyl, C _5-8 cycloalkyl, C _6-12 alkylcycloalkyl, C _7-12 aralkyl, or phenyl.

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