Phosphorus-based releasing agent, optical polymerizable composition comprising same and preparation thereof

Abstract

Embodiments relate to a polymerizable composition comprising a phosphorus-based mold releasing agent for an optical use whose preparation process is improved, and a process for preparing the phosphorus-based mold releasing agent. The phosphorus-based mold releasing agents can be prepared more easily and conveniently by using phosphorous pentoxide, which can easily react with a monoalcohol and/or water at room temperature in the absence of a catalyst or a solvent. In addition, byproducts are not generated during the reaction. Thus, when a lens is produced by using the mold release agent obtained therefrom, it is possible to prevent a defective appearance of the lens that may be caused by byproducts, thereby further enhancing the appearance properties thereof. Further, since separate steps for removing byproducts, specifically, such steps as washing and filtration, are not required, wastewater is not generated. Thus, it is not only environmentally friendly, but the production cost can also be reduced as the process is simple.

Claims

1. A process for preparing a phosphorus-based mold releasing agent, which comprises reacting a compound represented by the following Formula 3 with water, an alcohol, or a mixture thereof to prepare a mixture of a compound represented by the following Formula 1 and a compound represented by the following Formula 2: ##STR00006## wherein in the above Formulae, R.sub.1 to R.sub.3 are each independently C.sub.1-30 alkyl, C.sub.6-30 aryl, C.sub.7-30 aralkyl, C.sub.7-30 alkylaryl, or C.sub.8-30 alkylaralkyl, and wherein at least one of R.sub.1 to R.sub.3 is a group represented by the following Formula 5: ##STR00007## wherein, in the above Formula, R.sub.4 is C.sub.6-30 arylene, C.sub.7-30 aralkylene, C.sub.7-30 alkylarylene, or C.sub.8-30 alkylaralkylene, and R.sub.5 is C.sub.6-30 aryl, C.sub.7-30 aralkyl, C.sub.7-30 alkylaryl, or C.sub.8-30 alkylaralkyl.

2. The process for preparing a phosphorus-based mold releasing agent of claim 1, wherein 0.5 to 7 moles of water, the alcohol, or the mixture thereof is reacted with 1 mole of the compound represented by the above Formula 3.

3. The process for preparing a phosphorus-based mold releasing agent of claim 1, wherein the compound represented by the above Formula 3 is first reacted with water, followed by reaction with water, the alcohol, or the mixture thereof.

4. The process for preparing a phosphorus-based mold releasing agent of claim 1, wherein the compound represented by the above Formula 3 is reacted with the alcohol alone.

5. The process for preparing a phosphorus-based mold releasing agent of claim 1, wherein the compound represented by the above Formula 3 is divided and fed in a plurality of times during the reaction with water, the alcohol, or the mixture thereof.

6. The process for preparing a phosphorus-based mold releasing agent of claim 1, wherein the phosphorus-based mold releasing agent comprises 10% by weight or less of a compound represented by the following Formula 4 based on the total weight of the phosphorus-based mold releasing agent: ##STR00008##

7. The process for preparing a phosphorus-based mold releasing agent of claim 1, wherein the alcohol is octanol, butoxyethanol, dodecanol, 2-ethylhexanol, isotridecyl alcohol, oleyl alcohol, tetracosyl alcohol, tri(propylene glycol)n-butyl ether (wherein n is an integer of 1 to 10), triethylene glycol monomethyl ether, or a mixture thereof.

8. The process for preparing a phosphorus-based mold releasing agent of claim 1, wherein the alcohol has a water content of 1,500 ppm or less.

9. The process for preparing a phosphorus-based mold releasing agent of claim 1, wherein the phosphorus-based mold releasing agent comprises 10% by weight or less of an unreacted alcohol upon the reaction based on the total weight of the alcohol before the reaction.

10. A polymerizable composition for an optical use, which comprises a thiol compound; an isocyanate compound; and a phosphorus-based mold releasing agent, wherein the phosphorus-based mold releasing agent comprises a first phosphorus-based compound having one hydroxyl group and a second phosphorus-based compound having two hydroxy groups, the first phosphorus-based compound is a compound represented by the following Formula 1, and the second phosphorus-based compound is a compound represented by the following Formula 2: ##STR00009## wherein in the above Formulae, R.sub.1 to R.sub.3 are each independently C.sub.1-30 alkyl, C.sub.6-30 aryl, C.sub.7-30 aralkyl, C.sub.7-30 alkylaryl, or C.sub.8-30 alkylaralkyl, and at least one of R.sub.1 to R.sub.3 is a compound represented by the following Formula 5: ##STR00010## and wherein in the above Formulae, R.sub.4 is C.sub.6-30 arylene, C.sub.7-30 aralkylene, C.sub.7-30 alkylarylene, or C.sub.8-30 alkylaralkylene, and R.sub.5 is C.sub.6-30 aryl, C.sub.7-30 aralkyl, C.sub.7-30 alkylaryl, or C.sub.8-30 alkylaralkyl.

11. The polymerizable composition for an optical use of claim 10, wherein R.sub.1 to R.sub.3 are each independently selected from the group consisting of an octyl group, a butoxyethyl group, a 2-butoxyethyl group, a butoxy group, a 1-butoxy group, a dodecyl group, a tri(propylene glycol)n butylethyl group (wherein n is an integer of 1 to 10), a 2-(2-(2-methoxyethoxy)ethoxy)ethyl group, a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, a 1-pentyl group, an isopentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, a 3-methyl-2-butyl group, a tert-pentyl group, a 1-hexyl group, a 2-methyl-1-pentyl group, a 4-methyl-2-pentyl group, a 2-ethyl-1-butyl group, a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl, a 1-heptyl group, a 2-heptyl group, a 3-heptyl group, a methylcyclopentylmethyl group, an ethylcyclopentyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a benzoanthracenyl group, a benzophenanthrenyl group, a naphthacenyl group, a pyrenyl group, a dibenzoanthracenyl group, a pentacenyl group, a picenyl group, a benzopyranyl group, a tolyl group (a methylphenyl group), a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a cyclohexylphenyl group, a trimethylphenyl group, a methylnaphthyl group, a methylphenanthryl group, an ethylphenanthryl group, a propylphenanthryl group, a benzyl group, a phenethyl group, a 1-phenylpropyl group, a naphthylmethyl group, a naphthylethyl group, a methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group, a butylbenzyl group, and a dibutylbenzyl group.

12. The polymerizable composition for an optical use of claim 10, wherein the compound represented by the above Formula 1 is dioctyl hydrogen phosphate, bis(2-butoxyethyl) hydrogen phosphate, 1-(1-(1-butoxypropan-2-yloxy)propan-2-yloxy)propan-2-yl dodecyl hydrogen phosphate, bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl) hydrogen phosphate, di(1-methoxy-2-propyl) phosphate, di(1-ethoxy-2-propyl) phosphate, di(1-buthoxy-2-propyl) phosphate, di(2-buthoxy-3-butyl) phosphate, di(1-decyloxy-2-propyl) phosphate, di(1-cyclohexyloxy-2-propyl) phosphate, di(1-aryloxy-2-propyl) phosphate, di(1-(3,7,11,15-tetramethyl-2-hexadecyloxy)-2-propyl) phosphate, di(1-phenoxy-2-propyl) phosphate, di(1-o-methylphenoxy-2-propyl) phosphate, di(1-p-nonylphenoxy-2-propyl) phosphate, di(1-(p-chlorophenoxy-2-propyl) phosphate, di(1-(p-methoxyphenoxy-2-propyl) phosphate, di(1-benzyloxy-2-propyl) phosphate, di(1-(undecyloxy benzyloxy)-2-propyl) phosphate, di(1-(1-buthoxy-2-propoxy)-2-propyl) phosphate, di(tri(1,2-propylene glycol monobutyl ether)) phosphate, di(tetra(1,2-propylene glycol monobutyl ether)) phosphate, or di(penta(1,2-propylene glycol monobutyl ether, and the compound represented by the above Formula 2 is octyl dihydrogen phosphate, 2-butoxyethyl dihydrogen phosphate, dodecyl dihydrogen phosphate, 2-(2-(2-methoxyethoxy)ethoxy)ethyl dihydrogen phosphate, mono(1-methoxy-2-propyl) phosphate, mono(1-ethoxy-2-propyl) phosphate, mono(1-buthoxy-2-propyl) phosphate, mono(2-buthoxy-3-butyl) phosphate, mono(1-decyloxy-2-propyl) phosphate, mono(1-cyclohexyloxy-2-propyl) phosphate, mono(1-arlyoxy-2-propyl) phosphate, mono(1-(3,7,11,15-tetramethyl-2-hexadecyloxy)-2-propyl) phosphate, mono(1-phenoxy-2-propyl) phosphate, mono(1-o-methylphenoxy-2-propyl) phosphate, mono(1-p-nonylphenoxy-2-propyl) phosphate, mono(1-(p-chlorophenoxy-2-propyl) phosphate, mono(1-(p-methoxyphenoxy-2-propyl) phosphate, mono(1-benzyloxy-2-propyl) phosphate, mono(1-(undecyloxy benzyloxy)-2-propyl) phosphate, mono(1-(1-buthoxy-2-propoxy)-2-propyl) phosphate, mono(tri(1,2-propylene glycol monobutyl ether)) phosphate, mono(tetra(1,2-propylene glycol monobutyl ether)) phosphate, or mono(penta(1,2-propylene glycol monobutyl ether)) phosphate.

13. The polymerizable composition for an optical use of claim 10, wherein the phosphorus-based mold releasing agent comprises the compound represented by the above Formula 1 and the compound represented by the above Formula 2 in a molar ratio of 0.5:1 to 1:1.

14. The polymerizable composition for an optical use of claim 10, wherein the phosphorus-based mold releasing agent comprises 10 to 50% by weight of the compound represented by the above Formula 1 and 50 to 90% by weight of the compound represented by the above Formula 2 based on the total weight of the phosphorus-based mold releasing agent.

15. The polymerizable composition for an optical use of claim 10, wherein the phosphorus-based mold releasing agent further comprises an alcohol.

16. The polymerizable composition for an optical use of claim 15, wherein the alcohol is a compound represented by the following Formula 6:
R.sub.6—OH  Formula 6 and wherein in the above Formulae, R.sub.6 is C.sub.6-30 aryl, C.sub.7-30 aralkyl, C.sub.7-30 alkylaryl, or C.sub.8-30 alkylaralkyl.

17. The polymerizable composition for an optical use of claim 10, which has an (NCO)/(OH+SH) equivalent ratio of 0.8 to 1.2.

18. The polymerizable composition for an optical use of claim 10, wherein the isocyanate compound is at least one selected from the group consisting of m-xylene diisocyanate, toluene diisocyanate, bis(isocyanatomethyl cyclohexane), and isophorone diisocyanate.

19. The polymerizable composition for an optical use of claim 10, wherein the thiol compound is at least one selected from the group consisting of 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,9-dimercapto-3,7-dithianone, 1,13-dimercapto-3,7,11-trithiatridecane, glycol di(3-mercaptopropionate), 1,4-dithiane-2,5-diyl methanethiol, 2-mercaptomethyl-1,5-dimercapto-3-thiapentane, trimethylolpropane tri(3-mercaptopropionate), 4,8-di(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiandecane, 5,9-di(mercaptoethyl)-1,12-dimercapto-3,7,10-trithiadodecane, pentaerythritol tetra(3-mercaptopropionate), and pentaerythritol tetra(mercaptoacetate).

20. A phosphorus-based mold releasing agent, which comprises a first phosphorus-based compound having one hydroxyl group and a second phosphorus-based compound having two hydroxy groups, wherein the first phosphorus-based compound is a compound represented by the following Formula 1, the second phosphorus-based compound is a compound represented by the following Formula 2, and the molar ratio of the first phosphorus-based compound to the second phosphorus-based compound is 0.5:1 to 1:1: ##STR00011## wherein in the above Formulae, R.sub.1 to R.sub.3 are each independently C.sub.1-30 alkyl, C.sub.6-30 aryl, C.sub.7-30 aralkyl, C.sub.7-30 alkylaryl, or C.sub.8-30 alkylaralkyl, and wherein at least one of R.sub.1 to R.sub.3 is a group represented by the following Formula 5: ##STR00012## wherein, in the above Formula, R.sub.4 is C.sub.6-30 arylene, C.sub.7-30 aralkylene, C.sub.7-30 alkylarylene, or C.sub.8-30 alkylaralkylene, and R.sub.5 is C.sub.6-30 aryl, C.sub.7-30 aralkyl, C.sub.7-30 alkylaryl, or C.sub.8-30 alkylaralkyl.

Description

EXAMPLE

Preparation of a Phosphorus-Based Mold Releasing Agent

Example 1

(1) A 2-L, 3-neck reactor equipped with a mechanical stirrer, a thermometer, and a condenser tube was placed in a glove box filled with dry nitrogen. 18 parts by weight (1 mole) of distilled water was added thereto while agitation was carried out at a speed of 200 rpm. Then, 283.9 parts by weight (1 mole) of phosphorus pentoxide was divided into 5 portions and slowly added to the reactor. Thereafter, 651 parts by weight (5 moles) of 1-octanol having a water content of 200 ppm was added thereto, followed by reaction for 4 hours while the reaction temperature was maintained at 40° C. or lower, thereby preparing dioctyl hydrogen phosphate (the compound represented by Formula 1) and octyl dihydrogen phosphate (the compound represented by Formula 2).

(2) As a result of an analysis of the components by 1H-NMR in an integral ratio, the compounds of the above Formulae 1 and 2 were obtained in a ratio of 1:2, except for 6.3% of the unreacted alcohol, when the total weight of the obtained phosphate ester mixture was 100%.

Example 2

(3) The same procedures as Example 1 were carried out to obtain a phosphate ester mixture comprising dioctyl hydrogen phosphate (the compound represented by Formula 1) and octyl dihydrogen phosphate (the compound represented by Formula 2), except that only phosphorus pentoxide was added to the reactor without adding distilled water and that 1-octanol having a water content of 200 ppm was then added in an amount of 781.2 parts by weight (6 moles) instead of 651 parts by weight (5 moles).

(4) As a result of an analysis of the components by 1H-NMR in an integral ratio, the compounds of the above Formulae 1 and 2 were obtained in a ratio of 1:1, except for 5.1% of the unreacted alcohol, when the total weight of the obtained phosphate ester mixture was 100%.

Example 3

(5) The same procedures as Example 1 were carried out to obtain a phosphate ester mixture comprising bis(2-butoxyethyl) hydrogen phosphate (the compound represented by Formula 1) and 2-butoxyethyl hydrogen phosphate (the compound represented by Formula 2), except that 591 parts by weight (5 moles) of 2-butoxyethanol having a water content of 700) ppm was added to the reactor instead of 651 parts by weight (5 moles) of 1-octanol having a water content of 200 ppm.

(6) As a result of an analysis of the components by 1H-NMR in an integral ratio, the compounds of the above Formulae 1 and 2 were obtained in a ratio of 1:2, except for 9.4% of the unreacted alcohol, when the total weight of the obtained phosphate ester mixture was 100%.

Example 4

(7) The same procedures as Example 1 were carried out to obtain a phosphate ester mixture comprising dodecyl hydrogen phosphate (the compound represented by Formula 1) and dodecyl dihydrogen phosphate (the compound represented by Formula 2), except that only phosphorus pentoxide was added to the reactor without adding distilled water and that 745.2 parts by weight (3 moles) of tri(propylene glycol)-butyl ether having a water content of 300 ppm and 558.9 parts by weight (3 moles) of 1-dodecanol having a water content of 100 ppm were added instead of 651 parts (5 moles) of 1-octanol having a water content of 200 ppm.

(8) As a result of an analysis of the components by 1H-NMR in an integral ratio, the compounds of the above Formulae 1 and 2 were obtained in a ratio of 1:1, except for 7.1% of the unreacted alcohols, when the total weight of the obtained phosphate ester mixture was 100%.

Example 5

(9) The same procedures as Example 1 were carried out to obtain a phosphate ester mixture comprising bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl) hydrogen phosphate (the compound represented by Formula 1) and bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl) dihydrogen phosphate (the compound represented by Formula 2), except that 821 parts by weight (5 moles) of triethylene glycol monomethyl ether having a water content of 1,200 ppm was added to the reactor instead of 651 parts by weight (5 moles) of i-octanol having a water content of 200 ppm.

(10) As a result of an analysis of the components by 1H-NMR in an integral ratio, the compounds of the above Formulae 1 and 2 were obtained in a ratio of 1:2, except for 131% of the unreacted alcohol, when the total weight of the obtained phosphate ester mixture was 100%.

Comparative Example 1

(11) The same procedures as Example 1 were carried out to obtain a phosphate ester mixture comprising 2-butoxyethyl dihydrogen phosphate (the compound represented by Formula 2), except that 354.6 parts by weight (3 moles) of 2-butoxyethanol having a water content of 700 ppm and 54 parts by weight (3 moles) of distilled water were added to the reactor instead of 651 parts by weight (5 moles) of 1-octanol having a water content of 200 ppm and 18 parts by weight (1 mole) of distilled water.

(12) As a result of an analysis of the components by 1H-NMR in an integral ratio, the compound of the above Formula 2 was obtained (84.4%), except for 15.6% of the unreacted alcohol, when the total weight of the obtained phosphate ester mixture was 100%.

Preparation of a Polymerizable Composition

(13) 204.2 parts by weight of m-xylene diisocyanate, 188 parts by weight of 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 0.1 part by weight of dibutyltin dichloride as a catalyst, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole as an ultraviolet stabilizer, and one of the phosphate ester-based mold release agents prepared in Examples 1 to 4 and Comparative Example 1 were mixed. In such event, the phosphorus-based mold releasing agent was added in an amount of 20 ppm, 100 ppm, 500 ppm, 1,000 ppm, or 2,000 ppm as shown in Table 1 below. The mixture was degassed at a temperature of 20° C. and a pressure of 2 torrs for 1 hour and then filtered through a Teflon filter of 3 μm.

Preparation of a Plastic Lens

(14) The polymerizable composition was injected into a glass mold (cavity; 4 curves in all uneven surfaces, center thickness: 2 mm) assembled with a tape. The mold was heated from 20° C. to 120° C. at a rate of 5° C./min, and polymerization was carried out at 120° C. for 18 hours. Thereafter, the cured resin in the glass mold was further cured at 130° C. for 4 hours, and the molded article (or a plastic lens) was then released from the glass mold.

Evaluation Example

(15) The lenses produced using the phosphorus-based mold releasing agents of Examples 1 to 4 and Comparative Example 1 were evaluated according to the following methods. The results are shown in Table 1 below.

(16) (1) Striae

(17) The surface of the lenses produced using the phosphorus-based mold releasing agents of Examples 1 to 4 and Comparative Example 1 was observed by the naked eyes and evaluated according to the following criteria.

(18) x: Non-uniform phenomena such as wavy patterns appear on the surface of the lens

(19) Δ: The center of the lens is clean, but the edges are non-uniform

(20) ⊚: Non-uniform phenomena do not appear on the entire lens surface

(21) (2) Cloudiness

(22) The lenses produced using the phosphorus-based mold releasing agents of Examples 1 to 4 and Comparative Example 1 were each irradiated with light having a power of 300 W using a halogen lamp, observed by the naked eyes, and evaluated according to the following criteria.

(23) ⊚: good (no turbidity)

(24) Δ: slightly poor (a slight amount of turbidity)

(25) x: poor (noticeable turbidity)

(26) (3) Generation of Bubbles

(27) The lenses produced using the phosphorus-based mold releasing agents of Examples 1 to 4 and Comparative Example 1 were each observed with a microscope at a magnification of 100 times to check whether bubbles were generated in the lenses and evaluated according to the following criteria.

(28) S: the number of bubbles is 0

(29) A: the number of bubbles is 1 to 10

(30) B: the number of bubbles is 11 to 30

(31) C: the number of bubbles is 31 or more

(32) (4) Evaluation of Mold Releasability

(33) The mold releasability when the lens was released from the mold of the glass mold at room temperature at the time of producing the plastic lens was evaluated according to the following criteria.

(34) ⊚(excellent): At the time of cooling to room temperature, the entire contact surface of the molded article is naturally released from the mold

(35) ∘(good): At the time of cooling to room temperature, the contact surface of the molded article is partially released from the mold, and it is easily released by a mold release operation (i.e., a wedge-shaped mold release jig is inserted between the mold and the contact surface of the molded article to have the molded article released from the mold)

(36) Δ (slightly poor): Even if the mold is cooled to room temperature, the mold and the molded article are in close contact with each other, and the mold is finally released by a mold release operation. The lens or the mold is sometimes damaged

(37) x (poor): Even if the mold is cooled to room temperature and a mold release operation is performed, the mold and the molded article are in close contact with each other, or they are damaged by the mold release operation

(38) TABLE-US-00001 TABLE 1 Evaluation Content of a phosphorus-based mold releasing agent example 20 ppm 100 ppm 500 ppm 1,000 ppm 2,000 ppm Example 1 Stria Δ Δ ⊚ ⊚ ⊚ Cloudiness ⊚ ⊚ ⊚ ⊚ ⊚ Bubble A A S S S Releasability Δ Δ ◯ ◯ ⊚ Example 2 Stria Δ ⊚ ⊚ ⊚ ⊚ Cloudiness ⊚ ⊚ ⊚ ⊚ ⊚ Bubble A S S S S Releasability Δ Δ Δ ◯ ⊚ Example 3 Stria Δ ⊚ ⊚ ⊚ ⊚ Cloudiness ⊚ ⊚ ⊚ ⊚ ⊚ Bubble A S S S S Releasability Δ Δ ◯ ⊚ ⊚ Example 4 Stria Δ Δ Δ ⊚ ⊚ Cloudiness Δ Δ ⊚ ⊚ ⊚ Bubble A A A S S Releasability Δ ◯ ◯ ⊚ ⊚ Example 5 Stria Δ Δ Δ ⊚ ⊚ Cloudiness Δ Δ X X X Bubble A B C C C Releasability X X Δ Δ ◯ Comparative Stria ⊚ ⊚ ⊚ ⊚ ⊚ Example 1 Cloudiness Δ Δ Δ X X Bubble A S S S S Releasability X X Δ Δ ◯

(39) As shown in Table 1, the lenses produced using the phosphorus-based mold releasing agents prepared in Examples 1 to 4 were naturally released from the mold upon cooling to room temperature. The surface of the released lenses was clear and transparent, and no bubbles were present in the lenses. In contrast, in most cases of producing a lens using the phosphorus-based mold releasing agent (Comparative Example 1), which comprised only the compound represented by Formula 2 without the compound represented by Formula 1, the lens was not released from the mold even if it was cooled to room temperature, or the mold releasability was poor. Further, when a physical force was applied by performing a mold release operation, the lens was damaged, or even if it was released by the mold release operation, the appearance of the lens was poor or the lens was partially damaged. In addition, the released lens was not uniform since it had wave patterns on its surface, or it was not transparent since it was turbid. Since it had a large number of bubbles therein, the lens was also poor in terms of cloudiness and bubble generation.