Xylylene diisocyanate composition and non-foam resin comprising same

Abstract

The present invention relates to a xylylene diisocyanate composition and, more specifically, to a xylylene diisocyanate composition and a non-foam resin comprising same, wherein the composition, due to improved storage stability, exhibits no deterioration in its properties, such as yellow index and haze value, even during long-term storage, and resins and lenses manufactured from the corresponding composition are excellent in terms of optical stability, thermal stability, and strength, thereby not being easily damaged or scratched.

Description

Xylylene diisocyanate composition and non-foam resin comprising the same

[0001] The present invention relates to a xylylene diisocyanate composition, and more specifically, to a xylylene diisocyanate composition having improved storage stability so that the physical properties of the composition, such as yellowness and haze value, do not deteriorate even after long-term storage, and excellent optical stability, thermal stability and strength of a resin and a lens manufactured from the composition, so that the resin and the lens manufactured from the composition are not easily damaged or scratched, and a non-foam resin comprising the same.

[0002]

[0003] Xylylene diisocyanate (XDI) is widely used as a raw material for manufacturing polyurethane resins. For example, xylylene diisocyanate compounds are used for manufacturing optical lenses using polyurethane resins, and the physical properties of the xylylene diisocyanate compounds as a raw material for manufacturing can affect the optical properties of the optical lenses, such as transparency and refractive index.

[0004] For example, a polythiourethane resin manufactured by reacting a polythiol compound and a diisocyanate compound can be utilized as a base material of the optical lens.

[0005] These xylylene diisocyanates are widely used in various fields considering their chemical and optical properties such as reactivity and transparency.

[0006] However, xylylene diisocyanate has high reactivity due to the benzene, an electron-withdrawing group, increasing the reactivity of NCO in the molecule, which makes it prone to self-polymerization and side reactions during storage. In particular, the oxidation reaction of the xylylene diisocyanate composition is a representative side reaction, and due to impurities created by the oxidation reaction of xylylene diisocyanate, a yellowing phenomenon in which the yellowness index (YI) of the resin produced with the composition increases may occur.

[0007] In addition, impurities formed by the oxidation reaction also have the problem of weakening the physical properties of the resin and lens, such as increasing the Haze value of the resin and lens manufactured with the composition and reducing the clarity. To solve this problem, there have been attempts to increase the storage stability by including various additives in xylylene diisocyanate. For example, U.S. Patent No. US3715381A discloses 2,6-Di-tert-butyl-4-methylphenol (BHT) as a xylylene diisocyanate stabilizer, but the additives presented above do not have a good stabilizing effect on XDI, so there is still a problem that it is difficult to stably store XDI for more than one month at room temperature, and other stabilizers also have problems such as being easily oxidized or discolored when exposed to air.

[0008] In addition, in the case of existing compositions, there was also a problem that the lenses manufactured from them lacked thermal stability and strength, and were easily damaged or easily scratched by external friction.

[0009] Accordingly, compared to existing additives, the effect of preventing oxidation of xylylene diisocyanate and increasing the storage stability of the composition is excellent, so that even when the composition is stored for a long period of time, the increase in yellowness and haze value of the resin including the composition is minimized, and at the same time, the strength and thermal stability of the lens are excellent, so that it is not easily damaged or scratched by external stimuli, and there is a need for the development of a xylylene diisocyanate composition with excellent physical properties.

[0010]

[0011] [Prior Art Literature]

[0012] [Patent Document]

[0013] (Patent Document 1) U.S. Patent US3715381A

[0014]

[0015] The present invention has been proposed to solve the above problems, and its purpose is to provide a xylylene diisocyanate composition having excellent storage stability, such as minimizing changes in its physical properties even when the xylylene diisocyanate composition is stored at room temperature for a long period of time, and a non-foam resin comprising the same.

[0016] In addition, the present invention has been proposed to solve the above problems, and the purpose is to provide a xylylene diisocyanate composition and a non-foam resin comprising the same, which have excellent optical stability, such as the yellowness and haze values ​​of a resin and a lens manufactured from the composition not increasing even when the storage period of the composition is long, and are also excellent in terms of heat stability and strength, so that they are not easily damaged and are not easily scratched.

[0017]

[0018] In order to solve the above-described problem, the present invention,

[0019] A xylylene diisocyanate composition having excellent storage stability comprising xylylene diisocyanate and a compound of chemical formula 1 is provided.

[0020] <Chemical Formula 1>

[0021]

[0022] Additionally, the xylylene diisocyanate composition may further include phenol.

[0023] Additionally, the weight of the compound of the above chemical formula 1 relative to the total weight of the above xylylene diisocyanate composition may be 50 to 400 ppm.

[0024] In addition, in order to solve the above-described problem, the present invention provides a non-foam resin comprising a xylylene diisocyanate composition according to claim 1.

[0025] Additionally, the non-foam resin may further include an active hydrogen group-containing component.

[0026] In addition, the active hydrogen group-containing component may be at least one selected from the group consisting of a polyol component, a polythiol component, and a polyamine component.

[0027] Additionally, the non-foam resin may be used as one or more selected from the group consisting of a coating, an adhesive, a sealant, and an elastomer.

[0028] In addition, in order to solve the above-described problem, the present invention provides a molded article including the non-foam resin.

[0029] In addition, in order to solve the above-described problem, the present invention provides an optical element including the molded body.

[0030] In addition, in order to solve the above-described problem, the present invention provides a lens including the optical element.

[0031] In addition, in order to solve the above-described problem, the present invention provides a method for producing a non-foam resin, including the steps of: forming a mixture by mixing the composition and an active hydrogen group-containing component; and raising the temperature of the mixture to perform a polymerization reaction and converting the compound of the chemical formula 1 into a compound of the following chemical formula 2.

[0032] <Chemical Formula 2>

[0033]

[0034] Additionally, the above heating process may be performed at 100 to 150˚C.

[0035]

[0036] The xylylene diisocyanate composition according to the present invention is superior in terms of storage stability, as oxidation is prevented during storage of the xylylene diisocyanate composition, compared to conventional xylylene diisocyanate compositions.

[0037] In addition, the present invention has excellent optical stability, such that the yellowness and haze values ​​of the resin and lens manufactured from the composition do not increase even when the storage period of the composition is long, and is also excellent in terms of thermal stability and strength, so that it is not easily damaged or scratched.

[0038]

[0039] Figures 1a, 1b, and 1c respectively show the gas chromatography analysis results for Example 1, Figure 1b shows the gas chromatography analysis results for Comparative Example 1, and Figure 1c shows the gas chromatography analysis results for Comparative Example 2.

[0040] Figures 2a, 2b, and 2c respectively show the gel permeation chromatography analysis results for Example 1, Figure 2b shows the gel permeation chromatography analysis results for Comparative Example 1, and Figure 2c shows the gel permeation chromatography analysis results for Comparative Example 2.

[0041]

[0042] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the invention. The present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0043]

[0044] As described above, additives added to conventional xylylene diisocyanate compositions have problems in that they do not have a sufficient effect on increasing the storage stability of xylylene diisocyanate, making it impossible to store the composition for a long period of time, are easily oxidized upon contact with air, or are insufficient in preventing yellowing and increasing the strength of a resin including the xylylene diisocyanate composition, and thus do not properly perform their roles as additives.

[0045] Accordingly, the present invention sought to solve the above-described problem by adding a compound of the following chemical formula 1 to a xylylene diisocyanate composition. This composition is superior in terms of storage stability, such that its physical properties do not change significantly even over a long storage period due to the prevention of oxidation reactions compared to conventional additives.

[0046] In addition, the optical stability and strength of the resin and lens manufactured with the composition are greatly improved, so that the transparency of the lens is very excellent, and it also has a lower yellowness and haze value than conventional lenses, and is not easily damaged or scratched by external stimuli, which is very excellent.

[0047] <Chemical Formula 1>

[0048]

[0049]

[0050] Specifically, the xylylene diisocyanate composition provided by the present invention will be described.

[0051] The xylylene diisocyanate composition of the present invention is defined as a xylylene diisocyanate composition in that it is a compound having xylylene diisocyanate as a main component and includes the compound of the above chemical formula 1 as an additive.

[0052] The above xylylene diisocyanate may include at least one selected from the group consisting of o-xylylene diisocyanate, m-xylylene diisocyanate, and p-xylylene diisocyanate, and preferably m-xylylene diisocyanate.

[0053]

[0054] The above xylylene diisocyanate is a main component of a xylylene diisocyanate composition, and the xylylene diisocyanate composition may typically include some impurities known to be included in a xylylene diisocyanate composition.

[0055] The above xylylene diisocyanate can be manufactured by a commonly known manufacturing method.

[0056] Specifically, xylylene diisocyanate can be produced by the following phosgenation method.

[0057] First, it includes a step of reacting an amine compound with phosgene in a solvent to obtain a reaction mixture containing a xylylene diisocyanate compound.

[0058] Solvents that can be used in the above phosgenation reaction include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; chlorinated aromatic hydrocarbon solvents such as monochlorobenzene, 1,2-dichlorobenzene, and 1,4-dichlorobenzene; and chlorinated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride. Two or more of these can be used in combination.

[0059] The amine compound used in the above phosgenation reaction may be at least one selected from the group consisting of m-xylylene diamine, p-xylylene diamine, o-xylylene diamine, and salts thereof, and preferably, m-xylylene diamine or a salt thereof.

[0060] The above amine compound may be included in an amount of 1 to 20 parts by weight per 100 parts by weight of the solvent. If the content of the amine compound exceeds 20 parts by weight, there is a risk of precipitation of a large amount of the amine compound. Preferably, the content may be included in an amount of 1 to 15 parts by weight, and more preferably, in an amount of 3 to 10 parts by weight.

[0061] Specifically, the phosgenation reaction can be carried out by a direct phosgenation method (Method 1) in which an amine compound is directly reacted with phosgene; a method in which an amine compound is reacted with anhydrous hydrochloric acid to form an amine-hydrochloride compound and then the formed salt is reacted with phosgene (Method 2); or a method in which an amine compound is reacted with carbonic acid to form an aliphatic amine-carbonate compound and then the formed salt is reacted with phosgene (Method 3).

[0062] The direct phosgenation method of the above method 1 can be performed by reacting an amine compound and phosgene in the above organic solvent. At this time, the phosgene can be introduced all at once at the beginning of the reaction, or can be introduced in part at the beginning of the reaction and the remainder can be introduced in installments during the reaction.

[0063] Meanwhile, the above method 1 can be performed by a first step of dissolving a portion of phosgene in the solvent and then adding the amine compound; and a second step of adding the remaining phosgene after the addition of the amine compound is complete and causing a reaction. At this time, the first step is preferably performed at a temperature of -15˚C to -10˚C to prevent leakage of highly toxic phosgene and also to prevent rapid heat generation when the amine compound is added, and the phosgenation reaction in the second step can be controlled to 120˚C to 140˚C so that the reaction can occur at an appropriate reaction rate without concern for decomposition of the amine compound.

[0064] In the case of the above method 2, it can be carried out by a step of reacting an amine compound with hydrochloric acid in an organic solvent to form an amine-hydrochloride compound, and then introducing phosgene to cause the reaction. The formation of the amine-hydrochloride compound can be carried out at a temperature of 30˚C or lower, preferably about 23±5˚C, and the reaction after the introduction of phosgene can be controlled to 120˚C to 140˚C. When carried out under such temperature conditions, the solubility of the amine-hydrochloride compound is increased, and thermal decomposition of xylylene diisocyanate is prevented, thereby producing a high-purity xylylene diisocyanate compound in high yield.

[0065] In the case of the above method 3, it can be carried out by a step of reacting an amine compound with carbonic acid in a solvent to form an amine-carbonate compound, and then introducing phosgene to cause the reaction. At this time, the formation of the amine-carbonate compound can be carried out at a temperature of 30˚C or lower, preferably about 23±5˚C, and the reaction after the introduction of phosgene can be controlled to 80˚C to 180˚C. Preferably, it can be in the range of 100˚C or higher, or 120˚C or higher, and 150˚C or lower, or 140˚C or lower. When carried out under such temperature conditions, the solubility of the amine-carbonate compound is increased, and thermal decomposition of xylylene diisocyanate is prevented, thereby producing a high-purity xylylene diisocyanate compound in a high yield.

[0066] After the reaction with phosgene is completed according to each method, a removal process such as nitrogen bubbling for unreacted phosgene and hydrogen chloride gas and a solvent removal process such as distillation may be optionally further performed, and these processes may be performed according to a conventional method.

[0067]

[0068] Hereinafter, the compound of the above chemical formula 1 will be described in detail.

[0069] <Chemical Formula 1>

[0070]

[0071]

[0072] The compound of the above chemical formula 1 can prevent oxidation of the composition by being included in the xylylene diisocyanate composition, thereby increasing storage stability.

[0073] More specifically, in the xylylene diisocyanate composition containing the compound of the above chemical formula 1, the compound of the above chemical formula 1 contained in the composition can undergo an oxidation reaction as shown in the following reaction formula (1) to form a compound of the above chemical formula 2.

[0074] <Reaction formula (1)>

[0075]

[0076] [Chemical Formula 1] [Chemical Formula 2]

[0077] For example, the oxidation process of the above reaction formula (1) may be a reaction of the compound of chemical formula 1 included in the xylylene diisocyanate composition with oxygen in the air.

[0078] In the case of conventional xylylene diisocyanate compositions, various unintended by-products are formed due to the oxidation reaction of xylylene diisocyanate, and these by-products increase the yellowness and haze value of the composition. This effect increases as the storage period increases, so there was a problem that it was very disadvantageous in terms of storage stability.

[0079] Accordingly, according to the present invention, when the compound of the chemical formula 1 is added to the xylylene diisocyanate composition, the compound of the chemical formula 1 is oxidized instead of xylylene diisocyanate according to the reaction formula (1), so that the increase in yellowness and Haze value caused by oxidation of the xylylene diisocyanate composition described above is minimized, and thus the storage stability is excellent.

[0080] In addition, the compound of the chemical formula 2 formed by the reaction formula (1) does not exhibit a specific color even when included in a xylylene diisocyanate composition, and thus does not increase the yellowness value of the xylylene diisocyanate composition, nor does it increase the Haze value, so even if the compound of the chemical formula 1 included in the xylylene diisocyanate composition is oxidized instead of the xylylene diisocyanate composition, the yellowness and Haze value of the composition do not increase, and thus the properties are maintained even when stored for a long period of time, so the storage stability of the xylylene diisocyanate composition including the compound of the chemical formula 1 is very excellent.

[0081] At this time, depending on various storage conditions such as storage period and temperature, all or part of the compound of chemical formula 1 may be converted into a compound of chemical formula 2 during the storage period. At this time, in the case of the remaining compound of chemical formula 1, the reaction of the above reaction formula (1) occurs spontaneously in the process of heating at a high temperature during the lens forming process described later, and is converted into a compound of chemical formula 2 during the process. At this time, the compound of chemical formula 2 formed during the storage period and the compound of chemical formula 2 formed during the lens forming process serve as flame retardants, and when included in a resin or lens through the above-described process, there is an effect of increasing the thermal stability of the lens during the lens forming process exposed to high temperatures, and there is also an effect of increasing the strength of the lens.

[0082]

[0083] At this time, if the compound of the above chemical formula 2 is included from the composition stage, the heat stability and strength enhancement effects of the lens manufactured with the composition can be exerted, but since there is no antioxidant effect at the composition stage, the yellowness and haze value may increase due to the side reaction of xylylene diisocyanate, which can be very disadvantageous in terms of storage stability.

[0084] Accordingly, according to the present invention, when the compound of formula 1 is included in the composition stage, oxidation can be prevented in the composition stage, thereby increasing storage stability, and at the same time, as the compound of formula 1 is converted to the compound of formula 2 during the manufacturing process of the lens, the heat stability and strength enhancement effects of the lens manufactured with the composition can also be exhibited. Consequently, the composition according to the present invention is superior to conventional compositions in that it can simultaneously exhibit the effect of increasing the storage stability of the composition, thereby preventing an increase in yellowness and haze values, and the effect of strengthening the physical properties of the lens.

[0085]

[0086] In addition, the weight of the compound of the above chemical formula 1 relative to the total weight of the above xylylene diisocyanate composition may be 1000 ppm or less, preferably 800 ppm or less, more preferably 700 ppm or less, even more preferably 500 ppm or less, and most preferably 400 ppm or less.

[0087] In addition, the weight of the compound of the above chemical formula 1 relative to the total weight of the above xylylene diisocyanate composition may be 0.1 ppm or more, preferably 0.5 ppm or more, more preferably 1 ppm or more, even more preferably 10 ppm or more, and most preferably 50 ppm or more.

[0088] In addition, the weight of the compound of the above chemical formula 1 relative to the total weight of the xylylene diisocyanate composition may preferably be 50 to 400 ppm, and in this case, if the weight of the compound of the above chemical formula 1 relative to the total weight of the xylylene diisocyanate composition satisfies 50 to 400 ppm, the effect of increasing the storage stability of the composition described above is maximized, and the rate of increase in yellowness of a resin including the composition relative to the storage period of the composition is greatly reduced.

[0089] At this time, if the compound of the above chemical formula 1 is included in an amount exceeding 1000 ppm based on the total weight of the composition, problems such as white turbidity and streaking may occur in the resin produced from the composition stored for a long period of time, and the storage stability may be weakened in other areas except for the yellowing phenomenon, and the color change of the resin may be caused, which may be disadvantageous in terms of the transparency of the lens.

[0090] The aforementioned "stripe" refers to a phenomenon in which the refractive index locally differs from the surrounding normal refractive index due to differences in composition, etc. "White turbidity" refers to the cloudiness that appears in an optical lens due to uneven polymerization during curing of the resin composition for optical lenses. Both stripes and white turbidity negatively affect the quality and performance of optical materials.

[0091] At this time, the compound of chemical formula 1 can be added separately or achieved through impurity control during the manufacturing process and / or storage process of xylylene diisocyanate.

[0092] In addition, the compound of the above chemical formula 1 can be manufactured by a commonly known manufacturing method, and a commercially available material can be purchased and used.

[0093]

[0094] Additionally, the xylylene diisocyanate composition according to the present invention may further contain phenol.

[0095] The phenol included in the xylylene diisocyanate composition can act as a polymerization inhibitor to prevent unexpected polymerization of xylylene diisocyanate during the storage period of the composition. In this case, by simultaneously including the compound of Chemical Formula 1 and phenol in the xylylene diisocyanate composition, the polymerization inhibitory effect of phenol and the oxidation prevention effect of the compound of Chemical Formula 1 occur simultaneously, resulting in excellent storage stability.

[0096] More specifically, in the case of the phenol, it may be included in an amount of 200 to 1200 ppm, and more preferably, it may be included in an amount of 400 to 900 ppm, based on the total weight of the xylylene diisocyanate composition. In this case, if the phenol is included in an amount of less than 400 ppm, it may not sufficiently perform its role as a polymerization inhibitor, and thus may not prevent unexpected polymerization of xylylene diisocyanate, which may be disadvantageous in terms of physical properties, such as increased yellowness or decreased transparency. In addition, if the phenol is included in an amount exceeding 900 ppm, a polymerization reaction between excessively added phenols or a side reaction with other compounds may occur, and yellowing problems, etc., may occur due to oxidized phenol.

[0097]

[0098] The present invention also provides a non-foam resin comprising the composition described above. Specifically, the non-foam resin described above may further comprise an active hydrogen group-containing component. This will be described below.

[0099] The above-described xylylene diisocyanate composition can be suitably used as a raw material for a non-foam resin. Specifically, the composition comprises a xylylene diisocyanate component, and together with an active hydrogen group-containing component, which is a raw material for the resin, forms a polymerizable composition, from which a resin can be produced.

[0100] The above active hydrogen group-containing component may include at least one selected from the group consisting of a polyol component, a polythiol component, and a polyamine component.

[0101] The above polyol component is not limited as long as it is included in the xylylene diisocyanate composition and a resin can be manufactured therefrom, but is preferably selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, alitol, mannitol, dolcitol, iditol, glycol, inositol, hexanetriol, triglycerol, diglyperol, triethylene glycol, polyethylene glycol, tris(2-hydroxyethyl)isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, Aliphatic polyols such as cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,0,2,6]decane-dimethanol, bicyclo[4,3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3,1,1]dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,1]dodecane-diethanol, hydroxypropyltricyclo[5,3,1,1]dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, Aromatic polyols such as benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl)pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, and tetrabrombisphenol A, di-(2-hydroxyethyl)sulfide, 1,2-bis-(2-hydroxyethylmercapto)ethane, bis(2-hydroxyethyl)disulfide, 1,4-dithiane-2,5-diol, bis(2,3-dihydroxypropyl)sulfide, tetrakis(4-hydroxy-2-thiabutyl)methane, bis(4-hydroxyphenyl)sulfone (trade name: bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 1,It may be at least one selected from the group consisting of polyalkylene oxide ethers of polyols such as polyols containing sulfur atoms such as 3-bis(2-hydroxyethylthioethyl)-cyclohexane, polyoxypropylene glyceryl ether, polyoxyethylene glyceryl ether, polyoxypropylene trimethylol propyl ether, and polyoxypropylene pentaerythritol ether.

[0102] The above polythiol component is not limited as long as it is included in the xylylene diisocyanate composition and a resin can be produced therefrom, but is preferably selected from the group consisting of 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, methanedithiol, methanetrithiol, bis(2-mercaptoethyl)ether, tetrakis(mercaptomethyl)methane, 1,2-dimercaptopropane; 1,3-Dimercaptopropane, 1,4-Dimercaptobutane, 1,6-Dimercaptohexane, 2,2-Dimercaptopropane, 1,2-Bis(2-mercaptoethyloxy)ethane, 1,2-Bis(2-mercaptoethylthio)ethane, 2,3-Dimercapto-1-propanol, 1,2-Dimercaptoethane, 1,3-Dimercapto-2-propanol, 2-Mercaptomethyl-1,3-dimercaptopropane, 2-Mercaptomethyl-1,4-dimercaptobutane, 1,2,3-Trimercaptopropane, 2-(2-Mercaptoethylthio)-1,3-dimercaptopropane, 2,4-Dimercaptomethyl-1,5-dimercapto-3-thiapentane, bis(2-mercaptoethyl)sulfide, ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(2-mercaptoacetate), 1,4-butanediol bis(2-mercaptoacetate), trimethylolpropane trismercaptopropionate, pentaerythritol tetrakismercaptoacetate, diethylene glycol bis(3-mercaptopropionate), pentaerythritol tetrakis mercaptopropionate, 1,2-dimercaptocyclohexane, 1,1,1-tris(mercaptomethyl)propane, 1,4-butanediol bis(3-mercaptopropionate), 1,3-dimercaptocyclohexane, Trimethylolpropane trimercaptoacetate, 1,4-dimercaptocyclohexane, 1,3-bis(mercaptomethyl)cyclohexane, 1,4-bis(mercaptomethyl)cyclohexane, bis(4-mercaptophenyl)sulfone, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-bis(2-mercaptoethylthiomethyl)-1,4-dithiane, 2,5-Dimercaptomethyl-1-thiane, 2,5-dimercaptoethyl-1-thiane, 2,5-dimercaptomethylthiophene, bis(4-mercaptophenyl)sulfide, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 2,2'-dimercaptobiphenyl, bis(4-mercaptophenyl)methane, 2,2-bis(4-mercaptophenyl)propane, 4,4'-dimercaptobiphenyl, bis(4-mercaptophenyl)ether, bis(4-mercaptomethylphenyl)methane, It may be at least one selected from the group consisting of 1,1,3,3-tetrakis(mercaptomethylthio)propane, 2,2-bis(4-mercaptomethylphenyl)propane, bis(4-mercaptomethylphenyl)ether, bis(4-mercaptomethylphenyl)sulfide, 2.5-dimercapto-1,3,4-thiadiazole and 3,4-thiophenediol.

[0103] The above polyamine component is not limited as long as it is included in the xylylene diisocyanate composition and a resin can be manufactured therefrom, but preferably, it may be at least one selected from the group consisting of 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 3,5-dithiomethyl-2,4-diaminotoluene, and 3,5-dithiomethyl-2,6-diaminotoluene.

[0104] The mixing ratio of the xylylene diisocyanate compound and the active hydrogen compound may be such that the molar ratio of NCO group / active hydrogen group is typically 0.5 to 2.0, and preferably 0.95 to 1.05. Examples of the active hydrogen group include a hydroxyl group, a mercapto group, and an amino group.

[0105] A non-foam resin can be manufactured through a polymerization reaction of the above-described active hydrogen group-containing component and xylylene diisocyanate.

[0106] For example, a mixture of the above monomer compositions is injected into a mold combining a glass or metal mold and a resin gasket to perform polymerization.

[0107] The polymerization initiation temperature may be preferably 0 to 45˚C, more preferably 10 to 40˚C, and even more preferably 15 to 35˚C. In addition, the polymerization conditions may be appropriately set depending on the initial temperature. The temperature may be increased from the initial temperature, and then heated to form curing. For example, the temperature increase temperature may be 100 to 150˚C according to a typical standard. The heating time to the temperature may be preferably 5 to 48 hours, more preferably 10 to 40 hours, and even more preferably 20 to 30 hours. The heating time after the temperature increase may be preferably 10 to 30 hours, and even more preferably 20 to 30 hours.

[0108]

[0109] More specifically, during the temperature increase process of the non-foam resin manufacturing process described above, the compound of the chemical formula 1 included in the xylylene diisocyanate composition can react according to the following reaction formula (1) to form a compound of the chemical formula 2.

[0110] At this time, when storing the compound of the above chemical formula 1, depending on the storage conditions such as the storage period and temperature, all or part of it may be converted into the compound of the above chemical formula 2 through an oxidation reaction, and subsequently, during the temperature increase process of the lens manufacturing process, most of the remaining compound of the chemical formula 1 may be converted into the compound of the chemical formula 2. Through this process, ultimately, more than 90% by weight of the compound of the chemical formula 1 with respect to the composition may be converted into the compound of the chemical formula 2.

[0111] <Reaction formula (1)>

[0112]

[0113] [Chemical Formula 1] [Chemical Formula 2]

[0114]

[0115] When the compound of formula 2 is formed during the formation process of the non-foam resin, the compound of formula 2 is included in the non-foam resin. At this time, the compound of formula 2 is a flame retardant, and when the compound is formed during the manufacturing process of the non-foam resin, it imparts a flame retardant effect to the lens, thereby increasing thermal stability.

[0116] In addition, the compound of chemical formula 2 formed during the storage process is incorporated into the non-foam resin. At this time, the inclusion of the compound of chemical formula 2 in the non-foam resin has the effect of improving the transparency and increasing the thermal stability of the non-foam resin, and at the same time, increasing the strength and scratch resistance of the non-foam resin.

[0117]

[0118] In the past, lenses were manufactured using a composition containing a compound of chemical formula 2 from the composition stage of xylylene diisocyanate. In this case, compared to the present invention, which includes chemical formula 1 in the composition stage and forms a compound of chemical formula 2 during the lens manufacturing process, it may be disadvantageous in terms of scratch resistance.

[0119]

[0120] Additionally, the non-foam resin may be used as one or more selected from the group consisting of a coating, an adhesive, a sealant, and an elastomer.

[0121] More specifically, the non-foam resin can be used as one or more raw materials selected from the group consisting of coatings, adhesives, sealants, and elastomers in oil refineries, oil transport pipelines, buildings, ships, marine equipment, automobiles, aircraft, spacecraft, railway vehicles, sports equipment, and computers.

[0122]

[0123] The above resin is preferably molded by a known molding method to form a molded body.

[0124] Additionally, the molded body may be, for example, an optical element.

[0125] Additionally, the optical element may be, for example, a lens or a sheet film, and preferably a lens.

[0126] The above lens may be, for example, a transparent lens, a polarizing lens, a camera lens, a sunglass lens, a spectacle lens, a pickup lens, and a contact lens.

[0127] The above-described molded articles, optical elements, and lenses all comprise the xylylene diisocyanate composition. Therefore, yellowing is prevented, resulting in significantly superior yellowing resistance and transparency compared to conventional molded articles, optical elements, and lenses. Simultaneously, thermal stability, transparency, and strength are improved, which are also significantly superior to conventional molded articles, optical elements, and lenses.

[0128]

[0129] In addition, the present invention provides a method for producing a non-foam resin, comprising the steps of: forming a mixture by mixing the xylylene diisocyanate composition and an active hydrogen group-containing component; and raising the temperature of the mixture to perform a polymerization reaction and converting the compound of the chemical formula 1 into a compound of the chemical formula 2 below. The description of any part that overlaps with the description of the above-described xylylene diisocyanate is omitted, but is not limited thereto.

[0130] <Chemical Formula 2>

[0131]

[0132] More specifically, when the temperature raising process is performed, the compound of the above chemical formula 1 is converted into the compound of the chemical formula 2 by the following reaction formula (1).

[0133] Reaction formula (1)

[0134]

[0135] [Chemical Formula 1] [Chemical Formula 2]

[0136] Through this, the compound of chemical formula 1 can exert the effect of increasing storage stability through oxidation prevention at the composition stage, and at the same time, the compound of chemical formula 2 can exert the effect of improving the strength and thermal stability of the resin manufactured with such a composition.

[0137] More specifically, according to a preferred embodiment of the present invention, the heating process may be performed at 100 to 150˚C for 20 to 30 hours. At this time, if the temperature of the heating process is less than 100˚C, the conversion rate of the compound of chemical formula 1 to the compound of chemical formula 2 is low, so that the physical properties of the manufactured resin may not be sufficiently improved. In addition, if the temperature of the heating process exceeds 150˚C, an unexpected polymerization reaction may occur due to the excessively high temperature, which may cause a defect such as a striae phenomenon or an overall non-uniform physical property in the manufactured lens.

[0138]

[0139] The present invention will be described in more detail through the following examples, but the following examples do not limit the scope of the present invention, and should be interpreted as helping to understand the present invention.

[0140]

[0141] <Example 1: Preparation of xylylene diisocyanate composition 1>

[0142] A xylylene diisocyanate composition was obtained by adding the compound of the above formula 1 (Sigma-Aldrich, St. Louis, MO) to m-xylylene diisocyanate (Sigma-Aldrich, St. Louis, MO) so that the mass thereof was 100 ppm with respect to the total mass of the composition, and adding phenol (Sigma-Aldrich, St. Louis, MO) so that the mass thereof was 500 ppm with respect to the total mass of the composition.

[0143]

[0144] <Examples 2 to 5, Comparative Examples 1 to 2: Preparation of xylylene diisocyanate composition 2>

[0145] Except for the differences in the component ratios disclosed in Table 1, it was prepared in the same manner as in Example 1. The compound of Chemical Formula 2 was purchased from Sigma-Aldrich (St. Louis, MO).

[0146]

[0147] <Experimental Example 1: Measurement of APHA and Haze values ​​of resin according to the storage period of the composition>

[0148] Immediately after the xylylene diisocyanate compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 2 were prepared, or after they were stored for 90 days under nitrogen-substituted atmosphere, at a temperature of 15˚C and a humidity of 0.1% RH, a resin was prepared using the following method.

[0149] Each composition (20.8 g), 0.04 g of ZELEC™UN (manufactured by Stepan) as an internal release agent, and 0.04 g of Biosorb™583 (manufactured by Sakai Chemical industry Co., Ltd) as an ultraviolet absorber were stirred and mixed at room temperature (23-25˚C) for 20 minutes to prepare a mixture, 0.002 g of DBTC (dibutyltin dichloride) was added to the prepared mixture, stirred for 10 minutes, and 19.2 g of 2,3-bis(2-sulfanyl ethyl sulfanyl)propane-1-thiol was added, and stirred for 1 hour while degassing under a pressure condition of 5 mbar to prepare a composition for polyisocyanate polymerization.

[0150] The prepared polyisocyanate polymerization composition was filtered using a 1 μm PTFE filter and then injected into a mold formed from a glass mold and tape, respectively. The mold was then placed in an oven and polymerization was performed for 20 hours while gradually increasing the temperature from 10˚C to 120˚C. After completion of the polymerization, the mold was taken out of the oven and released to obtain each plastic resin. The obtained resin was annealed at 120˚C for 6 hours to produce each resin having a thickness of 9 mm.

[0151] For each of the above-mentioned manufactured resins, the APHA color and haze were measured (light source: C / 2) using HunterLab's Ultrascan Pro according to the method of ASTM E313, and are shown in Table 1 below.

[0152] The above APHA (Hazen color number) measurement was performed using a color difference analysis method under room temperature conditions according to ASTM D1003, and the Hazen color number was measured using a xenon lamp light source of Hunterlab's Ultrascane equipment.

[0153]

[0154] <Experimental Example 2: Measurement of the yellowness index (YI) of resin according to the storage period of the composition>

[0155] Immediately after the xylylene diisocyanate compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 2 were prepared, or after they were stored for 90 days under nitrogen-substituted atmosphere, temperature of 15˚C, and humidity of 0.1% RH, a resin was prepared using the method according to Experimental Example 1.

[0156] Each composition (20.8 g), 0.04 g of ZELEC™UN (manufactured by Stepan) as an internal release agent, and 0.04 g of Biosorb™583 (manufactured by Sakai Chemical industry Co., Ltd) as an ultraviolet absorber were stirred and mixed at room temperature (23-25˚C) for 20 minutes to prepare a mixture, 0.002 g of DBTC (dibutyltin dichloride) was added to the prepared mixture, stirred for 10 minutes, and 19.2 g of 2,3-bis(2-sulfanyl ethyl sulfanyl)propane-1-thiol was added, and stirred for 1 hour while degassing under a pressure condition of 5 mbar to prepare a composition for polyisocyanate polymerization.

[0157] The prepared polyisocyanate polymerization composition was filtered using a 1 μm PTFE filter and then injected into a mold formed from a glass mold and tape, respectively. The mold was then placed in an oven and polymerization was performed for 20 hours while gradually increasing the temperature from 10˚C to 120˚C. After completion of the polymerization, the mold was taken out of the oven and released to obtain each plastic resin. The obtained resin was annealed at 120˚C for 6 hours to produce each resin having a thickness of 9 mm.

[0158] For each optical lens manufactured above, the yellowness was measured using HunterLab's Ultrascan Pro according to the method of ASTM D1209, and is shown in Table 1.

[0159]

[0160] <Experimental Example 3: Measurement of heat resistance of resin manufactured with composition>

[0161] After preparing the xylylene diisocyanate compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 2, a resin was immediately prepared by the method according to Experimental Example 1. A differential scanning calorimeter (TA instruments, DSC2500) was used to measure the Tg of the sample. After the sample was ground into powder, 15 mg was placed in an aluminum pan to measure the Tg. The temperature range was increased from room temperature to 130˚C and then cooled in the first measurement (1st run), and increased from 30˚C to 130˚C in the second measurement (2nd run). The temperature increasing condition was 20˚C / min under a nitrogen flow. The thermal behavior was investigated based on the Tg value measured in the 2nd run. The results are shown in Table 1.

[0162]

[0163] <Experimental Example 4: Measurement of pencil hardness of resin manufactured with composition>

[0164] After preparing the xylylene diisocyanate compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 2, a resin was immediately prepared using the method of Experimental Example 1. Thereafter, the pencil hardness was measured using ASTM D3502 (pencil hardness tester) and is shown in Table 1.

[0165]

[0166] <Experimental Example 5: Measurement of elongation (strength) of resin manufactured with composition>

[0167] After preparing the xylylene diisocyanate compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 2, a resin was immediately prepared by the method according to Experimental Example 1. Thereafter, in accordance with JIS Standard K-7171, a flat plate having a thickness of 2.5 mm and a width of 10 mm was subjected to a three-point bending test at a distance of 40 mm between points using an autograph (AG-5000B, manufactured by Shimadzu Corporation), and the elongation at the point of fracture was measured, which is shown in Table 1.

[0168]

[0169]

[0170]

[0171] As can be seen in Table 1, in the case of Example 1 containing the compound of Chemical Formula 1, the increase in yellowness and APHA value of the composition manufactured with the composition after 90 days of storage was very small compared to Comparative Examples 1 and 2 which did not contain the compound of Chemical Formula 1, and thus the composition is very excellent in terms of storage stability.

[0172] In addition, when comparing Example 1 with Comparative Examples 1 and 2, it can be seen that it has a similar level of Haze value. In the case of Haze value, a value of 0.4% or less is generally considered very good, and there is no significant difference above that. In the case of Example 1, it is very excellent in that it has excellent characteristics such as excellent storage stability while also maintaining a very good Haze value.

[0173] Furthermore, in the case of Example 1 containing phenol, the increase in yellowness and APHA value of the composition manufactured with the composition after storing the composition for 90 days was smaller than in Example 2, indicating that the case where phenol and the compound of chemical formula 1 are simultaneously contained is superior in terms of storage stability compared to the case where the compound of chemical formula 1 is contained alone.

[0174] In addition, when Example 1 is compared with Example 3, it can be confirmed that in the case of Example 3, the content of the compound of Chemical Formula 1 is insufficient, and thus the increase in the yellowness and APHA value of the composition manufactured with the composition after storing the composition for 90 days is greater than in Example 1. In other words, Example 1, in which the compound of Chemical Formula 1 is within the range of 50 to 400 ppm, is superior in storage stability compared to Example 3.

[0175] In addition, when comparing Example 1 and Example 4, it can be confirmed that in the case of Example 4, the increase in yellowness and Haze value of the composition manufactured with the composition after storing the composition for 90 days is greater than in Example 1. That is, in the case of Example 1, where the compound of Chemical Formula 1 is within the range of 50 to 400 ppm, the storage stability is superior to that of Example 4.

[0176] In addition, when comparing Example 1 and Example 5, in the case of Example 5, the increase in yellowness and APHA value of the composition manufactured with the composition after storing the composition for 90 days is greater than in Example 1, and in particular, the increase in Haze value is very large compared to Example 1. That is, in the case of Example 1, where the compound of Chemical Formula 1 is within the range of 50 to 400 ppm, the storage stability is superior to that of Example 5, and in the case of Example 5, the compound of Chemical Formula 1 is included in an amount of 1000 ppm or more, so it is disadvantageous compared to Example 1 in terms of physical properties such as Haze value in particular.

[0177] In addition, it can be confirmed that the absolute value of the initial yellowness before storage is greater in Examples 4 and 5 than in Example 1, which contains the compound of Chemical Formula 1 at 50 to 400 ppm.

[0178] Additionally, when Example 1 and Comparative Example 1 are compared, it can be confirmed that Example 1 is superior to Comparative Example 1 in terms of heat resistance. This is because the compound of Chemical Formula 1 is converted to the compound of Chemical Formula 2, and the compound of Chemical Formula 2 acts as a flame retardant. In addition, when Example 1 and Comparative Example 2 are compared, Example 1, which included the compound of Chemical Formula 1 in the composition stage, is superior in terms of pencil hardness compared to Comparative Example 2, which included the compound of Chemical Formula 2, and thus has superior scratch resistance. Finally, when Example 1 and Comparative Example 1 are compared in terms of elongation, Example 1 has superior elongation, and thus can be said to be more advantageous in terms of strength.

[0179]

[0180] <Experimental Example 6: Gas Chromatography Analysis>

[0181] After the xylylene diisocyanate compositions manufactured in Example 1 and Comparative Examples 1 to 2 were manufactured, the compositions were stored for 90 days under nitrogen-substituted atmosphere, at a temperature of 15˚C and a humidity of 0.1% RH. The purity of the xylylene diisocyanate included in each Example and Comparative Example was measured through gas chromatography analysis as follows, and the results are shown in Figures 1a, 1b, 1c and Table 2.

[0182]

[0183] (Conditions for gas chromatography analysis)

[0184] Analysis device: Agilent 7890A (Agilent Technologies)

[0185] Analysis column: HP-5 (5%-phenyl-methylpolysiloxane capillary column) 30.0mX0.32mm(ID)X0.25μm(film)

[0186] Sample introduction conditions: Split sample introduction method (ratio 30:1), 300˚C, 6.1219 psi

[0187] Split gas flow rate and carrier gas: 34ml / min, N2

[0188] Gas flow rate of the column: 1ml / min

[0189] Detector and temperature: FID (hydrogen flame ionization detector), 280˚C, H2flow 30ml / min, Air flow 300ml / min, make up flow N225ml / min.

[0190] Temperature rising conditions: Increase the temperature from 100˚C to 165˚C at 10˚C / min and maintain for 3 minutes, then increase the temperature to 177˚C at 3˚C / min, then increase the temperature to 300˚C at 20˚C / min and maintain for 15 minutes.

[0191]

[0192] <Experimental Example 7: Gel Permeation Chromatography Analysis>

[0193] After the xylylene diisocyanate compositions prepared in Example 1 and Comparative Examples 1 to 2 were prepared, the compositions were stored for 90 days under nitrogen-substituted atmosphere, temperature of 15˚C, and humidity of 0.1%RH. The contents of dimers and oligomers of xylylene diisocyanate included in each Example and Comparative Example were measured through gel permeation chromatography analysis as follows, and the results are shown in Figures 2a, 2b, 2c and Table 2.

[0194]

[0195] (Conditions for gel permeation chromatography analysis)

[0196] Device used: Agilent

[0197] Column: Agilent PL Mixed D, Agilent PLgel 100ÅAgilent PLgel 50Å

[0198] Sample concentration: 1 wt / vol% in tetrahydrofuran (THF)

[0199] Carrier: THF

[0200] Detection method: RI

[0201] Flow rate: 1.0 ml / min

[0202] Column temperature: 25˚C

[0203] Detector: Agilent RI detector

[0204] When preparing the calibration curve, polystyrene standard foams with molecular weights of 104 to 24,600 g / mol were used.

[0205]

[0206]

[0207]

[0208] As can be seen in Table 2, when the composition of Example 1 was stored for 90 days, the purity of XDI was maintained at a similarly excellent level when compared to the compositions of Comparative Examples 1 and 2 when stored for 90 days, but in terms of its detailed composition, it can be confirmed that the content of dimers and oligomers generated by side reactions was lower. Through this, the storage stability of Example 1 was superior to that of Comparative Examples 1 and 2.

Claims

1. Xylylene diisocyanate; and A xylylene diisocyanate composition having excellent storage stability, comprising a compound of chemical formula 1. <Chemical Formula 1> 2. In paragraph 1, A xylylene diisocyanate composition characterized in that the above xylylene diisocyanate composition further comprises phenol.

3. In paragraph 1, A xylylene diisocyanate composition, wherein the weight of the compound of the above chemical formula 1 is 50 to 400 ppm based on the total weight of the above xylylene diisocyanate composition.

4. A non-foam resin comprising a xylylene diisocyanate composition according to paragraph 1.

5. In paragraph 4, A non-foam resin, wherein the non-foam resin further comprises an active hydrogen group-containing component.

6. In paragraph 5, A non-foam resin, wherein the active hydrogen group-containing component is at least one selected from the group consisting of a polyol component, a polythiol component, and a polyamine component.

7. In paragraph 4, A non-foam resin, wherein the non-foam resin is to be used as one or more selected from the group consisting of a coating, an adhesive, a sealant, and an elastomer.

8. A molded article comprising the non-foam resin described in paragraph 4.

9. An optical element comprising the molded body described in Article 8.

10. A lens comprising the optical element described in paragraph 9.

11. A step of forming a mixture by mixing the composition of any one of claims 1 to 3 and an active hydrogen group-containing component; and A method for producing a non-foam resin, comprising: a step of heating the mixture to perform a polymerization reaction and converting the compound of the chemical formula 1 into a compound of the chemical formula 2 below. <Chemical Formula 2> 12. In paragraph 11, A method for producing a non-foam resin, wherein the above heating process is performed at 100 to 150˚C.

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