WO2024090855A1 - Composition d'isocyanate - Google Patents

Composition d'isocyanate Download PDF

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Publication number
WO2024090855A1
WO2024090855A1 PCT/KR2023/015727 KR2023015727W WO2024090855A1 WO 2024090855 A1 WO2024090855 A1 WO 2024090855A1 KR 2023015727 W KR2023015727 W KR 2023015727W WO 2024090855 A1 WO2024090855 A1 WO 2024090855A1
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Prior art keywords
tert
butyl
isocyanate
bis
isocyanate composition
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PCT/KR2023/015727
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English (en)
Korean (ko)
Inventor
김지연
우은지
심유진
김종진
권도우
Original Assignee
한화솔루션 주식회사
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Priority claimed from KR1020230135186A external-priority patent/KR20240058767A/ko
Application filed by 한화솔루션 주식회사 filed Critical 한화솔루션 주식회사
Publication of WO2024090855A1 publication Critical patent/WO2024090855A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to an isocyanate composition that has improved storage stability, suppresses discoloration and cloudiness, and has improved workability such as shortened filter time.
  • Isocyanate-based compounds are compounds with high utility not only in the chemical industry and resin industry, but also in fine chemical products including optical materials.
  • Demand for xylylene diisocyanate (XDI) is increasing as a high-value chemical material as a raw material for advanced optical lenses.
  • isocyanate-based compounds exhibit high reactivity, they tend to react with moisture in the air during storage, causing discoloration or white turbidity.
  • discoloration or white turbidity occurs as oligomers larger than dimers are formed through self-polymerization.
  • Isocyanate-based compounds are raw materials for polyurethane and are used in a variety of applications such as coatings, adhesives/adhesives, paints, foams, and optical materials.
  • Polyurethane lenses are manufactured using isocyanate-based compounds that cause discoloration or white clouding.
  • the rapid increase in the molecular weight of the polymer solution causes a decrease in stirring power, an increase in filter time, and filter clogging, which reduces workability, and also causes problems such as decreased transparency and discoloration of the manufactured lens.
  • the purpose of the present invention is to provide an isocyanate composition that improves storage stability, suppresses discoloration and cloudiness, improves transparency when applied to the resulting product, and improves workability, such as shortening the filter time.
  • an isocyanate composition comprising an isocyanate-based compound and a phosphonate-based compound represented by the following formula (1):
  • R a and R b are each independently a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 6-20 aryl group, a substituted or unsubstituted C 7-30 alkylaryl group, or a substituted or unsubstituted It is a C 7-30 arylalkyl group.
  • the isocyanate composition and at least one of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, and a polyfunctional episulfide-based compound.
  • an article comprising a polymer obtained by polymerizing the isocyanate composition and at least one of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, and a polyfunctional episulfide-based compound is provided.
  • the isocyanate composition according to the present invention has improved storage stability, suppresses discoloration and white cloudiness, and can improve transparency when applied to the resulting product.
  • the isocyanate composition can exhibit improved workability, such as shortening the filter time.
  • the polymerization composition containing the isocyanate composition and a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, or a multifunctional episulfide-based compound is used in plastic paints, automotive paints, film coatings, and various inks due to its excellent physical properties.
  • It can be used in a wide range of fields such as various adhesives/adhesives, sealing materials, various microcapsules, plastic lenses, artificial and synthetic leather, reaction injection molding (RIM) products, slush powder, elastic molded products (spandex), and urethane foam.
  • the isocyanate composition is particularly useful as a material for optical products such as optical adhesives, optical adhesives, spectacle lenses, camera lenses, and prisms, due to its excellent viscosity/adhesion properties and transparency.
  • substituted or unsubstituted refers to deuterium; halogen group; Nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy group; silyl group; boron group; Alkyl group; Cycloalkyl group; alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; or substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroaryl group containing one or more of N, O and S atoms, or a combination thereof, specifically, two or more of the above-exe
  • a substituent group in which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.
  • ordinary temperature means 23 ⁇ 5°C, which is a typical laboratory temperature
  • ordinary pressure means 1 ⁇ 0.05 atm, which is a typical laboratory pressure.
  • a nitrogen atmosphere means the presence of nitrogen in the atmospheric gas. Specifically, the nitrogen concentration in the atmospheric gas is greater than 0% by volume and less than 100% by volume.
  • isocyanate-based compounds Due to the high reactivity of isocyanate-based compounds with moisture or alcohol, after production, they are filled with nitrogen, completely sealed, and stored in refrigeration. However, when opened for use, it reacted with moisture in the air, or discoloration or white clouding occurred depending on the air temperature. In addition, when an isocyanate-based compound that was stored in a closed container was opened and used, the oligomer content increased or yellowing occurred during the storage time until it was used up.
  • the present inventors studied an isocyanate composition that can suppress the rate of increase in oligomers generated by self-polymerization of isocyanate-based compounds during long-term storage of isocyanate-based compounds and can show improved workability during lens manufacturing.
  • the oligomerization rate of the isocyanate-based compound can be reduced, and as a result, discoloration and whitening caused by the oligomer can be suppressed, and
  • the present invention was completed after confirming that lens color change due to various additives added to improve lens workability can be prevented and workability can be improved by shortening the filter time during lens manufacturing.
  • the isocyanate composition according to the present invention includes an isocyanate-based compound and a phosphonate-based compound represented by the following formula (1):
  • R a and R b are each independently a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 6-20 aryl group, a substituted or unsubstituted C 7-30 alkylaryl group, or a substituted or unsubstituted It is a C 7-30 arylalkyl group.
  • R a and R b are substituted, specifically selected from the group consisting of alkyl group, cycloalkyl group, aryl group, arylalkyl group, alkylaryl group, hydroxy group, alkoxy group, alkoxyalkyl group, aryloxy group and combinations thereof. It may be substituted with one or more substituents.
  • R a and R b are each independently a substituted or unsubstituted C 1-18 alkyl group, a substituted or unsubstituted C 6-18 aryl group, or a substituted or unsubstituted C 7-18 alkylaryl. group, or a substituted or unsubstituted C 7-18 arylalkyl group, and when R a and R b are substituted, each independently a C 1-12 alkyl group, a C 3-12 cycloalkyl group, or a C 6-12 aryl group.
  • R a and R b may each independently be a C 1-8 alkyl group, a phenyl group, or a benzyl group, where R a and R b are each independently a C 1-6 alkyl group or a phenyl group. It may be substituted or unsubstituted with one or more substituents selected from the group consisting of , hydroxy groups, and combinations thereof.
  • a combined group means that two or more functional groups are combined.
  • the combination of a hydroxy group and a methyl group can be a methoxy group or a hydroxymethyl group
  • the combination of a hydroxy group and a phenyl group can be a phenoxy group or a hydroxyphenyl group.
  • the combined group of a methyl group and a phenyl group may be a benzyl group or a methylphenyl group.
  • R a and R b are each independently selected from a methyl group, ethyl group, t-butyl group, hexyl group, 3,3-dimethylbutan-2-yl group, 2-ethylhexyl group, phenyl group, It may be a hydroxybenzyl group, or a 3,5-di-tert-butyl-4-hydroxybenzyl group.
  • phosphonate-based compounds include ethyl methylphosphonate (CAS NO. 1832-53-7), pinacolyl methylphosphonate, mono-2-ethylhexyl (2 -Ethylhexyl)phosphonate (mono-2-ethylhexyl(2-ethylhexyl)phosphonate), or monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (monoethyl 3,5-di- tert-butyl-4-hydroxybenzylphosphonate), etc., and any one or a mixture of two or more of these may be used.
  • the reaction rate of the isocyanate decreases, and as a result, oligomerization of the isocyanate may be delayed or suppressed.
  • the phosphonate-based compound reacts with alcohol to provide a free acid component. Accordingly, the acidity of the isocyanate composition can be increased, and as a result, the reaction rate and oligomerization of the isocyanate can be delayed or suppressed, and discoloration and clouding caused by the oligomer can be suppressed.
  • the phosphonate-based compound prevents changes in lens color due to additives added to improve lens workability, and also suppresses an increase in viscosity of the isocyanate composition, thereby shortening the filter time when manufacturing lenses.
  • the phosphonate-based compound Compared to phosphonic acid (HPO(OH) 2 ) and phosphorous acid (P(OH) 3 ), the phosphonate-based compound exhibits a superior effect in terms of storage stability due to the difference in reactivity. You can.
  • phosphoric acid H 3 PO 4 (or PO(OH) 3 )
  • H 3 PO 4 or PO(OH) 3
  • the phosphoric acid Nate-based compounds exhibit an appropriate level of reactivity, so there is no concern about the generation of precipitates.
  • phosphoric acid ester may have some effect of increasing the acidity of the isocyanate composition, but has the problem of increasing the viscosity of the polymerization composition and resulting in filter clogging during lens manufacturing.
  • the phosphonate-based compound has no risk of increasing viscosity.
  • the acidity (as HCl) (ppm) of the isocyanate composition is calculated by converting the amount of acid component liberated by reaction with alcohol at room temperature (23 ⁇ 5°C) into HCl, and then calculating it relative to the total weight of the isocyanate compound. This value is expressed as a weight ratio.
  • the acidity in the isocyanate composition according to the present invention is determined depending on the content of acidic groups derived from the phosphonate-based compound. Accordingly, acidity can be adjusted by controlling the type and/or input amount of the phosphonate-based compound, and the effect of using the phosphonate-based compound can be further improved by optimizing the acidity range.
  • the isocyanate composition according to the present invention may have an acidity of 500 ppm or less.
  • the reaction rate of the isocyanate decreases, and as a result, oligomerization of the isocyanate may be delayed or suppressed.
  • the acidity is too high, the reaction rate of the isocyanate becomes too slow, leading to the formation of polymers and use in the manufacture of products such as lenses. This can be difficult.
  • the phosphonate-based compound may be added in an amount such that the acidity of the isocyanate composition is 500 ppm or less, and more specifically, it may be added so that the acidity of the isocyanate composition is 500 ppm or less, or 300 ppm or less, or 200 ppm or less, or 150 ppm or less, or 130 ppm or less. You can. Meanwhile, in order to fully realize the effect of increasing acidity due to the addition of the phosphonate-based compound, the phosphonate-based compound may be added so that the acidity of the isocyanate composition is 100 ppm or more, 110 ppm or more, or 113 ppm or more.
  • the acidity was specifically calculated by performing potentiometric titration on the isocyanate composition with a 0.01N potassium hydroxide (KOH) methanol solution and using the resulting measured value according to Equation 1 below.
  • KOH potassium hydroxide
  • 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
  • the phosphonate-based compound may be included in an amount of 100 to 3,000 ppm based on the total weight of the isocyanate-based compound under conditions that meet the above-mentioned acidity range.
  • the isocyanate composition exhibits an acidity within the above-described range, thereby realizing the effect of delaying the oligomerization rate within the optimal range.
  • the phosphonate-based compound is 100ppm or more, or 200ppm or more, or 300ppm or more, or 350ppm or more, or 380ppm or more, or 600ppm or more, or 900ppm or more, and 3,000ppm or less, based on the total weight of the isocyanate-based compound. , or 2000 ppm or less, or 1500 ppm or less, or 1200 ppm or less, or 1100 ppm or less.
  • the isocyanate-based compound is a monomer compound containing one or more, two or more, or two to four isocyanate groups in the molecule. More specifically, the isocyanate-based compound is a diisocyanate compound containing two isocyanate groups in the molecule.
  • diisocyanate compound examples include 1,5-pentamethylene diisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and cyclohexylene diisocyanate.
  • examples include isocyanate, isophorone diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, or p-xylylene diisocyanate, and any one or a mixture of two or more of these may be used.
  • o-xylylene diisocyanate m-xylylene diisocyanate, p-xylylene diisocyanate, or mixtures thereof may be used as the isocyanate-based compound.
  • the isocyanate composition according to the present invention may further include a phenol-based stabilizer.
  • discoloration and white turbidity in isocyanate compositions are caused not only by oligomerization of isocyanate, but also by quinoidization of the benzene ring within the molecule, or by adducts generated by oxygen, moisture, or high heat during synthesis and purification.
  • the phenol-based stabilizer can prevent coloring and whitening of the isocyanate composition by suppressing the above-mentioned side reactions through radical capture reaction.
  • the phenol-based stabilizer is included in an amount of 5 ppm to 1000 ppm based on the total weight of the isocyanate-based compound.
  • it is 5 ppm or more, or 8 ppm or more, or 10 ppm or more, and 1000 ppm or less, or 500 ppm or less, or 200 ppm or less, or 100 ppm or less, or 50 ppm or less, or 30 ppm or less, based on the total weight of the isocyanate-based compound.
  • ppm or more or 8 ppm or more, or 10 ppm or more, and 1000 ppm or less, or 500 ppm or less, or 200 ppm or less, or 100 ppm or less, or 50 ppm or less, or 30 ppm or less, based on the total weight of the isocyanate-based compound.
  • the phosphonate-based compound and the phenol-based stabilizer may be included in a weight ratio of 1.5:1 to 6:1. More specifically, it may be 1.5:1 or more, or 1.9:1 or more, or 2:1 or more, or 3:1 or more, and 6:1 or less, or 5.5:1 or less, or 4.5:1 or less. At this time, when describing the weight ratio, “above” and “below” are based on the amount of phosphonate-based compound used.
  • the phenol-based stabilizer is specifically phenol or a derivative thereof containing a phenol structure in the molecule, and specific examples include phenol; Or dibutylhydroxytoluene (BHT), t-Butylhydroquinone (TBHQ), butylhydroxyanisol (BHA), pentaerythritol tetrakis [3- (3,5-di-tert-butyl -4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by BASF), thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1035 , manufactured by BASF), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by BASF), N,N'-hexane-1,6-diyl Bis[3-(3,5-
  • phenol, dibutylhydroxytoluene, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4, 6-di-tert-pentylphenyl acrylate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 6-[3-(3-tert-butyl-4) -hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine or mixtures thereof may be used.
  • the isocyanate composition may further include an oligomer in which two or more of the above-described isocyanate-based compounds are bonded as a by-product.
  • the oligomer of the isocyanate-based compound may be a dimer in which two isocyanate-based compounds are bonded, a trimer in which three isocyanate-based compounds are bonded, 4 or more, or 4 to 10 isocyanate-based compounds bonded together.
  • the oligomer may be produced by a side reaction during the synthesis of an isocyanate-based compound by reacting an amine compound with a phosgene compound, or may be a result of a synthesized isocyanate compound forming its own polymer with high reactivity. These oligomers cause problems not only in the transparency of the isocyanate composition itself, but also in discoloration and cloudiness of the polymerization composition in which the isocyanate composition is used.
  • the isocyanate composition according to the present invention may further include the oligomers that are inevitably generated, but the transparency and color characteristics of the product can be improved while maintaining fairness by controlling the content through the manufacturing process and the use of phosphonic acid. there is.
  • the isocyanate composition may contain less than 1 area% of oligomers immediately after production.
  • the oligomer content is calculated as a percentage of the ratio of the peak area corresponding to the oligomer based on the total peak area in the molecular weight distribution curve obtained through gel permeation chromatography analysis of the isocyanate composition immediately after preparation. Additionally, the area of the peak is calculated through integration.
  • the oligomer content measurement and calculation method is as described in the experimental examples below.
  • the isocyanate composition contains a phosphonate-based compound that retards the oligomerization reaction rate of isocyanate as described above, the oligomer content and the rate of increase in oligomer content are low even after passage of time compared to the conventional method.
  • the isocyanate composition has an oligomer content increase rate of 600% or less, more specifically, 100 to 600%, or 300 to 590%, calculated according to Equation 2 below.
  • Oligomer content increase rate (%) [(C f - Ci)/Ci] ⁇ 100
  • Ci is the oligomer content (area %) in the isocyanate composition immediately after production, calculated through gel permeation chromatography analysis,
  • C f is the content (area %) of oligomers in the isocyanate composition calculated through gel permeation chromatography analysis after storing the isocyanate composition at 15°C for 8 weeks under a nitrogen atmosphere.
  • the ‘under nitrogen atmosphere’ specifically refers to the condition of 100% by volume of nitrogen based on the total volume of the atmospheric atmosphere through nitrogen filling.
  • Ci and C f are calculated values calculated according to Equation 3 below.
  • Oligomer content (area%) [E/D] ⁇ 100
  • D is the total area under the curve in the molecular weight distribution curve (GPC curve) obtained through gel permeation chromatography (GPC) analysis of the isocyanate composition
  • E is the area of the peak corresponding to the oligomer in the molecular weight distribution curve for the isocyanate composition.
  • the total area under the curve of the GPC curve for the isocyanate composition and the area of the fraction corresponding to the oligomer can each be obtained through integration.
  • the oligomer refers to a polymer with a weight average molecular weight (Mw) of 600 to 2000 g/mol, and the fraction corresponding to the oligomer in the GPC curve is 19.42 ⁇ logMw ⁇ 22.18.
  • the isocyanate composition was stored at 15°C for 8 weeks under a nitrogen atmosphere, specifically under conditions of 100% by volume of nitrogen in the atmosphere through nitrogen filling, and then the oligomer content calculated through GPC analysis, that is, GPC
  • the oligomer area ratio may be 0.5 area% or less, or 0.45 area% or less. Since a lower oligomer content means superior discoloration resistance, the lower limit is not particularly limited, but may be greater than 0 area % or greater than 0.1 area %. In the present invention, nitrogen with a purity of 99.999% was used when filling the nitrogen.
  • the content (area%) of oligomers in the isocyanate composition is determined through GPC analysis by using the logarithmic value (log M) of the weight average molecular weight (M) as the x-axis, and the molecular weight distribution for the logarithmic value (Obtain a molecular weight distribution curve (GPC curve) for the isocyanate composition with dwt/dlog M) as the y-axis, and express the area ratio of the fraction corresponding to the oligomer out of the total area of the GPC curve as a percentage, using the above equation It can be calculated according to Equation 3.
  • GPC curve molecular weight distribution curve
  • the isocyanate composition has an APHA value of 15 or less as measured according to ASTM D1209 after being stored at 15°C for 8 weeks in a nitrogen atmosphere, specifically in an atmosphere of 100% by volume nitrogen through nitrogen filling. More specifically, it is 14.5 or less, or 14 or less. Since the lower the APHA value, the better the discoloration resistance, the lower limit is not limited, but may be greater than 0 or greater than 1, for example.
  • the isocyanate composition has a haze of 0.5% or less as measured according to ASTM D1003 after being stored at 15°C for 8 weeks in a nitrogen atmosphere. More specifically, it is 0.45% or less, or 0.4% or less. Since a smaller haze value means lower white turbidity and better transparency, the lower limit is not limited, but may be, for example, more than 0%, 0.01 % or more, or 0.1 % or more.
  • the isocyanate composition does not show any cloudiness even after being stored at 15°C for 12 weeks in a nitrogen atmosphere.
  • the above isocyanate composition can be prepared by mixing an isocyanate-based compound and a phosphonate-based compound represented by Formula 1.
  • the isocyanate composition includes the steps of reacting an amine or a salt thereof with phosgene to produce an isocyanate-based compound; and mixing the isocyanate-based compound with the phosphonate-based compound represented by Formula 1.
  • the amine is an aromatic, alicyclic, or aliphatic diamine containing two amine groups in the molecule.
  • the amine is 1,3-xylylene diamine (m-xylylene diamine, m-XDA), 1,4-xylylene diamine (p-xylylene diamine, p-XDA), 1,3-bis ( It may be aminomethyl)cyclohexane, or 1,4-bis(aminomethyl)cyclohexane, and depending on the structure of the desired diisocyanate, any one or a mixture of two or more of these may be used.
  • the salt of the amine refers to a salt produced by the reaction of the amine and an acid, and may be, for example, a hydrochloride salt produced by the reaction of an amine and anhydrous hydrochloric acid, a carbonate produced by the reaction of an amine and carbonic acid, etc. While amines react rapidly with phosgene, the reaction rate can be slowed when converted to a solid salt.
  • salts of the amine include 1,3-xylylene diamine hydrochloride, 1,4-xylylene diamine hydrochloride, 1,3-bis(aminomethyl)cyclohexane hydrochloride, and 1,4-bis(aminomethyl)cyclo.
  • the preparation of the amine salt by reaction between the amine and the acid can be performed in a solvent.
  • the solvent includes aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; Chlorinated aromatic hydrocarbon solvents such as monochlorobenzene, 1,2-dichlorobenzene, and 1,4-dichlorobenzene; Chlorinated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride can be used, and two or more of these can be used in combination.
  • these solvents can also be used as solvents for the phosgenation reaction, so after obtaining an amine salt by reacting an amine with an acid in the solvent, phosgene can be added to perform the phosgenation reaction without a separate purification process.
  • the amine salt preparation may be performed at a temperature of 40°C or lower, more specifically, 5 to 30°C. Additionally, the temperature may increase during the reaction due to the heat of reaction, but it is preferable that the maximum temperature in the reactor is maintained at 90°C or lower.
  • the reaction between the amine or its salt and phosgene may be performed at a temperature range of 80°C or higher, or 90°C or higher, and 140°C or lower, or 130°C or lower. If the reaction temperature is too low, problems such as plugging may occur due to precipitation of solids, and if the temperature is too high, there may be side reaction problems such as phosgene decomposition, so it is preferable to carry out the reaction in the above temperature range.
  • reaction between the amine or its salt and phosgene may be carried out in an organic solvent.
  • the organic solvent may include at least one of an aromatic hydrocarbon-based organic solvent and an ester-based organic solvent.
  • the aromatic hydrocarbon-based organic solvent may specifically be a halogenated aromatic hydrocarbon-based organic solvent such as monochlorobenzene, 1,2-dichlorobenzene, or 1,2,4-trichlorobenzene.
  • ester-based organic solvent specifically includes amyl formate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, methylisoamyl acetate, methoxybutyl acetate, sec-hexyl acetate, 2 -Ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, ethyl acetate, butyl stearate, butyl lac.
  • fatty acid esters such as tate or amyl lactate
  • aromatic carboxylic acid esters such as metal salicylate, dimethyl phthalate, or methyl benzoate.
  • the organic solvent includes at least one of aromatic hydrocarbon-based organic solvents and ester-based organic solvents having a boiling point of 100°C or higher, or 100 to 200°C, among the aromatic hydrocarbon-based organic solvents and ester-based organic solvents. It may be.
  • the amine or its salt may be used at a concentration of 20% by volume or less, for example, 1 to 20% by volume, or 5 to 20% by volume.
  • concentration of amine or its salt exceeds 20% by volume, there is a risk that a large amount of amine salt may precipitate.
  • R 1 to R 4 are each independently a substituted or unsubstituted C 1-12 alkyl group, a substituted or unsubstituted C 3-12 cycloalkyl group, or a substituted or unsubstituted C 6-12 aryl group,
  • X is hydrogen, hydroxy or acetamido
  • Y is oxyl, substituted or unsubstituted C 1-12 alkoxy, or substituted or unsubstituted C 6-12 aryloxy.
  • the compound represented by Formula 2 promotes the forward reaction by eliminating hydrogen from carbamoyl chloride, an amine or intermediate product during the phosgenation reaction, and suppresses side reactions, thereby producing by-products ethylbenzyl isocyanate (EBI) and chloromethylbenzyl isocyanate (CMBI). It plays a role in suppressing the generation of monoisocyanates such as
  • R 1 to R 4 are each independently C 1-12 alkyl
  • X is hydrogen, hydroxy group or acetamido group
  • Y is oxyl It may be a (O ⁇ ) compound.
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
  • 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4- Hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl; hereinafter referred to as 4-hydroxy TEMPO)
  • 4-acetamido-2,2,6,6-tetramethylpiperidin 1-oxyl Any one or a mixture of two or more of these may be used.
  • the compound represented by Formula 2 may be used in an amount of 0.05 to 2 moles based on 100 moles of the amine or its salt. More specifically, it may be used in a ratio of 0.05 mol or more, or 0.1 mol or more, or 0.15 mol or more, and 2 mol or less, or 1 mol or less, or 0.8 mol or less. When used in the above content range, it is preferable because the generation of oligomers of diisocyanate is minimized and diisocyanate can be synthesized with high purity and high yield.
  • the isocyanate formed as a result of the above-described phosgenation reaction is obtained as a mixture of solvent, unreacted phosgene, and by-products mixed together with hydrogen chloride. Accordingly, a purification process, distillation, to separate the isocyanate compound from the reaction mixture with high purity
  • One or more of the solvent removal process through, nitrogen bubbling of unreacted phosgene and hydrogen chloride gas, etc. may be performed.
  • the purification step may be performed by a conventional method used for purifying isocyanate compounds, for example, by reduced pressure distillation and/or thin film distillation.
  • the purification step is preferably performed at a temperature of 100 to 170° C. for 5 to 16 hours. If the maximum temperature of the purification step exceeds 170°C or the residence time of the purification step exceeds 16 hours, the prepared isocyanate may absorb excessive heat and lower stability.
  • the obtained isocyanate compound is mixed with the phosphonate-based compound represented by Chemical Formula 1 to prepare an isocyanate composition.
  • the mixing process can be performed according to a conventional method, and the type and amount of the phosphonate-based compound to be mixed are as described above.
  • additional additives used in the isocyanate composition may be added.
  • a phenol-based stabilizer may be further added to improve the storage stability of the isocyanate composition.
  • the type and amount of the phenolic stabilizer used are the same as previously described.
  • the isocyanate composition prepared by the production method of the present invention described above has excellent storage stability and high transparency, it can be suitably used as a polymerization composition for manufacturing optical articles.
  • a composition for polymerization containing the above-described isocyanate composition and at least one of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, and a polyfunctional episulfide-based compound is provided.
  • the composition for polymerization may include the isocyanate composition and any one or more of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, and a polyfunctional episulfide-based compound in a mixed state, or may be included in a state separated from each other. You may. That is, in the polymerization composition, the isocyanate composition and the polyfunctional thiol-based compound, polyfunctional alcohol-based compound, or polyfunctional episulfide-based compound are blended in contact with each other, or are separated so as not to contact each other. It can be.
  • the polyfunctional thiol-based compound is a compound containing two or more thiol groups (-SH) in one molecule, specifically, two or more, three or more, and eight or less in the molecule. Alternatively, it may be a compound having 5 or less thiol groups.
  • the polyfunctional thiol-based compound is, for example, 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol. , 1,9-dimercapto-3,7-dithianonane (1,9-dimercapto-3,7-dithianonane), 1,13-dimercapto-3,7,11-trithiatridecane (1 ,13-dimercapto-3,7,11-trithiatridecane), glycol di(3-mercaptopropionate), 1,4-dithiane-2,5-diylmethanethiol (1,4-Dithiane-2,5-diyldimethanethiol), 2-mercaptomethyl-1,5-dimercapto-3-thiapentane (2-mercaptomethyl-1,5-dimercapto-3-thiapentane), trimethylol Propane tri(3-mercaptopropionate) (trimethyl
  • the polyfunctional alcohol-based compound is a compound containing two or more hydroxy groups in one molecule, specifically, a compound having two or more, or three or more, eight or fewer, or four or fewer hydroxy groups in the molecule. It can be. Specific examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 2-methyl-2,3-butanediol, and 1,6-hexanediol.
  • dihydric alcohols such as , 1,2-hexanediol, etc.
  • Trihydric alcohols such as glycerol, trimethylolethane, and trimethylolpropane (TMP); tetrahydric alcohols such as diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.
  • Pentahydric alcohols such as L-arabinitol, ribitol, and xylitol
  • Hexahydric alcohols such as D-glucitol, D-mannitol, and galactitol, and heptahydric alcohols such as trehalose
  • Examples include octahydric alcohols such as sucrose and maltose, or low molecular weight polyols, and any one or a mixture of two or more of these can be used.
  • the multifunctional episulfide-based compound may be a compound containing two or more episulfide groups, that is, a thioepoxy group, in the molecule, and may have an aliphatic, alicyclic, or aromatic skeleton.
  • Specific examples include bis( ⁇ -epithiopropylthio)methane, 1,2-bis( ⁇ -epithiopropylthio)ethane, 1,3-bis( ⁇ -epithiopropylthio)propane, 1,2-bis( ⁇ -epithiopropylthio)propane, 1-( ⁇ -epithiopropylthio)-2-( ⁇ -epithiopropylthiomethyl)propane, 1,4-bis( ⁇ -epithiopropylthio)butane, 1, 3-bis( ⁇ -epithiopropylthio)butane, 1-( ⁇ -epithiopropylthio)-3-( ⁇ -epithiopropylthiomethyl)butane, 1,5-bis( ⁇ -epithiopropylthio) Pentane, 1-( ⁇ -epithiopropylthio)-4-( ⁇ -epithiopropylthio
  • the molar ratio of functional groups such as thiol groups, hydroxy groups, or episulfide groups to isocyanate groups may be 0.5 to 1.5, or 0.8 to 1.2, or 0.9 to 1.1, but the present invention is not necessarily limited thereto. no.
  • the polymerization composition may further include additives such as an internal mold release agent, ultraviolet absorber, urethane reaction catalyst, polymerization initiator, heat stabilizer, color corrector, chain extender, cross-linking agent, light stabilizer, filler, and photosensitizer, if necessary.
  • additives such as an internal mold release agent, ultraviolet absorber, urethane reaction catalyst, polymerization initiator, heat stabilizer, color corrector, chain extender, cross-linking agent, light stabilizer, filler, and photosensitizer, if necessary.
  • the content can be appropriately determined within a range that does not impair the discoloration and discoloration inhibition properties of the composition.
  • the polymerization composition may further include an internal mold release agent to improve release properties from the mold during subsequent product molding.
  • the internal release agent specifically includes a phosphate release agent, an alkyl phosphate release agent, a fatty acid ester release agent, etc., and any one or a mixture of two or more of these may be used.
  • a phosphoric acid ester-based mold release agent may be preferably used.
  • phosphoric acid ester-based mold release agent products such as ZELEC UNTM (manufactured by Stepan Company) can be obtained commercially and used.
  • the internal release agent may be included in an amount of 0.01% by weight or more, or 0.05% by weight or more, and 10% by weight or less, or 5% by weight or less, based on the total weight of the polymerization composition.
  • the polymerization composition may further include an ultraviolet absorber.
  • the UV absorber specifically includes a benzotriazole-based UV absorber and a formamidine-based UV absorber, and any one or a mixture of two or more of these may be used. Among these, a formamidine-based ultraviolet absorber can be preferably used.
  • the formamidine-based ultraviolet absorbers include Zikasorb R, Zikasorb BS, ZIKA-FA02, ZIKA-FUA, ZIKA-FLS', ZIKA-UVS3, and ZIKA-UVS4 (manufactured by ZIKO); Products such as Biosorb 583 (manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.) can also be obtained and used commercially.
  • the ultraviolet absorber may be included in an amount of 0.01% by weight or more, or 0.05% by weight or more, and 0.1% by weight or less, or 0.08% by weight or less, based on the total weight of the polymerization composition.
  • the urethane reaction catalyst includes dialkyl tin halide 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; Alternatively, dialkyl tin sulfide-based compounds may be used, and any one or a mixture of two or more of these may be used.
  • the urethane reaction catalyst is present in an amount of 0.001% by weight or more, or 0.002% by weight or more, or 0.004% by weight or more, and 0.1% by weight or less, or 0.05% by weight or less, or 0.01% by weight or less, or 0.008% by weight, based on the total weight of the polymerization composition. It may be included in an amount of less than %.
  • the polymerization composition described above can exhibit excellent discoloration resistance by delaying or suppressing the reaction rate and oligomerization of isocyanate due to the phosphonate-based compound contained in the isocyanate composition, and various substances used to improve workability when manufacturing lenses. Lens color discoloration due to additives can be prevented, and the increase in viscosity of the polymerization composition is suppressed, thereby improving workability, such as reducing filter time during product manufacturing.
  • the polymerization composition can be used in a wide range of fields due to its excellent physical properties, and can be used in applications that require excellent appearance properties, especially transparency, such as optical adhesives, optical adhesives, spectacle lenses, camera lenses, plastic lenses, and prisms. It is useful as a material for optical products.
  • the isocyanate composition in the polymerization composition described above An article containing a polymer obtained by polymerizing at least one of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, and a polyfunctional episulfide is provided.
  • the polymerization reaction consists of a urethanization reaction between the isocyanate group in the isocyanate compound and the thiol group in the polyfunctional thiol-based compound.
  • polyurethane produced by reaction with a polyfunctional thiol-based compound exhibits excellent transparency and is therefore particularly useful in the production of optical products, especially optical lenses such as spectacle lenses and camera lenses.
  • the polymerization reaction consists of a urethanation reaction (or condensation polymerization reaction) between an isocyanate in an aromatic diisocyanate and a hydroxy group in the polyfunctional alcohol.
  • a urethanation reaction or condensation polymerization reaction
  • polyurethane produced by reaction with a polyfunctional alcohol-based compound exhibits excellent transparency and excellent adhesive/adhesive properties, so it can be useful as an optical adhesive or optical adhesive.
  • the polymerization reaction may be performed under normal pressure conditions and an inert gas atmosphere such as nitrogen or argon.
  • the polymerization reaction is carried out at a temperature range of -15°C or higher, or 0°C or higher, and 150°C or lower, or 120°C or lower, so that the reaction rate can be easily controlled without concern about discoloration, and reaction efficiency It is also desirable because it can be increased.
  • the polymerization reaction may be performed under catalyst-free conditions, or may be performed in the presence of a urethanization reaction catalyst as described above.
  • the catalyst may be added when mixing a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, or a polyfunctional episulfide-based compound with the isocyanate composition.
  • the progress of the polymerization reaction can be predicted by measuring the concentration of isocyanate groups in the polymerization reaction product or measuring the refractive index using the n-dibutyl amine method using a potentiometric titration device.
  • the isocyanate group in the polymerization reaction product can be predicted. This can be carried out until the concentration of the group reaches the calculated value of the isocyanate group remaining after reaction with the polyfunctional thiol-based compound.
  • articles containing the polymer include, specifically, paints such as paints for plastics or paints for automobiles; Coating agents such as film coating agents; various inks; Sealing material; various microcapsules; Artificial leather, such as artificial and synthetic leather; Reaction injection molding (RIM) products; slush powder; Elastic molded articles (spandex); urethane foam; Alternatively, it may be an optical product such as an optical adhesive, an optical adhesive, a spectacle lens, a camera lens, a plastic lens, or a prism. Considering the excellent transparency of the polymerization composition, it may be an optical article, especially an optical adhesive or optical adhesive, or an optical lens such as a spectacle lens or a camera lens.
  • the article may be manufactured by performing a molding process after the polymerization reaction in the polymerization composition described above, or may be manufactured through a molding process using the polymerization composition. In the latter case, the polymerization reaction occurs simultaneously during the molding process.
  • the polymerization composition is injected into a lens mold, then the temperature of the mold is raised to perform a polymerization reaction between the isocyanate-based compound and the polyfunctional thiol-based compound or polyfunctional episulfide-based compound. . At this time, the mold is heated to the temperature range where the urethane polymerization reaction occurs, as described above. After the polymerization reaction is completed, the prepared polymer, specifically polythiourethane, can be separated from the mold to obtain an optical lens.
  • the polymer prepared from the composition for polymerization according to the present invention specifically polythiourethane, exhibits excellent transparency and improved workability, and is therefore particularly useful in the production of optical articles, especially optical point/adhesives or optical lenses. .
  • an optical lens containing a polymer prepared from the composition for polymerization according to the present invention exhibits a YI value of 1.6 or less, or 1.5 or less, when measured according to ASTM E313. Since a lower YI value means superior discoloration resistance, the lower limit is not particularly limited, but may specifically be greater than 0 or greater than 0.1.
  • 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 to ensure that the reaction solution became transparent. After the solution became transparent, the inside of the reactor was cooled to 80°C, nitrogen was blown in, and phosgene was discharged and removed. 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 m-xylylene diisocyanate (m-XDI).
  • m-XDI m-xylylene diisocyanate
  • An isocyanate composition was prepared by adding 380 ppm of ethyl methylphosphonate (boiling point: 181°C) to the m-XDI and mixing.
  • An isocyanate composition was prepared in the same manner as in Example 1-1, except that 900 ppm of Mono-2-ethylhexyl(2-Ethylhexyl)phosphonate was added instead of Ethyl methylphosphonate.
  • An isocyanate composition was prepared in the same manner as in Example 1-1, except that 1100 ppm of Monoethyl 3,5-Di-tert-butyl-4-hydroxybenzylphosphonate was added instead of Ethyl methylphosphonate.
  • An isocyanate composition was prepared in the same manner as in Example 1-1, except that 600 ppm of pinacolyl methylphosphonate was added instead of ethyl methylphosphonate.
  • An isocyanate composition was prepared in the same manner as in Example 1-1, except that 380 ppm of ethyl methylphosphonate and 200 ppm of phenol were added to m-XDI.
  • An isocyanate composition was prepared in the same manner as in Example 1-2, except that 900 ppm of Mono-2-ethylhexyl(2-Ethylhexyl)phosphonate and 200 ppm of phenol were added to m-XDI. Manufactured.
  • Example 1-3 The same method as in Example 1-3 was carried out except that 200 ppm of phenol was added along with 1100 ppm of Monoethyl 3,5-Di-tert-butyl-4-hydroxybenzylphosphonate to m-XDI. An isocyanate composition was prepared.
  • An isocyanate composition was prepared in the same manner as in Example 1-4, except that 600 ppm of pinacolyl methylphosphonate and 200 ppm of phenol were added to m-XDI.
  • An isocyanate composition was prepared in the same manner as in Example 1-1, except that ethyl methylphosphonate was not added in Example 1-1.
  • An isocyanate composition was prepared in the same manner as in Example 1-1, except that ethyl methylphosphonate was not added and 200 ppm of phenol was added.
  • An isocyanate composition was prepared in the same manner as in Example 1-1, except that 250 ppm of ZELECTM UN (manufactured by Stepan Company), a phosphoric acid ester compound, was added instead of ethyl methylphosphonate. did.
  • An isocyanate composition was prepared in the same manner as in Example 1-1, except that 250 ppm of Bis (2-ethylhexyl) phosphate, a phosphoric acid ester compound, was added instead of ethyl methylphosphonate. .
  • An isocyanate composition was prepared in the same manner as in Example 1-1, except that 250 ppm of phosphoric acid was added instead of ethyl methylphosphonate.
  • An isocyanate composition was prepared in the same manner as in Example 1-1, except that 250 ppm of Ethyl Phosphate (mono and di ester mixture) (DEP) was added instead of Ethyl methylphosphonate. .
  • Ethyl Phosphate mono and di ester mixture
  • the polymerization composition prepared above was filtered through a 1 ⁇ m PTFE filter and then injected into a mold consisting of a glass mold and tape. This mold was placed in an oven and the temperature was gradually raised from 10°C to 120°C, and a polymerization reaction was performed for 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.
  • the polymerization composition and A lens was manufactured.
  • the isocyanate composition of Comparative Example 1-5 was not suitable for producing a polymerization composition due to the generation of precipitates, so the production of the composition for polymerization and the production of lenses were not carried out.
  • the acidity of the isocyanate compositions prepared in the above examples and comparative examples was measured by the following method.
  • 1.2 n-Propyl Alcohol Use diluted hydrochloric acid solution by first adjusting the pH to 4 ⁇ 4.5.
  • Apparent acidity occurs between pH 5.5 and 7.0.
  • 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.
  • the isocyanate composition of Comparative Example 1-1 in which no additives capable of providing a free acid component by reacting with alcohol were added when preparing the isocyanate composition, showed low acidity.
  • Comparative Examples 1-3 in which a commercially available phosphoric acid ester compound was added at the same level as in the Examples when preparing the isocyanate composition, also showed low acidity.
  • the isocyanate composition prepared in the above examples and comparative examples was refrigerated and stored at a temperature of 15°C for 8 weeks under a nitrogen atmosphere, specifically, 100% by volume of nitrogen in the atmosphere filled with nitrogen with a purity of 99.999%, and stored over time.
  • the increase in oligomer content in the isocyanate composition was confirmed, and storage stability was evaluated from the results.
  • the oligomer content (area%) in the isocyanate composition was determined by performing gel permeation chromatography (GPC) analysis on the isocyanate composition according to the following conditions, and measuring the molecular weight distribution curve (GPC curve) for the isocyanate composition (x-axis: weight) Obtain the log value (log M) of the average molecular weight (M), Y axis: molecular weight distribution (dwt/dlog M) for the log value, and calculate the area of the fraction corresponding to the oligomer out of the total area of the GPC curve as a percentage. indicated. Specifically, the oligomer content (area%) was calculated according to Equation 3 below.
  • Oligomer content (area%) [E/D] ⁇ 100
  • D is the total area under the curve in the molecular weight distribution curve (GPC curve) obtained through gel permeation chromatography analysis of the isocyanate composition
  • E 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.
  • the oligomer refers to a polymer with a weight average molecular weight (Mw) of 600 to 2000 g/mol, and the fraction corresponding to the oligomer in the GPC curve is 19.42 ⁇ logMw ⁇ 22.18.
  • Oligomer content increase rate (%) [(C f - Ci)/Ci] ⁇ 100
  • Ci is the oligomer content (area %) in the isocyanate composition immediately after production
  • C f is the content (area %) of oligomers in the isocyanate composition when the isocyanate composition is stored for 8 weeks at 15°C in a nitrogen atmosphere, specifically in an atmosphere of 100% by volume nitrogen filled with 99.999% purity nitrogen,
  • Ci and C f are each calculated values according to Equation 3 above.
  • the oligomer content increased over time, and the rate of increase in oligomer content varied depending on the type of additive. Specifically, the increase rate of oligomer content over time in Examples was lower than that in Comparative Examples.
  • the isocyanate composition prepared in the above examples and comparative examples was refrigerated and stored at a temperature of 15°C for 12 weeks in a nitrogen atmosphere, specifically an atmosphere of 100% by volume nitrogen filled with nitrogen with a purity of 99.999%, to determine whether white turbidity occurred. was confirmed visually.
  • the observation results were evaluated according to the following criteria and are shown in Table 3.
  • the isocyanate compositions prepared in the above examples and comparative examples were refrigerated and stored at 15°C for 8 weeks under a nitrogen atmosphere, and then haze was measured according to ASTM D1003.
  • the isocyanate compositions prepared in the above examples and comparative examples were refrigerated and stored at a temperature of 15°C in a nitrogen atmosphere for 8 weeks, and then APHA was measured under the following measurement conditions according to the method of ASTM D1209 using HunterLab's Ultrascan Pro. The results are shown in Table 3 below. The smaller the APHA value, the better the discoloration resistance.
  • the isocyanate composition of the example did not exhibit white clouding, and also showed an improved effect compared to the comparative example in terms of discoloration resistance.
  • 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 ⁇ m, and the From the results, the effect of improving workability was evaluated.
  • Filtration time refers to the time from when 200 g of the polymerization composition passes through the filter to when the passage is completed.
  • Example 2-1 in which the phosphonate-based compound of Chemical Formula 1 was added when preparing the isocyanate composition, showed a significantly shorter filtration time compared to the comparative example, resulting in improved workability. Confirmed to have it.
  • YI Yellowness Index
  • the isocyanate composition of Comparative Example 1-3 had an increased viscosity, making it difficult to manufacture a composition for polymerization, and as a result, a lens could not be manufactured.
  • the isocyanate composition of Comparative Example 1-5 was not suitable for producing a composition for polymerization due to the generation of precipitates, so lens production was not carried out.
  • the manufactured lenses were visually checked for defects and evaluated according to the following standards.
  • the lens manufactured using the polymerization composition of the example showed a lower YI value compared to the comparative example, and thus had a better discoloration inhibition effect.
  • the lenses of Comparative Examples 2-4 and 2-6 using phosphate-based compounds showed high YI, and in particular, the lenses of Comparative Example 2-4 using Bis(2-ethylhexyl) phosphate showed defects. occurred.
  • the release property was evaluated according to the following criteria based on the degree of difficulty in separating the lens from the lens mold by hand, and the results are shown in Table 6.
  • ⁇ Difficulty in mold release. Force must be applied and does not release easily.

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Abstract

La présente invention concerne une composition d'isocyanate comprenant un composé à base de phosphonate d'une structure spécifique conjointement avec un composé à base d'isocyanate pour améliorer la stabilité au stockage et par conséquent supprimer la décoloration et le phénomène de turbidité blanche, améliorer la maniabilité telle qu'un temps de filtration réduit, et augmenter la résistance à la décoloration lorsqu'elle est utilisée dans des produits.
PCT/KR2023/015727 2022-10-26 2023-10-12 Composition d'isocyanate WO2024090855A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6474204A (en) * 1987-09-14 1989-03-20 Tokuyama Soda Kk Manufacture of liquid prepolymer
US20020050587A1 (en) * 2000-08-25 2002-05-02 Kureha Kagaku Kogyo Kabushiki Kaisha Optical material
US20100041810A1 (en) * 2006-11-22 2010-02-18 Kaneka Corporation Curable composition and catalyst composition
KR20170030808A (ko) * 2015-09-10 2017-03-20 동우 화인켐 주식회사 하드코팅 조성물 및 이를 이용한 하드코팅 필름
KR20210023483A (ko) * 2019-08-23 2021-03-04 한화솔루션 주식회사 폴리이소시아네이트 조성물의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6474204A (en) * 1987-09-14 1989-03-20 Tokuyama Soda Kk Manufacture of liquid prepolymer
US20020050587A1 (en) * 2000-08-25 2002-05-02 Kureha Kagaku Kogyo Kabushiki Kaisha Optical material
US20100041810A1 (en) * 2006-11-22 2010-02-18 Kaneka Corporation Curable composition and catalyst composition
KR20170030808A (ko) * 2015-09-10 2017-03-20 동우 화인켐 주식회사 하드코팅 조성물 및 이를 이용한 하드코팅 필름
KR20210023483A (ko) * 2019-08-23 2021-03-04 한화솔루션 주식회사 폴리이소시아네이트 조성물의 제조방법

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