KR101643802B1 - Sucrose aromatic monocarboxylic acid ester - Google Patents

Abstract

(식 중, R¹∼R⁵는, 독립적으로 수소 원자, 알킬기 및 알콕시기로부터 선택되는 기이다.)로 표시되는 방향족 모노카르본산과의 에스테르를 제공한다. 할로겐의 함유량이 적은 상기 에스테르는, 비결정성 수지나 결정성 수지와의 상용해성이 뛰어나고, 이들의 성형 가공성, 물성, 유연성, 내충격성 등을 향상시키며, 또한 가열에 의한 착색을 억제할 수 있는 열안정성이 뛰어난 수지 개질제로서 유용하다. 푸르푸랄 및 히드록시 메틸 푸르푸랄의 함유량이 적은 상기 에스테르는, 2-시아노아크릴레이트계 접착제의 접착 성능을 저하시키지 않고 악취를 개선할 수 있는 악취 개선·증량제로서 유용하다.A sucrose having a small content of a predetermined impurity,

(Wherein R ¹ to R ⁵ are independently a group selected from a hydrogen atom, an alkyl group and an alkoxy group). The ester having a low content of halogen is excellent in compatibility with amorphous resin or crystalline resin and improves the molding processability, physical properties, flexibility, impact resistance and the like of the amorphous resin and the crystalline resin, And is useful as a resin modifier excellent in stability. The ester having a small content of furfural and hydroxymethyl furfural is useful as a malodor improving / increasing agent capable of improving the odor without deteriorating the adhesive performance of the 2-cyanoacrylate adhesive.

Description

Sucrose aromatic monocarboxylic acid ester < RTI ID = 0.0 >

The present invention relates to a sucrose aromatic monocarboxylic ester having a small content of impurities, and more particularly to a sucrose aromatic monocarboxylic acid ester having a low content of halogen and a furfural and a hydroxymethyl furfural The present invention relates to a sucrose aromatic monocarboxylic acid ester having a low content.

The present invention (the first embodiment of the present invention) in a form in which the content of halogen is small is excellent in compatibility with noncrystalline resin or crystalline resin, and is excellent in moldability, physical properties, flexibility and impact resistance The present invention relates to a sucrose aromatic monocarboxylic acid ester useful as a resin modifier and capable of inhibiting coloration due to heating and having excellent thermal stability.

The present invention (second embodiment of the present invention) in a form in which the content of furfural and hydroxymethyl furfural is small relates to an increasing agent of a 2-cyanoacrylate adhesive, and more particularly, A sucrose aromatic monocarboxylic acid ester capable of improving the odor without deteriorating the adhesion performance, a 2-cyanoacrylate-based adhesive comprising the ester as an odor improving and increasing agent, and a process for producing the ester.

As the resin modifier, a sucrose derivative such as sucrose benzoate is known, and the molding processability and physical properties of an amorphous resin such as an ABS resin, a polyvinyl chloride resin, an epoxy resin and an unsaturated polyester resin are improved Or improve the flexibility and impact resistance of the crystalline polyester (Patent Documents 1 to 3).

However, since sucrose benzoate is a sucrose derivative, when it is added as a modifier, there is a problem in the color stability and the color stability of a product made of these resins. That is, sucrose benzoate is generally produced using an organic solvent, but coloring occurs in the heating step of removing the organic solvent in the production process. More specifically, since the melting point of sucrose benzoate is 80 to 90 占 폚, heating of 100 占 폚 or more, preferably 110 占 폚 or more is usually required to remove the organic solvent used in the production process. However, C, the coloring of the sucrose benzoate proceeds. The degree of coloring tends to become more remarkable as the proportion of components having a low degree of esterification in sucrose benzoate is increased or the average degree of ester substitution is lowered. In addition, even if coloring is suppressed as much as possible by suppressing thermal history of sucrose benzoate when an organic solvent is removed in an effort to shorten the treatment time by using a special treatment facility (for example, a thin film distillation apparatus) , There has been a problem in that after the addition of sucrose benzoate to the resin, the resin is colored due to thermal history during processing and molding.

For this reason, sucrose benzoate has never been satisfactory as a modifier for resins requiring optical transparency.

On the other hand, the 2-cyanoacrylate-based adhesive has a high adhesive strength to most materials, regardless of wood, plastic, and metal, and is also applicable to adhesion between different materials, and is also capable of high-speed bonding. The adhesive is expensive compared to other general-purpose adhesives, but has a great merit as described above, and its usage is steadily increasing year by year.

In the 2-cyanoacrylate adhesive, a sucrose benzoic acid ester is used as an extender for the purpose of cost reduction and odor improvement (Patent Document 4). However, the odor improvement was never satisfactory.

(Patent Document 1) JPS52-81362 (Patent Document 2) JPS62-15582 (Patent Document 3) JPH06-255274 (Patent Document 4) JPH05-222340

The present invention in the first aspect is a sucrose aromatic monocarboxylic acid ester useful as a resin modifier which is excellent in compatibility with amorphous resin or crystalline resin and improves molding processability, physical properties, flexibility, impact resistance, , And to provide a sucrose aromatic monocarboxylic acid ester excellent in thermal stability capable of inhibiting coloration due to heating.

The second aspect of the present invention is to provide a sucrose aromatic monocarboxylic acid ester capable of improving odor without deteriorating its adhesive performance even when it is added to a 2-cyanoacrylate adhesive.

DISCLOSURE OF THE INVENTION The inventors of the present invention conducted diligent research for solving the above-mentioned problems related to the first aspect, and as a result, they found that by suppressing the content of halogen in the sucrose aromatic monocarboxylic acid ester to a low level, Thus, the present invention has been completed.

That is,

Sucrose,

(Wherein R ¹ to R ⁵ are each independently a group selected from a hydrogen atom, an alkyl group and an alkoxy group), the ratio of the number of moles of the sucrose aromatic monocarboxylic acid having a halogen content of 100 ppm or less to the aromatic monocarboxylic acid (II) < / RTI >

The sucrose aromatic monocarboxylic acid ester (II) is preferably a sucrose aromatic monocarboxylic acid ester (II-1) having a substituent content of not more than 6 substituents of not less than 5% by weight.

The sucrose aromatic monocarboxylic acid ester (II-1) preferably has an average degree of substitution of 5.0 or more.

The sucrose aromatic monocarboxylic acid ester (II-1) preferably has a hue of 50 or less in a 50% toluene solution of 30 or less.

The sucrose aromatic monocarboxylic acid ester (II-1) preferably has a hue of 50 or less in APHA of 30% in a 50% toluene solution after being heated at 110 DEG C for 12 hours.

The present invention also relates to a resin modifier comprising the sucrose aromatic monocarboxylic acid ester (II-1).

Alternatively, the present invention relates to a sucrose aromatic monocarboxylic acid ester (sucrose aromatic monocarboxylic acid ester (II-2)) having a substituent content of not more than 5 substituents in the sucrose aromatic monocarboxylic acid ester (II) of not more than 2.0% will be.

The sucrose aromatic monocarboxylic acid ester (II-2) preferably has an average degree of substitution of 7.0 or more.

The sucrose aromatic monocarboxylic acid ester (II-2) preferably has a hue of 50 or less in a 50% toluene solution of 10 or less.

The sucrose aromatic monocarboxylic acid ester (II-2) preferably has a hue of 50 or less in APHA of 30% in a 50% toluene solution after being heated at 160 DEG C for 3 hours.

The present invention also relates to a resin modifier comprising the sucrose aromatic monocarboxylic acid ester (II-2).

Further, the present invention relates to a process for producing a sucrose aromatic monocarboxylic acid ester (II) in which the content of halogen is 100 ppm or less in a process for producing a sucrose aromatic monocarboxylic acid ester (II) .

The sucrose aromatic monocarboxylic acid ester (II) in which the coloration is suppressed is preferably a sucrose aromatic monocarboxylic acid ester (II-1) having a hue of 50 or less in APHA of 30 or less in a 50% toluene solution, Is preferably a sucrose aromatic monocarboxylic acid ester (II-2) having a color of APHA of 10 or less.

Further, as a result of intensive studies for solving the above-mentioned problems related to the second aspect, the present inventors have found that by controlling the content of prescribed impurities (furfural and hydroxymethyl furfural) in the sucrose aromatic monocarboxylic acid ester to be low, It has been found that an odor can be improved as an extender of a 2-cyanoacrylate-based adhesive without deteriorating its adhesive performance, and the present invention has been completed upon further examination.

That is,

Sucrose,

(Formula 1)

(Wherein R ¹ to R ⁵ are each independently a group selected from a hydrogen atom, an alkyl group and an alkoxy group), the content of the furfural is 50 ppm or less, (III) having a methylfurfural content of 500 ppm or less.

The sucrose aromatic monocarboxylic acid ester (III) preferably has an average degree of esterification of 6.0 or less.

The present invention also relates to a 2-cyanoacrylate-based adhesive comprising the sucrose aromatic monocarboxylic acid ester (III) as an odor improving improver.

The present invention also provides a process for producing a sucrose aromatic monocarboxylic acid ester (III) having a furfural content of 50 ppm or less and a hydroxymethyl furfural content of 500 ppm or less, wherein the sucrose aromatic monocarboxylic acid ester (III) , Sucrose and the compound of formula

(Formula 1)

(III) wherein R ¹ to R ⁵ are independently a hydrogen atom, a group selected from an alkyl group and an alkoxy group, and the aromatic monocarboxylic acid ester (III) is an ester with an aromatic monocarboxylic acid represented by the following formula In an organic solvent solution in the form of a liquid film having a thickness of 10 cm or less in contact with a heating surface, followed by drying.

The drying is preferably performed under reduced pressure.

The reduced-pressure drying is preferably carried out under a pressure of from 0.01 to 15 KPa · abs and a heating temperature of from 90 to 300 ° C.

Preferably, the reduced-pressure drying is carried out using one or more machines selected from a vacuum drum dryer, a vacuum belt dryer, a thin film still, a flash distiller and a vacuum extruder.

With respect to the first aspect of the present invention, the sucrose aromatic monocarboxylic acid ester (II) is excellent in compatibility with amorphous resin or crystalline resin, and can be improved in molding processability, physical properties, flexibility and impact resistance On the other hand, it has an excellent characteristic that coloration due to heating can be suppressed. Therefore, it can be used as a modifier for a resin that requires optical transparency.

In addition, the sucrose aromatic monocarboxylic acid ester (II-1) of the present invention has a characteristic of exhibiting excellent heat stability even when the ratio of esterification of the alcohol portion of sucrose is at least, that is, .

In addition, the sucrose aromatic monocarboxylic acid ester (II-2) of the present invention has a high ester stability of the alcohol portion of sucrose, that is, a relatively low proportion of the low substitution, and thus exhibits more excellent thermal stability.

Further, according to the production method of the present invention, since the sucrose aromatic monocarboxylic acid ester (II) exhibiting such excellent properties can be easily produced without using special treatment equipment (for example, a thin film distillation apparatus) The manufacturing cost, and the like.

With respect to the second aspect of the present invention, the sucrose aromatic monocarboxylic acid ester (III) has an excellent characteristic that it can improve the odor without decreasing the adhesive performance as an extender of the 2-cyanoacrylate-based adhesive . Therefore, it can be used as a malodor improving / increasing agent for the adhesive.

Further, according to the production method of the present invention, since the sucrose aromatic monocarboxylic acid ester (III) exhibiting such excellent properties can be easily and efficiently produced, it is industrially advantageous.

In the present invention, sucrose aromatic monocarboxylic acid esters (II-1), (II-2) and (III) are present in the sucrose aromatic monocarboxylic acid ester as a target, Carboxylic acid ester " as used herein means any one of them, or any one of them, or one of them, depending on the context.

In the aromatic monocarboxylic acid (I) of the sucrose aromatic monocarboxylic acid ester of the present invention, each of R ¹ to R ⁵ is preferably independently a hydrogen atom or an alkyl group, and a benzoic acid in which all of R ¹ to R ⁵ are hydrogen atoms or a , It is more preferable that R ³ ) is an alkyl group and the remainder is a hydrogen atom.

Examples of the alkyl group include those having 1 to 20 carbon atoms, and those having 1 to 5 carbon atoms are preferable, and a methyl group, an ethyl group, a propyl group or an isopropyl group is more preferable. The alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably a methoxy group, an ethoxy group, a propyloxy group or an isopropyloxy group.

(A) for sucrose carboxylic acid ester (II)

<Objects>

In the sucrose aromatic monocarboxylic acid ester (II) of the present invention, the content of halogen is 100 ppm or less. Examples of the halogen include fluorine, chlorine, bromine, and iodine. Among them, the chlorine content has a large effect.

The content of the halogen is preferably 90 ppm or less, more preferably 60 ppm or less, further preferably 30 ppm or less, further preferably 20 ppm or less. The content of the preferable chlorine is preferably 80 ppm or less, more preferably 55 ppm or less, still more preferably 25 ppm or less, further preferably 17 ppm or less.

The sucrose aromatic monocarboxylic acid ester (II-1) of the present invention exhibits excellent thermal stability even when the ratio of esterification of the alcohol portion of sucrose is at least, for example, relatively low, The proportion of the substituents below the substituent is preferably 95% by weight or less, more preferably 85% by weight or less, still more preferably 50% by weight or less and 10% by weight or less. Here, the 6-substituent means that six hydroxyl groups out of the total of 8 hydroxyl groups of sucrose are subjected to esterification with an aromatic monocarboxylic acid. In the present specification, as far as the sucrose aromatic monocarboxylic acid ester (II-1) is concerned, a substituent having six or less substituents is referred to as a low substituent for convenience.

In the sucrose aromatic monocarboxylic acid ester (II-1) of the present invention, the average value (hereinafter referred to as "average ester substitution degree" or "average degree of substitution") of the ratio of esterification of the alcohol portion of sucrose is small But the average degree of ester substitution is, for example, not less than 5.0, preferably not less than 6.0, and more preferably not less than 7.0.

In the sucrose aromatic monocarboxylic acid ester (II-1) of the present invention, the hue in the 50% toluene solution is preferably 30 or less, more preferably 25 or less, still more preferably 15 or less. In the sucrose aromatic monocarboxylic acid ester (II-1) of the present invention, the hue in the 50% toluene solution after heating at 110 DEG C for 12 hours is preferably 30 or less, more preferably 25 or less, And preferably 15 or less. When the hue exceeds 30, it tends to lower the appearance (color) and optical transparency of the resin when used as a resin modifier.

The sucrose aromatic monocarboxylic acid ester (II-2) of the present invention preferably has a high ratio of esterification of the alcohol moiety of sucrose, and more specifically, the content of the substituent at the 5-substituent or less is 2.0% Is preferably 1.0 wt% or less, more preferably 0.5 wt% or less, and further preferably 0.3 wt% or less. Here, the term "5-substituent" means that five of the eight hydroxyl groups in total of sucrose are subjected to esterification with an aromatic monocarboxylic acid. In the present specification, as far as the sucrose aromatic monocarboxylic acid ester (II-2) is concerned, a substituent of five or less substituents is referred to as a low substituent for convenience, and the remaining substituent is referred to as a high substituent.

In addition, a preferable example other than the sucrose aromatic monocarboxylic acid ester (II-2) of the present invention is that the content of 6 substituents is less than 5% by weight.

The sucrose aromatic monocarboxylic acid ester (II-2) of the present invention preferably has a large average esterification degree (hereinafter referred to as "average ester substitution degree" or "average degree of substitution") of the alcohol portion of sucrose Specifically, the average ester substitution degree is, for example, 7.0 or more, and preferably 7.3 or more.

In the sucrose aromatic monocarboxylic acid ester (II-2) of the present invention, the hue in the 50% toluene solution is preferably 10 or less. In the sucrose aromatic monocarboxylic acid ester (II-2) of the present invention, the hue in a 50% toluene solution after heating at 160 ° C for 3 hours is preferably 30 or less, more preferably 25 or less, and 15 or less Is more preferable. When the hue exceeds 30, it tends to lower the appearance (color) and optical transparency of the resin when used as a resin modifier.

<Manufacturing method>

(Halogen removal process)

The sucrose aromatic monocarboxylic acid ester (II) of the present invention can be produced by a production method comprising a step of adjusting the content of halogen to 100 ppm or less.

As the step of setting the content of halogen to 100 ppm or less, any method generally used in this field can be used as long as the above object can be achieved. Specific examples of these methods include, for example, a method in which sucrose and an aromatic monocarboxylic acid And esterifying the ester obtained according to the esterification reaction. The washing can be carried out by a conventional method. For example, water can be added to the mixture after completion of the esterification reaction, stirring is conducted while bathing, and the mixture is allowed to stand to separate the water phase and remove the water phase. The bath temperature is preferably 40 to 60 占 폚. There is a tendency that the cleaning is insufficient at 40 DEG C or lower, and the decomposition of the ester tends to proceed at 60 DEG C or higher. Stirring is not particularly limited as long as it is sufficient for the compound containing halide ions or other halogens to migrate to the water phase, and it is usually sufficient to conduct the stirring for about 30 minutes.

In the sucrose aromatic monocarboxylic acid ester (II-1), the number of times of washing varies depending on the raw material to be used and the ester reaction conditions, but a raw material having a high purity with a small amount of impurities (for example, high purity benzoyl chloride (> 99.5% It is usually sufficient to perform about five times.

In the sucrose aromatic monocarboxylic acid ester (II-2), the number of times of washing is varied depending on raw materials to be used, ester reaction conditions and the like, but a raw material with high purity with a small amount of impurities (for example, high purity benzoyl chloride (> 99.5% It is usually sufficient to perform about 5 to 8 times.

In the present invention, it is effective to use a raw material having a small halogen content in advance in order to reduce the content of halogen in the sucrose aromatic monocarboxylic acid ester (II) to 100 ppm or less. Therefore, it is preferable to use a halogenated aromatic monocarboxylic acid of high purity as an esterifying agent. Examples of such high purity halogenated aromatic monocarboxylic acids include high purity benzoyl chloride (&gt; 99.5%) (manufactured by Kawaguchi Yakuhin Co., Ltd.) and the like.

After the step of reducing the content of halogen in the sucrose aromatic monocarboxylic acid ester (II) to 100 ppm or less as described above, the solvent used for the esterification reaction is removed by a conventional method to obtain the desired product of the present invention Can be obtained. In this case, since the content of halogen is not more than 100 ppm in advance, the present invention does not use a special treatment facility (for example, a thin film distillation apparatus) or the like, and even if the solvent is removed by a conventional method, The inhibited target can be obtained.

(Ester synthesis)

In the present invention, the esterification reaction between sucrose and an aromatic monocarboxylic acid can be carried out by a conventional method. For example, in accordance with the method for producing sucrose benzoate described in JP-A-61-4839 Can be manufactured.

That is, the sucrose as the raw material and the chloride of the aromatic monocarboxylic acid can be produced in a mixed liquid of a hydrophilic solvent and water in the presence of an alkaline compound according to an esterification reaction. Examples of the hydrophilic solvent include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ether solvents such as dioxane and tetrahydrofuran, ester solvents such as methyl acetate, and alcohol solvents such as tertiary butanol. All of the solvents can be suitably used.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonia, trimethylamine, triethylamine and the like.

The mixing ratio of the hydrophilic solvent and water is preferably such that the water content of the uniform liquid layer made of both is 7 to 80%. This is because, in these hydrophilic solvents, the chloride of the aromatic monocarboxylic acid, which is one of the raw materials, and the ester as a product are dissolved, but sucrose as the other one of the raw materials is not solely dissolved at all or is useful for practical use in terms of reaction efficiency This is because the sucrose can be dissolved to such an extent that the mixed solution can be practically used by mixing the two kinds of sucrose water. Therefore, by using such a property of the hydrophilic solvent, the reaction rate of the sucrose and the aromatic monocarboxylic acid chloride can be controlled, and as a result, the ratio of the low substitution ratio (molar ratio) of the sucrose / aromatic monocarboxylic acid Or an ester having a different average degree of ester substitution can be produced. For example, by increasing the mixing amount of the aromatic monocarboxylic acid chloride with respect to the mixing amount of sucrose, it is possible to obtain an ester having a relatively low proportion of a low substituent or a relatively large average degree of ester substitution, and conversely, By reducing the incorporation of the acid chloride to the amount of the sucrose incorporated, it is possible to obtain an ester having a relatively low proportion of a low substituent or a relatively small average degree of ester substitution.

Examples of the method of the reaction include a method of dissolving or suspending sucrose and an aromatic monocarboxylic acid chloride in a mixture of a hydrophilic solvent and water and dropping an equivalent amount or a slight excess of an alkaline compound to the aromatic monocarboxylic acid chloride or adding sucrose and an alkaline The compound may be dissolved or suspended to drop the aromatic monocarboxylic acid chloride or the aromatic monocarboxylic acid chloride and the alkaline compound may be added simultaneously or alternately by dissolving or suspending the sucrose in the mixed solution.

The reaction temperature can be from -15 캜 to 100 캜, but more preferably from -10 캜 to 30 캜. However, after dropping the entire reaction material, it may be heated in a high temperature region to promote the completion of the reaction.

It is preferable that the pH during the reaction be maintained at a weakly alkaline state. On the other hand, side reactions of hydrolysis of an aromatic monocarboxylic acid are remarkable in a strongly alkaline state (for example, depending on the reaction temperature and the like but at a pH of 13 or more), and therefore, the reaction is preferably carried out at a pH of about 8 to 13 .

The reaction time is not particularly limited as long as the reaction between the raw materials can sufficiently complete the reaction. The specific time depends on the amount of the starting compound and various conditions, but it is usually sufficient to conduct the reaction for about 3 hours.

<Applications>

The sucrose aromatic monocarboxylic acid ester (II) of the present invention is useful as a resin modifier, and can be used as a modifier for a resin that requires optical transparency because it has excellent characteristics of suppressing coloration by heating.

As the resin to which the sucrose aromatic monocarboxylic acid ester (II) of the present invention is added, an amorphous resin such as an ABS resin, a polyvinyl chloride resin, an epoxy resin, or an unsaturated polyester, and a crystalline resin . The resin can be appropriately selected depending on the use thereof. Further, the sucrose aromatic monocarboxylic acid ester (II) of the present invention to be added to the resin can be suitably selected in accordance with the type and use of the resin, more suitably in accordance with the ratio of the low substituent and the degree of ester substitution.

The ABS resin is not particularly limited and includes, for example, polybutadiene, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, chlorinated polyethylene, acrylic rubber (e.g., methyl acrylate, ethyl acrylate, Acrylonitrile, styrene,? -Methylstyrene, methyl methacrylate and the like to a rubber-like polymer such as acrylonitrile, a copolymer of styrene, acrylic acid, acrylic acid amide, 2-chloroethyl vinyl ether and the like. Also, acrylonitrile polybutadiene styrene-based graft copolymers and the like can be given. The ABS resin may be used alone, or two or more kinds may be used in combination.

The polyvinyl chloride resin is not particularly limited and includes, for example, a vinyl chloride homopolymer resin, a chlorinated vinyl chloride resin, a chlorinated vinyl chloride resin obtained by random copolymerization or block copolymerization of at least one monomer copolymerizable with a vinyl chloride monomer A resin obtained by grafting a functional group such as a hydroxyl group to the above resin, or a resin obtained by reacting such a functional group with a reactive compound and graft-bonding the functional resin to the resin (for example, &Lt; / RTI &gt; The polyvinyl chloride resin may be used alone, or two or more kinds may be used in combination.

Examples of the epoxy resin include, but are not limited to, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, alkylphenol novolac epoxy resin, phenol biphenyl Araliphatic epoxy resins such as aralkyl epoxy resins, biphenol type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, anthracene type epoxy resins, aromatic aldehydes having phenols and phenolic hydroxyl groups , Epichlorohydrin epoxy resin, triglycidyl isocyanurate, and alicyclic epoxy resin. The epoxy resin may be used alone or in combination of two or more.

The unsaturated polyester resin is not particularly limited and is synthesized, for example, by addition reaction or dehydration condensation reaction of an?,? - olefin unsaturated dicarboxylic acid or an anhydride thereof with glycol. In addition, saturated dicarboxylic acids, aromatic dicarboxylic acids, anhydrides thereof, or dicyclopentadiene reacting with carboxylic acids can also be used in combination. Examples of the?,? - olefinically unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid and anhydrides of these dicarboxylic acids. Examples of dicarboxylic acids to be used in combination with these?,? - olefinically unsaturated dicarboxylic acids include adipic acid, sebacic acid, succinic acid, phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, Phthalic acid and the like. Of these, it is preferable to use fumaric acid as the?,? - olefin-based unsaturated dicarboxylic acid and isophthalic acid as the dicarboxylic acid. The unsaturated polyester resin may be used singly or in combination of two or more kinds.

The crystalline polyester resin is not particularly limited, and examples thereof include polyethylene terephthalate, poly-1,4-butylene terephthalate, polyethylene-2,6-naphthalate, polycyclohexanedimethanol terephthalate, poly -1,4-butylenediphenyl-4,4'-dicarboxylate, polyethyleneoxybenzoate, poly-1,3-propylene terephthalate and poly-1,6-hexylene terephthalate. Among them, polyethylene terephthalate, poly-1,4-butylene terephthalate and polyethylene-2,6-naphthalate are preferable. The crystalline polyester resin may be used singly or in combination of two or more kinds.

If necessary, various additives such as an impact modifier, a stabilizer, a lubricant, a filler, a pigment, a foaming agent, and a UV stabilizer may be added to these resins.

The blending ratio of the sucrose aromatic monocarboxylic acid ester (II) of the present invention to the resin is preferably 1 to 40 parts, more preferably 1 to 30 parts, per 100 parts of the resin. When the amount is less than 1 part, the desired performance tends to be not obtained. When the amount is more than 40 parts, the possibility of bleeding out due to long-term storage or the like becomes large.

(B) For the sucrose carboxylic acid ester (III)

<Objects>

The sucrose carboxylic acid ester (III) of the present invention has a furfural content of 50 ppm or less, or a content of hydroxymethyl furfural (HMF: 5- (hydroxymethyl) -2-furaldehyde) Is a predetermined sucrose aromatic monocarboxylic acid ester. That is, when the content of these two impurities in the predetermined sucrose aromatic monocarboxylic acid ester is controlled to be low, the odor of the adhesive composition is remarkably improved when it is blended in the 2-cyanoacrylate adhesive as an extender. The content of furfural is preferably 5 ppm or less, more preferably 0.5 ppm or less. On the other hand, the content of HMF is preferably 50 ppm or less, more preferably 5 ppm or less.

In the sucrose aromatic monocarboxylic acid ester (III) of the present invention, the average value (hereinafter also referred to as "average esterification degree") of the ratio of esterification of the alcohol portion of sucrose is preferably 6.0 or less, more preferably 5.0 or less to be. When the average degree of esterification exceeds 6.0, the odor reducing effect tends to be small. On the other hand, the average degree of esterification is preferably 3.0 or more, and more preferably 4.5 or more. When the average degree of esterification is less than 3.0, the adhesiveness tends to decrease.

<Manufacturing method>

(Purification process)

The sucrose aromatic monocarboxylic acid ester (III) according to the present invention may be produced by any known method so long as the furfural content is 50 ppm or less and the HMF content is 500 ppm or less. As such a method, For example, there can be mentioned a method of purifying an ester obtained by subjecting sucrose and an aromatic monocarboxylic acid to a common esterification reaction. The purification may be carried out by first raising the furfural content to 50 ppm or less, then reducing the HMF to 500 ppm or less, or vice versa. However, from the viewpoints of simplicity and efficiency, it is preferable that both are simultaneously set to a predetermined concentration or less.

As a method of simultaneously making both of them lower than a predetermined concentration, that is, a method of making the furfural to 50 ppm or less or the HMF to 500 ppm or less, for example, a method in which sucrose and an aromatic monocarboxylic acid are reacted with an ester- Is dissolved in an organic solvent such as toluene, o-xylene or m-xylene, and the solution is dried. The concentration of the ester compound in the organic solvent is preferably 10% by weight or more, and more preferably 30% by weight or more. When the concentration is less than 10% by weight, it is industrially inefficient. On the other hand, the concentration is preferably 80% by weight or less, more preferably 50% by weight or less. When the concentration exceeds 80 wt%, the viscosity is very high and it tends to be difficult to adapt to the reduced pressure concentration apparatus. These organic solvents may be used alone or in combination of two or more.

As a means for drying the organic solvent solution of the sucrose aromatic monocarboxylic acid ester (III), any conventionally known method can be used. Specifically, for example, the solution is brought into contact with the heating surface to remove the solvent and the like &Lt; / RTI &gt; In contact with the heating surface, the solution is preferably brought into contact with a liquid film having a thickness of 10 cm or less, more preferably 5 cm or less, further preferably 5 mm or less and 1 mm or less. When the thickness of the liquid film exceeds 10 cm, furfural or HMF tends to increase during drying. The lower limit of the thickness of the liquid film is not particularly limited as long as it is a practicable thickness, but if the thickness is thinner, the purification cost tends to increase, which tends to become industrially unfavorable. Here, the "thickness of the liquid film" of the organic solvent solution of the sucrose aromatic monocarboxylic acid ester specifically refers to the distance from the lower surface of the liquid film in contact with the heating surface to the surface of the opposite side.

The drying is preferably carried out under reduced pressure, which is carried out under reduced pressure. The conditions for the reduced-pressure drying vary depending on various conditions such as the amount of the raw material to be used, the drying efficiency to be obtained, the kind of the organic solvent to be used, and the like, but the pressure is preferably 0.01 KPa · abs or more. The equipment tends to be expensive to make the pressure less than 0.01 KPa · abs. On the other hand, the pressure is preferably 15 KPa · abs or less, more preferably 4 KPa · abs or less. If the pressure exceeds 15 KPa · abs, the drying efficiency tends to be lowered. The temperature of the heating surface in drying (referred to as &quot; heating temperature &quot;) is preferably 90 ° C or higher, and more preferably 100 ° C or higher. If the heating temperature is less than 90 ° C, the drying efficiency tends to be lowered. On the other hand, the heating temperature is preferably 300 DEG C or lower, more preferably 200 DEG C or lower and 160 DEG C or lower. When the heating temperature exceeds 300 ° C, furfural and HMF tend to increase.

The contact of the organic solvent solution of the sucrose aromatic monocarboxylic acid ester (III) with the heating surface can be carried out, for example, by using a vacuum drum drier, a vacuum belt dryer, a thin film distiller, a flash distiller, a vacuum extruder, It can be carried out using equipment. These devices may be used alone, or two or more of the same or different devices may be used in combination. When two or more are used in combination, it is preferable to connect them in series, in particular, because the level of the tablets is improved. Specific examples of the connection include, for example, a connection between a thin film still and a thin film still, a connection between a flash still and a thin film still, a connection between a stirring tank and a thin film still, and a connection between a stirring tank and a vacuum compressor. Further, in the case of using a mono-tube type condensation type apparatus (in the embodiment, using a mono-tube type concentrated flash type still), the diameter of the pipe (introduction pipe diameter) into which the organic solvent solution is introduced, Quot; thickness &quot;.

The drying can be carried out in all of the batch type or continuous type. However, since furfural and HMF tend to increase as the heating time is prolonged, a continuous type which can suppress the thermal history is preferable.

(Ester synthesis)

The sucrose aromatic monocarboxylic acid ester (III) used as a raw material for the above purification process (for the sake of convenience, the term "crude sucrose aromatic monocarboxylic acid ester (III)" or "crude ester (III)" ) Can be prepared by esterification reaction of sucrose and an aromatic monocarboxylic acid (I) by a conventional method, and the esterification reaction is carried out, for example, in Japanese Patent Application Laid-Open No. 61-4839 Or by reacting sucrose with a chloride of an aromatic monocarboxylic acid (I) in accordance with the process for producing sucrose benzoate described in JP-A-40-5688.

For example, when the method described in Japanese Patent Application Laid-Open No. 61-4839 is used, the preparation can be carried out according to the description of "(A) for the sucrose carboxylic acid ester (II)".

On the other hand, when the method described in JP-A-40-5688 is followed, the esterification reaction can be carried out in the same manner as in the method described in JP-A-61-4839, , That is, one or two or more solvents selected from aromatic or substituted aromatic hydrocarbons, chlorinated aliphatic hydrocarbons and lower aliphatic ethers. Examples of the aromatic or substituted aromatic hydrocarbon include benzene, toluene, xylene, ethylbenzene, chlorobenzene and chlorotoluene. Examples of the chlorinated aliphatic hydrocarbon include methylene dichloride, chloroform, carbon tetrachloride and tetrachlorethylene Examples of the lower aliphatic ether include diethyl ether and diisopropyl ether.

The reaction temperature can be from -15 캜 to 100 캜, but more preferably from -10 캜 to 30 캜. The reaction time depends on various conditions, but it is usually sufficient to conduct the reaction for about 3 hours.

<Applications>

The sucrose aromatic monocarboxylic acid ester (III) of the present invention can be used as an increasing agent for the 2-cyanoacrylate-based adhesive and as an odor improving agent. Examples of the adhesive component of the 2-cyanoacrylate adhesive include 2-cyanoacrylic acid methyl ester, 2-cyanoacrylic acid ester, 2-cyanoacrylic acid propyl ester, 2-cyanoacrylic acid butyl ester, Ester, 2-cyanoacrylic acid methoxyethyl ester, 2-cyanoacrylic acid ethoxyethyl ester, 2-cyanoacrylic acid 2-chloroethyl ester, 2-cyanoacrylic acid cyclohexyl ester, Acrylate is used, but 2-cyanoacrylic acid ethyl ester is particularly preferable.

The blending amount of the sucrose aromatic monocarboxylic acid ester (III) of the present invention to the 2-cyanoacrylate-based adhesive when preparing the adhesive composition is preferably 5 parts or more with respect to 100 parts of the adhesive, Is more than 15 parts. When the blending amount is less than 5 parts, the effect of adding the sucrose aromatic monocarboxylic acid ester (III) tends to be insufficient. On the other hand, the blending amount is preferably 60 parts or less, more preferably 30 parts or less. If the blending amount exceeds 60 parts, the adhesive performance tends to decrease. However, even if the ratio of the sucrose aromatic monocarboxylic acid ester (III) is extremely increased and the adhesive force is lowered, it is rather preferable for the purpose of adhesion. Therefore, the upper limit value mentioned above is preferably the combination of the sucrose aromatic monocarboxylic acid ester It does not limit the ratio.

In addition to the 2-cyanoacrylate-based adhesive component and the sucrose aromatic monocarboxylic acid ester (III) of the present invention, the adhesive composition of the present invention may contain various conventionally used additives such as preservative stabilizers, organic solvents, plasticizers, Additives such as thickeners (polymers), fillers, thixotropic improvement agents, heat resistance imparting agents, polarity reducing agents, adhesion promoters, curing accelerators, curing inhibitors, coloring agents and carbonate compounds can be appropriately added.

When the sucrose aromatic monocarboxylic acid ester (III) of the present invention is added to the 2-cyanoacrylate-based adhesive component, it easily dissolves into the 2-cyanoacrylate-based adhesive component at an arbitrary ratio, Adhesive property, stability, viscosity and the like of the cyanoacrylate-based adhesive component are hardly changed.

In the present specification, the term &quot; part &quot; simply means &quot; part by weight &quot;. The "average substitution degree", the "average ester substitution degree" and the "average esterification degree" in the sucrose aromatic monocarboxylic acid ester all have the same meaning and values obtained by proton nuclear magnetic resonance ( ¹ H-NMR) . In the sucrose aromatic monocarboxylic acid ester (II), the ratio of each substituent when calculating the ratio of "low substitution" is a value obtained by liquid chromatography mass spectrometry (LC-MS). The content of halogen (ppm) is a value measured by inductively coupled plasma emission spectrometry (ICP). The amount of "furfural" and "HMF" in the sucrose aromatic monocarboxylic acid ester (III) was determined by high performance liquid chromatography (HPLC) and the amount of "toluene" was determined by gas chromatography (GC) Value.

(Example)

The present invention will be described in detail based on examples, but the present invention is not limited thereto.

<Materials Used>

Sucrose: ≥99.9%, manufactured by Shinko Seito Kabushiki Kaisha

Benzoyl chloride (1): High purity product (> 99.5%), manufactured by Kawaguchi Chemical Industries Co., Ltd.

Benzoyl chloride (2): a product of> 99.0%, manufactured by Jiangsu Qiangsheng Chemical Co., Ltd.)

(A) a sucrose aromatic monocarboxylic acid ester (II-1)

1. Synthesis

Example 1

&Lt; Sucrose benzoate (ratio of 6 substituents or less: 93.5%) &gt;

After adding 34.2 parts of sucrose and 70 parts of water into five 1 liter flasks equipped with a stirrer, a thermometer, a cooling condenser, a dropping funnel and a pH electrode connected to a pH meter, the solution was dissolved. Thereafter, 100 parts of cyclohexanone containing 75.0 parts of the compound (1) were gradually added. 48.5 parts of a 48% caustic soda aqueous solution was then added at a rate such that the pH was maintained at 10 to 11 with a dropping funnel while maintaining the temperature at 20 캜 or lower. After the water bath was removed, agitation was continued at room temperature of 20 to 30 ° C for 1 hour. After aging and completion of the reaction, a small amount of sodium carbonate was added and heated. The remaining benzoyl chloride was converted into sodium benzoate. Thereafter, the mixture was allowed to stand for about 30 minutes, and the water phase was separated and removed. 70 parts of water was newly added, the temperature was raised to 40 to 50 占 폚 with a water bath, and the mixture was stirred for 30 minutes, left to stand for about 30 minutes, and the water phase was separated and removed. After repeating the same operation twice again (total number of washings: 3 times), the temperature was raised to 120 ° C and the solvent was removed under reduced pressure to obtain sucrose benzoate. The average degree of substitution, the proportion of each substituent, the proportion of six substituents or less, and the halogen content were measured (the same applies to the objects of the following examples and comparative examples).

Example 2

&Lt; Sucrose benzoate (ratio of 6 substituents or less: 83.5%) &gt;

Except that 82.1 parts of benzoyl chloride (1) and 53.1 parts of 48% caustic soda aqueous solution were used and the number of times of rinsing was 4 times, thereby obtaining sucrose benzoate of the same name.

Example 3

<Sucrose benzoate (ratio of 6 substituents or less: 49.8%)>

Except that 93.7 parts of benzoyl chloride (1) and 60.6 parts of a 48% caustic soda aqueous solution were used and the number of times of washing was changed to 2, thereby obtaining sucrose benzoate of the same name.

Example 4

<Sucrose benzoate (ratio of 6 substituents or less: 9.0%)>

106.7 parts of benzoyl chloride (1) and 69.0 parts of a 48% caustic soda aqueous solution were used, and the number of times of rinsing was 4 times, thereby obtaining sucrose benzoate of the same name.

Comparative Example 1

<Sucrose benzoate (ratio of 6 substituents or less: 9.0%)>

The procedure of Example 4 was repeated except that the number of washings was changed to one cycle to obtain sucrose benzoate.

Comparative Example 2

<Sucrose benzoate (ratio of 6 substituents or less: 9.6%)>

The procedure of Example 4 was repeated except that benzoyl chloride (2) was used in place of benzoyl chloride (1) and the number of times of washing was changed to 8 times to obtain sucrose benzoate.

Comparative Example 3

<Sucrose benzoate (ratio of 6 substituents or less: 9.6%)>

The same procedure as in Comparative Example 2 was carried out except that the number of washings was changed to three times to obtain sucrose benzoate of the same name.

Comparative Example 4

&Lt; Sucrose benzoate (ratio of 6 substituents or less: 6.0%) &gt;

111.0 parts of benzoyl chloride (1) and 71.8 parts of a 48% caustic soda aqueous solution were used and treated in the same manner as in Example 1 except that the washing with water was not carried out again to obtain sucrose benzoate.

2. Evaluation

<Color>

The color of each of the esters obtained in the above Examples and Comparative Examples was determined according to the method described in JIS K2421. That is, each sample was diluted to 50% with toluene, and the numerical value of the APHA standard solution (Hazen color number: APHA), which is judged to be the same when the color of the diluted solution was visually compared, was recorded.

<Color stability>

5 g of the respective esters obtained in the above Examples and Comparative Examples were placed in a test tube and heated in an oil bath at 110 DEG C for 12 hours. For each of the thus obtained samples, the hue was judged by the same method as described in the above &lt; Color &gt; &gt;.

The results are shown in Tables 1 and 2.

As shown in Table 1, not only the product colors of all of Examples 1 to 4 of the present invention are superior to those of APHA 30, but also show a change in color (APHA) even after heating at 110 DEG C for 12 hours. And showed high thermal stability. On the other hand, as shown in Table 2, in Comparative Examples 1 to 4, a large change in hue was observed before and after heating, and the degree of change tended to increase as the content of halogen increased .

(B) a sucrose aromatic monocarboxylic acid ester (II-2)

1. Synthesis

Example 5

&Lt; Sucrose benzoate (ratio below 5 substituents: 0.2%) &gt;

Into a 1 liter flask equipped with a stirring rod, a thermometer, a cooling condenser, a dropping funnel, and a pH electrode connected to a pH meter, 34.2 parts of sucrose and 70 parts of water were added to dissolve in a 1 liter flask, 100 parts of cyclohexanone containing 106.7 parts of the compound (1) were gradually added. Thereafter, while maintaining the temperature at 20 ° C or lower, 69.0 parts of a 48% aqueous sodium hydroxide solution was added at a rate such that the pH was maintained at 10 to 11 with a dropping funnel. After the water bath was removed, agitation was continued for 1 hour at room temperature of 20 to 30 DEG C, and the reaction was completed. After adding a small amount of sodium carbonate and heating, the remaining benzoyl chloride was converted into sodium benzoate. Thereafter, the mixture was allowed to stand for about 30 minutes, and the water phase was separated and removed. 70 parts of water was newly added, and the temperature was raised to 40 to 50 占 폚 with a water bath. After stirring for 30 minutes, the mixture was allowed to stand for about 30 minutes to separate and remove the water phase. The same operation was repeated 7 times (total number of washings: 8 times), and the temperature was raised to 120 ° C, and the solvent was removed under reduced pressure to obtain sucrose benzoate of the formula. The average degree of substitution, the proportion of each substituent, the proportion of five substituents or less, and the halogen content were measured (the same applies to the objects of the following examples and comparative examples).

Example 6

&Lt; Sucrose benzoate (ratio below 5 substituents: 0.0%) &gt;

113.8 parts of benzoyl chloride (1) and 73.6 parts of 48% caustic soda aqueous solution were used, and the number of times of washing was changed to 5 cycles, thereby obtaining sucrose benzoate of the title.

Comparative Example 5

&Lt; Sucrose benzoate (ratio below 5 substituents: 0.0%) &gt;

The procedure of Example 6 was repeated except that the number of washings was changed to one cycle to obtain sucrose benzoate.

For Examples 5 to 6 and Comparative Examples 1 to 3 and 5, the average degree of substitution, the proportion of each substituent, the proportion of five substituents or less, and the halogen content were measured.

2. Evaluation

<Color>

The color of each of the esters obtained in the above Examples and Comparative Examples was determined according to the method described in JIS K2421. That is, each sample was diluted with toluene to 50%, and the value of the APHA standard solution (Hagen color number: APHA), which is judged to be the same when the color of the diluted solution was visually compared, was recorded.

<Color stability>

5 g of the respective esters obtained in the above Examples and Comparative Examples were put in a test tube and heated in an oil bath at 160 캜 for 3 hours. With respect to each sample thus obtained, the hue was judged by the same method as described in the above &lt; Color &gt; &gt;.

The results are shown in Table 3.

As shown in Table 3, in Examples 5 and 6 of the present invention, all of the product colors were not only excellent in APHA of 10 or less, but also changed in color (APHA) even after heating at 160 DEG C for 3 hours And showed high thermal stability. On the other hand, in Comparative Examples 1 to 3 and 5, a large change in hue was observed before and after heating, and the degree of change tended to increase as the content of halogen increased.

(C) a sucrose aromatic monocarboxylic acid ester (III)

1. Synthesis of crude sucrose benzoic acid ester

Preparation Example 1 (crude sucrose benzoate ester (1) (average degree of esterification: 5.5))

30.0 parts of sucrose and 70.0 parts of water were dissolved in a 1 liter flask equipped with a stirrer, a thermometer, a cooling condenser, a dropping funnel, and a pH electrode connected to a pH meter, and the mixture was cooled to 10 DEG C or lower. 100 parts of cyclohexanone containing 67.7 parts of the compound (1) were gradually added. Thereafter, 42.9 parts of 48% caustic soda aqueous solution was added at a rate such that the pH was maintained at 10 to 11 with a dropping funnel while maintaining the temperature at 20 캜 or lower. After the water bath was removed, agitation was continued at room temperature of 20 to 30 ° C for 1 hour. After aging and completion of the reaction, a small amount of sodium carbonate was added and heated. The remaining benzoyl chloride was converted into sodium benzoate. Thereafter, the mixture was allowed to stand for about 30 minutes, and the water phase was separated and removed. 100 parts of water was newly added, the temperature was raised to 40 to 50 占 폚 with a water bath, and the mixture was stirred for 30 minutes, allowed to stand for about 30 minutes, and the water phase was separated and removed. The solvent was removed under reduced pressure to obtain the title compound (crude SB (1)).

Preparation Example 2 (crude sucrose benzoate ester (2) (average esterification degree: 4.9)) The same procedure as in Production Example 1 was conducted except that 50.0 parts of sucrose and 60.3 parts of benzoyl chloride (1) were used, )).

Production Example 3 (crude sucrose benzoate ester (3) (average esterification degree: 4.5))

Except that 30.0 parts of sucrose and 55.4 parts of benzoyl chloride (1) were used in the same manner as in Preparation Example 1 to obtain the title compound (SB (3)).

Production Example 4 (crude sucrose benzoate ester (4) (average degree of esterification: 5.7))

Except that 30.0 parts of sucrose and 70.2 parts of benzoyl chloride (1) were used in the same manner as in Preparation Example 1, to obtain the title compound (SB (4)).

Production Example 5 (crude sucrose benzoate ester (5) (average esterification degree: 4.8))

Except that 30.0 parts of sucrose and 59.1 parts of benzoyl chloride (1) were used in the same manner as in Preparation Example 1 to give the title compound (SB (5)).

2. Purification process (removal of furfural and HMF)

Example 7

The crude SB (1) obtained above was dissolved in toluene to prepare a toluene solution of 50 wt% crude sucrose benzoic acid ester (crude SB). The above solution was applied to a 50-wt% crude SB toluene solution at a flow rate of 1.5 l / h, a 10-cm thick liquid film made of the same solution in the air, a pressure of 13 KPa · abs in the air, (1) (SB (1)) was obtained by drying under the conditions of a temperature of 130 deg. The amount of furfural (ppm), the amount of HMF (ppm), the amount of toluene (ppm) and the average degree of esterification were measured for SB (1).

Examples 8-14

Sucrose benzoic acid esters (2) to (8) (SB (2) to SB (8)) were obtained in the same manner as in Example 7 except that the corresponding starting compounds were subjected to the conditions described in Table 4. For each, the amount of impurities and the degree of esterification were measured.

Comparative Example 6

Sucrose benzoic acid ester (I) (SB (I)) was obtained in the same manner as in Example 7 except that the corresponding starting compound was subjected to the conditions described in Table 4. The amount of impurities and the degree of esterification were measured.

The results are shown in Table 4.

3. Preparation of adhesive composition

Each SB obtained above was used as an extender, and each adhesive composition was prepared. That is, 30 parts of each SB was added to and dissolved in 100 parts of 2-cyanoacrylic acid ethyl ester containing a small amount of stabilizer (SO ₂ and hydroquinone) to prepare adhesive compositions (1) to (8) &Lt; / RTI &gt;

4. Performance evaluation of adhesives

(Acceleration test)

Each adhesive composition was filled in a polyethylene container having a capacity of 20 ml, sealed, and held at 70 캜 for 5 days. In Table 4, the &quot; state &quot; indicates the state before the acceleration test, and the &quot; after the test &quot; indicates the state after the acceleration test.

(Set time)

The set time was measured in accordance with JIS K-6861 using a cold-rolled steel sheet of 25 mm x 100 mm x 1.6 mm.

(Tensile shear strength)

The tensile shear strength was measured by using a tensile tester after being polished and degreased by using a cold-rolled steel sheet of 25 mm x 100 mm x 1.6 mm and having a contact area of 12.5 mm x 25 mm piled on each other for 24 hours.

(stink)

The odor was judged by the following criteria based on the case of no addition of sucrose benzoate ester (C).

A: When odor reduction is noticeable

B: When a reduction in odor is recognized

C: In the case of no addition of sucrose benzoate ester

D: If the odor becomes stronger on the contrary

The results are shown in Table 4.

Note 1) Flash distiller (heating tube heat transfer area: 0.8 m 2) (mono-tube condensation type, manufactured by Sakuma Seisakusho Co., Ltd.)

Note 2) Vacuum drum dryer (heating tube heat transfer area: 0.25 m 2) (DDV025, manufactured by Chuo Kouki KK)

Note 3) Thin-film distillation apparatus (heating tube heat transfer area: 0.3 m 2) (manufactured by Hitachi Plant Technologies Co., Ltd., vertical control)

Note 4) Under the conditions of Example 12, two thin films of the same thin film still were connected in series.

Note 5) A flash distiller under the condition of Example 7 and a thin film still under the condition of Example 12 were connected in series to each other.

Note 6) Distillation pot (SU 304, 300 L capacity) was used.

As described above, when the sucrose aromatic monocarboxylic acid ester (III) of the present invention is used as an extender, it has an excellent effect that the odor can be remarkably reduced without largely affecting the set time or tensile shear strength .

The sucrose aromatic monocarboxylic acid ester (II) of the present invention is excellent in compatibility with amorphous resin or crystalline resin, and can improve molding processability, physical properties, flexibility, impact resistance, and the like, It is useful as a modifier for a resin, particularly a resin which is required to have optical transparency.

The sucrose aromatic monocarboxylic acid ester (III) according to the present invention is an extender of a 2-cyanoacrylate-based adhesive and has excellent characteristics of improving odor without deteriorating its adhesive performance. Therefore, Useful as an extender.

Claims (19)

delete delete delete delete delete delete delete delete delete delete delete delete A process for producing an ester of sucrose and an aromatic monocarboxylic acid represented by the formula (1)
(Formula 1)

(Wherein R ¹ to R ⁵ are independently a group selected from a hydrogen atom, an alkyl group and an alkoxy group)
Esterification with sucrose and a halogen-containing esterifying agent having a purity of more than 99.5%; And
And removing furfural and hydroxymethyl furfural from the obtained ester form until the content of furfural is 50 ppm or less and the content of hydroxymethyl furfural is 500 ppm or less,
The step of removing the furfural and hydroxymethyl furfural comprises reacting an organic solvent solution of the sucrose aromatic monocarboxylic ester with a heating surface in a liquid film state with a thickness of 0.5 cm or less and drying the sucrose aromatic mono carboxylic acid ester, Gt; carboxylic &lt; / RTI &gt; ester. delete delete delete 14. The method of claim 13,
Wherein the drying is a reduced-pressure drying. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 18. The method of claim 17,
Wherein the reduced pressure drying is carried out under a pressure of 0.01 to 15 KPa · abs and a heating temperature of 90 to 300 ° C. 18. The method of claim 17 or 18,
Wherein the reduced-pressure drying is carried out using one or more machines selected from a vacuum drum dryer, a vacuum belt dryer, a thin-film distiller, a flash distiller and a vacuum extruder. .