KR101156119B1 - Ultraviolet violet curable carbodiimide oligomer and method of manufacturing thereof - Google Patents

Abstract

Ultraviolet curable carbodiimide oligomers and methods for their preparation are disclosed. Reacting with 1 equivalent of the hydroxy group-containing acrylate and 0.95-1.05 equivalent of the first aromatic difunctional isocyanate compound to form a compound containing an acrylate group and an isocyanate group, and the compound containing the acrylate group and the isocyanate group is carbodiimidized catalyst. React in the presence or react the compound containing the acrylate group and the isocyanate group with the second aromatic difunctional isocyanate compound to have an average molecular weight of 400 to 10,000 and ultraviolet curable carbodiimide containing 1 to 10 carbodiimide groups in the molecule. Prepare oligomers. UV curable carbodiimide oligomers can be applied to UV curable optical materials and coatings that require high refractive index properties.

Description

UV curable carbodiimide oligomers and methods for producing the same {ULTRAVIOLET VIOLET CURABLE CARBODIIMIDE OLIGOMER AND METHOD OF MANUFACTURING THEREOF}

The present invention relates to an ultraviolet curable carbodiimide oligomer and a method for producing the same. More specifically, the present invention relates to an ultraviolet curable carbodiimide oligomer having a high refractive index and a method for producing the same.

Recently, in the coating industry, a material having a transparent high refractive index has been in the spotlight, and has been used for thin optical lenses, photosynthetic adhesives, films and the like. Commonly known high refractive materials are those containing large molecules, such as bromine and iodine, which are halogenated materials. However, halogenated elements are one of the harmful substances, and in many countries, they are restricted because they are vaporized to remove ozone from the air layer or changed into harmful substances when burned. As a substitute for such a material, a large number of high refractive polymers using phosphazene or sulfur have been researched and developed. Polycarbodiimide has a refractive index of about 1.757, which is known to be the highest designed among the transparent polymer materials, but it is proposed to be designed as a solution type rather than photocurable or UV curable (US Patent Publication 2004-0158021).

The solution form is unsuitable for environmental regulation by emitting VOCs. Raw materials and coating methods are rapidly changing in the paint industry due to environmental protection campaigns in the coating industry around the world and government regulations on the emission of volatile organic compounds (VOCs). The overall paint industry is growing slowly, but the environmentally friendly coatings industry, such as UV curable coatings, waterborne paints and powder paints, which can reduce air pollution, are growing at a rapid pace. In particular, the UV curing process is an environmentally friendly coating that is 100% solids, can be cured at a low temperature, and has a large economical advantage due to improved productivity due to fast curing speed. In addition, energy saving, simple operation management, high product reliability, and especially in high refractive coatings have a large effect on the refractive index by increasing the volume as it hardens.

Accordingly, an object of the present invention is to provide an ultraviolet curable carbodiimide oligomer for forming a transparent polymer film exhibiting a high refractive index.

Another object of the present invention is to provide a method for producing an ultraviolet curable carbodiimide oligomer for forming a transparent polymer film exhibiting high refractive index.

The ultraviolet curable carbodiimide oligomer according to the embodiments for achieving the object of the present invention comprises a acrylate group and an isocyanate group by reacting with 1 equivalent of hydroxy group-containing acrylate and 0.95 to 1.05 equivalent of first aromatic difunctional isocyanate compound A compound is formed and the compound containing the acrylate group and the isocyanate group is 3-methyl-1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2 -Phosphorene-1-sulfide, 1-ethyl-3-methyl-2-phosphorene-1-oxide, 3-methyl-1-phenyl-1-phosphor-3-cyclopentene-1-oxide, 2,5 Obtained by reacting a second aromatic difunctional isocyanate compound in the presence of at least one carbodiimidation catalyst selected from the group consisting of -dihydro-3-methyl-1-phenylphosphol-1-oxide and the corresponding isomers minute The amount of 400 to 10,000, and from 1 to 10 carbodiimide number in the molecule.

According to embodiments of the present invention, the hydroxy group-containing acrylate is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or 2-hydroxy-3-phenoxy It may be propyl acrylate, wherein the first aromatic difunctional isocyanate and the second aromatic difunctional isocyanate may be toluene diisocyanate (TDI) or methylene diphenyl diisocyanate (MDI), or naphthalene diisocyanate (NDI).

According to embodiments of the present invention, the ultraviolet curable carbodiimide oligomer may include 1 to 5 carbodiimide groups in the molecule.

According to another aspect of the present invention, there is provided a method of preparing an ultraviolet curable carbodiimide oligomer, which is reacted with one equivalent of a hydroxy group-containing acrylate and 0.95 to 1.05 equivalents of a first aromatic difunctional isocyanate compound. A compound containing an isocyanate group is formed. 3-methyl-1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-sulfide, 1-ethyl-3-methyl 2-phosphorene-1-oxide, 3-methyl-1-phenyl-1-phosphor-3-cyclopentene-1-oxide, 2,5-dihydro-3-methyl-1-phenylphosphol-1 An average molecular weight of 400 to 10,000 by reacting a compound comprising the acrylate group and an isocyanate group with a second aromatic difunctional isocyanate compound in the presence of at least one carbodiimidation catalyst selected from the group consisting of -oxides and the corresponding isomers, The carbodiimide in a molecule | numerator obtains the ultraviolet curable carbodiimide oligomer containing 1-10.

According to embodiments of the present invention, the number of carbodiimides in the ultraviolet curable carbodiimide oligomer molecule may be controlled by controlling the equivalent ratio of the compound including the acrylate group and the isocyanate group and the second aromatic difunctional isocyanate compound.

In a method for preparing an ultraviolet curable carbodiimide oligomer according to another embodiment for achieving another object of the present invention, by reacting with 1 equivalent of hydroxy group-containing acrylate and 0.95 to 1.05 equivalent of the first aromatic difunctional isocyanate compound A compound containing a late group and an isocyanate group is formed. 3-methyl-1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-sulfide, 1-ethyl-3-methyl 2-phosphorene-1-oxide, 3-methyl-1-phenyl-1-phosphor-3-cyclopentene-1-oxide, 2,5-dihydro-3-methyl-1-phenylphosphol-1 A compound containing an acrylate group and an isocyanate group in the presence of at least one carbodiimidation catalyst selected from the group consisting of an oxide and an isomer thereof, having an average molecular weight of 400 to 10,000, and a carbodiimide group in the molecule of 1 to 10 The ultraviolet curable carbodiimide oligomer containing dog is obtained.

The ultraviolet curable carbodiimide oligomer of the present invention described above has high thermal stability, chemical stability, and high refractive index. The ultraviolet curable carbodiimide oligomer has a high refractive index by having a carbodiimide group having an ultraviolet curable acrylate group at both ends and linearly connecting the structure derived from the first and second aromatic difunctional isocyanate Can be. In addition, the UV-curable carbodiimide oligomer can be easily adjusted by controlling the equivalent ratio of the carbodiimide number in the molecule to the compound comprising an acrylate group and an isocyanate group and the second aromatic difunctional isocyanate compound, thereby providing an appropriate viscosity and refractive index. The ultraviolet curable carbodiimide oligomer which has can be manufactured easily. The UV curable carbodiimide oligomer, when applied to a paint, can be easily cured through an ultraviolet curing process, it is possible to form a film with excellent adhesion, hardness is environmentally friendly.

1 is a graph showing the result of measuring the UV-curable carbodiimide oligomer prepared in Examples 1 to 4 after dilution with diluent ethyl 2-phenylacrylate, using an Abbe refractometer at a temperature of about 25 ℃ .
Figure 2 is a graph showing the refractive index increase rate according to the number of carbodiimide groups contained in the ultraviolet curable carbodiimide oligomer molecule prepared according to Examples 1 to 4.

While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments. However, this is not intended to limit the present invention to a specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "consist of" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described on the specification, but one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

Hereinafter, the ultraviolet curable carbodiimide oligomer and the method for producing the same according to the present invention will be described in detail.

UV curable carbodiimide oligomer

The ultraviolet curable carbodiimide oligomer according to the present invention reacts about 1 equivalent of a hydroxy group-containing acrylate with about 0.95-1.05 equivalents of a first aromatic difunctional isocyanate compound to form a compound including an acrylate group and an isocyanate group, and A compound containing an acrylate group and an isocyanate group may be formed by reacting a second aromatic difunctional isocyanate compound in the presence of the carbodiimidation catalyst. The average molecular weight of the ultraviolet curable carbodiimide oligomer is about 400 to 10,000, and includes about 1 to 10 carbodiimide groups. The ultraviolet curable carbodiimide oligomer has an acrylate group which is an ultraviolet curable functional group at both ends, and linearly connects a structure in which a carbodiimide group is derived from the first and second aromatic difunctional isocyanates as shown in the following Formula 7, 8 Can have a structure The ultraviolet curable carbodiimide oligomer may have a high refractive index by having a structure in which carbodiimide groups linearly connect the structures derived from the first and second aromatic difunctional isocyanates.

As an example, the hydroxy group-containing acrylate may include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and the like. It may include.

As an example, the first aromatic difunctional isocyanate compound may include toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), naphthalene diisocyanate (NDI), or the like.

The hydroxy group-containing acrylate reacts with the first aromatic difunctional isocyanate compound to form a compound including an acrylate group and an isocyanate group. The first aromatic difunctional isocyanate compound may react about 0.95 to 1.05 equivalents to about 1 equivalent of the hydroxy-containing acrylate. In other words, the equivalent ratio of the first aromatic difunctional isocyanate compound to the mono hydroxy alkyl acrylate may be about one to one.

For example, toluene diisocyanate (TDI) comprising a mixture of 2,4-toluene diisocyanate of formula (2) and 2,6-toluene diisocyanate of formula (3) relative to one equivalent of hydroxypropyl acrylate of formula (1) About 1 equivalent may be reacted to form a compound including an acrylate group and an isocyanate group including the following Formula 4, Formula 5, Formula 6, and the like.

<Formula 1> <Formula 2> <Formula 3>

<Formula 4> <Formula 5>

(6)

<Scheme 1>

The compound containing the acrylate group and the isocyanate group is reacted with a second aromatic difunctional isocyanate compound in the presence of the carbodiimidation catalyst to form an ultraviolet curable carbodiimide oligomer.

As an example, the second aromatic difunctional isocyanate compound may include toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), naphthalene diisocyanate (NDI), or the like.

As an example, the carbodiimide-ized catalyst is 3-methyl-1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene- 1-sulfide, 1-ethyl-3-methyl-2-phosphorene-1-oxide, 3-methyl-1-phenyl-1-phosphor-3-cyclopentene-1-oxide, 2,5-dihydro- 3-methyl-1-phenylphosphol-1-oxide and the corresponding isomers and 3-phosphorene and the like.

For example, about 1 compound containing an acrylate group and an isocyanate group having the above formulas (4), (5) and (6) in the presence of 3-methyl-1-phenyl-2-phosphorene-1-oxide which is a carbodiimidation catalyst The equivalent is reacted with about 0.5 equivalents of toluene diisocyanate (TDI) comprising a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, so that the number of carbodiimides in the ultraviolet curable carbodiimide oligomer molecule is about It is possible to form an ultraviolet curable carbodiimide oligomer comprising the formula (7) and the like.

<Formula 7>

For example, in the presence of 3-methyl-1-phenyl-2-phosphorene-1-oxide, which is a carbodiimidation catalyst, a compound including an acrylate group and an isocyanate group including Formulas 4, 5, and 6 About 1 equivalent may be reacted with about 0.5 equivalents of methylene diphenyl diisocyanate to form an ultraviolet curable carbodiimide oligomer comprising Formula 8 or the like having a carbodiimide number of about 2 in the ultraviolet curable carbodiimide oligomer molecule.

(8)

By controlling the equivalent ratio of the second aromatic difunctional isocyanate compound reacting with about 1 equivalent of the compound including the acrylate group and the isocyanate group, the number of carbodiimide groups included in the ultraviolet curable carbodiimide oligomer molecule can be controlled. For example, when the equivalent ratio of the second aromatic difunctional isocyanate compound to one equivalent of the compound including the acrylate group and the isocyanate group is about 2: 1, 2: 2, 2: 3 and 2: 4, ultraviolet curable carbodies The number of carbodiimide groups included in the mid oligomer may be about 2, 3, 4, 5, respectively.

As an example, the carbodiimide number in the ultraviolet curable carbodiimide oligomer molecule may be about 1-5. As the number of carbodiimides included in the molecule increases, the refractive index and the viscosity may increase. However, as the carbodiimide number increases, the degree of increase of the refractive index may be lowered. Therefore, when the number of carbodiimides in the ultraviolet curable carbodiimide oligomer molecule is more than 5, the effect of increasing viscosity and inferior adhesion can be greater than the advantage of increasing the refractive index.

In another embodiment, a UV curable carbodiimide oligomer having a number of carbodiimide groups included in the ultraviolet curable carbodiimide oligomer molecule by reacting the compound including the acrylate group and the isocyanate group in the presence of a carbodiimide catalyst. Can be formed. For example, a UV curable carbodiimide oligomer comprising the following Chemical Formula 9, Chemical Formula 10, and the like by reacting a compound including an acrylate group and an isocyanate group having Formulas 4, 5, and 6 in the presence of a carbodiimide catalyst The ultraviolet curable carbodiimide oligomer whose number of carbodiimide groups contained in a molecule | numerator is 1 can be formed.

<Formula 9>

<Formula 10>

Method for producing ultraviolet curable carbodiimide oligomer

According to the method for preparing the ultraviolet curable carbodiimide oligomer of the present invention, a compound containing an acrylate group and an isocyanate group is formed by reacting with about 1 equivalent of a hydroxy group-containing acrylate and about 0.95-1.05 equivalent of a first aromatic difunctional isocyanate compound. do. In this case, the IR spectrum can be used to confirm the progress of the reaction, and when there is no change in the area of the IR spectrum, the reaction can be terminated.

As an example, the hydroxy group-containing acrylate may be hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or 2-hydroxy-3-phenoxypropyl acrylate. It may include.

As an example, the first aromatic difunctional isocyanate compound may include toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), naphthalene diisocyanate (NDI), and the like.

The hydroxy group-containing acrylate reacts with the first aromatic difunctional isocyanate compound to form a compound including an acrylate group and an isocyanate group. The first aromatic difunctional isocyanate compound may react about 0.95 to 1.05 equivalents to about 1 equivalent of the hydroxyl group-containing acrylate. In other words, the equivalent ratio of the first aromatic difunctional isocyanate compound to the hydroxyl group-containing acrylate may be about one to one. For example, about 1 toluene diisocyanate (TDI) comprising a mixture of 2,4-toluene diisocyanate of Formula 2 and 2,6-toluene diisocyanate of Formula 3 at a temperature of about 20 to 35 ° C The equivalent weight of the hydroxypropyl acrylate of Formula 1 is slowly dropped to the equivalent to form a compound including the acrylate group and the isocyanate group including Formula 4, Formula 5, Formula 6, and the like.

The reaction temperature between the hydroxy group-containing acrylate and the first aromatic difunctional isocyanate compound is determined in consideration of the kind of reactant, the heat of reaction, the reaction rate, the viscosity of the compound, and the like. For example, when the hydroxy group-containing acrylate is hydroxypropyl acrylate and the first aromatic difunctional isocyanate compound is toluene diisocyanate (TDI), the reaction temperature may be about 20 ° C to 35 ° C. When the reaction temperature is about 20 ° C or less, the reaction rate may be slow to complete the reaction completion time. When the reaction temperature is about 35 ° C or more, it may be difficult to control the reaction temperature reaction rate because the reaction is exothermic.

The compound comprising the acrylate group and the isocyanate group is reacted with a second aromatic difunctional isocyanate compound in the presence of the carbodiimidation catalyst to have an average molecular weight of about 400 to 10,000, and an ultraviolet ray containing about 1 to 10 carbodiimide groups in a molecule. Curable carbodiimide oligomers are formed. The compound comprising the acrylate group and the isocyanate group and the second aromatic difunctional isocyanate compound may be mixed, and the mixture of the diluent and the catalyst may be slowly dropped to allow the reaction.

As an example, the second aromatic difunctional isocyanate compound may include toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), naphthalene diisocyanate (NDI), or the like.

The diluent may include ethyl 2-phenylacrylate, benzyl acrylate, benzyl methacrylate, phenylthioethyl acrylate, 2-phenylphenoxyethyl acrylate or 2-phenoxyethyl acrylate, and the like.

The carbodiimide-ized catalyst is 3-methyl-1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-sulfide, 1-ethyl-3-methyl-2-phosphorene-1-oxide, 3-methyl-1-phenyl-1-phosphor-3-cyclopentene-1-oxide, 2,5-dihydro-3-methyl- 1-phenylphosphol-1-oxide and the corresponding isomers and 3-phosphorene and the like.

For example, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate with respect to about 1 equivalent of a compound containing an acrylate group and an isocyanate group including the above-described formulas (4), (5) and (6), etc. When about 0.5 equivalents of toluene diisocyanate (TDI) containing is mixed and reacted, the ultraviolet curable carbodiimide oligomer having the number of carbodiimides in the ultraviolet curable carbodiimide oligomer molecule including Formula 7 or the like is about 2 Can be formed.

For example, about 1 equivalent of a compound containing an acrylate group and an isocyanate group having the above formulas (4), (5) and (6) in the presence of 3-methyl-1-phenyl-2-phosphorene-1-oxide as a carbodiimidation catalyst May be reacted with about 0.5 equivalents of methylene diphenyl diisocyanate to form an ultraviolet curable carbodiimide oligomer comprising the above formula (8) having a carbodiimide number of about 2 in the ultraviolet curable carbodiimide oligomer molecule.

By controlling the equivalent ratio of the second aromatic difunctional isocyanate compound reacting with about 1 equivalent of the compound including the acrylate group and the isocyanate group, the number of carbodiimide groups included in the ultraviolet curable carbodiimide oligomer molecule can be controlled. For example, when the equivalent ratio of the second aromatic difunctional isocyanate compound to one equivalent of the compound including the acrylate group and the isocyanate group is about 2: 1, 2: 2, 2: 3 and 2: 4, ultraviolet curable carbodies The number of carbodiimide groups included in the mid oligomer molecule may be about 2, 3, 4, 5, respectively.

As an example, the carbodiimide number in the ultraviolet curable carbodiimide oligomer molecule may be about 1-5. When the number of carbodiimide groups included in the ultraviolet curable carbodiimide oligomer molecule is increased, the refractive index and viscosity of the ultraviolet curable oligomer may be increased. However, as the number of carbodiimides increases, the degree of increase in refractive index may be lowered. Therefore, when the number of carbodiimides in the ultraviolet curable carbodiimide oligomer is more than 5, the effect of increasing viscosity and inferior adhesion can be greater than the advantage of the increase rate of the refractive index.

In another embodiment, the compound including the acrylate group and the isocyanate group is reacted in the presence of a carbodiimidation catalyst, thereby including a carbodiimide group having a number of carbodiimide groups included in the ultraviolet curable carbodiimide oligomer molecule. Ultraviolet curable oligomers may be formed. For example, the ultraviolet curable carbodiimide including the chemical formulas 9 and 10 by reacting a compound containing an acrylate group and an isocyanate group including the chemical formulas 4, 5 and 6 in the presence of a carbodiimidation catalyst An ultraviolet curable oligomer including a carbodiimide group having a number of carbodiimide groups included in the oligomer molecule may be formed.

Hereinafter, a UV curable oligomer including a carbodiimide group and a method of manufacturing the same will be described through specific examples and experimental examples. However, the present invention is not limited thereto.

Example 1

Toluene diisocyanate comprising a mixture of about 80:20 ratios of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate in a five-necked reactor equipped with a mechanical stirrer, a stirring rod, a thermometer and a thermostat under argon atmosphere About 1 equivalent of (TDI) was added and the temperature inside the reactor was slowly raised to about 30 ° C. When the temperature stabilized, about 1 equivalent of hydroxypropyl acrylate (HPA) was slowly added using a dropping funnel. At this time, since the exothermic reaction occurred, the HPA was slowly dropped while being careful not to exceed the temperature inside the reactor of about 35 ℃. After the HPA was added, the mixture was stirred at room temperature for about 2 hours to obtain a TDI-HPA precursor, which is a compound including an acrylate group and an isocyanate group including Formulas 4, 5, and 6, and the like.

In an argon atmosphere, about 1 equivalent of the TDI-HPA precursor was added to a 5-neck reactor equipped with a mechanical stirrer, a stirring rod, a thermometer, and a temperature controller, and the temperature inside the reactor was slowly raised to about 45 ° C. When the temperature was stabilized, about 75 g of ethyl 2-phenylacrylate and about 0.3 g of 3-methyl-1-phenyl-2-phosphorene-1-oxide were added thereto and stirred for about 30 minutes. And the temperature was heated up to about 75 degreeC, reaction was maintained for about 24 hours, and the ultraviolet curable carbodiimide oligomer whose number of carbodiimide groups contained in an ultraviolet curable carbodiimide oligomer molecule was about 1. The viscosity value at 25 degrees C of the obtained oligomer was 1,180,000 cP.

Example 2

In an argon atmosphere, about 1 equivalent of TDI-HPA precursor and about 0.5 equivalent of TDI formed in a substantially five-necked reactor equipped with a mechanical stirrer, a stirring rod, a thermometer, and a temperature controller were prepared in the same manner as in Example 1. The temperature was slowly raised to ℃. When the temperature was stabilized, about 96 g of ethyl 2-phenylacrylate and 0.39 g of a catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide) were added thereto, followed by stirring for 30 minutes. And the temperature was heated up to 75 degreeC, reaction was maintained for about 24 hours, and the ultraviolet curable carbodiimide oligomer whose number of carbodiimide groups contained in an ultraviolet curable carbodiimide oligomer molecule was about 2. The viscosity value at 25 degrees C of the obtained oligomer was 2,312,000 cP.

Example 3

Except using about 1.0 equivalent of TDI, the ultraviolet curable carbodiimide oligomer whose number of carbodiimide groups contained in an ultraviolet curable carbodiimide oligomer molecule was about 3 was obtained by the method similar to Example 2. The viscosity value at 25 degrees C of the obtained oligomer was 3,002,000 cP.

Example 4

Except for using about 1.5 equivalents of TDI, the ultraviolet curable carbodiimide oligomer having the number of carbodiimide groups contained in the ultraviolet curable carbodiimide oligomer molecule was about 4 in the same manner as in Example 2. The viscosity value at 25 degrees C of the obtained oligomer was 3,502,000 cP.

Example 5

Except using about 2.0 equivalents of TDI, the ultraviolet curable carbodiimide oligomer which the number of carbodiimide groups contained in an ultraviolet curable carbodiimide oligomer molecule was about 5 was obtained by the same method as Example 2. The viscosity value at 25 degrees C of the obtained oligomer was 3,780,000 cP.

Example 6

In an argon atmosphere, about 1 equivalent of TDI-HPA precursor and about 0.5 equivalents of methylene diphenyl diisocyanate (MDI) formed in a five-necked reactor equipped with a mechanical stirrer, a stirring rod, a thermometer, and a temperature controller in substantially the same manner as in Example 1. The temperature inside the reactor was slowly heated up to 45 ° C. When the temperature was stabilized, about 106g of ethyl 2-phenylacrylate and 0.42g of 3-methyl-1-phenyl-2-phosphorene-1-oxide were added thereto and stirred for 30 minutes. And the temperature was raised to about 75 degreeC, reaction was maintained for about 24 hours, and the ultraviolet curable carbodiimide oligomer whose number of carbodiimide groups contained in an ultraviolet curable carbodiimide oligomer molecule was about two. The viscosity value at 25 degrees C of the obtained oligomer was 2,950,000 cP.

<Refractive index evaluation>

The ultraviolet curable carbodiimide oligomers prepared in Examples 1 to 6 were diluted with diluent ethyl 2-phenylacrylate and measured at a temperature of about 25 ° C. using an ABBE Refractometer. The refractive index of the ultraviolet curable carbodiimide oligomer diluted with the diluent was obtained, and the refractive index of the stock solution was obtained from the extrapolated expected value of the graph. The stock refractive index obtained with the extrapolated expected value of Example 6 was about 1.6624, respectively.

1 is a graph showing the result of measuring the UV-curable carbodiimide oligomer prepared in Examples 1 to 4 after dilution with diluent ethyl 2-phenylacrylate, using an Abbe refractometer at a temperature of about 25 ℃ .

Here, the dilution rate of the ultraviolet curable carbodiimide oligomer means the weight ratio of the ultraviolet curable carbodiimide oligomer to the total solution. Through the above results, it was found that the refractive index increases as the number of carbodiimide groups included in the ultraviolet curable carbodiimide oligomer molecule increases.

Figure 2 is a graph showing the refractive index increase rate according to the number of carbodiimide groups contained in the ultraviolet curable carbodiimide oligomer molecule prepared according to Examples 1 to 4. Through the above results, it was found that as the number of carbodiimide groups included in the ultraviolet curable carbodiimide oligomer molecule increases, the tendency of increasing the refractive index slows down.

<Viscosity Evaluation>

The viscosity of the ultraviolet curable oligomer prepared according to Examples 1 to 6 is the result obtained according to the following method. This was measured at a temperature of about 25 ° C. using a Brookfield viscometer. Spin numbers used were 6 to 7 and torque ranges were repeated three times between about 40 to 65. The results are summarized in Table 1. The unit of viscosity is cP.

Through the above results, it can be seen that the viscosity increases as the number of carbodiimide groups included in the ultraviolet curable carbodiimide oligomer molecule increases. In particular, Example 5 showed a high viscosity liquid phenomenon that is difficult to measure the viscosity at room temperature.

Experimental Example

The UV curable carbodiimide oligomers prepared in Examples 2 to 6 were used to apply UV curable paints and then evaluated after UV curing. Table 2 shows a coating formulation of the ultraviolet curable paint. Each of the ultraviolet curable carbodiimide oligomers of Examples 2 to 6, 1-hydroxy cyclohexyl phenyl ketone (Irgacure 184 (I-184): Ciba-Geigy), phenyl ethyl acrylate (PEA), phenylthioethyl acrylic The rates (PTEA) were mixed in the weight ratios in Table 2. The characteristics evaluation results after UV curing of the ultraviolet curable paint are shown in Table 3.

Curing condition: Line speed: 14m / min, Light quantity: 220mJ / ㎠

1) Refractive index: It is the result measured at 25 ℃ using Abbe refractometer.

2) Adhesiveness: After cross cut (1mm interval, based on 100 squares), measure the coating state using 3M transparent tape and evaluate as ok if the cross cut does not drop.

3) Pencil Hardness: Conductive pencil hardness tester is used (pressurization load 500g, scraping angle 45 degrees, pencil 5B ~ 9H (including 16 types)

Referring to the results of Table 3, the ultraviolet curable paints of Experimental Examples 1 to 5 had a high refractive index, excellent hardness, and adhesiveness with the lower coating film was excellent in adhesive strength, according to the embodiments of the present invention. It was confirmed that the carbodiimide oligomer can be applied to an ultraviolet curable coating composition or the like.

The ultraviolet curable carbodiimide oligomer of the present invention described above has high thermal stability, chemical stability, and high refractive index. In addition, when applied to the paint, it can be easily cured through an ultraviolet curing process, it can form a film with excellent adhesion, hardness can be applied to a high refractive coating. In addition, the number of carbodiimides in the ultraviolet curable carbodiimide oligomer molecule can be adjusted by controlling the equivalent ratio of the compound containing the acrylate group and the isocyanate group and the second aromatic difunctional isocyanate compound. By controlling the number of carbodiimide in the ultraviolet curable carbodiimide oligomer molecule, an ultraviolet curable carbodiimide oligomer having an appropriate viscosity and refractive index can be easily produced.

As described above with reference to the preferred embodiment of the present invention, those skilled in the art without departing from the spirit and scope of the present invention described in the claims below various modifications and It will be appreciated that it can be changed.

Claims (10)

Reacting with 1 equivalent of the hydroxy group-containing acrylate and 0.95-1.05 equivalent of the first aromatic difunctional isocyanate compound to form a compound comprising an acrylate group and an isocyanate group, the compound comprising the acrylate group and an isocyanate group is 3-methyl-1 -Phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-sulfide, 1-ethyl-3-methyl-2-phosphorene -1-oxide, 3-methyl-1-phenyl-1-phosphor-3-cyclopentene-1-oxide, 2,5-dihydro-3-methyl-1-phenylphosphol-1-oxide and the corresponding UV-curable having an average molecular weight of 400 to 10,000 prepared by reacting with a second aromatic difunctional isocyanate compound in the presence of at least one carbodiimidation catalyst selected from the group consisting of isomers, wherein the molecule contains 1 to 10 carbodiimide groups Ka Bodyimide oligomers. The hydroxy group-containing acrylate is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and 2-hydroxy-3-phenoxypropyl acrylic. And at least one selected from the group consisting of acrylates, wherein the first aromatic difunctional isocyanate and the second aromatic difunctional isocyanate comprise toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI) and naphthalene diisocyanate (NDI). UV-curable carbodiimide oligomer, characterized in that at least one selected from the group consisting of. The ultraviolet curable carbodiimide oligomer according to claim 2, wherein the ultraviolet curable carbodiimide oligomer comprises 1 to 5 carbodiimide groups in the molecule. Reacting with 1 equivalent of the hydroxy group-containing acrylate and 0.95-1.05 equivalent of the first aromatic difunctional isocyanate compound to form a compound including an acrylate group and an isocyanate group; And
3-methyl-1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-sulfide, 1-ethyl-3-methyl 2-phosphorene-1-oxide, 3-methyl-1-phenyl-1-phosphor-3-cyclopentene-1-oxide, 2,5-dihydro-3-methyl-1-phenylphosphol-1 An average molecular weight 400 comprising reacting a compound comprising the acrylate group and an isocyanate group with a second aromatic difunctional isocyanate compound in the presence of at least one carbodiimidation catalyst selected from the group consisting of an oxide and the corresponding isomer To 10,000, and a method for producing an ultraviolet curable carbodiimide oligomer comprising 1 to 10 carbodiimide groups in a molecule. The hydroxy group-containing acrylate is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and 2-hydroxy-3-phenoxypropyl acrylic. UV curable carbodiimide oligomer, characterized in that it comprises at least one selected from the group consisting of the rate. The method of claim 4, wherein the first aromatic difunctional isocyanate and the second aromatic difunctional isocyanate are one selected from the group consisting of toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI) and naphthalene diisocyanate (NDI). The method of manufacturing the ultraviolet curable carbodiimide oligomer characterized by the above. The method of claim 4, wherein the hydroxy group-containing acrylate is hydroxypropyl acrylate and the first difunctional isocyanate is toluene diisocyanate (TDI). The compound comprising the acrylate group and the isocyanate group and the second difunctional isocyanate according to claim 4, wherein the compound comprising the acrylate group and the isocyanate group and the second difunctional isocyanate compound are reacted in the presence of the carbodiimidation catalyst. A method for producing an ultraviolet curable carbodiimide oligomer, wherein the number of carbodiimide in the ultraviolet curable oligomer molecule is controlled by controlling the equivalent ratio of the compound. The method of claim 8, wherein the number of carbodiimide in the ultraviolet curable carbodiimide oligomer molecule is 1 to 5. Reacting with 1 equivalent of the hydroxy group-containing acrylate and 0.95-1.05 equivalent of the first difunctional isocyanate compound to form a compound including an acrylate group and an isocyanate group; And
3-methyl-1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-sulfide, 1-ethyl-3-methyl 2-phosphorene-1-oxide, 3-methyl-1-phenyl-1-phosphor-3-cyclopentene-1-oxide, 2,5-dihydro-3-methyl-1-phenylphosphol-1 A compound containing an acrylate group and an isocyanate group in the presence of at least one carbodiimidation catalyst selected from the group consisting of an oxide and an isomer thereof, having an average molecular weight of 400 to 10,000, and a carbodiimide group in the molecule of 1 to 10 A method for producing a UV curable carbodiimide oligomer comprising a dog.

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