KR102150592B1 - Polymerizable composition for optical material - Google Patents

Abstract

One embodiment relates to a polymerizable composition for an optical material and a polythiourethane-based compound prepared therefrom, wherein the polythiourethane-based compound has excellent appearance due to low streak and bubble generation.

Description

Polymerizable composition for optical materials TECHNICAL FIELD [POLYMERIZABLE COMPOSITION FOR OPTICAL MATERIAL]

One embodiment relates to a polymerizable composition for a polythiourethane-based optical material and a polythiourethane-based compound prepared therefrom, wherein the polythiourethane-based compound has excellent appearance due to low streak and bubble generation.

Since optical materials using plastics are lighter and less fragile than optical materials made of inorganic materials such as glass and have excellent dyeing properties, various resin plastic materials are widely used as optical materials such as spectacle lenses and camera lenses. . In recent years, as the demand of users for higher performance and convenience increases, research on optical materials having characteristics such as high transparency, high refractive index, high Abbe number, low specific gravity, high heat resistance, and high impact resistance has been continued. .

Examples of widely used optical materials include polythiourethane-based compounds obtained by polymerizing a polythiol compound and a polyisocyanate compound. However, when a polythiol compound and a polyisocyanate compound are reacted to prepare a polythiourethane-based optical material, the reactivity changes depending on the type of the polythiol compound and the polyisocyanate compound and the type and content of the catalyst, and the resulting polythiourethane There has been a problem that appearance defects such as streaks and/or bubbles occur in the urethane-based optical material.

As an alternative to this, Korean Patent Registration No. 10-1704951 discloses a method of preparing a polyurethane resin composition by adding an alcohol compound so that the ratio of the hydroxyl group to the isocyanate group is 10 to 20 mol%.

Korean Patent Registration No. 10-1704951

However, the Korean registered patent has a problem that the improvement of striae or air bubbles is not sufficient, and the manufacturing yield is low.

Accordingly, one embodiment is to provide a polymerizable composition capable of manufacturing a plastic lens having excellent appearance, regardless of the type of polyisocyanate, polythiol, and catalyst, and no streaks and/or bubbles are generated.

One embodiment includes 1 to 5 polyisocyanate compounds, 1 to 5 polythiol compounds, and a catalyst represented by Formula 1 below,

R calculated by the following equation (1) is a real number of 9.5 to 19.5 to provide a polymerizable composition:

[Equation 1]

In Equation 1,

이며,

이며,

이며,

Is,

Is,

Is,

n is the number of types of polyisocyanate compounds,

N _i is the content (% by weight) of NCO of the i polyisocyanate compound,

m _i is the number of functional groups of the i polyisocyanate compound,

W _i is the input amount (g) of i polyisocyanate compound,

o _i is the weight average molecular weight (g/mol) of the i polyisocyanate compound,

이며,

Is,

l is the number of types of polythiol compounds,

S _j is the equivalent weight (g/eq) of the j polythiol compound,

이며,

이며,

Is,

Is,

u _j is the number of functional groups of the j polythiol compound,

V _j is the input amount (g) of the j polythiol compound,

t _j is the weight average molecular weight (g/mol) of the j polythiol compound,

로서,Q is

as,

[Formula 1]

In Formula 1,

E is a halogen compound,

F is an aliphatic hydrocarbon having 1 to 30 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms,

h and g are each independently an integer of 1 to 3,

h+g is 4,

K is the amount of the compound represented by Chemical Formula 1 added based on the total amount of the polyisocyanate compound and the polythiol compound added, 100,

D is the rate of viscosity change over time of the polymerizable composition, and is a value derived from Equation 2 defined as follows,

[Equation 2]

In Equation 2,

x is the time (hours) elapsed from the preparation of the composition to the viscosity measurement, and is 5 to 24,

y is the viscosity (cps) of the polymerizable composition at 10° C. after x hours,

G is the initial viscosity (cps) of the polymerizable composition at 10°C.

Another embodiment provides a polythiourethane-based compound prepared from the polymerizable composition.

Another embodiment provides an optical material molded from the polythiourethane-based compound.

The polymerizable composition of the embodiment is not limited to the type of polyisocyanate, polythiol, and catalyst, and does not generate streaks and/or bubbles, so that a plastic lens having excellent appearance can be manufactured. Specifically, the appearance, workability, and numerical stability of the manufactured plastic lens vary depending on the type of polyisocyanate, polythiol and catalyst as raw materials, and the type of raw material and the type of raw material and so that R calculated by Equation 1 satisfies a specific numerical range. By controlling the content accordingly, it is possible to provide a polymerizable composition in which the above-described properties are comprehensively considered.

The polymerizable composition according to an embodiment includes 1 to 5 polyisocyanate compounds, 1 to 5 polythiol compounds, and a catalyst represented by the following Formula 1,

R calculated by the following equation (1) is a real number of 9.5 to 19.5:

[Equation 1]

In Equation 1,

이며,

이며,

이며,

Is,

Is,

Is,

n is the number of types of polyisocyanate compounds,

N _i is the content (% by weight) of NCO of the i polyisocyanate compound,

m _i is the number of functional groups of the i polyisocyanate compound,

W _i is the input amount (g) of i polyisocyanate compound,

o _i is the weight average molecular weight (g/mol) of the i polyisocyanate compound,

이며,

Is,

l is the number of types of polythiol compounds,

S _j is the equivalent weight (g/eq) of the j polythiol compound,

이며,

이며,

Is,

Is,

u _j is the number of functional groups of the j polythiol compound,

V _j is the input amount (g) of the j polythiol compound,

t _j is the weight average molecular weight (g/mol) of the j polythiol compound,

로서,Q is

as,

[Formula 1]

In Formula 1,

E is a halogen compound,

F is an aliphatic hydrocarbon having 1 to 30 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms,

h and g are each independently an integer of 1 to 3,

h+g is 4,

K is the amount of the compound represented by Chemical Formula 1 added based on the total amount of the polyisocyanate compound and the polythiol compound added, 100,

D is the rate of viscosity change over time of the polymerizable composition, and is a value derived from Equation 2 defined as follows,

[Equation 2]

In Equation 2,

x is the time (hours) elapsed from the preparation of the composition to the viscosity measurement, and is 5 to 24,

y is the viscosity (cps) of the polymerizable composition at 10° C. after x hours,

G is the initial viscosity (cps) of the polymerizable composition at 10°C.

For example, when the polymerizable composition contains two types of polyisocyanates of a first polyisocyanate and a second polyisocyanate, in Equation 1, n is 2, and W1 is the amount of the first polyisocyanate (g ), W2 is the amount (g) of the second polyisocyanate, and other factors may be substituted in the same manner.

In the polymerizable composition, R calculated by Equation 1 may be a real number of 9.5 to 19.5. Specifically, in the polymerizable composition, R calculated by Equation 1 may be a real number of 9.5 to 19, a real number of 9.8 to 19, a real number of 9.8 to 18.5, or a real number of 9.8 to 18. When R is greater than or equal to 9.5, the reactivity between the polyisocyanate and the polythiol is too late, and thus streaks and air bubbles due to the unbalanced reaction at the end of the polymerization increase, and the production yield decreases. In addition, when the R is 19.5 or less, the reactivity is too high, so that streaks and bubbles due to an unbalanced reaction in the initial stage of polymerization increase, and the production yield decreases. Therefore, in order to minimize the occurrence of streaks and bubbles in the manufactured plastic lens to prevent appearance defects and maximize manufacturing yield, it is preferable to use a polymerizable composition in which R is within the above range.

A may be a real number of 80 to 120, and B may be a real number of 80 to 115. Specifically, A may be a real number of 82 to 117, a real number of 86 to 112, or a real number of 90 to 105, and B may be a real number of 82 to 114, a real number of 85 to 112, or a real number of 87 to 110. .

When A and B are within the above range, it may be more advantageous in improving heat resistance and suppressing the occurrence of cracks by improving dimensional stability in the polymerization and curing process.

D may be a real number of 0.08 to 0.25, a real number of 0.09 to 0.24, or a real number of 0.10 to 0.23. When D is within the above range, since uniform polymerization of the polymerizable composition is possible, there is an effect of improving appearance and workability by suppressing generation of bubbles and streaks.

E may be at least one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). Specifically, E may be chlorine.

F may be an alkyl group having 1 to 10 carbon atoms. Specifically, F may be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.

The polymerizable composition includes 1 to 5 polyisocyanate compounds, 1 to 5 polythiol compounds, and a catalyst represented by Formula 1 above. Specifically, the polymerizable composition comprises one to three polyisocyanates, one to four polythiols, and a catalyst represented by the above formula (1), or one or two polyisocyanates, one or two It may include a species of polythiol and a catalyst represented by Formula 1 above.

In addition, the polymerizable composition may include one to three polyisocyanates and one to four polythiols.

Polyisocyanate compound

The polyisocyanate compound may be a conventional one used for the synthesis of polythiourethane, for example, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, hexamethylene diisocyanate, 2,2- Dimethylpentanediisocyanate, 2,2,4-trimethylhexanediisocyanate, butenediisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylenediisocyanate, 1,6,11 -Undecatriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl) Aliphatic isocyanate compounds such as ether; Isophorone diisocyanate, 1,2-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, Dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, 2,2-dimethyldicyclohexylmethane isocyanate, norbornane diisocyanate Alicyclic isocyanate compounds such as; Bis(isocyanatomethyl)benzene, bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, Bis(isocyanatomethyl)diphenyl ether, phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, Benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (Isocyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4-diisocyanate, o-xylene diisocyanate, aromatic isocyanate compounds such as m-xylene diisocyanate, p-xylene diisocyanate, and toluene diisocyanate; Bis(isocyanatoethyl)sulfide, bis(isocyanatopropyl)sulfide, bis(isocyanatohexyl)sulfide, bis(isocyanatomethyl)sulfone, bis(isocyanatomethyl) ) Disulfide, bis(isocyanatopropyl) disulfide, bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane, bis(isocyanatoethylthio)ethane, bis( Sulfur-containing aliphatic isocyanate compounds such as isocyanatomethylthio)ethane and 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane; Diphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis(4-isocyane Itomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyldisulfide-4,4-diisocyanate, 2,2-dimethyldiphenyldisulfide-5,5 -Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4-dimethyldiphenyldisulfide-5, Sulfur-containing aromatic isocyanate compounds such as 5-diisocyanate, 3,3-dimethoxydiphenyldisulfide-4,4-diisocyanate, and 4,4-dimethoxydiphenyldisulfide-3,3-diisocyanate; And 2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethyl) ) Tetrahydrothiophene, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 2,5-diisocyanato-1,4-ditian, 2,5-bis(isocyanatomethyl) )-1,4-dithiolane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis(isocyanatomethyl)-1,3-dithiolane, 4,5-bis It may contain at least one selected from the group consisting of sulfur-containing heterocyclic isocyanate compounds such as (isocyanatomethyl)-2-methyl-1,3-dithiolane. Specifically, the polyisocyanate compound may be one to five selected from the group consisting of isophorone diisocyanate, norbornene diisocyanate, m-xylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

The number of types (n) of the polyisocyanate compound may be 1 to 5. Specifically, the number (n) of the types of the polyisocyanate compound may be 1 to 3, or 1 to 2.

The NCO content (Ni) of the polyisocyanate compound can be obtained by the method specified in ISO 14896 “Plastics-Polyurethane raw materials-Determination of isocyanate content”.

The number of functional groups (mi) of the polyisocyanate compound may be 2 to 3.

The weight average molecular weight (oi) of the polyisocyanate compound may be 100 to 900 g/mol, or 150 to 800 g/mol.

Polythiol compound

The polythiol compound may be a conventional one used in the synthesis of polythiourethane, for example, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)sulfide, 4-mercaptomethyl -1,8-dimercapto-3,6-dithiaoctane, 2,3-bis(2-mercaptoethylthio)propane-1-thiol, 2,2-bis(mercaptomethyl)-1,3 -Propanedithiol, bis(2-mercaptoethyl)sulfide, tetrakis(mercaptomethyl)methane, 2-(2-mercaptoethylthio)propane-1,3-dithiol, 2-(2,3- Bis(2-mercaptoethylthio)propylthio)ethanethiol, bis(2,3-dimercaptopropanyl)sulfide, bis(2,3-dimercaptopropanyl)disulfide, 1,2-bis(2 -Mercaptoethylthio)-3-mercaptopropane, 1,2-bis(2-(2-mercaptoethylthio)-3-mercaptopropylthio)ethane, 2-(2-mercaptoethylthio)- 3-2-mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 2,2-bis-(3-mercapto- Propionyloxymethyl)-butyl ester, 2-(2-mercaptoethylthio)-3-(2-(2-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]ethylthio )Ethylthio)propane-1-thiol, (4R,11S)-4,11-bis(mercaptomethyl)-3,6,9,12-tetrathiatetradecane-1,14-dithiol, (S) -3-((R-2,3-dimercaptopropyl)thio)propane-1,2-dithiol, (4R,14R)-4,14-bis(mercaptomethyl)-3,6,9, 12,15-pentathiaheptane-1,17-dithiol, (S)-3-((R-3-mercapto-2-((2-mercaptoethyl)thio)propyl)thio)propyl)thio) -2-((2-mercaptoethyl)thio)propane-1-thiol, 3,3'-dithiobis(propane-1,2-dithiol), (7R,11S)-7,11-bis(mer Captomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R,12S)-7,12-bis(mercaptomethyl)-3,6,9,10 ,13,16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-di Mercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane , 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris ( 3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hexakis (3-mercaptopropionate), 1,1,3,3- Tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-ditian, 1,4 -Dithian-2,5-dimethaneol and 2-(2,2-bis(mercaptodimethylthio)ethyl)-1,3-dithian may contain at least one selected from the group. Specifically, the polythiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6 ,9-trithiaundecane, pentaerythritol tetrakis (3-mercaptopropionate), pentaethritol tetrakis (2-mercaptoacetate) and 1,4-dithian-2,5-dimethane It may be one to five kinds selected from the group consisting of thiols.

The number (l) of the kind of the polythiol compound may be 1 to 5, 1 to 3, or 2 to 3.

The equivalent weight (g/eq) (Sj) per unit molecular weight of the polythiol compound can be measured by a dose titration method using a redox reaction between thiol and iodine.

The number of functional groups (uj) of the polythiol compound may be an integer of 2 to 6, or an integer of 2 to 4.

The weight average molecular weight (tj) of the polythiol compound may be 100 to 1,000 g/mol, or 200 to 800 g/mol.

The polymerizable composition may include a polythiol compound and an isocyanate compound in a molar ratio of 0.5 to 1.5:1. Specifically, the polymerizable composition may include a polythiol compound and an isocyanate compound in a molar ratio of 0.8 to 1.2:1.

The catalyst may be a compound represented by Chemical Formula 1. Specifically, the catalyst is 1 selected from the group consisting of dibutyltin dichloride, dimethyltin dichloride, diethyltin dichloride, dipropyltin dichloride, di-isopropyltin dichloride and di-tertbutyltin dichloride. It can be more than a species.

The polymerizable composition may have a viscosity of 1,000 cps (centipoise) or more after standing at 10° C. for 24 hours. Specifically, the polymerizable composition may have a viscosity of 1,000 to 10,000 cps, or 1,500 to 10,000 cps after standing at 10° C. for 24 hours. When the viscosity of the polymerizable composition after standing at 10° C. for 24 hours is within the above range, it is possible to prevent the problem that the reactivity of the composition is too high and workability is deteriorated, or the reactivity of the composition is too small, and the production yield is lowered.

When the polymerizable composition is prepared as a specimen having a diameter of 75 mm and a thickness of 10 mm, the bubble generation rate may be 0 to 10%, and the streak generation rate may be 0 to 8%. Specifically, when the polymerizable composition is prepared as a specimen having a diameter of 75 mm and a thickness of 10 mm, the bubble generation rate may be 0 to 8%, or 0 to 5%, and the streak generation rate may be 0 to 7%, or 0 to 5%. have.

additive

The polymerizable composition may further include additives such as an internal release agent, an ultraviolet absorber, a polymerization initiator, a heat stabilizer, a blueing agent, a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, and a filler, if necessary. .

The internal mold release agent may be, for example, a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate ester group; Silicone-based nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Quaternary alkyl ammonium salts such as trimethylcetyl ammonium salt, trimethylstearyl ammonium salt, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, and diethylcyclohexadodecyl ammonium salt; And it may include one or more selected from the group consisting of acidic phosphate esters.

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

Examples of the polymerization initiator include amine-based, phosphorus-based, organic tin-based, organic copper-based, organic gallium, organic zirconium, organic iron, organic zinc, and organic aluminum.

Examples of the heat stabilizer include metal fatty acid salts, phosphorus, lead, and organotin.

The bluing agent has an absorption band in a wavelength range from orange to yellow in the visible light region, and has a function of adjusting the color of an optical material made of a resin. The bluing agent may specifically include a material exhibiting blue to purple color, but is not particularly limited. In addition, the bluing agent may include a dye, a fluorescent whitening agent, a fluorescent pigment, an inorganic pigment, and the like, but may be appropriately selected according to the physical properties or resin color required for the manufactured optical component. Each of the bluing agents may be used alone or in combination of two or more. The bluing agent is preferably a dye from the viewpoint of solubility in the polymerizable composition and from the viewpoint of transparency of the resulting optical material. In terms of absorption wavelength, the dye may be, specifically, a dye having a maximum absorption wavelength of 520 to 600 nm, and more specifically, a dye having a maximum absorption wavelength of 540 to 580 nm. In addition, from the viewpoint 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 is a method of dissolving it in a monomer, or a method of preparing a master solution containing a high concentration of bluing agent and diluting it with a monomer or other additive using the master solution, etc. Several methods can be used.

Polythiourethane compound

Another embodiment provides a polythiourethane-based compound obtained from the polymerizable composition as described above.

The polythiourethane-based compound is prepared by polymerizing (and curing) a polythiol compound and a polyisocyanate compound. In the polymerization reaction, the reaction molar ratio of the SH group/NCO group may be 0.5 to 3.0, specifically 0.6 to 2.0, or 0.8 to 1.3. If it is within the above range, properties and balance such as refractive index and heat resistance required for an optical material can be improved.

Optical material

Another embodiment provides an optical material molded from the polythiourethane-based compound as described above. Specifically, the optical material may be formed of a molded article obtained by curing the polymerizable composition. In addition, the optical material may be prepared by polymerizing and molding a polymerizable composition (polythiol compound + polyisocyanate compound + catalyst).

First, the polymerizable composition is degassed under reduced pressure and then injected into a mold for molding an optical material. Such degassing and mold injection may be performed at, for example, 5 to 40°C, or 10 to 30°C. After injection into the mold, polymerization is carried out by heating gradually from low temperature to high temperature. The temperature of the polymerization reaction may be, for example, 30 to 150°C, and specifically 40 to 130°C. In addition, in order to control the reaction rate, a reaction catalyst commonly used in the production of polythiourethane may be added, and specific types thereof are as exemplified above.

Thereafter, the polyurethane-based optical material is separated from the mold.

The optical material may have various shapes by changing the mold of a mold used in manufacturing. Specifically, it may be in the form of a spectacle lens, a camera lens, or a light emitting diode (LED). The optical material may be, for example, an optical lens, specifically a plastic optical lens.

The optical material may have a refractive index of 1.55 to 1.70 for light of 546 nm, and an Abbe number of 25 to 50. Specifically, the optical material may have a refractive index of 1.58 to 1.68 for light of 546 nm, and an Abbe number of 30 to 45.

[Example]

Hereinafter, it will be described in more detail by the following examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

Polyisocyanates and polythiols used in the following Examples and Comparative Examples are shown in Tables 1 and 2 below.

division Chemical structure Chemical name Weight average molecular weight (g/mol)(o) Functional group
Number (m) NCO%
(weight%) Iso 1

m-xylene diisocyanate 188.2 2 43.8~ 44.7 Iso 2

1,3-bis(isocyanatomethyl)cyclohexane 194.2 2 42.4~ 43.3 Iso 3

Hexamethylene diisocyanate 168.2 2 49.1~ 50.0 Iso 4

Toluene diisocyanate 174.2 2 48.4~ 48.3 Iso 5

Norbornene diisocyanate 206.3 2 39.9~ 40.8 Iso 6

Isophorone diisocyanate 222.3 2 37.0~ 37.9

division Chemical structure Chemical name Weight average molecular weight (g/mol)(t) Functional group
Number(u) equivalent weight
weight
(g/eq) Thiol 1

4-mercaptomethyl-3,6-
Dithia-1,8-octanethiol 260.5 3 87~93 Thiol 2

5,7-dimercaptomethyl-1,11-
Dimercapto-3,6,9-trithiaundecan 366.7 4 94~102 Thiol 3

Pentaerythritol tetrakis
(3-mercaptopropionate) 488.7 4 124~127 Thiol 4

Pentaerythritol
Tetrakis (2-mercaptoacetate) 446.6 4 112~116 Thiol 5

1,4-dithian-2,5-dimethanol 212.4 2 106~109

-Catalyst 1: DMTC, dimethyl tin dichloride

-Catalyst 2: DBTC, dibutyltin dichloride

Example 1.

Polyisocyanate, polythiol and catalyst were mixed in the composition shown in Table 3 below, and 2-(2-hydroxy-5-tert-oxylphenyl)benzotria as ultraviolet stabilizers based on a total of 100 parts by weight of polyisocyanate and polythiol A polymerizable composition was prepared by mixing 1.0 part by weight of the sol and 0.2 part by weight of Zelec® UN (acidic alkyl phosphate release agent, Stepan) as an internal release agent.

Examples 2 to 9 and Comparative Examples 1 to 3.

A polymerizable composition was prepared in the same manner as in Example 1, except that polyisocyanate, polythiol, and catalyst were mixed in the composition shown in Table 3 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Iso 1 - - - - - - 121.5g - - - - - Iso 2 154.4g 155.4g 155.4g 155.2g - - - 95.1g 93.6g 154.5g 97.1g - Iso 3 - - - - - 16.8g - 13.7g - - - 33.6g Iso 4 - - - - - - 12.1g - - - - 139.4g Iso 5 - - - - 164.9g - - - - - - - Iso 6 - - - - 88.9g - 42.6g 36.0g - - - Thiol 1 - - - - 111.2g 32.6g 60.4g 56.7g 29.9g - - 130.3g Thiol 2 87.6g 88.2g - - - - 63.7g 59.9g 31.6g 88.1g - - Thiol 3 - - - - 39.3g - - 39.9g 50.4g - 122.3g - Thiol 4 78.7g 77.3g 69.2g 68.9g - 61.1g - - - 78.7g - - Thiol 5 - - 101.9g 102.2g - - - - 29.3g - - - catalyst DMTC DBTC DMTC DMTC DBTC DBTC DBTC DBTC DMTC DMTC DBTC DMTC Catalyst amount 300 ppm 210 ppm 200 ppm 295 ppm 320 ppm 150 ppm 75 ppm 120 ppm 180 ppm 30 ppm 500 ppm 75 ppm

Experimental example. Physical property measurement

For the polymerizable compositions of Examples 1 to 9 and Comparative Examples 1 to 3, the viscosity change at 10° C., the occurrence rate of streaks and bubbles, the refractive index, and Abbe number of the plastic lenses prepared therefrom were measured. Table 4 shows the measurement results.

(1) viscosity measurement

The polymerizable compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were degassed at 10° C. and 2 torr for 1 hour, and filtered through a 3 μm Teflon filter. The filtered polymerizable composition was measured for a viscosity change at 10° C. for 24 hours using a non-contact viscometer (EMS-1000, Kyoto Electronics Co., Ltd.), and the rate of viscosity change over time was calculated by the following equation (2).

[Equation 2]

(2) incidence of stria

The polymerizable composition filtered in the same manner as in the above item (1) was poured into a glass mold mold assembled by tape. The mold was allowed to stand at 10° C. for 5 hours, then heated from 10° C. to 120° C. at a rate of 5° C./min, and polymerized at 120° C. for 20 hours. Then, a specimen having a diameter of 75 mm and a thickness of 10 mm cured in a glass mold mold was further cured at 130° C. for 4 hours, and then a molded body (plastic lens) was released from the glass mold mold.

A light source of a mercury lamp was transmitted through a plastic lens, and the transmitted light was projected onto a white plate to determine the presence or absence of streaking by the presence or absence of a contrast difference. 100 plastic lenses were prepared to evaluate the incidence of stria.

(3) Bubble generation rate

For the plastic lens manufactured in the same manner as in item (2), the lens was visually observed under a mercury lamp, and microbubbles were observed. 100 plastic lenses were prepared to evaluate the bubble generation rate.

(4) refractive index and Abbe number

The refractive index and Abbe number of the plastic lens manufactured in the same manner as in the above item (2) were measured at 20°C with an E-line (nE) using an Abbe refractometer DR-M4 (ATAGO).

Specifically, the refractive index was measured for the refractive index of light of 546 nm.

D R Refractive index Abbesu Streak incidence rate (%) Bubble generation rate (%) Example 1 0.1596 11.01 1.5993 41 4 One Example 2 0.1702 11.16 1.5995 41 3 2 Example 3 0.1495 11.25 1.6031 42 One 2 Example 4 0.0973 9.88 1.6029 42 One One Example 5 0.0615 10.32 1.6024 41 2 One Example 6 0.1159 10.31 1.5760 44 4 3 Example 7 0.2214 16.77 1.6698 32 2 3 Example 8 0.1356 12.01 1.5947 42 4 2 Example 9 0.1674 12.30 1.5865 42 3 2 Comparative Example 1 0.2409 35.19 1.5994 41 22 29 Comparative Example 2 0.0265 7.73 1.5671 41 69 45 Comparative Example 3 0.3357 20.02 1.6715 30 56 39

As shown in Table 4, the polymerizable compositions of Examples 1 to 9 had an R of 9.5 to 19.5, and the plastic lens produced therefrom had low streaks and bubbles and had excellent appearance. On the other hand, in the polymerizable compositions of Comparative Examples 1 to 3, R did not satisfy the above range, and as a result, the occurrence rate of streaks and air bubbles in the plastic lens produced therefrom was high, resulting in poor appearance.

Claims (13)

1 to 5 polyisocyanate compounds, 1 to 5 polythiol compounds, and a catalyst represented by the following formula (1),
R calculated by Equation 1 below is a real number of 9.5 to 19.5,
A polymerizable composition having a bubble generation rate of 0 to 10% and a streaking rate of 0 to 8% when prepared as a specimen having a diameter of 75 mm and a thickness of 10 mm:
[Equation 1]

In Equation 1,

Is,

Is,

Is,
n is the number of types of polyisocyanate compounds,
N _i is the content (% by weight) of NCO of the i polyisocyanate compound,
m _i is the number of functional groups of the i polyisocyanate compound,
W _i is the input amount (g) of i polyisocyanate compound,
o _i is the weight average molecular weight (g/mol) of the i polyisocyanate compound,

Is,
l is the number of types of polythiol compounds,
S _j is the equivalent weight (g/eq) of the j polythiol compound,

Is,

Is,
u _j is the number of functional groups of the j polythiol compound,
V _j is the input amount (g) of the j polythiol compound,
t _j is the weight average molecular weight (g/mol) of the j polythiol compound,
Q is

as,
[Formula 1]

In Formula 1,
E is a halogen compound,
F is an aliphatic hydrocarbon having 1 to 30 carbon atoms, or an aromatic hydrocarbon having 6 to 30 carbon atoms,
h and g are each independently an integer of 1 to 3,
h+g is 4,
K is the amount of the compound represented by Chemical Formula 1 added based on the total amount of the polyisocyanate compound and the polythiol compound added, 100,
D is the rate of viscosity change over time of the polymerizable composition, and is a value derived from Equation 2 defined as follows, and the polymerizable composition has a viscosity of 1,500 to 10,000 cps (centipoise) after standing at 10° C. for 24 hours. ,
[Equation 2]

In Equation 2,
x is the time (hours) elapsed from the preparation of the composition to the viscosity measurement, and is 5 to 24,
y is the viscosity (cps) of the polymerizable composition at 10° C. after x hours,
G is the initial viscosity (cps) of the polymerizable composition at 10 °C,
D is a real number of 0.0615 to 0.2214. The method of claim 1,
A is a real number of 80 to 120,
B is a real number of 80 to 115, the polymerizable composition. delete The method of claim 1,
The polymerizable composition, wherein R is a real number of 9.8 to 18. The method of claim 1,
E is at least one selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), the polymerizable composition. The method of claim 1,
The polymerizable composition, wherein F is an alkyl group having 1 to 10 carbon atoms. The method of claim 6,
Wherein F is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. delete delete The method of claim 1,
The polymerizable composition, wherein the polymerizable composition contains one to three polyisocyanates and one to four polythiols. A polythiourethane-based compound prepared from the polymerizable composition of any one of claims 1, 2, 4 to 7, and 10. An optical material molded from the polythiourethane-based compound of claim 11. The method of claim 12,
The optical material has a refractive index of 1.55 to 1.70 for light of 546 nm, and an Abbe number of 25 to 45.