KR101805292B1 - Composition and method for producing the same, and unsaturated compound and method for producing the same - Google Patents

Abstract

The present invention provides a composition which can reduce the addition amount of a polymerization inhibitor for producing a colored component when producing an unsaturated compound, and which is excellent in stability during storage and stability in use, and a method for producing the composition. The composition of the present invention contains an unsaturated isocyanate compound and 0.01 to 10 ppm of a tertiary amine hydrochloride on a mass basis. The composition may contain 0.1 ppm or more of a tertiary amine hydrochloride on a mass basis. The unsaturated isocyanate compound is preferably acryloyloxyethyl isocyanate or methacryloyloxyethyl isocyanate.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a composition, a method for preparing the same, a method for producing the unsaturated compound, and a method for producing the unsaturated compound and an unsaturated compound,

The present invention relates to a composition containing an unsaturated isocyanate compound, a process for producing the composition, and a process for producing an unsaturated compound and an unsaturated compound.

Conventionally, unsaturated urethane compounds, unsaturated thiourethane compounds, unsaturated urea compounds, unsaturated amide compounds and other unsaturated compounds are prepared by reacting an unsaturated isocyanate compound with a compound having an active hydrogen. The unsaturated compound thus produced is used for various purposes.

For example, there is an unsaturated urethane compound prepared by reacting an unsaturated isocyanate compound, methacryloyloxyethyl isocyanate (hereinafter also referred to as MOI), with a polyalkylene glycol which is a compound having a hydroxyl group. This unsaturated urethane compound can be suitably used as a material for a contact lens (see, for example, Patent Document 1), a solid solvent of a solid polymer electrolyte (for example, see Patent Document 2), a material for immobilizing a biological material , Patent Document 3 and Patent Document 4).

Patent Document 5 describes an unsaturated urea compound obtained by reacting an MOI with an organopolysiloxane having amino groups at both ends of the molecule. Patent Document 5 discloses that the unsaturated urea compound is used as a material for a radiation-curable adhesive organopolysiloxane composition.

Patent Document 6 discloses a urethane acrylate synthesized by reacting an unsaturated isocyanate compound such as MOI with a product obtained by reacting a dimer diol with a polyisocyanate. Further, Patent Document 6 discloses a curable composition containing the urethane acrylate.

Examples of the unsaturated isocyanate compound used as the material of the unsaturated compound include acryloyloxyethyl isocyanate (hereinafter also referred to as AOI), methacryloyl isocyanate (hereinafter also referred to as MAI), and the like in addition to MOI. MOI, AOI, and MAI are industrially manufactured and marketed, and are readily available.

The MOI is synthesized by the reaction of isopropenyl oxazoline or 2-aminoethyl methacrylate hydrochloride with phosgene. AOI is synthesized by the reaction of 2-vinyloxazoline or 2-aminoethyl acrylate hydrochloride with phosgene. MAI is synthesized by the reaction of methacrylic acid amide with oxalyl chloride.

The unsaturated isocyanate compound thus synthesized includes impurities such as by-products and catalyst residues. Accordingly, after an unsaturated isocyanate compound is synthesized, an operation of removing impurities to increase the purity is generally performed (see, for example, Patent Document 7 and Patent Document 8).

In addition, for the unsaturated isocyanate compound thus synthesized, a variety of methods have conventionally been used to determine the quality of the unsaturated isocyanate compound. Specifically, a method of confirming the appearance of the unsaturated isocyanate compound, such as turbidity and hue, a method of confirming the purity of the unsaturated isocyanate compound using gas chromatography, and a method of titrating the hydrolyzable chlorine content in the unsaturated isocyanate compound by potentiometric titration A method for identifying soluble impurities in an unsaturated isocyanate compound using gel permeation chromatography (GPC) (see, for example, Patent Document 9), and the like.

Generally, an unsaturated isocyanate compound is added with a polymerization inhibitor to stably transport and store the unsaturated isocyanate compound. As the polymerization inhibitor, hydroquinone or the like is used and added at a concentration of several tens to several hundreds ppm. For example, Patent Document 6 discloses that when an unsaturated urethane compound is synthesized by using an unsaturated isocyanate compound, 0.01 to 10 parts by weight of a polymerization inhibitor is added to 100 parts by weight of the total weight component.

Patent Document 6 describes triethylamine hydrochloride as a polymerization inhibitor to be used when an unsaturated compound is produced from an unsaturated isocyanate compound as a raw material.

However, the tertiary amine hydrochloride salt such as triethylamine hydrochloride has a low solubility in the unsaturated isocyanate compound. Therefore, when the tertiary amine hydrochloride is used as the polymerization inhibitor, when the temperature of the unsaturated isocyanate compound becomes low, precipitation and precipitation or clouding of the unsaturated isocyanate compound are likely to occur. As a result, the tertiary amine hydrochloride is not generally used as a polymerization inhibitor for an unsaturated isocyanate compound.

Japanese Patent Application Laid-Open No. 6-322051 Japanese Unexamined Patent Application Publication No. 6-187822 Japanese Patent Application Laid-Open No. 60-234582 Japanese Patent Application Laid-Open No. 60-234583 Japanese Unexamined Patent Application Publication No. 6-184256 International Publication No. 2011/074503 Japanese Patent No. 4273531 Japanese Patent No. 4823546 Japanese Patent Laid-Open No. 2007-8828

CMC Technical Library "Polymer degradation mechanism and stabilization technology" CMC publication (2005/04 release) Page 168 Figure 5

In the conventional unsaturated isocyanate compound, unexpected increase in viscosity or gelation may occur during storage and / or transportation even if a large difference in quality is not observed in the conventional determination method. Further, in the conventional unsaturated isocyanate compound, there is a case where the unsatisfactory compound is produced by using a conventional determination method, even if there is no significant difference in quality, the viscosity of the reaction product is rapidly increased or gelated during the production .

A polymerization inhibitor may be added to the unsaturated isocyanate compound sufficiently in order to prevent viscosity increase or gelation during storage and transportation of the unsaturated isocyanate compound and to improve stability during storage. In addition, the addition of the polymerization inhibitor to the unsaturated isocyanate compound sufficiently improves the stability (hereinafter referred to as " stability at the time of use ") when the unsaturated compound is prepared from the same as the raw material, Can be inhibited from increasing rapidly or gelling.

However, when a large amount of the polymerization inhibitor is added to the unsaturated isocyanate compound, a colored component due to the polymerization inhibitor is likely to be generated together with the unsaturated compound when the unsaturated compound is prepared using the same as a raw material (see, for example, 1). As a result, the produced unsaturated compound may be colored.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a composition which can reduce the addition amount of a polymerization inhibitor for producing a colored component in the production of an unsaturated compound, And the like.

It is another object of the present invention to provide an unsaturated compound which is difficult to gel in the course of production using the above composition as a raw material, and a process for producing the unsaturated compound.

It is known that triethylamine hydrochloride has a function as a polymerization inhibitor. In addition, even when triethylamine hydrochloride is contained in the raw material of the unsaturated compound together with the unsaturated isocyanate compound, no coloring component is produced when the unsaturated compound is produced. In addition, triethylamine hydrochloride can be a by-product in the course of the synthesis of an unsaturated isocyanate compound. Therefore, the inventors of the present invention have studied the use of triethylamine hydrochloride to reduce the amount of the polymerization inhibitor for producing a colored component when producing an unsaturated compound to be added to an unsaturated isocyanate compound.

The inventors of the present invention adjusted the amount of triethylamine hydrochloride remaining after the triethylamine hydrochloride was produced as a by-product in the course of the synthesis of the unsaturated isocyanate compound, followed by purification by controlling the removal amount of the supernatant by distillation. Then, the relationship between the content of triethylamine hydrochloride and the stability of the unsaturated isocyanate compound in storage was examined. As a result, it was found that the smaller the content of the triethylamine hydrochloride having the function as the polymerization inhibitor, the more difficult the gelation of the unsaturated isocyanate compound was.

From these results, it is presumable that the reason for deteriorating the stability of the unsaturated isocyanate compound during storage is not a triethylamine hydrochloride, but an unspecified impurity which is purified as a supernatant with triethylamine hydrochloride by purification by distillation . Therefore, the inventors of the present invention thought that the content of the triethylamine hydrochloride in the unsaturated isocyanate compound purified by the distillation method can be used as an index of the unspecified impurity content which deteriorates the stability in storage.

Further, the inventors of the present invention have found that triethylamine hydrochloride is not a source of triethylamine hydrochloride when the content of triethylamine hydrochloride is used as an index of an unspecified impurity content in an unsaturated isocyanate compound. That is, it has been found that the triethylamine hydrochloride used as the index may be a by-product in the course of the synthesis of the unsaturated isocyanate compound or may be added before the purification of the unsaturated isocyanate compound.

The inventor of the present invention has found that the amount of the tertiary amine hydrochloride mixed in the unsaturated isocyanate compound is 0.01 to 10 ppm and the amount of removal of the supernatant is adjusted by distillation to purify the unidentified impurities A sufficiently removed composition was obtained. Further, it has been confirmed that the composition in which the above-described unspecific impurities are sufficiently removed has not only stability during storage but also stability during use, and has completed the present invention.

In addition, even when triethylamine hydrochloride is added to a composition in which the unspecific impurities are sufficiently removed, even when the content of triethylamine hydrochloride in the composition is 10 ppm or more, the stability during storage and the stability during use deteriorate none. Further, the triethylamine hydrochloride is not required to be removed even if it is contained in the unsaturated isocyanate compound unless it is precipitated. Thus, when the by-produced triethylamine hydrochloride is conventionally removed from the unsaturated isocyanate compound, a method of removing the precipitate by filtration has been used. When triethylamine hydrochloride is produced as a by-product in the synthesis process and is removed by filtration, the content of triethylamine hydrochloride remaining in the unsaturated isocyanate compound after filtration is 100 to 300 ppm, and the concentration is not 10 ppm or less.

Further, conventionally, when the by-produced triethylamine hydrochloride is removed, it is not necessary to adjust the concentration to 10 ppm or less. Therefore, distillation for making triethylamine hydrochloride not more than 10 ppm has not been conducted. In the present invention, "ppm" is on a mass basis.

The present invention is based on the above findings, and has the following forms.

[1] A composition comprising an unsaturated isocyanate compound and 0.01 to 10 ppm by weight of a tertiary amine hydrochloride. The composition preferably contains 98% or more, preferably 98.3% or more of an unsaturated isocyanate compound and 0.01 to 10 ppm of a tertiary amine hydrochloride.

[2] A composition according to [1], which contains 0.1 ppm or more of a tertiary amine hydrochloride on a mass basis.

[3] The composition according to [1] or [2], wherein the unsaturated isocyanate compound is acryloyloxyethyl isocyanate or methacryloyloxyethyl isocyanate.

[4] The composition according to any one of [1] to [3], wherein the tertiary amine hydrochloride is triethylamine hydrochloride.

[5] A process for preparing a mixture comprising an unsaturated isocyanate compound and a tertiary amine hydrochloride in an amount of more than 10 ppm by mass, and a step of purifying the mixture to obtain a composition wherein the content of the tertiary amine hydrochloride is 0.01 to 10 ppm by mass ≪ / RTI > by weight, based on the total weight of the composition.

[6] The method for producing a composition according to [5], wherein the purification step is performed to form a composition having a tertiary amine hydrochloride content of 0.1 ppm or more on a mass basis.

[7] The method for producing a composition according to [5] or [6], wherein the step of producing the mixture comprises a step of synthesizing the unsaturated isocyanate compound and by-produced the tertiary amine hydrochloride. The method for synthesizing the unsaturated isocyanate compound preferably has a step of producing a 3-chloropropionic acid ester derivative having an isocyanato group represented by the following formula (1) and dehydrochlorinating it in the presence of a trialkylamine.

(1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having a straight or branched structure of 1 to 10 carbon atoms or a cycloalkylene group having 3 to 6 carbon atoms, And R < ² > is preferably methylene, ethylene, or propylene, more preferably ethylene)

[8] The method for producing a composition according to any one of [5] to [7], wherein the step of preparing the mixture comprises a step of mixing the unsaturated isocyanate compound and the tertiary amine hydrochloride.

[9] The process for producing a composition according to any one of [5] to [8], wherein the unsaturated isocyanate compound is acryloyloxyethyl isocyanate or methacryloyloxyethyl isocyanate.

[10] The method for producing a composition according to any one of [5] to [9], wherein the tertiary amine hydrochloride is triethylamine hydrochloride.

[11] The method for producing a composition according to any one of [5] to [10], wherein in the purification step, the mixture is purified by distillation.

[12] A process for producing an amorphous isocyanate compound, which comprises preparing a mixture containing an unsaturated isocyanate compound and a tertiary amine hydrochloride in an amount of more than 10 ppm on a mass basis by distillation and having a tertiary amine hydrochloride content of 0.01 to 10 ppm, Composition. The method for synthesizing the unsaturated isocyanate compound preferably has a step of producing a 3-chloropropionic acid ester derivative having an isocyanato group represented by the following formula (1) and dehydrochlorinating it in the presence of a trialkylamine.

(1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having a straight or branched structure of 1 to 10 carbon atoms or a cycloalkylene group having 3 to 6 carbon atoms, R ² is preferably a methylene group, an ethylene group or a propylene group, more preferably an ethylene group)

[13] The composition according to [12], wherein the removal amount of the supernatant is controlled in the distillation method.

[14] The composition according to [12] or [13], wherein the removal amount of the supernatant is 4% or more.

[15] A process for producing a polymer composition, which comprises mixing a composition according to any one of [1] to [4] and [12] to [14] with a compound having an active hydrogen and reacting the unsaturated isocyanate compound and the active hydrogen- To obtain an unsaturated compound. ≪ RTI ID = 0.0 > 11. < / RTI >

[16] The process for producing an unsaturated compound according to [15], wherein the compound having an active hydrogen is a polyol, a polythiol, a polyamine or a polycarboxylic acid.

[17] The method for producing an unsaturated compound according to [15] or [16], wherein the unsaturated compound is an unsaturated urethane compound, an unsaturated thiourethane compound, an unsaturated urea compound, or an unsaturated amide compound.

[18] An unsaturated compound produced by the method for producing an unsaturated compound according to any one of [15] to [17].

[19] The unsaturated compound according to [18], wherein the unsaturated compound is an unsaturated urethane compound, an unsaturated thiourethane compound, an unsaturated urea compound, or an unsaturated amide compound.

Since the composition of the present invention contains an unsaturated isocyanate compound and a tertiary amine hydrochloride in an amount of 0.01 to 10 ppm, the stability during storage is excellent because unexpected increase in viscosity or gelation of the composition during storage and transportation is difficult to occur. In addition, the composition of the present invention is excellent in stability at the time of use because the reaction product formed during the production of the unsaturated compound by using the composition is unlikely to increase rapidly in viscosity or gelation.

Since the composition of the present invention is excellent in stability at the time of storage and stability in use, it is not necessary to include a large amount of a polymerization inhibitor for producing a colored component when producing an unsaturated compound. Therefore, it is possible to prevent the unsaturated compound produced by using the composition of the present invention from being colored by the coloring component caused by the polymerization inhibitor.

The process for preparing the composition of the present invention comprises the steps of: preparing a mixture containing an unsaturated isocyanate compound and a tertiary amine hydrochloride in an amount of more than 10 ppm; and purifying the mixture to form a composition having a tertiary amine hydrochloride content of 0.01 to 10 ppm . ≪ / RTI > Therefore, unspecified impurities that deteriorate the stability during storage and stability in use contained in the mixture are sufficiently removed together with the excess tertiary amine hydrochloride in the purification process. As a result, the composition of the present invention having less unspecified impurities and excellent stability in storage and stability in use can be obtained.

The method for producing an unsaturated compound of the present invention includes a step of mixing the composition of the present invention with a compound having active hydrogen and reacting the unsaturated isocyanate compound contained in the composition with a compound having active hydrogen to obtain an unsaturated compound. Therefore, the reaction product is hardly increased in viscosity or gelation during the production, and excellent productivity is obtained.

In addition, since the unsaturated compound of the present invention is produced by using the method for producing an unsaturated compound of the present invention, it is difficult for the reaction product to increase in viscosity or gelation during the production.

&Quot; Composition &

The composition of the present embodiment contains an unsaturated isocyanate compound and 0.01 to 10 ppm of a tertiary amine hydrochloride. The composition of the present embodiment is preferably prepared by purifying a mixture containing an unsaturated isocyanate compound and a tertiary amine hydrochloride in an amount of more than 10 ppm by distillation. In the present invention, the mixture means a composition before purification.

In the present invention, the unsaturated isocyanate compound means a compound containing both an ethylenic unsaturated bond and an isocyanato group in the molecule. The unsaturated isocyanate compound may have one ethylenic unsaturated bond or two or more ethylenic unsaturated bonds. The number of isocyanato groups contained in the unsaturated isocyanate compound may be one or two or more.

Specific examples of the unsaturated isocyanate compound contained in the composition include (meth) acryloyloxyalkyl isocyanate, (meth) acryloyl isocyanate, (meth) acrylate containing a hydroxyl group (for example, 2-hydroxyethyl Methacrylate) and a diisocyanate compound, particularly, a 1: 1 adduct of 2,4-tolylene diisocyanate or isophorone diisocyanate having different reactivity of two isocyanato groups.

Examples of the (meth) acryloyloxyalkyl isocyanate include 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate , 6- (meth) acryloyloxyhexyl isocyanate, and the like.

Among these unsaturated isocyanate compounds, from the viewpoint of selectivity of the reaction, compounds containing a (meth) acryloyl group and an isocyanato group in the molecule are preferable, and (meth) acryloyloxyalkyl isocyanate or (meth) Isocyanate is more preferable, and (meth) acryloyloxyalkyl isocyanate is more preferable.

The alkyl group in the (meth) acryloyloxyalkyl isocyanate is preferably a straight chain alkyl group having no substituent in view of the selectivity of the reaction. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. In particular, the number of carbon atoms of the alkyl group is preferably 2, and specifically acryloyloxyethyl isocyanate (AOI) or methacryloyloxyethyl isocyanate (MOI) is preferable.

In the present invention, the term "(meth) acryloyl group" means an acryloyl group having a hydrogen atom bonded to α or a methacryloyl group having a methyl group bonded to α. The term "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylic acid" means acrylic acid or methacrylic acid.

The composition of the present invention contains 0.01 to 10 ppm of a tertiary amine hydrochloride salt in the composition.

The content of the tertiary amine hydrochloride has a correlation with the content of unspecified impurities which deteriorates the stability of the composition during storage and the stability at the time of use. Therefore, the tertiary amine hydrochloride contained in the composition functions as an index indicating stability in storage and stability in use. The tertiary amine hydrochloride also functions as a polymerization inhibitor in the composition. In addition, the tertiary amine hydrochloride is a compound that does not produce a colored component even when an unsaturated compound is produced using the composition of the present embodiment.

As the tertiary amine hydrochloride contained in the composition, for example, various trialkylamine hydrochloride salts, compounds in which two or three alkyl groups bonded to a nitrogen atom are bonded to each other to form a cyclic structure (oxygen, sulfur, (For example, N, N-dialkylaniline, N, N-dialkylaminopyridine, etc.) in which one of the groups bonded to the nitrogen atom is an aromatic group And the like.

Of these tertiary amine hydrochloride salts, trialkylamine hydrochloride salts such as triethylamine hydrochloride and tripropylamine hydrochloride, and tetramethylethylenediamine hydrochloride are preferably used. Among them, it is preferable to use triethylamine hydrochloride which is easily produced as a by-product in the process of synthesizing the unsaturated isocyanate compound.

The tertiary amine hydrochloride may be used singly or in combination of two or more kinds.

In order to make the content of the tertiary amine hydrochloride less than 0.01 ppm, it is necessary to perform the purification step described later for a long time, and the productivity is lowered. Therefore, the content of the tertiary amine hydrochloride contained in the composition should be 0.01 ppm or more.

The content of the tertiary amine hydrochloride in the composition is preferably 0.1 ppm or more. When the content of the tertiary amine hydrochloride contained in the composition is 0.1 ppm or more, the function as the polymerization inhibitor of the tertiary amine hydrochloride is sufficiently obtained. Therefore, when the composition contains a polymerization inhibitor, the amount of the polymerization inhibitor to be used can be further suppressed. For example, when the composition contains hydroquinone or the like which produces a colored component when producing an unsaturated compound as a polymerization inhibitor, the amount of the hydroquinone to be used can be effectively reduced by setting the content of the tertiary amine hydrochloride to 0.1 ppm or more . Therefore, it is possible to prevent the unsaturated compound produced by using the composition of this embodiment from being colored by the coloring component caused by the polymerization inhibitor.

On the other hand, if the content of the tertiary amine hydrochloride contained in the composition exceeds 10 ppm, the unspecific impurities are not removed sufficiently, so that the stability at the time of storage and / or stability at the time of use becomes insufficient. The content of the tertiary amine hydrochloride contained in the composition is preferably 8 ppm or less, and more preferably 5 ppm or less, in order to further improve the stability in storage and the stability in use.

The composition of the present invention may contain an additive in addition to the unsaturated isocyanate compound and the tertiary amine hydrochloride, so long as the effect of the present invention is not impaired.

As the additives, for example, polymerization inhibitors such as hydroquinone can be mentioned.

&Quot; Method of producing composition "

The process for preparing the composition of the present embodiment comprises the steps of preparing a mixture containing an unsaturated isocyanate compound and a tertiary amine hydrochloride in an amount of more than 10 ppm and a step of purifying the mixture to obtain a composition having a tertiary amine hydrochloride content of 0.01 to 10 ppm Lt; / RTI >

&Quot; Process for preparing a mixture "

As the unsaturated isocyanate compound contained in the mixture, the above-mentioned unsaturated isocyanate compounds are exemplified, and acryloyloxyethyl isocyanate or methacryloyloxyethyl isocyanate is particularly preferable.

As the tertiary amine hydrochloride contained in the mixture, the above-mentioned ones can be mentioned, and it is particularly preferable to be triethylamine hydrochloride.

It is preferable that the step of preparing the mixture has a step of synthesizing an unsaturated isocyanate compound and forming a tertiary amine hydrochloride as a by-product.

In this case, a crude unsaturated isocyanate compound (before purification) synthesized by the method of synthesizing an unsaturated isocyanate compound in which a tertiary amine hydrochloride is a by-product in the step of producing the mixture may be produced, and the crude unsaturated isocyanate compound Which contains more than 10 ppm of a tertiary amine hydrochloride, may be produced.

As the step of producing a tertiary amine hydrochloride, conventionally known methods can be used, and there is no particular limitation. For example, the following final steps included in the method for synthesizing an unsaturated isocyanate compound can be mentioned.

A 3-chloropropionic acid ester derivative having an isocyanato group represented by the following formula (1) is produced, and this is dehydrochlorinated in the presence of a trialkylamine. As a result, a (meth) acrylic acid ester derivative (unsaturated isocyanate compound) having an isocyanato group represented by the following formula (2) is obtained.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 10 carbon atoms, a linear or branched alkylene group having 3 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, Chain hydrocarbon group having an alkylene group having 0 to 3 carbon atoms before and after the alkylene group)

In this production method, when the unsaturated isocyanate compound represented by the above formula (2) is produced, a trialkylamine hydrochloride which is a tertiary amine hydrochloride is by-produced. When triethylamine is used as the trialkylamine, when the unsaturated isocyanate compound represented by the above formula (2) is produced, triethylamine hydrochloride is produced as a by-product.

The step of preparing the mixture may be a method in which the content of the tertiary amine hydrochloride in the mixture is made to exceed 10 ppm by mixing the unsaturated isocyanate compound and the tertiary amine hydrochloride.

In this case, the unsaturated isocyanate compound may be a compound synthesized using a synthesis method in which a tertiary amine hydrochloride is by-produced, or a compound synthesized using a synthesis method in which a tertiary amine hydrochloride is not produced as a by-product. May be used. As the unsaturated isocyanate compound, the synthesized crude unsaturated isocyanate compound (before purification) may be used, or the purified unsaturated isocyanate compound may be used during purification of the crude unsaturated isocyanate compound, or an unsaturated isocyanate compound after purification may be used.

As the method for producing the unsaturated isocyanate compound in which the tertiary amine hydrochloride is not produced as a by-product, conventionally known methods can be used and are not particularly limited. For example, the method described in Japanese Patent Application Laid-Open No. 54-005921, And a method of synthesizing a salt of (meth) acrylic acid with an amino alcohol such as alkyl (meth) acrylate hydrochloride by reacting with phosgene.

When the unsaturated isocyanate compound and the tertiary amine hydrochloride are mixed, the content of the tertiary amine hydrochloride in the mixture may be more than 10 ppm. The content of the tertiary amine hydrochloride in the mixture is preferably 100 ppm or more in order to more effectively remove unspecified impurities along with the tertiary amine hydrochloride in the purification step described later. The content of the tertiary amine hydrochloride in the mixture is preferably 300 ppm or less and more preferably 250 ppm or less in order to facilitate the purification step to be described later.

&Quot; Purification process "

In the present embodiment, the mixture containing the unsaturated isocyanate compound thus obtained and the tertiary amine hydrochloride salt in an amount exceeding 10 ppm is purified to obtain a composition having a tertiary amine hydrochloride content of 0.01 to 10 ppm (purification step). The purification step may be a step of making a composition having a tertiary amine hydrochloride content of 0.1 to 10 ppm.

The method for purifying the mixture may be a method for obtaining a composition in which the content of the tertiary amine hydrochloride is 0.01 to 10 ppm. From the viewpoint of productivity, the distillation method is preferably used.

In the distillation method, in order to obtain a composition in which the content of the tertiary amine hydrochloride is 0.01 to 10 ppm, the removal amount of the evaporated crude oil is adjusted until the steam temperature of the mixture becomes a stable constant temperature after the heating of the mixture is started . Specifically, after starting the heating of the mixture, the effluent is collected at predetermined intervals, and the concentration of the tertiary amine hydrochloride in the effluent is measured.

It is preferable to remove the effluent until the concentration of the tertiary amine hydrochloride in the effluent reaches a predetermined concentration or less as the supernatant. Thereby, a composition having a tertiary amine hydrochloride content of 0.01 to 10 ppm is obtained. The removal amount of the fresh feed is preferably 4% or more so as to make the content of the tertiary amine hydrochloride 10 ppm or less.

As a method of purifying the mixture, two or more purifying methods may be combined. Concretely, for example, a filtration method or the like may be performed before and / or after the distillation method.

When the filtration method is used, the removal amount of the tertiary amine hydrochloride can be adjusted by changing the temperature of the mixture and / or the kind of filter used for filtration. Specifically, the amount of the tertiary amine hydrochloride to be removed can be increased by filtering the cooled mixture and / or using a filter having a small eye size.

In the case of using the distillation method in the purification step, the polymerization inhibitor may be added to the mixture before heating of the mixture is started. By adding a polymerization inhibitor to the mixture before starting the heating of the mixture, it is possible to prevent the unsaturated isocyanate compound from polymerizing and gelation due to the temperature rise accompanying distillation.

The polymerization inhibitor added to the mixture is partially removed by distillation. The polymerization inhibitor remaining in the composition after distillation prevents gelation of the composition during storage and transportation of the composition and contributes to improvement of stability during storage of the composition. The polymerization inhibitor may be added to the composition obtained after distillation, if necessary.

Specific examples of the polymerization inhibitor include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, 2,6-di-tert- -tert-butylphenol and the like.

[Production method of unsaturated compound]

The method for producing an unsaturated compound of the present invention includes a step of mixing any of the above compositions with a compound having an active hydrogen to react an unsaturated isocyanate compound contained in the composition with a compound having active hydrogen to obtain an unsaturated compound .

In the present embodiment, the unsaturated isocyanate compound contained in the composition used as the material of the unsaturated compound is not particularly limited and may be appropriately selected depending on the structure of the unsaturated compound.

The active hydrogen in the active hydrogen-containing compound is a hydrogen atom bonded to a nitrogen atom, an oxygen atom, a sulfur atom or the like and exhibits a higher reactivity than a hydrogen atom bonded to a carbon atom.

The compound having an active hydrogen is not particularly limited and can be appropriately selected depending on the structure of the unsaturated compound.

For example, when a compound having an active hydrogen-containing group such as a hydroxyl group, a mercapto group, an amino group (including a cyclic amine, an amide, and an imide), or a carboxyl group is used as a compound having an active hydrogen, (Unsaturated compound) shown in Fig.

When an unsaturated isocyanate compound contained in the composition is reacted with a hydroxyl group-containing compound, the isocyanato group of the unsaturated isocyanate compound reacts with the hydroxyl group to form an unsaturated urethane compound. In the present embodiment, the unsaturated urethane compound means a compound containing an ethylenic unsaturated bond and a urethane bond in the molecule.

When an unsaturated isocyanate compound contained in the composition is reacted with a compound having a mercapto group, the isocyanato group of the unsaturated isocyanate compound reacts with the mercapto group to produce an unsaturated thiourethane compound. In the present embodiment, the unsaturated thiourethane compound means a compound containing an ethylenically unsaturated bond and a thiourethane bond in the molecule.

When an unsaturated isocyanate compound contained in the composition is reacted with a compound having an amino group, the isocyanato group of the unsaturated isocyanate compound reacts with the amino group to form an unsaturated urea compound. In the present embodiment, the unsaturated urea compound means a compound containing an ethylenic unsaturated bond and a urea bond in the molecule.

When an unsaturated isocyanate compound contained in the composition is reacted with a compound having a carboxyl group, the isocyanato group of the unsaturated isocyanate compound reacts with the carboxyl group to form an unsaturated amide compound. In the present embodiment, the unsaturated amide compound means a compound containing an ethylenic unsaturated bond and an amide bond in the molecule.

Examples of the compound having a hydroxyl group include aliphatic alcohol compounds such as ethanol, n- or iso-propanol, butanol, or isomers thereof, pentanol, hexanol, octanol and decanol; Phenol compounds such as phenol, cresol, p-nonylphenol and methyl salicylate; But are not limited to, ethylene glycol, diethylene glycol, propylene glycol, tetramethylene diol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, pentaerythritol, (2-hydroxyethyl) isocyanurate, cyclohexanediol, cyclohexanediol, cyclohexanediol, cyclohexanediol, cyclohexanediol, cyclohexanediol, cyclohexanediol, cyclohexanediol, cyclohexanediol, , Aliphatic polyols such as cyclohexanedimethanol, hydroxypropylhexanol, tricyclo [5,2,3,02,6] decanedimethanol and dicyclohexanediol; Aromatic polyols such as dihydroxynaphthalene, dihydroxybenzene, bisphenol-A, bisphenol-F, pyrogallol, xylene glycol and bisphenol-A (2-hydroxyethyl ether); Halogenated polyols such as dibromonopentyl glycol; A hydroxyl group-containing epoxy resin; Phenoxy resins; High molecular polyols such as polyvinyl alcohol and (co) polymers of hydroxyethyl (meth) acrylate; A reaction product of an organic acid such as phthalic acid, pyromellitic acid, trimellitic acid, adipic acid and dimeric acid, and a terminal hydroxyl group of the polyol; An addition reaction product of the polyol and an alkylene oxide (ethylene oxide, propylene oxide, etc.); Glucose derivatives such as hydroxyethylcellulose, nitrocellulose and the like; Alcohols containing heterocyclic rings such as carboxylic esters of pentaerythritol (formic acid, acetic acid, benzoic acid, etc.) ortho esters; Having both a hydrogen group and a mercapto group like 2-mercaptoethanol; Oxime compounds such as dimethyl ketone oxime, diethyl ketone oxime, and methyl ethyl ketone oxime; And the like.

As the compound having a hydroxyl group, among the above-mentioned compounds, a polyol is preferable, and an aliphatic polyol is more preferable.

Examples of the compound having a mercapto group include 1-butanethiol, 1-pentanethiol, 1-octanethiol, 1-dodecanethiol, n-octanedecanethiol, Thiazoline-2-thiol, 2-methyl-2-propanethiol, O-aminothiophenol and the like; Butanediol bis-thioglycolate, ethylene glycol bis-thioglycolate, ethylene glycol bis-thiophosphate, trimethylolpropane tris-thioglycolate, Pentaerythritol tetrakisthiopropionate, trimercapto propionic acid tris (2-hydroxyphenyl) propionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Dimercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto- s-triazine, tetraethylene glycol bis 3-mercaptopropionate, trimethylolpropane tris 3-mercaptopropionate, tris (3-mercaptopropyloxyethyl) isocyanurate, pentaerythritol tetra Mercapto propionate, dipentaerythritol tetrakis 3-mercaptopropionate, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (1H, 3H, 5H) -thione and pentaerythritol tetrakis (3-mercaptobutyrate); aliphatic polyanhydrides such as trimethylolpropane tri (meth) acrylate; And the like.

As the compound having a mercapto group, among the above-mentioned compounds, polythiol is preferable, and aliphatic polythiol is more preferable.

Examples of the compound having an amino group include monoamines such as butylamine, hexylamine and aniline; Aliphatic polyamines such as diethylenetriamine, triethylenetetramine, 1,3- or 1,4-bisaminomethylcyclohexane, isophoronediamine, hexamethylenediamine and bis (4-aminocyclohexyl) methane; aromatic polyamines such as m- or p-xylylenediamine, bis (4-aminophenyl) methane, 2,4- or 2,6-tolylenediamine; Glycosaminics such as chitosan; Silicone compounds such as bis (3-aminopropyl) polydimethylsiloxane and bis (3-aminopropyl) polydiphenylsiloxane; Heterocyclic compounds such as imidazole, epsilon -caprolactam and phthalic acid imide; Amides; Imide; 2 - [(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, and 3,5-dimethylpyrazole.

As the compound having an amino group, among the above-mentioned compounds, a polyamine is preferable, and an aliphatic polyamine is more preferable.

Examples of the compound having a carboxyl group include monocarboxylic acids such as acetic acid, propionic acid and decanoic acid; Aliphatic and aromatic polycarboxylic acids such as succinic acid, adipic acid, dimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; And polymeric polycarboxylic acids such as (co) polymers of polyamic acid and acrylic acid.

Among the above-mentioned compounds having a carboxyl group, polycarboxylic acid is preferable and aliphatic / aromatic polycarboxylic acid is more preferable.

As the compound having an active hydrogen, a halogen substituent such as a fluorine substituent or a chlorine substituent of the compound having an active hydrogen may be used. These may be used alone or in combination of two or more.

Among the above-mentioned compounds having an active hydrogen, polyol, polythiol, polyamine or polycarboxylic acid is preferable in view of versatility, and polyol is particularly preferable.

In the reaction of the unsaturated isocyanate compound and the compound having active hydrogen contained in the composition of the present invention, the ratio of the use of the unsaturated isocyanate compound and the compound having active hydrogen is set in consideration of the ratio of isocyanato group / active hydrogen do.

The ratio of the isocyanato group / active hydrogen may be the same as the ratio applied in the conventional reaction between the unsaturated isocyanate compound and the compound having active hydrogen. The ratio of isocyanato group / active hydrogen differs depending on the kind of compound having active hydrogen. For example, when the active hydrogen-containing compound is a monoalcohol, a diol or the like, the ratio of isocyanato group / active hydrogen is almost 1/1 in many cases. When the active hydrogen-containing compound is a polymer polyol or the like, the proportion of the isocyanato group is usually smaller than that of the above-mentioned ratio, for example, is often in the range of isocyanato group / active hydrogen = 0.01 / 1 to 0.5 / 1 .

The unsaturated isocyanate compound and the compound having active hydrogen contained in the composition of the present invention may be reacted in the presence of a reaction catalyst. The reaction rate can be controlled according to the addition amount of the reaction catalyst.

As the reaction catalyst, a known reaction catalyst may be used. Specific examples of the reaction catalyst include dibutyltin dilaurate, copper naphthenate, cobalt naphthenate, zinc naphthenate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl A mixture of bismuth tris (2-ethylhexanoate) and 2-ethylhexanoic acid, titanium diisopropoxybis (ethylacetoacetate), zirconium acetylacetonate, , And the like. These reaction catalysts may be used singly or in combination of two or more.

The amount of the reaction catalyst to be used is preferably 0.025 to 2.5 mass%, more preferably 0.05 to 2 mass%, based on the unsaturated isocyanate compound (100 mass%). When the addition amount of the reaction catalyst is 0.025 mass% or more, the reactivity is not significantly lowered. When the addition amount of the reaction catalyst is 2.5 mass% or less, the side reaction is less likely to occur during the reaction.

The reaction temperature for the reaction of the unsaturated isocyanate compound and the active hydrogen-containing compound contained in the composition of the present invention is preferably -10 to 100 占 폚, more preferably 0 to 80 占 폚.

When the unsaturated isocyanate compound and the active hydrogen-containing compound contained in the composition of the present invention are reacted, a polymerization inhibitor may be added, if necessary. As the polymerization inhibitor, those generally used can be used, and for example, phenol compounds, hydroquinone compounds and the like can be used. Specific examples of the polymerization inhibitor include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, 2,6-di-tert- -tert-butylphenol and the like.

In addition, various substances such as known light stabilizers, ultraviolet absorbers, antioxidants, dye fillers, reactive diluents and the like may be added during the reaction in accordance with the purpose.

The unsaturated compound of the present invention thus obtained is preferably used as materials in various fields such as painting and coating, point and adhesive, photoresist, contact lens, solid electrolyte and solidification of physiologically active substance.

[Unsaturated compound]

The unsaturated compound of the present invention is a reaction product prepared by using any of the above-described methods for producing an unsaturated compound.

The reaction product includes, for example, an unsaturated urethane compound, an unsaturated thiourethane compound, an unsaturated urea compound, or an unsaturated amide compound.

Since the composition of the present embodiment contains an unsaturated isocyanate compound and 0.01 to 10 ppm of a tertiary amine hydrochloride salt, the composition has excellent stability in storage and stability in use. Therefore, it is not necessary to include a large amount of the polymerization inhibitor. Therefore, it is possible to prevent the unsaturated compound produced by using the composition of this embodiment from being colored by the coloring component caused by the polymerization inhibitor.

The process for preparing the composition of the present embodiment comprises the steps of preparing a mixture containing an unsaturated isocyanate compound and a tertiary amine hydrochloride in an amount of more than 10 ppm and a step of purifying the mixture to obtain a composition having a tertiary amine hydrochloride content of 0.01 to 10 ppm Lt; / RTI > Therefore, unspecific impurities which deteriorate the stability during storage and stability in use contained in the mixture are sufficiently removed together with the excess tertiary amine hydrochloride in the purification process. As a result, the composition of the present invention having less unspecified impurities and excellent stability in storage and stability in use can be obtained.

The method for producing an unsaturated compound of the present embodiment is a method for producing an unsaturated compound by mixing a composition of the present embodiment and a compound having active hydrogen and reacting the unsaturated isocyanate compound contained in the composition with a compound having active hydrogen to obtain a reaction product (unsaturated compound) . Therefore, the reaction product is hardly raised in viscosity or gelation during the production, and excellent productivity is obtained. In addition, for example, the unsaturated isocyanate compound contained in the composition and the compound having active hydrogen can be reacted at a higher temperature than in the prior art to increase the reaction rate, thereby improving the productivity.

In addition, since the unsaturated compound of the present embodiment is a reaction product produced by using the production method of the unsaturated compound of the present embodiment, the reaction product hardly increases in viscosity or gelation during production, and has excellent productivity.

[Example]

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. The following examples are for the purpose of facilitating understanding of the contents of the present invention, and the present invention is not limited to these examples.

&Quot; Preparation of composition "

AOI 1 to AOI 5 shown in Table 1 and MOI 1 to AOI shown in Table 2 were prepared by the following method (purification step), and the mixture was purified (purified) A composition of MOI 5 was obtained.

&Quot; Process for preparing a mixture "

For AOI 1 to AOI 5, a step of synthesizing acryloyloxyethyl isocyanate (AOI) represented by the following chemical formula (5) as a step of producing a mixture and triethylamine hydrochloride being a by-product of tertiary amine hydrochloride Was carried out as shown below.

First, 2-aminoethyl acrylate hydrochloride represented by the formula (3), which is a salt of acrylic acid and ethanolamine, was produced. Subsequently, the obtained 2-aminoethyl acrylate hydrochloride was reacted with phosgene to produce a 3-chloropropionic acid ester derivative having an isocyanato group represented by the formula (4). Subsequently, the obtained 3-chloropropionic acid ester derivative was dehydrochlorinated in the presence of triethylamine (TEA) to obtain a crude AOI (mixture).

In this production method, when crude AOI is produced, triethylamine hydrochloride (TEA hydrochloride) is produced as a by-product. The content of TEA hydrochloride contained in the crude AOI (mixture) thus obtained was measured by the method described below. As a result, about 240 ppm of TEA hydrochloride was contained in the crude AOI.

&Quot; Purification process "

Subsequently, 500 g of the crude AOI (mixture) was purified by distillation, and the removal amount ((amount removed (g) / amount (g) of mixture) × 100 (%)) AOI 1 to AOI 5 containing TEA hydrochloride and acryloyloxyethyl isocyanate represented by the above formula (5) (AOI (boiling point 200 ° C)) was obtained.

The distillation for obtaining the compositions of AOI 1 to AOI 5 was carried out at an internal temperature of the distillation apparatus of 62 to 67 ° C and a pressure of 0.7 kPa.

&Quot; Process for preparing a mixture "

For MOI 1 to MOI 5, as shown below, the synthesis of methacryloyloxyethyl isocyanate (MOI) represented by the following chemical formula (7) is carried out by using a method in which tertiary amine hydrochloride is not produced as a by- As a process for producing a mixture, the following processes were carried out, which had a step of mixing MOI and triethylamine hydrochloride.

First, 2-aminoethyl methacrylate hydrochloride represented by the formula (6), which is a salt of methacrylic acid and ethanolamine, was produced. Subsequently, the obtained 2-aminoethyl methacrylate hydrochloride was reacted with phosgene to obtain crude MOI.

Thereafter, triethylamine hydrochloride (TEA hydrochloride) was added to the crude MOI obtained and mixed to obtain a mixture containing 250 ppm of TEA hydrochloride.

&Quot; Purification process "

Subsequently, 500 g of a mixture of TEA hydrochloride and crude MOI was purified using a distillation method, and the removal amount ((removal amount (g) / (g) / To obtain a composition of MOI 1 to MOI 5 containing TEA hydrochloride and methacryloyloxyethyl isocyanate represented by the above formula (7) (MOI (boiling point: 211 캜)).

The distillation for obtaining the compositions of MOI 1 to MOI 5 was carried out at an internal temperature of the distillation apparatus of 75 to 78 ° C and a pressure of 0.7 kPa.

The compositions of MOI 1 to MOI 5 and AOI 1 to AOI 5 thus obtained were measured for purity, color, viscosity, and content of triethylamine hydrochloride (TEA hydrochloride) in the composition by the following procedure. The results are shown in Tables 1 and 2.

<Purity>

With regard to purity, each component was separated by gas chromatography (GC) analysis, and the content (mass (wt / wt)%) of MOI or AOI was quantified by the internal standard method.

<Color>

For the hue, a standard chromaticity solution was prepared, and it was judged using a colorless tube.

<Viscosity>

The kinematic viscosity (cm &lt; 2 &gt; / sec) of the sample at 25 [deg.] C was measured with a rightward viscometer. The measured value was multiplied by the relative density (AOI: 1.13 g / cm3, MOI: 1.096 g / cm3) to calculate the viscosity (mPa · sec).

<TEA hydrochloride>

A specified amount of a sample (composition) was poured into a filtration apparatus equipped with a polytetrafluoroethylene (PTFE) membrane filter (scale 0.5 mu m), and suction filtration was performed at a pressure of 30 kPa to remove insoluble components (solid content). The obtained filtrate was separated by gas chromatography under the following conditions, and the content (ppm (by mass)) of triethylamine hydrochloride was measured by an internal standard method.

(Conditions of gas chromatography)

Column: inner diameter 0.32 mm, length 30 m, liquid film thickness 1.0 占 퐉 (DB-1 manufactured by J &

Column temperature: initial temperature 50 캜, then 10 캜 / min, final temperature 300 캜 (for 15 minutes)

Inlet temperature: 300 ° C

Detector temperature: 300 ° C

Detector: Hydrogen ionization detector

Carrier gas: helium

Flow rate (column): 1.2 ml / min

As shown in Tables 1 and 2, with respect to purity, color, and viscosity, there was no significant difference in compositions of MOI 1 to MOI 5 and AOI 1 to AOI 5. On the other hand, the contents of triethylamine hydrochloride (TEA hydrochloride) showed a clear difference between MOI 1 to MOI 5 and AOI 1 to AOI 5.

[Examples 1 to 5, Comparative Example 1: MOI Storage Test and Synthesis of Unsaturated Urethane Compound]

2,6-di-tert-butyl-4-methylphenol (BHT) as a polymerization inhibitor was added to any one of MOI 1 to 5 shown in Table 2 in the addition amounts shown in Table 3, And stored at 45 DEG C for 14 days, and the appearance was evaluated by the following method. The results are shown in Table 3.

"Appearance evaluation"

○: No change.

X: Polymerization occurred (gelation).

77.5 g of any one of the above-mentioned MOI 1 to 5 and 165 g of polyethylene glycol (number average molecular weight 660) were placed in a 500 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, Deg.] C and reacted for 5 hours to synthesize an unsaturated urethane compound.

The viscosity (Pa 占 퐏) of the obtained unsaturated urethane compound at 25 占 폚 was measured using an SV type (tuning fork type) viscometer (model SV-10 manufactured by A & D Co., Ltd.). The results are shown in Table 3.

As shown in Table 3, in Examples 1 to 5 using MOIs 1 to 4 having a content of triethylamine (TEA) hydrochloride of 0.01 to 10 ppm, all the evaluation results after storage were evaluated as ○, and it was confirmed that the stability was good I could.

Further, in Examples 1 to 5, the viscosity of the unsaturated urethane compound produced using the same as a raw material was adequate, and no significant difference was found.

On the other hand, in Comparative Example 1 using MOI 5 having a content of triethylamine (TEA) hydrochloride of higher than 10 ppm, the evaluation result after storage was?. However, when the unsaturated urethane compound was used as a raw material, it was gelled. That is, in Comparative Example 1, no change was observed even after storage under the storage conditions assumed in summer because of the effect of the polymerization inhibitor by BHT and triethylamine (TEA) hydrochloride. However, in Comparative Example 1, it is presumed that gelation of the unsaturated urethane compound was promoted by the impurity unknown in MOI 5.

From the results shown in Tables 2 and 3, it can be seen that the content of triethylamine hydrochloride (TEA hydrochloride) in the composition containing MOI is increased with respect to viscosity increase and gelation in the case of preparing an unsaturated urethane compound using a composition containing MOI as a raw material Has become clear.

[Examples 6 to 10, Comparative Example 2: Storage test of AOI and synthesis of unsaturated urethane compound]

To each of AOI 1 to 5 shown in Table 1, the same polymerization inhibitor (BHT) as used in Example 1 was added at the addition amount shown in Table 4, and stored and evaluated in the same manner as in Example 1. The results are shown in Table 4.

70.5 g of any one of the above-mentioned AOIs 1 to 5 and 165 g of polyethylene glycol (number average molecular weight 660) were placed in a 500 mL four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, Deg.] C and allowed to react for 5 hours to synthesize an unsaturated urethane compound. The mixture was stored at room temperature for one week, and the appearance was evaluated by the following method. The results are shown in Table 4.

"Appearance evaluation"

○: No change.

X: polymerization occurred (viscosity increase and / or gelation).

As shown in Table 4, in Examples 6 to 10 using AOIs 1 to 4 having a content of triethylamine (TEA) hydrochloride of 0.01 to 10 ppm, all the evaluation results after storage were evaluated as ○, and it was confirmed that the stability was good I could.

Further, in Examples 6 to 10, the unsaturated urethane compound produced using the same as a raw material was not gelated even after being stored at room temperature for one week.

On the other hand, in Comparative Example 2 using AOI 5 having a content of triethylamine (TEA) hydrochloride of higher than 10 ppm, the evaluation result after storage was?. However, when the unsaturated urethane compound was used as a raw material, it was gelled. That is, in Comparative Example 2, no change was observed even after storage under the storage conditions assumed in the summer due to the effect of the polymerization inhibitor by BHT and triethylamine (TEA) hydrochloride. However, in Comparative Example 2, it is presumed that gelation of the unsaturated urethane compound was promoted by the impurity unknown in AOI 5.

From the results of Tables 1 and 4, it can be seen that the content of triethylamine hydrochloride (TEA hydrochloride) in the composition containing AOI is determined by the relationship between viscosity increase and gelation in the case of preparing an unsaturated urethane compound using a composition containing AOI as a raw material Has become clear.

[Example 11, Comparative Example 3: Synthesis of unsaturated urethane compound]

273 g of AOI 4 or AOI 5 shown in Table 1 and 72.4 g of pentaerythritol were placed in a 500 mL four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, to obtain 2,6-di- Butyl-4-methylphenol (BHT) was added in an amount of 50 ppm, and the mixture was allowed to react at the temperature of 80 DEG C for 5 hours to synthesize an unsaturated urethane compound. The unsaturated urethane compound was stored at room temperature for one week, .

As a result, the unsaturated urethane compound of Example 11 using AOI 4 having a content of triethylamine (TEA) hydrochloride of 0.01 to 10 ppm showed no problems such as coloration and gelation.

On the contrary, the unsaturated urethane compound of Comparative Example 3 using AOI 5 having a content of triethylamine (TEA) hydrochloride of higher than 10 ppm had a high viscosity and resulted in trouble in use.

[Example 12, Comparative Example 4: Synthesis of unsaturated urethane compound]

616 g of MEK oxime (methyl ethyl ketone oxime) and 0.1 g of 2,6-di-tert-butyl-4-methylphenol (BHT) as a polymerization inhibitor were placed in a 2 L separable flask equipped with a stirrer, a condenser and a thermometer And cooled to 10 ° C. Subsequently, while adjusting the temperature in the separable flask to 20 to 25 캜, 988 g of AOI 4 or AOI 5 shown in Table 1 was added dropwise over 4 hours. After the addition of AOI was completed, the temperature in the separable flask was adjusted to 25 캜 and stirred for 2 hours to synthesize methacrylic acid 2 - ([1'-methylpropylideneamino] oxycarbonylamino) ethyl, And the appearance was evaluated in the same manner as in Example 6.

The unsaturated urethane compound of Example 12 using AOI 4 having a content of triethylamine (TEA) hydrochloride of 0.01 to 10 ppm showed no problems such as coloring and gelation.

On the contrary, the unsaturated urethane compound of Comparative Example 4 using AOI 5 having a content of triethylamine (TEA) hydrochloride of more than 10 ppm had a high viscosity and resulted in trouble in use.

From the results of Examples 11 and 12 and Comparative Examples 3 and 4, it is clear that the content of triethylamine hydrochloride (TEA hydrochloride) in the composition containing AOI correlates with the viscosity of the unsaturated urethane compound prepared from the raw material It has become.

[Examples 13 to 15, Comparative Example 5: Synthesis of unsaturated urea compound]

66.4 g of 2 - [(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate and 77.4 g of 3,5-dimethylpyrazole were placed in a 500 ml four-necked flask equipped with a stirrer, , 111.5 g of any one of AOI 1, 3 to 5 shown in Table 1 was supplied, and the same polymerization inhibitor (BHT) as in Example 1 was added at the addition amount shown in Table 5 And reacted for 2 hours to synthesize an unsaturated urea compound.

The viscosity (Pa 占 퐏 ec) of the obtained unsaturated urea compound at 25 占 폚 was measured in the same manner as in Example 1. The results are shown in Table 5.

As shown in Table 5, in Examples 13 to 15 using AOIs 1, 3 and 4, an unsaturated urea compound having an appropriate viscosity was obtained.

On the other hand, in Comparative Example 5 using AOI 5, gelation occurred during the production of the unsaturated urea compound.

[Examples 16 to 18 and Comparative Example 6: Synthesis of unsaturated urea compound]

66.4 g of 2 - [(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate and 77.4 g of 3,5-dimethylpyrazole were placed in a 500 ml four-necked flask equipped with a stirrer, , 122.7 g of any one of MOI 1, 3 to 5 shown in Table 2 was supplied, and the same polymerization inhibitor (BHT) as in Example 1 was added at the addition amount shown in Table 6 And reacted for 2 hours to synthesize an unsaturated urea compound.

The resulting unsaturated urea compound was stored at room temperature for one week, and the appearance was evaluated by the same method as in Example 6. [ The results are shown in Table 6.

As shown in Table 6, in Examples 16 to 18 in which MOIs 1, 3 and 4 were used, even when the unsaturated urea compound prepared using the same as a raw material was stored at room temperature for one week, gelation did not occur.

In contrast, in Comparative Example 6 using MOI 5, the viscosity increased during the production of the unsaturated urea compound.

[Examples 19 to 21, Comparative Example 7: Synthesis of unsaturated amide compound]

177.3 g of decanoic acid and 0.8 g of dibutyltin dilaurate were placed in a 500 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and the temperature was kept at 80 캜. AOI 1, 169.4 g of any one of 3 to 5 was fed and the same polymerization inhibitor (BHT) as used in Example 1 was added at the addition amount shown in Table 7 and reacted for 12 hours to synthesize an unsaturated amide compound.

The viscosity (Pa · sec) of the obtained unsaturated amide compound at 25 ° C was measured in the same manner as in Example 1. [ The results are shown in Table 7.

As shown in Table 7, in Examples 19 to 21 using AOI 1, 3 and 4, an unsaturated amide compound having an appropriate viscosity was obtained.

In contrast, in Comparative Example 7 using AOI 5, it was gelled during the production of the unsaturated amide compound.

[Examples 22 to 24, Comparative Example 8: Synthesis of unsaturated amide compound]

177.3 g of decanoic acid and 0.8 g of dibutyltin dilaurate were placed in a 500 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and the temperature was maintained at 80 ° C. 186.3 g of any one of 3 to 5 was fed and the same polymerization inhibitor (BHT) as in Example 1 was added at the addition amount shown in Table 8 and reacted for 12 hours to synthesize an unsaturated amide compound.

The obtained unsaturated amide compound was stored at room temperature for one week, and then evaluated for appearance by the same method as in Example 6. The results are shown in Table 8.

As shown in Table 8, in Examples 22 to 24 using MOIs 1, 3 and 4, the unsaturated amide compound prepared using the same as raw material was not gelated even when stored at room temperature for one week.

In contrast, in Comparative Example 8 using MOI 5, the viscosity increased during the production of the unsaturated amide compound.

[Examples 25 to 27, Comparative Example 9: Synthesis of unsaturated thiourethane compound]

177.3 g of 1-octanethiol was placed in a 500 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and 169.4 g of any one of AOI 1, 3 to 5 shown in Table 1 was supplied, The polymerization inhibitor (BHT) as in Example 1 was added in an amount shown in Table 1, and the reaction was carried out for 24 hours at a temperature of 80 캜 to synthesize an unsaturated thiourethane compound.

The viscosity (Pa · sec) of the obtained unsaturated thiourethane compound at 25 ° C was measured in the same manner as in Example 1. [ The results are shown in Table 9.

As shown in Table 9, in Examples 25 to 27 using AOIs 1, 3 and 4, an unsaturated thiourethane compound having an appropriate viscosity was obtained.

In contrast, in Comparative Example 9 using AOI 5, gelation occurred during the production of the unsaturated thiourethane compound.

[Examples 28 to 30, Comparative Example 10: Synthesis of unsaturated thiourethane compound]

177.3 g of 1-octanethiol was placed in a 500 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and 186.3 g of any one of MOI 1, 3 to 5 shown in Table 2 was supplied, The polymerization inhibitor (BHT) as in Example 1 was added in an amount shown in Table 1, and the reaction was carried out for 24 hours at a temperature of 80 캜 to synthesize an unsaturated thiourethane compound.

The obtained unsaturated thiourethane compound was stored at room temperature for one week, and the appearance was evaluated by the same method as in Example 6. [ The results are shown in Table 10.

As shown in Table 10, in Examples 28 to 30 using MOIs 1, 3 and 4, the unsaturated thiourethane compound prepared using the same as a raw material was not gelated even after being stored at room temperature for one week.

In contrast, in Comparative Example 10 using MOI 5, the viscosity increased during the production of the unsaturated thiourethane compound.

As can be seen from the above results, when the composition containing triethylamine hydrochloride in an amount of 0.01 to 10 ppm in a composition containing MOI or AOI, which is an unsaturated isocyanate compound, and triethylamine hydrochloride, viscosity increase or gelation can be prevented .

Also, when the content of triethylamine hydrochloride contained in the composition is in the range of 0.01 to 10 ppm, it is possible to prevent the viscosity of the reaction product from rising sharply or gelation during the production of the unsaturated compound using the composition as a raw material And it was confirmed that gelation of the produced unsaturated compound can be prevented.

Claims (19)

The unsaturated isocyanate compound,
0.01 to 10 ppm of a tertiary amine hydrochloride on a mass basis,
Wherein the tertiary amine hydrochloride is triethylamine hydrochloride or tripropylamine hydrochloride. The method according to claim 1,
Wherein the composition contains 0.1 ppm to 10 ppm of a tertiary amine hydrochloride on a mass basis. 3. The method according to claim 1 or 2,
Wherein the unsaturated isocyanate compound is acryloyloxyethyl isocyanate or methacryloyloxyethyl isocyanate. delete Preparing a mixture comprising an unsaturated isocyanate compound and a tertiary amine hydrochloride salt in an amount of more than 10 ppm by mass;
And purifying the mixture to obtain a composition having a tertiary amine hydrochloride content of 0.01 to 10 ppm by mass,
Wherein the tertiary amine hydrochloride is triethylamine hydrochloride or tripropylamine hydrochloride. 6. The method of claim 5,
Wherein the purification step is carried out to produce a composition having a tertiary amine hydrochloride content of 0.1 ppm to 10 ppm by mass. The method according to claim 5 or 6,
Wherein the step of preparing the mixture comprises a step of synthesizing the unsaturated isocyanate compound and by-producting the tertiary amine hydrochloride. The method according to claim 5 or 6,
Wherein the step of preparing the mixture comprises mixing the unsaturated isocyanate compound and the tertiary amine hydrochloride. The method according to claim 5 or 6,
Wherein the unsaturated isocyanate compound is acryloyloxyethyl isocyanate or methacryloyloxyethyl isocyanate. delete The method according to claim 5 or 6,
In the purification step, the mixture is purified by distillation. Characterized in that a mixture comprising an unsaturated isocyanate compound and a tertiary amine hydrochloride in an amount of more than 10 ppm by mass is prepared by distillation and the content of the tertiary amine hydrochloride is 0.01 to 10 ppm by mass,
Wherein the tertiary amine hydrochloride is triethylamine hydrochloride or tripropylamine hydrochloride. 13. The method of claim 12,
In the distillation method, the removal amount of the feedstock is controlled. 14. The method of claim 13,
Wherein the removal amount of the supernatant is 4% or more. A process for producing an isocyanate compound by mixing the composition according to any one of claims 1, 2, 12 and 13 with a compound having an active hydrogen and reacting the unsaturated isocyanate compound contained in the composition with a compound having an active hydrogen A process for producing an unsaturated compound, which comprises the step of obtaining an unsaturated compound. 16. The method of claim 15,
Wherein the compound having an active hydrogen is a polyol, a polythiol, a polyamine or a polycarboxylic acid. 16. The method of claim 15,
Wherein the unsaturated compound is an unsaturated urethane compound, an unsaturated thiourethane compound, an unsaturated urea compound, or an unsaturated amide compound. An unsaturated compound produced by the method for producing an unsaturated compound according to claim 15. 19. The method of claim 18,
Wherein the unsaturated compound is an unsaturated urethane compound, an unsaturated thiourethane compound, an unsaturated urea compound, or an unsaturated amide compound.