KR20240053365A - Isocyanate composition and optical composition - Google Patents

Abstract

The present invention relates to an isocyanate composition having excellent storage stability and an optical lens manufactured from such an isocyanate composition.

Description

Isocyanate composition and optical composition {ISOCYANATE COMPOSITION AND OPTICAL COMPOSITION}

It relates to isocyanate compositions and optical compositions.

Compared to inorganic materials such as glass, polymer materials are lightweight, not easily broken, have excellent dyeability, and have excellent other mechanical and optical properties. Recently, various types of polymer resins have been widely used as replacement materials for glass in the optical field. It is being used.

Recently, with the development of electronic and optical technologies, there is a growing demand for higher performance of optical materials in terms of optical properties such as high transparency and high refractive index, and mechanical properties such as low specific gravity, high heat resistance, and high impact resistance.

Among these, lenses made of polythiourethane-based compounds have a high refractive index, are lightweight, and have high impact resistance, so they are widely used as optical materials.

Since these polythiourethane-based compounds are made through a polymerization reaction of a polyfunctional polythiol compound and a polyfunctional isocyanate compound, the optical properties of the lens, such as transparency and refractive index, may be influenced by the chemical properties of the polyfunctional diisocyanate compound.

Accordingly, research on the chemical properties, such as the stability, of the diisocyanate-based compound itself is necessary.

The present specification seeks to provide an isocyanate composition with excellent storage stability and an optical composition prepared from this isocyanate composition.

The present specification provides an isocyanate composition containing a diisocyanate-based compound and a sulfonyl isocyanate-based compound.

According to one example, the diisocyanate-based compound may be represented by the following formula (1).

[Formula 1]

In Formula 1, R1 and R2 are each independently alkylene having 1 to 5 carbon atoms, and the other carbon in the benzene ring to which R1 or R2 is not connected is each independently alkyl having 1 to 5 carbon atoms. This can be replaced.

And, the sulfonyl isocyanate-based compound may be represented by the following formula (2).

[Formula 2]

In Formula 2, R31 to R35 are hydrogen or alkyl having 1 to 5 carbon atoms, and R4 is a single bond or alkylene having 1 to 5 carbon atoms.

According to one example, the isocyanate composition contains about 1 to about 5000 ppmw, or about 1 ppmw or more, or about 10 ppmw or more, or about 100 ppmw or more of the sulfonyl isocyanate-based compound, relative to the diisocyanate-based compound. or about 400 ppmw or more, or about 500 ppmw or more, or about 600 ppmw or more, or about 900 ppmw or less, or about 5000 ppmw or less, or about 4000 ppmw or less, or about 3000 ppmw or less, or about 2500 ppmw or less. You can.

And, the isocyanate composition has an acidity value of about 10 ppm or more, or about 20 ppm or more, or about 40 ppm or more, or about 50 ppm or more, or about 100 ppm or more, and about 500 ppm or less, or about 400 ppm or less. , or about 300 ppm or less, or about 200 ppm or less.

According to one example, the isocyanate composition may have an aromatic diisocyanate-based oligomer content of about 3 area% or less as measured after being stored for 40 weeks at 5°C in a nitrogen atmosphere.

In addition, the isocyanate composition has an APHA value of about 150 or less, or about 100 or less, or about 50 or less, or about 30 or less, as measured according to the ASTM D1209 standard (C/2) after being stored for 40 weeks at 5°C under a nitrogen atmosphere. or about 20 or less, or about 15 or less, and the lower limit is not significant, but may be greater than 0 or greater than or equal to about 1.

Additionally, the present specification provides a polymerizable composition comprising i) the above-described isocyanate composition and ii) any one or more of a polyfunctional thiol-based compound and a polyfunctional episulfide-based compound.

According to one example, the multifunctional thiol-based compound is 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,7-bis(mercapto methyl)-3,6,9-trithiaundecane-1,11-dithiol, 5,7-bis(mercaptomethyl)-3,6,9-trithiaoundecan-1,11-dithiol, Bis(2-mercaptoethyl)sulfide, 4-mercaptomethyl-3,6-dithioctane-1,8-dithiol, 2,3-bis(2-mercaptoethylthio)propane-1-thiol , 2,2-bis(mercaptomethyl)propane-1,3-dithiol, 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-(2- Mercaptoethylthio)-3-mercaptopropylthio)ethane, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)disulfide, 2-(2-mercaptoethylthio)-2- Mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 2-(2-mercaptoethylthio)-3-mercapto- 3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 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, 4 ,14-bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-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(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R,12S)-7 ,12-bis(mercaptomethyl)-3,6,9,10,13,16-hexathioctadecane-1,18-dithiol, 2-(2-mercaptoethylthio)-3-[4- (1-{4-[3-Mercapto-2-(2-mercaptoethylthio)-propoxy]-phenyl}-1-methylethyl)-phenoxy]-propane-1-thiol, 2,2 - Bis-(3-mercapto-propionyloxymethyl)-butyl ester, pentaerythritol tetrakis(3-mercaptopropionate), pentaethritol tetrakis(2-mercaptoacetate), bispentaerythritol -Ether-hexakis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), glycerol trimercaptopropionate, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1, At least one selected from 3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiane, and 2,5-bismercaptomethyl-1,4-dithiane may include.

Additionally, the present specification provides an optical lens comprising i) the above-described isocyanate composition and ii) polythiourethane obtained by polymerizing at least one of a polyfunctional thiol-based compound and a polyfunctional episulfide-based compound.

In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another component.

Additionally, the terminology used herein is only used to describe exemplary embodiments and is not intended to limit the invention.

Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this specification, terms such as “comprise,” “comprise,” or “have” are used to describe implemented features, numbers, steps, components, or combinations thereof, and include one or more other features, numbers, or steps. , does not exclude the possibility of components, combinations or additions thereof.

Additionally, in this specification, when each layer or element is referred to as being formed “on” or “on” each layer or element, it means that each layer or element is formed directly on each layer or element, or other This means that layers or elements can be additionally formed between each layer, on the object, or on the substrate.

Since the present invention can make various changes and take various forms, specific embodiments will be illustrated and described in detail below. However, this does not limit the present invention to the specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

Hereinafter, the present invention will be described in detail.

The present specification provides an isocyanate composition containing a diisocyanate-based compound and a sulfonyl isocyanate-based compound.

Diisocyanate-based compounds, along with polythiol, are widely used to produce polythiourethane-based lenses.

However, due to the high reactivity of the isocyanate group, isocyanate-based compounds have the problem of deterioration by reacting with moisture in the air in a general storage environment, and must be strictly managed under nitrogen conditions.

Xylylene diisocyanate-based compounds, which are widely used recently, are filled with nitrogen by the manufacturer, completely sealed, and distributed under refrigerated conditions, so deterioration can be prevented before purchase and use, but they do not undergo such treatment. It is very difficult to store unused products or materials left after purchase and use.

In particular, in the case of xylylene diisocyanate-based compounds, when stored for a long time, the content of dimers or multimers (oligomers) increases, and as a result, yellowing or white turbidity occurs and optical properties deteriorate.

When a lens is manufactured using such a modified xylylene diisocyanate-based compound, the molecular weight of the polymer solution rapidly increases, which causes a problem in that processability is greatly reduced and the optical properties of the manufactured lens are also greatly reduced.

The inventors of the present invention discovered that adding a sulfonyl isocyanate-based compound when storing a diisocyanate-based compound greatly improved long-term storage stability and prevented deterioration, and completed the present invention.

According to one aspect, an isocyanate composition comprising a diisocyanate-based compound and a sulfonyl isocyanate-based compound is provided.

Diisocyanate-based compounds contain two isocyanate groups within the molecule, so oligomerization or polymerization reactions that form dimers, trimers, multimers, etc. can proceed through intermolecular reactions of the isocyanate groups. When a diisocyanate-based compound forms a multimer as described above, problems with optical properties such as white clouding may occur, and storage stability may be significantly reduced.

Sulfonyl isocyanate-based compounds have excellent compatibility with diisocyanate-based compounds and contain one isocyanate group in the molecule, allowing the oligomerization or polymerization reaction of the diisocyanate-based compounds to be terminated. It has the advantage of not significantly changing physical properties, so when storing diisocyanate-based compounds, storage stability can be greatly improved.

Specific examples of the diisocyanate include orthoxylylene diisocyanate, metaxylylene diisocyanate, paraxylylene diisocyanate, hexamethylene diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1] Heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,2 -Diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, dimethylphenylene diisocyanate, biphenyldi Isocyanate, toluidine diisocyanate, 4,4'-methylenebis(phenylisocyanate), 1,2-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)benzene, 1,4- Bis(isocyanatomethyl)benzene, 1,2-bis(isocyanatoethyl)benzene, 1,3-bis(isocyanatoethyl)benzene, 1,4-bis(isocyanatoethyl) Benzene, 4,4'-diisocyanatodicyclohexylmethane, α,α,α',α'-tetramethylxylylene diisocyanate, bis(isocyanatomethyl)naphthaline, bis(isocyanatomethylphenyl) ) Ether, bis(isocyanatomethyl)sulfide, bis(isocyanatoethyl)sulfide, bis(isocyanatopropyl)sulfide, 2,5-diisocyanatotetrahydrothiophene, 2 ,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyane Itomethyl-1,4-dithiane, etc. can be mentioned.

As another independent example, the diisocyanate-based compound may be an aromatic diisocyanate-based compound.

As another independent example, the diisocyanate-based compound may be a compound represented by the following formula (1).

[Formula 1]

In Formula 1, R1 and R2 are each independently alkylene having 1 to 5 carbon atoms, and the other carbon in the benzene ring to which R1 or R2 is not connected is each independently alkyl having 1 to 5 carbon atoms. This can be replaced.

Specifically, R1 and R2 may each independently be methylene, ethylene, propylene, butylene, pentylene, etc., and if the chain has three or more carbon atoms, it may have a branched chain structure.

The compound represented by Formula 1 may be, for example, xylylene diisocyanate, which may have an ortho, meta, or para structure, but the present invention is not necessarily limited thereto.

Additionally, the sulfonyl isocyanate-based compound may be an aromatic sulfonyl isocyanate-based compound.

As another independent example, the sulfonyl isocyanate-based compound may be a compound represented by the following formula (2).

[Formula 2]

In Formula 2, R31 to R35 are hydrogen or alkyl having 1 to 5 carbon atoms, and R4 is a single bond or alkylene having 1 to 5 carbon atoms.

Specifically, the alkyl may be methyl, ethyl, propyl, butyl, or pentyl, and if it has a carbon chain of three or more, it may have a branched chain structure.

In addition, R4 may be methylene, ethylene, propylene, butylene, pentylene, etc., and if it has three or more carbon chains, it may have a branched chain structure.

The compound represented by Formula 2 may be, for example, toluenesulfonyl isocyanate, which may have an ortho, meta, or para structure, but the present invention is not necessarily limited thereto.

According to one example, the isocyanate composition contains about 1 to about 5000 ppmw, or about 1 ppmw or more, or about 10 ppmw or more, or about 50 ppmw or more of the sulfonyl isocyanate-based compound, relative to the diisocyanate-based compound. Or it may include about 5000 ppmw or less, or about 4000 ppmw or less, or about 3000 ppmw or less, or about 2500 ppmw or less.

If the content of the sulfonyl isocyanate-based compound is too small, the effect of improving the long-term storage stability of the above-mentioned diisocyanate-based compound may not appear, and if the content of the sulfonyl isocyanate-based compound is too high, the original physical properties of the diisocyanate-based compound may be lost. changes, and when optical articles are manufactured with these diisocyanate-based compounds, problems such as a decrease in refractive index or a decrease in thermal stability may occur.

And, the isocyanate composition has an acidity value of about 10 ppm or more, or about 20 ppm or more, or about 40 ppm or more, or about 50 ppm or more, or about 100 ppm or more, and about 500 ppm or less, or about 400 ppm or less. , or about 300 ppm or less, or about 200 ppm or less.

In this specification, the “acidity” value of the isocyanate composition refers to the amount of acid liberated when the isocyanate-based compound reacts with alcohol at room temperature. Specifically, for example, when the amount of free acid is converted to HCl, the total weight of It may refer to a value expressed as a ratio to . Acidity can be expressed in ppm.

The acidity of a general diisocyanate-based compound itself may be less than about 10 ppm, but when a diisocyanate-based compound and a sulfonyl isocyanate-based compound are mixed as in the present invention, the acidity may partially increase. Due to this increased acidity value, the reactivity of the diisocyanate-based compound decreases, which can improve the storage stability of the composition. When manufacturing lenses with this composition, the filtration rate increases, and processability and productivity can also be improved. .

However, if the acidity value is too high, the speed of the urethane reaction may slow down in the lens manufacturing process, resulting in a decrease in productivity.

According to one example, the aromatic diisocyanate-based oligomer content of the isocyanate composition measured after 40 weeks of storage at 5°C under a nitrogen atmosphere is about 3 area% or less, and the oligomer production rate is very low even during long-term storage, so storage stability is very low. It can be excellent.

In addition, the isocyanate composition has an APHA value of about 150 or less, or about 100 or less, or about 50 or less, or about 30 or less, as measured according to the ASTM D1209 standard (C/2) after being stored for 40 weeks at 5°C under a nitrogen atmosphere. Or about 20 or less, or about 15 or less, and the lower limit does not have much significance, but when it is greater than 0 or about 1 or more, discoloration may not substantially appear even during long-term storage.

Meanwhile, the present specification provides a polymerizable composition comprising i) the above-described isocyanate composition and ii) any one or more of a polyfunctional thiol-based compound and a polyfunctional episulfide-based compound.

The polymerizable composition may include the isocyanate composition, the polyfunctional thiol-based compound, and the polyfunctional episulfide-based compound in a mixed state or in a separated state. That is, in the polymerizable composition, the isocyanate composition and the polyfunctional thiol-based compound or polyfunctional episulfide-based compound may be blended in contact with each other, or may be separated so as not to contact each other.

The multifunctional thiol-based compound may be a compound containing two or more Thio (-SH) groups in the molecule, and may have an aliphatic, alicyclic, or aromatic skeleton.

The multifunctional episulfide-based compound may be a compound containing two or more episulfides, that is, a thioepoxy group, in the molecule, and may have an aliphatic, alicyclic, or aromatic skeleton.

According to one example, the multifunctional thiol-based compound is 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,7-bis(mercapto methyl)-3,6,9-trithiaundecane-1,11-dithiol, 5,7-bis(mercaptomethyl)-3,6,9-trithiaoundecan-1,11-dithiol, Bis(2-mercaptoethyl)sulfide, 4-mercaptomethyl-3,6-dithioctane-1,8-dithiol, 2,3-bis(2-mercaptoethylthio)propane-1-thiol , 2,2-bis(mercaptomethyl)propane-1,3-dithiol, 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-(2- Mercaptoethylthio)-3-mercaptopropylthio)ethane, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)disulfide, 2-(2-mercaptoethylthio)-2- Mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 2-(2-mercaptoethylthio)-3-mercapto- 3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 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, 4 ,14-bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-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(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R,12S)-7 ,12-bis(mercaptomethyl)-3,6,9,10,13,16-hexathioctadecane-1,18-dithiol, 2-(2-mercaptoethylthio)-3-[4- (1-{4-[3-Mercapto-2-(2-mercaptoethylthio)-propoxy]-phenyl}-1-methylethyl)-phenoxy]-propane-1-thiol, 2,2 - Bis-(3-mercapto-propionyloxymethyl)-butyl ester, pentaerythritol tetrakis(3-mercaptopropionate), pentaethritol tetrakis(2-mercaptoacetate), bispentaerythritol -Ether-hexakis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), glycerol trimercaptopropionate, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1, At least one selected from 3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiane, and 2,5-bismercaptomethyl-1,4-dithiane may include.

According to one example, the multifunctional episulfide-based compound is bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropylthio)ethane, 1,3-bis(β-epithiopropyl) thio)propane, 1,2-bis(β-epithiopropylthio)propane, 1-(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)propane, 1,4-bis(β -Epitiopropylthio)butane, 1,3-bis(β-epithiopropylthio)butane, 1-(β-epithiopropylthio)-3-(β-epithiopropylthiomethyl)butane, 1,5 -bis(β-epithiopropylthio)pentane, 1-(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)pentane, 1,6-bis(β-epithiopropylthio)hexane , 1-(β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)hexane, 1-(β-epithiopropylthio)-2-[(2-β-epithiopropylthioethyl) thio]ethane, 1-(β-epithiopropylthio)-2-[[2-(2-β-epithiopropylthioethyl)thioethyl]thio]ethane, tetrakis(β-epithiopropylthiomethyl) Methane, 1,1,1-tris(β-epithiopropylthiomethyl)propane, 1,5-bis(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)-3-thiapentane , 1,5-bis(β-epithiopropylthio)-2,4-bis(β-epithiopropylthiomethyl)-3-thiapentane, 1-(β-epithiopropylthio)-2,2- Bis(β-epithiopropylthiomethyl)-4-thiahexane, 1,5,6-tris(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3-thiahexane, 1 ,8-bis(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3,6-dithioctane, 1,8-bis(β-epithiopropylthio)-4,5 -bis(β-epithiopropylthiomethyl)-3,6-dithioctane, 1,8-bis(β-epithiopropylthio)-4,4-bis(β-epithiopropylthiomethyl)-3 ,6-Dithioctane, 1,8-bis(β-epithiopropylthio)-2,4,5-tris(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8- Bis(β-epithiopropylthio)-2,5-bis(β-epithiopropylthiomethyl)-3,6-dithioctane, 1,9-bis(β-epithiopropylthio)-5-( β-Epitiopropylthiomethyl)-5-[(2-β-epithiopropylthioethyl)thiomethyl]-3,7-dithianonane, 1,10-bis(β-epithiopropylthio)-5 ,6-bis[(2-β-epithiopropylthioethyl)thio]-3,6,9-trithiadecane, 1,11-bis(β-epithiopropylthio)-4,8-bis(β -Epitiopropylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(β-epithiopropylthio)-5,7-bis(β-epithiopropylthiomethyl)-3, 6,9-Trithiaoundecane, 1,11-bis(β-epithiopropylthio)-5,7-[(2-β-epithiopropylthioethyl)thiomethyl]-3,6,9-tri Thioundecan, 1,11-bis(β-epithiopropylthio)-4,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithioundecane, 1,3-bis( β-Epitiopropylthio)cyclohexane, 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane, 1,4-bis(β -Epitiopropylthiomethyl)cyclohexane, bis[4-(β-epithiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane, bis[ 4-(β-epithiopropylthio)cyclohexyl] sulfide, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithian, 2,5-bis(β-epithiopropylthio) Ethylthiomethyl)-1,4-dithian, 1,3-bis(β-epithiopropylthio)benzene, 1,4-bis(β-epithiopropylthio)benzene, 1,3-bis(β- Epithiopropylthiomethyl)benzene, 1,4-bis(β-epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,2-bis[4-(β -epithiopropylthio)phenyl]propane, bis[4-(β-epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfone, and 4,4'-bis. It may contain one or more types selected from (β-epithiopropylthio)biphenyl.

In the polymerizable composition, the molar ratio of (thio group + episulfide group) to isocyanate group may be about 0.5 to about 1.5, or about 0.8 to about 1.2, or about 0.9 to about 1.1, but the present invention does not necessarily include this. It is not limited.

In addition, the polymerizable composition may further include additives such as mold release agents, heat stabilizers, UV stabilizers, pigments, urethane reaction catalysts, etc. in appropriate amounts.

The mold release agent is a type of surfactant component, for example, a fluorine-based nonionic surfactant containing a perfluoroalkyl group; Silicone-based nonionic surfactant containing a dimethylpolysiloxane group; and quaternary ammonium salts such as trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, and diethylcyclohexadodecyl ammonium salt.

The heat stabilizer may be, for example, a metal fatty acid salt-based, phosphorus-based, lead-based, or organotin-based compound. These may be used alone or in combination of two or more.

The UV stabilizer may be, for example, a benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, or oxanilide-based compound.

Examples of the dye include fluorescent whitening agents, fluorescent pigments, and inorganic pigments.

The urethane reaction catalyst includes, for example, dialkyl tin halide-based compounds such as dibutyltin dichloride and dimethyltin dichloride; dialkyltin dicarboxylate compounds such as dimethyltin diacetate, dibutyltin dioctanoate, and dibutyltin dilaurate; Dialkyl tin dialkoxide-based compounds such as dibutyltin dibutoxide and dioctyltin dibutoxide; dialkyltin dithioalkoxide-based compounds such as dibutyltin di(thiobutoxide); dialkyl tin oxide-based compounds such as di(2-ethylhexyl)tin oxide, dioctyltin oxide, and bis(butoxydibutyltin) oxide; Dialkyl tin sulfide-based compounds, etc. may be used individually or in combination of two or more types.

Additionally, the present specification provides an optical lens comprising i) the above-described isocyanate composition and ii) polythiourethane obtained by polymerizing at least one of a polyfunctional thiol-based compound and a polyfunctional episulfide-based compound.

Such optical lenses can be manufactured, for example, by the following method.

First, the polymerizable composition is degassed under reduced pressure conditions and injected into a mold for forming a lens. Mold injection may be performed under conditions where a polymerization reaction does not occur, specifically, for example, in a temperature range of about 20 to about 40° C., or room temperature.

Then, after completely injecting the polymerizable composition into the mold, the temperature of the mold is gradually raised to allow the polymerization reaction of the diisocyanate compound and the polyfunctional thiol-based compound or polyfunctional episulfide-based compound, that is, the polythiourethane formation reaction, to proceed. there is.

At this time, the temperature of the polymerization reaction may be about 30 to about 150°C.

After the polymerization reaction is completed, the polythiourethane resin can be separated from the mold to obtain an optical lens.

The refractive index of the manufactured optical lens may vary depending on the purpose of use, and may be specifically adjusted depending on the type of diisocyanate-based compound, polyfunctional thiol-based compound, or polyfunctional episulfide-based compound used.

The isocyanate composition according to an example of the present invention has high storage stability and can maintain excellent quality, and accordingly, lenses manufactured using it can implement excellent optical properties.

Hereinafter, the operation and effects of the invention will be described in more detail through specific examples of the invention. However, these examples are merely presented as examples of the invention and do not determine the scope of the invention rights.

Diisocyanate-based compound production

Manufacturing example

In a flask, 471 g of 1,2-dichlorobenzene, 32.5 g of m-xylylenediamine (m-XDA) of 99.4% purity, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl ( 0.24 g of 4-hydroxy TEMPO) was placed and anhydrous hydrochloric acid was injected at a rate of 20 g/hr and stirred at room temperature (23 ± 5°C).

Anhydrous hydrochloric acid was injected and the temperature rose to 50°C.

After injection for 4 hours, the formed salt was cooled to room temperature, 43 g of phosgene was added into the reactor, and the reactor temperature was heated to 130°C. From the time of phosgene introduction to the end of the reaction, a dry ice-acetone cooler was used to prevent phosgene from leaking out.

After the reactor temperature reached 130°C, the reactor temperature was maintained at 125-135°C for 2 hours so that the reaction solution became transparent. After the solution became transparent, the inside of the reactor was cooled to 80°C and nitrogen was blown in to cool it. The reaction solution from which phosgene was removed was subjected to vacuum distillation to remove the solvent, and the product was purified under reduced pressure at a high temperature of 160°C to obtain meta-xylylene diisocyanate (m-XDI) compound.

Isocyanate composition preparation

Comparative Example 1

An isocyanate composition containing only meta-xylylene diisocyanate (m-XDI) compound was used without adding any additional additives. The prepared isocyanate composition was filled with nitrogen and stored under refrigerated conditions at about 5°C.

Example 1

An isocyanate composition was prepared by adding 1000 ppm of para-toluenesulfonyl isocyanate (p-TSI) to the m-XDI compound obtained in the above preparation example and mixing. The prepared isocyanate composition was filled with nitrogen and stored under refrigerated conditions at about 5°C.

Example 2

An isocyanate composition was prepared in the same manner as Example 1, except that 500 ppm of p-TSI was added. The prepared isocyanate composition was filled with nitrogen and stored under refrigerated conditions at about 5°C.

Example 3

An isocyanate composition was prepared in the same manner as Example 1, except that 1500 ppm of p-TSI was added. The prepared isocyanate composition was filled with nitrogen and stored under refrigerated conditions at about 5°C.

Example 4

An isocyanate composition was prepared in the same manner as in Example 1, except that 2000 ppm of p-TSI was added. The prepared isocyanate composition was filled with nitrogen and stored under refrigerated conditions at about 5°C.

The physical properties of the isocyanate composition were measured using the following method.

Acidity measurement

1. Instruments and reagents

1.1 0.01N KOH standard solution (methanolic): 0.01mol Potassium hydroxide methanolic standard solution (0.01N), DAEJUNG, S/T

1.2 n-Propyl Alcohol: Use diluted hydrochloric acid solution by first adjusting the pH to 4~4.5.

1.3 300ml beaker

1.4 Potentiometric titrator with glass and caromel electrodes: Metrohm E 536

2. Test procedure

2.1 Add 100 ml of n-Propyl Alcohol to a 300 ml beaker and stir.

2.2 Add 15 g of isocyanate composition sample to the beaker containing the n-Propyl Alcohol, cover with a watch glass, and stir for 10 minutes.

2.3 After cooling the beaker, titrate with 0.01N methanolic KOH standard solution in a potentiometric titrator and read the apparent acidity.

Condition: Mode; pH 14, V 0, titration speed 0.05㎖ increasement

Apparent acidity occurs between pH 5.5 and 7.0.

2.4 A blank test is performed in parallel by performing steps 2.1 to 2.3 in the same manner as above, except that the isocyanate composition sample is not added in step 2.2.

3. Calculation

[Equation 1]

Acidity (as HCl)(ppm)=[(A-B)×N×f×36.5×10^6]/(C×10^3)

In Equation 1 above,

A: Volume of KOH methanol solution consumed for titration of isocyanate composition sample (ml)

B: Volume of KOH methanol solution consumed in blank titration (ml)

N: normality of KOH methanol solution

f: When the normal concentration of the KOH methanol solution used during measurement changes, it is a correction factor to be the same as a 0.01N KOH methanol solution, and is measured according to ASTM D-1638, TOLOCHIMIE 04-01-68. For 0.01N KOH methanol solution, the f value is 1.

C: Weight of isocyanate composition sample (g)

lens manufacturing

20.8 g of the isocyanate composition prepared in the above examples and comparative examples, 0.04 g of zelec UN (manufactured by Stepan), and 0.04 g of biosorb 583 (manufactured by Sakai Chemical industry Co., Ltd) were placed in a flask, stirred and mixed at room temperature for about 20 minutes. Thus, polyisocyanate was prepared.

After visually confirming that each component was well mixed with the polyisocyanate, 0.002 g of dibutyltin chloride was added as a catalyst and mixed by stirring for 10 minutes.

19.2 g of 2,3-bis(2-sulfanyl ethyl sulfanyl)propane-1-thiol was added to the resulting mixture, degassed under 5 mbar conditions and stirred for 1 hour to prepare a polymerizable composition.

The polyisocyanate composition was filtered through a 1㎛ PTFE filter and then injected into a mold made of a glass mold and tape. The molding mold was placed in an oven, the temperature of the oven was gradually raised from 10°C to 120°C, and the polymerization reaction was performed for about 20 hours.

After completion of polymerization, the mold was taken out of the oven and released to obtain a plastic lens. The obtained lens was annealed at 120°C for 6 hours.

Filter time measurement

For the polyisocyanate polymerization composition prepared in Examples and Comparative Examples, the time (min) required for filtration was measured using a PTFE filter (25 mm Diameter Syringe Filter, manufactured by Whatman) with a pore size of 1.0 μm, From the results, the effect of improving workability was evaluated.

Filtration time refers to the time from when 200 g of the composition for polyisocyanate polymerization passes through the filter to when passage is completed.

Yellow Index (YI) measurement

Measurements were made according to ASTM E313 standards (D65/10) using a colorimeter (Ultrascan Pro, HunterLab).

The measurement results are summarized in the table below.

Example 1 Example 2 Example 3 Example 4 Comparative example Acidity (ppm) 130 48 162 188 5 Filter time (min) 5 15 5 5 35 Lens Y.I. 1.5 1.5 1.6 1.7 1.4

Referring to Table 1, it can be clearly seen that the composition according to an example of the present invention has a relatively high acidity value compared to the comparative example, and the filter time reaches about 1/7 of the comparative example. That is, the composition according to one example of the present invention is believed to have significantly better workability or processability than the comparative example.

Oligomer content

The oligomer content in the isocyanate composition was measured by the following method.

First, gel permeation chromatography (GPC) analysis was performed on the isocyanate composition according to the conditions below to obtain a molecular weight distribution curve (GPC curve) for the isocyanate composition, and among the total area of the GPC molecular weight distribution curve, the fraction corresponding to the oligomer The area was expressed as a percentage. Specifically, the oligomer content (area%) was calculated according to Equation 2 below.

[Equation 2]

Oligomer content (%) = [B/A]

In the above equation,

A is the total area under the curve in the molecular weight distribution curve (GPC curve) for the isocyanate composition,

B is the area of the peak corresponding to the oligomer in the molecular weight distribution curve for the isocyanate composition.

The total area of the GPC curve and the area of the fraction corresponding to the oligomer are each obtained through integration. At this time, the oligomer was evaluated based on polymers with a weight average molecular weight (Mw) value of 600 to 2000 g/mol, and the fraction corresponding to the oligomer in the GPC curve was 19.42 ≤ logMw ≤ 22.18.

<GPC analysis conditions>

Equipment used: Agilent

Columns: Agilent PL Mixed D, Agilent PLgel 100Å, Agilent PLgel 50Å

Sample concentration: 1wt/vol% in tetrahydrofuran (THF)

Carrier: THF

Detection method: RI

Outflow: 1.0 ml/min

Column temperature: 25℃

Detector: Agilent RI detector

When preparing the calibration curve, standard polystyrene foam with a molecular weight of 104 to 24,600 g/mol was used.

APHA color index measurement

The color index value of the composition was measured according to ASTM D1209 standard (C/2, 10 mm quartz cell) using a colorimeter (Ultrascan Pro).

Optical property measurement

The presence or absence of haze of the composition was visually observed and evaluated as follows. Clear: Clear and transparent throughout

Light haze: Overall transparent, but haze is observed when exposed to light (fluorescent lamp)

Haze: Opacity is clearly visible to the naked eye.

Purity Measurement

The purity of m-XDI of the above examples and comparative examples was analyzed using GC. First, GC analysis was performed on the m-XDI composition immediately after purification, and the content of m-XDI was measured after being stored under refrigerated (5°C) conditions for 5 to 40 weeks. For m-XDI in which white turbidity occurred, GC analysis was not possible because the white turbidity was an insoluble substance, so the purity was measured after filtering, and a separate analysis was performed for the content of the white turbidity.

The GC used for analysis was HP-6890, and detection was performed using FID. The column used was DB-17 (30m * 0.25mm * 0.5㎛), the carrier gas was nitrogen (1.0mL/min), and the oven temperature was 80℃ -> 5℃/min -> 160℃ (8 min) -> 20℃. /min -> 280℃ (18min).

Oligomer content (area%) Storage period 0 months 5 months 40 weeks Example 1 0.62 2.20 2.92 Comparative Example 1 0.62 2.21 3.06 APHA(C/2, 10mm) Storage period 0 months 5 months 40 weeks Example 1 8 11 13 Comparative Example 1 2 28 174 m-XDI clarity (whether haze occurs) Storage period 0 months 5 months 40 weeks Example 1 X X light haze Comparative Example 1 X haze haze Purity (area%) Storage period 0 months 5 months 40 weeks Example 1 99.70 99.74 99.75 Comparative Example 1 99.85 99.84 99.70

Referring to the table above, it can be seen that the composition according to an example of the present invention has no significant change in color index value compared to the composition of the comparative example even when stored for a long period of time, hardly generates haze, and maintains high purity. .

In addition, it can be confirmed that the composition according to an example of the present invention has a lower oligomer content than the composition of the comparative example even when stored for a long period of time.

However, when measuring the oligomer content by GPC, the sample is diluted in THF, filtered through a 1.0㎛ PTFE filter (25mm Diameter Syringe Filter, manufactured by Whatman), and then introduced into GPC. Since polymer substances are filtered during filtration, accurate There was a difficult problem in measuring the oligomer content.

Therefore, in order to more accurately compare the parts related to oligomer formation, the thermal decomposition temperature was measured.

Thermal decomposition temperature measurement

It was confirmed that m-XDI prepared in the above Examples and Comparative Examples was stored under refrigerated (5°C) conditions for about 10 months and that white turbidity occurred.

10 ml of m-XDI was dissolved in 50 ml of n-hexane, and n-hexane was removed so that insoluble components remained. After n-hexane was removed, 50ml of THF was added and it was confirmed that it was transparent to the naked eye. Here again, an excessive amount of n-hexane was added until an opaque insoluble material was visible. When an opaque substance was identified, n-hexane was removed and evaporated at approximately 40°C to leave no residual solvent. After visually confirming that the solvent had been removed, it was dried at about 40°C under vacuum conditions for about 12 hours to ensure that all solvents were completely removed, and then dried at about 120°C under vacuum conditions for about 8 hours.

The dried sample was cooled to room temperature, and using TGA, the temperature was raised from room temperature to 700°C at 10°C/min, and the change in mass was measured. The mass loss rate was 10%, 20%, 30%, and 40%. The temperatures are summarized in the table below.

Weight Loss
(%) 10 20 30 40 Example 1 195℃ 217 235 279 Comparative Example 1 253 285 357 410

When isocyanate compounds react to form oligomers, thermal decomposition becomes more difficult, requiring more energy for thermal decomposition, and thus thermal decomposition tends to occur at higher temperatures.

Referring to the table above, it can be clearly seen that in the comparative example, thermal decomposition occurs at a much higher temperature than in the example, and the temperature difference is very large.

Measurement of Tg and Tm values

The cloudy material was recovered in the same manner as in the TGA measurement, and the glass transition temperature and melting point were measured using differential scanning calorimetry.

Equipment: DSC

Measuring conditions:

Primary heating: -70℃ ~180℃, 20℃/min; Cooling: 180℃~-70℃, -100℃/min; Secondary heating: -70℃~180℃, 20℃/min;

Tg
(℃) Tm
(℃) Example 1 - -6.3 Comparative Example 1 12.2 -

Referring to the table above, it can be seen that Tg was confirmed in Comparative Example 1 without adding pTSI. This means that a polymer material having a Tg value was formed in Comparative Example 1, and that the storage stability of the composition according to Comparative Example 1 was significantly low.

Claims (10)

An isocyanate composition comprising a diisocyanate-based compound and a sulfonyl isocyanate-based compound.
According to paragraph 1,
The diisocyanate-based compound is an isocyanate composition represented by the following formula (1):
[Formula 1]

In Formula 1,
R1 and R2 are each independently alkylene having 1 to 5 carbon atoms,
The other carbons in the benzene ring to which R1 or R2 are not connected may be independently substituted with alkyl having 1 to 5 carbon atoms.
According to paragraph 1,
The sulfonyl isocyanate-based compound is an isocyanate composition represented by the following formula (2):
[Formula 2]

In Formula 2,
R31 to R35 are hydrogen or alkyl having 1 to 5 carbon atoms,
R4 is a single bond or alkylene having 1 to 5 carbon atoms.
According to paragraph 1,
An isocyanate composition comprising 1 to 5000 ppmw of the sulfonyl isocyanate-based compound relative to the diisocyanate-based compound.
According to paragraph 1,
An isocyanate composition having an acidity value of at least 10 ppm.
According to paragraph 1,
An isocyanate composition having a diisocyanate-based oligomer content of 3 area% or less measured after 40 weeks of storage at 5°C under a nitrogen atmosphere.
According to paragraph 1,
An isocyanate composition having an APHA value of 150 or less as measured according to ASTM D1209 standard (C/2) after 40 weeks of storage at 5°C under a nitrogen atmosphere.
The isocyanate composition according to any one of claims 1 to 7, and
Containing at least one of i) a multifunctional thiol-based compound and ii) a polyfunctional episulfide-based compound,
Polymerizable composition.
According to clause 8,
The multifunctional thiol-based compounds include 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,7-bis(mercaptomethyl)-3, 6,9-Trithiaundecane-1,11-dithiol, 5,7-bis(mercaptomethyl)-3,6,9-Trithiaoundecan-1,11-dithiol, bis(2-mer Captoethyl) sulfide, 4-mercaptomethyl-3,6-dithioctane-1,8-dithiol, 2,3-bis(2-mercaptoethylthio)propane-1-thiol, 2,2- Bis(mercaptomethyl)propane-1,3-dithiol, 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-(2-mercaptoethylthio) -3-mercaptopropylthio)ethane, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)disulfide, 2-(2-mercaptoethylthio)-2-mercapto-3- [3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 2-(2-mercaptoethylthio)-3-mercapto-3-[3- Mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 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, 4,14-bis( mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (S)-3-((R-3-mercapto-2-((2-mercapto Ethyl)thio)propyl)thio)propyl)thio)-2-((2-mercaptoethyl)thio)propane-1-thiol, 3,3'-dithiobis(propane-1,2-dithiol), ( 7R,11S)-7,11-bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R,12S)-7,12-bis( mercaptomethyl)-3,6,9,10,13,16-hexathioctadecane-1,18-dithiol, 2-(2-mercaptoethylthio)-3-[4-(1-{4 -[3-mercapto-2-(2-mercaptoethylthio)-propoxy]-phenyl}-1-methylethyl)-phenoxy]-propane-1-thiol, 2,2-bis-(3- Mercapto-propionyloxymethyl)-butyl ester, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hexakis (3-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), glycerol trimercaptopropionate, 1,1,3 ,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, Polymerization comprising at least one selected from 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiane, and 2,5-bismercaptomethyl-1,4-dithiane. Sex composition.
The isocyanate composition according to any one of claims 1 to 7, and
An optical lens comprising polythiourethane in which at least one of i) a multifunctional thiol-based compound and ii) a polyfunctional episulfide-based compound is polymerized.