KR102077653B1 - Polymerizable composition and optical material using same - Google Patents

Abstract

An embodiment relates to a polymerizable composition and an optical material using the same. The polymerizable composition contains a bifunctional or higher isocyanate compound not containing a benzene ring; and a thiol compound, wherein the thiol compound comprises a first thiol compound that does not include an ester group and a second thiol compound that includes an ester group, thereby having improved refractive index, Abbe′s number, and heat resistance, as well as the dyeing properties.

Description

POLYMERIZABLE COMPOSITION AND OPTICAL MATERIAL USING SAME

Embodiments relate to polymeric compositions having improved refractive index, Abbe's number and heat resistance, as well as dyeing properties and optical materials using the same.

Since the plastic optical material is lighter than the optical material made of an inorganic material such as glass and is not easily broken and has excellent dyeability, plastic materials of various resins are widely used as optical materials such as spectacle lenses and camera lenses. In recent years, higher performance of optical materials is required, and in particular, high transparency, high refractive index, low specific gravity, high heat resistance, high impact resistance, and the like are required.

In order to further improve the dyeing property of the plastic lens with high performance of such an optical material, one or two or more benzophenone compounds, alcohol compounds, and the like have been used as dyeing accelerators. However, when the dyeing accelerator is used, the dyeing of the plastic lens is promoted, but the light resistance of the dyed lens is lowered, and agglomeration of the dye occurs in the dyeing solution, resulting in a problem of not uniform dyeing.

For example, in Korean Patent Publication No. 1987-0008928, xylene diisocyanate and pentaerythritol tetrakismercaptopropionate are thermally cured to produce a lens having excellent tensile strength and dyeing property, but such a lens has a low Abbe number. have.

Republic of Korea Patent Publication 1987-0008928

Accordingly, embodiments provide a polymerizable composition having improved refractive index, Abbe's number and heat resistance, as well as dyeability and an optical material using the same.

The polymerizable composition according to one embodiment may include a bifunctional or higher functional isocyanate compound that does not include a benzene ring; And a thiol compound, wherein the thiol compound includes a first thiol compound not containing an ester group and a second thiol compound including an ester group.

The polymerizable composition according to the embodiment may provide an optical material having excellent heat resistance and dyeability without including a dyeing accelerator.

Hereinafter, the present invention will be described in detail through embodiments. The embodiments are not limited to the contents disclosed below and may be modified in various forms as long as the gist of the invention is not changed.

In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding other components, unless specifically stated otherwise.

All numbers and expressions indicative of the amount of ingredients, reaction conditions, and the like described herein are to be understood as being modified in all instances by the term "about" unless otherwise specified.

The polymerizable composition according to one embodiment includes a bifunctional or higher isocyanate compound and a trifunctional or higher thiol compound that do not include a benzene ring, and the trifunctional or higher thiol compound includes a first thiol compound and an ester group that do not include an ester group. It includes a second thiol compound.

The bifunctional or higher isocyanate compound does not include a bifunctional or higher aromatic isocyanate compound.

According to one embodiment, the polymerizable composition comprises a bifunctional or higher isocyanate compound that does not include a benzene ring. For example, the bifunctional or more than tetrafunctional isocyanate compound can be included.

According to one embodiment, the isocyanate compound may be 1,3-bis (isocyanatomethyl) cyclohexane, noborene diisocyanate, isophorone diisocyanate or bis (4-isocyanatocyclohexyl) methane. Specifically, 1,3-bis (isocyanatomethyl) cyclohexane is preferred, but is not limited thereto.

According to one embodiment, the trifunctional or higher thiol compound may include a trifunctional first thiol compound and a tetrafunctional second thiol compound.

According to one embodiment, the first thiol compound is 4,8-di (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundane or 4-mercaptomethyl-1, 8-dimercapto-3,6-dithiaoctane. Specifically, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is preferred, but is not limited thereto.

According to one embodiment, the second thiol compound may be pentaerythritol tetrakis (mercaptoacetate) or pentaerythritol tetrakis (3-metcaptopropionate). Specifically, pentaerythritol tetrakis (3-methcaptopropionate) is preferred, but is not limited thereto.

According to one embodiment, the isocyanate compound is 1,3-bis (isocyanatomethyl) cyclohexane, and the first thiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-di And thiaoctane, and the second thiol compound may be pentaerythritol tetrakis (3-methcaptopropionate). Specifically, the polymerizable composition comprises 1,3-bis (isocyanatomethyl) cyclohexane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and pentaerythritol tetrakis ( When 3-methcaptopropionate) is included, there is an advantageous effect in that the refractive index, Abbe's number and heat resistance are not lowered, and the dyeing property can be improved without further using a dyeing accelerator.

According to one embodiment, the equivalent ratio of the isocyanate compound: the thiol compound may be 1.00: 0.95 to 1.00: 1.10. The equivalent weight of the thiol compound refers to the total equivalent weight of the first thiol compound and the second thiol compound. For example, the equivalent ratio of the isocyanate compound: the thiol compound is 1.00: 0.95, 1.00: 1.00, 1.00: 1.10 or 1.10: 1.00. When the above range is satisfied, the numerical stability of the cured product can be ensured, the reaction rate can be controlled to suppress appearance defects, and the proper curing density can be maintained to improve heat resistance and strength, as well as dyeability.

According to one embodiment, the equivalent ratio of the first thiol compound: the second thiol compound may be 0.30: 0.70 to 0.70: 0.30. For example, the equivalent ratio of the first thiol compound: the second thiol compound may be 0.35: 0.65 to 0.70: 0.30, 0.40: 0.60 to 0.70: 0.30 or 0.40: 0.60 to 0.65: 0.36. When the above range is satisfied, more transparent lenses can be manufactured and are more advantageous in terms of heat resistance and impact resistance.

According to one embodiment, the weight ratio of the first thiol compound: the second thiol compound may be 20:80 to 80:20. For example, the weight ratio of the first thiol compound: the second thiol compound may be 25:75 to 75:25, 30:70 to 80:20 or 30:70 to 60:40. When the above range is satisfied, more transparent lenses can be manufactured and are more advantageous in terms of heat resistance and impact resistance.

According to one embodiment, the polymerizable composition may further include a polymerization catalyst. Specifically, the polymerization catalyst may use a tin-based catalyst, for example, dibutyltin dichloride, thibutyltin dilaurate or dimethyltin dichloride.

The polythiourethane-based composition may further include additives such as an internal mold release agent, a heat stabilizer, a UV absorber, etc. according to the purpose.

The internal mold release agent includes 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; Alkyl quaternary ammonium salts such as trimethylcetyl ammonium salt, trimethylstearyl ammonium salt, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt and the like; And components selected from acidic phosphate esters may be used alone or in combination of two or more thereof.

The thermal stabilizer may be one or more of metal fatty acid salts, phosphorus, lead, organotin.

As the ultraviolet absorber, at least one of benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, and oxanilide-based may be used.

According to one embodiment, the polymerizable composition may be heat cured in a mold to prepare a polythiourethane-based optical material. Specifically, the molded object obtained by hardening the said polymeric composition and the optical material which consists of the said molded object can be provided. The optical material may be prepared by polymerizing and molding the polymerizable composition.

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 can be carried out for 10 to 60 minutes in a temperature range of, for example, 20 ° C to 40 ° C. After injection into the mold, polymerization is usually carried out by gradually heating from a low temperature to a high temperature.

The temperature of the polymerization reaction may be, for example, 20 ℃ to 150 ℃ or 25 ℃ to 120 ℃. In addition, in order to control the reaction rate, a reaction catalyst commonly used in the preparation of polythiourethane may be added, and specific types thereof are as described above.

The filtered polymerizable composition may be injected into the mold assembled by the adhesive tape using nitrogen pressure. The mold into which the composition is injected can be polymerized by gradually raising the temperature in a forced circulation oven. Specifically, the temperature may be raised from 25 ° C. to 120 ° C. at a rate of 5 ° C./min, polymerized at 120 ° C. for 18 hours, then further cured at 130 ° C. for 4 hours, and released from the mold to obtain a lens.

According to one embodiment, after immersing the plastic lens specimen prepared by heat curing the polymerizable composition in a dye solution containing no dyeing accelerator, the transmittance in the wavelength range of 525 nm measured may be 30% or less. Specifically, after immersing the plastic lens specimen prepared by heat-curing the polymerizable composition in a dyeing solution containing no dyeing accelerator, the transmittance in the measured wavelength range of 525 nm may be 20% or less. The dyeing promoter may be benzophenone-based or benzyl alcohol, but is not limited thereto.

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

The optical material may be subjected to surface polishing, antistatic treatment, hard coat treatment, anti-reflective coating treatment, and dimming for antireflection, high hardness, abrasion resistance, chemical resistance, and anti-fogging, as necessary. Physical and chemical treatments, such as treatment, can be performed and improved.

According to one embodiment, the refractive index of the polyurethane-based optical material may be 1.55 to 1.62. For example, the refractive index of the polyurethane-based optical material may be 1.57 to 1.62, 1.59 to 1.62 or 1.59 to 1.61.

The above content is described in more detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited thereto.

Example 1

97.1 parts by weight of 1,3-bis (isocyanatomethyl) cyclohexane, 50.3 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and pentaerythritol tetrakis (3- 57.9 parts by weight of metcaptopropionate) were uniformly mixed. 0.04 parts by weight of dimethyltin dichloride (DMCT) as a polymerization catalyst, 0.3 parts by weight of Zelec® UN as an internal release agent and 0.9 parts by weight of Tinuvin 329 (BASF) as an ultraviolet absorber, and mixed uniformly. Was prepared.

The polymerizable composition was degassed at 600 Pa for 1 hour and then filtered through a 3 μm Teflon filter. The filtered poly T o urethane composition was injected into a glass mold assembly by a tape mold. The mold mold was slowly warmed from 25 ° C. to 120 ° C. over 12 to 15 hours and held at 120 ° C. for 6 hours to polymerize. Thereafter, the mixture was slowly cooled to 20 ° C. to 25 ° C., then released in a glass mold, and further cured at 120 ° C. for 4 hours to prepare a specimen of an optical lens.

[Examples 2 to 8 and Comparative Examples 1 to 10]

As shown in Table 1, except that the type and content of the isocyanate compound, the first thiol compound and the second thiol compound were changed in the same manner as in Example 1 to prepare a specimen of the optical lens.

Isocyanate
(Iso) First thiol
(Thiol 1) Second thiol
(Thiol 2) Equivalence ratio
(Iso: Thiol) Equivalence ratio
(Thiol 1: Thiol 2) Weight ratio
(Thiol 1: Thiol 2) Example 1 A-1 B-1 C-1 1.00: 0.95 0.55: 0.45 46:54 Example 2 A-1 B-1 C-1 1.00: 0.95 0.65: 0.35 57:43 Example 3 A-1 B-1 C-1 1.00: 1.05 0.50: 0.50 41:59 Example 4 A-1 B-1 C-1 1.00: 1.00 0.60: 0.40 51:49 Example 5 A-1 B-1 C-1 1.00: 1.00 0.50: 0.50 41:59 Example 6 A-1 B-1 C-1 1.00: 1.10 0.55: 0.45 46:54 Example 7 A-1 B-1 C-1 1.10: 1.00 0.60: 0.40 51:49 Example 8 A-1 B-1 C-1 1.10: 1.00 0.40: 0.60 32:68 Comparative Example 1 A-1 B-1 C-1 1.50: 1.00 0.60: 0.40 51:49 Comparative Example 2 A-2 B-1 C-1 1.00: 1.00 0.60: 0.40 51:49 Comparative Example 3 A-1 B-2 C-2 1.00: 1.00 0.60: 0.40 49:51 Comparative Example 4 A-1 B-1 - 1.00: 1.00 - - Comparative Example 5 A-1 - C-1 1.00: 1.00 - - Comparative Example 6 A-1 B-1 C-2 1.00: 1.00 0.60: 0.40 55:45 Comparative Example 7 A-3 B-1 C-1 1.00: 1.00 0.65: 0.35 57:43 Comparative Example 8 A-4 B-1 - 1.00: 1.00 - - Comparative Example 9 A-1 B-3 - 1.00: 1.00 - - Comparative Example 10 A-3 - C-1 1.00: 1.00 - -

* A-1: 1,3-bis (isocyanatomethyl) cyclohexane

* A-2: Novorene diisocyanate

* A-3: isophorone diisocyanate

* A-4: bis (4-isocyanatocyclohexyl) methane

* B-1: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane

* B-2: 2,5-bis (mercaptomethyl) -1,4-dithiane

B-3: 2,2'-thiobis (3- (2-mercapdoethylthio) propane-1-thiol)

C-1: pentaerythritol tetrakis (3-methcaptopropionate)

* C-2: pentaerythritol tetrakis (mercaptoacetate)

Evaluation Example 1: Evaluation of Heat Resistance

The specimens of the prepared lenses were evaluated by measuring the glass transition temperature by a penetrating method (50g load, 0.5mm? Pin, temperature increase rate 10 ° C./min) using a thermal expansion analyzer (TMA Q400, TA Co.).

Evaluation Example 2: Refractive Index and Abbe's Number Evaluation

It measured at 20 degreeC using the Abbe refractometer DR-M4.

Evaluation Example 3: Dyeability Evaluation

2 parts by weight of Dianix Red AC-E (Dystar) as a disperse dye and 1 part by weight of Sunsolt 7000 (Nicca) as a surfactant were added to 1 L of water, heated to 90 ° C, and warmed to prepare a dyeing solution. Further, 50 ml of a solution in which 10 parts by weight of 2,2'-dihydroxy-4-methoxybenzophenone as a dyeing accelerator and 10 parts by weight of Sunsolt 7000 as a surfactant were previously added to 1 L of water and warmed at 90 ° C. Was added to prepare a dyeing solution containing a dyeing accelerator. After immersing the specimen of the prepared lens in the dyeing solution and the dyeing solution not containing the dyeing accelerator, respectively, the transmittance of 525 nm was measured. Evaluation criteria were evaluated as O when the transmittance was 30% or less, Δ when more than 30% to less than 50%, and X when 50% or more.

The results of Evaluation Examples 1 to 3 are shown in Table 2 below.

Refractive index Abbesu Heat resistance
(℃) Dyeability Use of Dye Promoter X Use of dye promoter O Example 1 1.599 41 98.6 O O Example 2 1.604 40 97.9 O O Example 3 1.600 40 98.2 O O Example 4 1.603 41 98.4 O O Example 5 1.598 40 98.1 O O Example 6 1.604 41 97.6 O O Example 7 1.599 41 98.3 O O Example 8 1.593 41 99.9 O O Comparative Example 1 1.588 41 92.6 X △ Comparative Example 2 1.607 40 99.8 △ O Comparative Example 3 1.596 41 98.5 X △ Comparative Example 4 1.626 37 89.9 △ O Comparative Example 5 1.575 42 96.2 X △ Comparative Example 6 1.603 40 97.8 △ O Comparative Example 7 1.601 41 96.6 X △ Comparative Example 8 1.610 39 89.3 X △ Comparative Example 9 1.629 37 102.1 X X Comparative Example 10 1.572 42 99.4 X X

As shown in Table 2, in the case of the optical film produced in the example, it can be seen that the dyeing is superior to the comparative example using the dyeing accelerator, even though the dyeing accelerator, Abbe's number and heat resistance are excellent, even without using the dyeing accelerator. .

Claims (9)

Bifunctional or higher functional isocyanate compounds containing no benzene ring; And thiol compounds,
Pentaerythritol tetrakis, which is the second thiol compound containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, which is the first thiol compound that the thiol compound does not contain an ester group, and an ester group (3-methcaptopropionate),
As the polymerizable composition, the isocyanate compound is composed of 1,3-bis (isocyanatomethyl) cyclohexane,
The polymerizable composition does not include a ketone compound and an alcohol compound,
The polymer obtained by heat-curing the said polymerizable composition is dyed with the dyeing liquid containing no dyeing accelerator, and the transmittance | permeability measured in the wavelength range of 525 nm with respect to the said lens is 30% or less. delete delete delete delete delete The method of claim 1,
Isocyanate compound: The equivalent ratio of the thiol compound is 1.00: 0.95 to 1.00: 1.10,
The polymerizable composition of claim 1, wherein the equivalent ratio of the second thiol compound is 0.30: 0.70 to 0.70: 0.30. A polythiourethane-based optical material prepared from the polymerizable composition of claim 1. The method of claim 8,
The polythiourethane-based optical material has a refractive index of 1.55 to 1.62.