TWI615397B - Sucrose aromatic monocarboxylate - Google Patents

Abstract

The present invention provides an ester of sucrose and an aromatic monocarboxylic acid represented by the general formula (I) with a small content of specific impurities.

(In the formula, R ¹ to R ⁵ are each independently a group selected from a hydrogen atom, an alkyl group, and an alkoxy group). This ester with a low halogen content has excellent compatibility with non-crystalline resins or crystalline resins, and can be used to improve its moldability, physical properties, softness, impact resistance, and other properties, and it has good thermal stability to suppress coloration due to heating. Resin modifier. This ester having a small amount of furanal and hydroxymethylfuranal can be effectively used as an odor-improving bulking agent that can improve the odor without reducing the bonding performance of the 2-cyanoacrylate-based adhesive.

Description

Sucrose aromatic monocarboxylic acid ester

The present invention relates to a sucrose aromatic monocarboxylic acid ester having a low content of specific impurities, and particularly to a sucrose aromatic monocarboxylic acid ester having a low content of halogen, and has a low content of furfural and hydroxyl methyl furfural Sucrose aromatic monocarboxylic acid ester.

The aspect of the present invention with a low halogen content (the first aspect of the present invention) is that it has excellent compatibility with amorphous resins or crystalline resins, and can improve its formability, physical properties, flexibility, and impact resistance. For example, the sucrose aromatic monocarboxylic acid ester as a resin modifier can suppress the sucrose aromatic monocarboxylic acid ester which has good thermal stability due to heating.

The form in which the content of furanaldehyde and hydroxymethylfuran formaldehyde of the present invention is small (the second aspect of the present invention) is an extender for 2-cyanoacrylate-based adhesives. More specifically, it is not A sucrose aromatic monocarboxylic acid ester capable of reducing the adhesive property of the adhesive to improve the odor, a 2-cyanoacrylate-based adhesive formed by including the ester as an odor improving extender, and the ester Production method.

In terms of resin modifiers, sucrose derivatives such as sucrose benzoate have been generally known and are known to improve non-crystalline resins such as ABS resins, polymers The molding processability and physical properties of vinyl chloride resin, epoxy resin, unsaturated polyester resin, etc., and the flexibility and impact resistance of crystalline polyester are improved (Patent Documents 1 to 3).

However, since a sucrose benzoate derivative of sucrose, when it is added as a modifier, the thermal stability of the hue or hue of a product formed from these resins becomes a problem. That is, sucrose benzoate is generally produced using an organic solvent, but in the manufacturing process, coloring may occur during the heating step of removing the organic solvent. More specifically, the melting point of sucrose benzoate is 80-90 ° C. When the organic solvent used is removed during its manufacturing process, it must generally be heated above 100 ° C or better, above 110 ° C. Under such heating conditions as 100 ° C or higher, the sucrose benzoate is colored. Therefore, the degree of coloring tends to become more significant as the proportion of components with a lower degree of esterification in sucrose benzoate increases or the average ester substitution rate decreases. In addition, if special processing equipment (such as a thin film evaporation device) is used to shorten the processing time, although the thermal history of sucrose benzoate can be reduced by removing organic solvents, the coloration can be suppressed as much as possible. After the ester is added to the resin, the resin is colored due to thermal history during processing and molding.

Therefore, it is not satisfactory to use sucrose benzoate as a modifier for resins requiring optical transparency.

On the other hand, 2-cyanoacrylate-based adhesives have the characteristics that they can be used for bonding between dissimilar materials regardless of the adhesion force of most materials such as wood, plastic, and metal, and can be bonded in seconds. Although this adhesive is more expensive than other widely used adhesives, due to its great advantages as described above, its usage is still steadily increasing every year.

2-cyanoacrylate adhesive, in order to reduce cost and improve odor For the purpose of goodness, sucrose benzoate can be used as an extender (Patent Document 4). However, the improvement of odor is still not satisfactory.

[Previous Technical Literature]

Patent literature

[Patent Document 1] Japanese Patent Laid-Open No. 52-81362

[Patent Document 2] Japanese Patent Publication No. 62-15582

[Patent Document 3] Japanese Patent Laid-Open No. 6-255274

[Patent Document 4] Japanese Patent Laid-Open No. 5-222340

In the first aspect, the present invention provides a sucrose aroma that is excellent in compatibility with amorphous resins or crystalline resins, and can improve molding processability, physical properties, softness, and impact resistance, and is effective as a resin modifier. It is a group of monocarboxylic acid esters, and can suppress the coloring under heating, and has good thermal stability.

In a second aspect, the present invention provides a sucrose aromatic monocarboxylic acid ester, which is a 2-cyanoacrylate-based adhesive agent, and does not reduce the adhesion performance when it is increased, and can also make Odor improved.

The present inventors have deliberately conducted research on solving the above-mentioned problem regarding the first state, and have found that by suppressing the content of halogen in the sucrose aromatic monocarboxylic acid ester, the coloration during cumulative heating can be suppressed. Repeated review to complete the present invention.

(式中，R¹至R⁵各自獨立為選自氫原子、烷基及烷氧基之基)，且其鹵素之含量為100ppm以下的蔗糖芳香族單羧酸酯(Ⅱ)。 That is, the present invention relates to: an ester of sucrose and an aromatic monocarboxylic acid represented by the general formula (I) [Chem. 1]

(Wherein R ¹ to R ⁵ are each independently a group selected from a hydrogen atom, an alkyl group, and an alkoxy group), and the sucrose aromatic monocarboxylic acid ester (II) whose halogen content is 100 ppm or less.

The content of the sucrose aromatic monocarboxylic acid ester (II) with a hexa-substituent or less is preferably 5% by weight or more (sucrose aromatic monocarboxylic acid ester (II-1)).

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

The aforementioned sucrose aromatic monocarboxylic acid ester (II-1) preferably has a hue in a 50% toluene solution of less than APHA30.

The sucrose aromatic monocarboxylic acid ester (II-1) preferably has a hue in a 50% toluene solution after being heated at 110 ° C. for 12 hours to be less than APHA30.

Meanwhile, the present invention also relates to a resin modifier containing the aforementioned sucrose aromatic monocarboxylic acid ester (II-1).

The present invention also relates to a sucrose aromatic monocarboxylic acid ester (sucrose aromatic monocarboxylic acid) in which the content of the penta-substituent is less than 2.0% by weight in the sucrose aromatic monocarboxylic acid ester (II). Ester (II-2)).

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

In the aforementioned sucrose aromatic monocarboxylic acid ester (II-2), it is also preferable that the hue in a 50% toluene solution is below APHA10.

The aforementioned sucrose aromatic monocarboxylic acid ester (II-2) has a hue in a 50% toluene solution after heating at 160 ° C for 3 hours, which is more preferably APHA30 or less.

Meanwhile, the present invention also relates to a resin modifier containing the aforementioned sucrose aromatic monocarboxylic acid ester (II-2).

The present invention also relates to a method for producing a sucrose aromatic monocarboxylic acid ester, which is a method for producing a sucrose aromatic monocarboxylic acid ester (II) capable of suppressing coloration, and includes a step of reducing the halogen content to 100 ppm or less.

The above-mentioned sucrose aromatic monocarboxylic acid ester (II) capable of inhibiting coloring is also preferably a sucrose aromatic monocarboxylic acid ester (II-1) whose hue in a 50% toluene solution is less than APHA30. The sucrose aromatic monocarboxylic acid ester (II-2) with a hue in a 50% toluene solution of less than APHA10 is more preferred.

At the same time, the present inventors have deliberately conducted research on solving the above-mentioned problem regarding the second aspect, and found that it is possible to suppress specific impurities (furan formaldehyde and hydroxymethyl furan formaldehyde) in the sucrose aromatic monocarboxylic acid ester by suppressing it. When used as an extender for 2-cyanoacrylate-based adhesives, the content of the additive does not decrease the adhesive performance and improve the odor. The present invention has been completed after repeated review.

(式中，R¹至R⁵各自獨立為選自氫原子、烷基及烷氧基之基)，呋喃甲醛之含量為50ppm以下且羥甲基呋喃甲醛之含量為500ppm以下的蔗糖芳香族單羧酸酯(Ⅲ)。 That is, the present invention relates to: an ester of sucrose and an aromatic monocarboxylic acid represented by the general formula (I) [Chem. 2]

(Wherein R ¹ to R ⁵ are each independently a group selected from a hydrogen atom, an alkyl group, and an alkoxy group), a sucrose aromatic monomer having a furanal content of 50 ppm or less and a hydroxymethylfuranal content of 500 ppm or less Carboxylate (III).

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

At the same time, the present invention also relates to a 2-cyanoacrylate-based adhesive, which includes the aforementioned sucrose aromatic monocarboxylic acid ester (III) as an odor improving / increasing agent.

(式中，R¹至R⁵各自獨立為選自氫原子、烷基及烷氧基之 基)，以該蔗糖芳香族單羧酸酯(Ⅲ)的有機溶劑溶液，在厚度10cm以下的液膜之狀態下與加熱面接觸而乾燥。 The present invention also relates to a method for producing a sucrose aromatic monocarboxylic acid ester (III), which is a method for producing a sucrose aromatic monocarboxylic acid ester (III) having a furan formaldehyde content of 50 ppm or less and a methylolfuran formaldehyde content of 500 ppm or less. Method, and the sucrose aromatic monocarboxylic acid ester (III) comprises an ester of sucrose and an aromatic monocarboxylic acid represented by the general formula (I)

(Wherein R ¹ to R ⁵ are each independently a group selected from a hydrogen atom, an alkyl group, and an alkoxy group). The organic solvent solution of the sucrose aromatic monocarboxylic acid ester (III) is a solution having a thickness of 10 cm or less. When the film is in contact with the heating surface, it is dried.

The aforementioned drying is preferably performed under reduced pressure.

The aforementioned drying under reduced pressure is preferably performed under the conditions of an internal pressure of 0.01 to 15 KPa · abs and a heating temperature of 90 to 300 ° C.

The aforementioned reduced-pressure drying is preferably performed by using one or more types of machinery selected from the group consisting of a vacuum drum dryer, a vacuum belt dryer, a film evaporator, a rapid evaporator, and a vacuum extruder. .

According to the first aspect of the present invention, the sucrose aromatic monocarboxylic acid ester (II) has excellent compatibility with non-crystalline resins and crystalline resins, and can improve its formability, physical properties, softness, and resistance. On the other hand, it has excellent characteristics such as the ability to suppress heating and coloring. Therefore, it can be used as a modifier for resins requiring optical transparency.

At the same time, the sucrose aromatic monocarboxylic acid ester (II-1) of the present invention shows that even when the proportion of esterification in the alcohol portion of sucrose is small, that is, when the proportion of the low-substituent is high, it can still show thermal stability. Good sexual characteristics.

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

At the same time, the manufacturing method of the present invention is based on such a sucrose aromatic monocarboxylic acid ester (II) exhibiting excellent characteristics, and can be easily manufactured without using special processing equipment (such as a thin film evaporation device). The cost is excellent in industrial aspects.

A second aspect related to the present invention is a sucrose aromatic monocarboxylic acid ester. (III). It has excellent properties that can be used as an extender for 2-cyanoacrylate adhesives, and can improve the odor without reducing the adhesive performance. Therefore, an odor improvement / expansion agent can be used as the adhesive.

In addition, the production method of the present invention has an industrial advantage because the sucrose aromatic monocarboxylic acid ester (III) exhibiting such excellent characteristics can be easily and efficiently produced.

In the present invention, as for the sucrose aromatic monocarboxylic acid ester of the objective, as described above, the sucrose aromatic monocarboxylic acid esters (II-1), (II-2), and (III) are separately referred to as When referring to "sucrose aromatic monocarboxylic acid ester", depending on its context, it includes any of them, and it also includes and may include its owner.

In the aromatic monocarboxylic acid (I) of the sucrose aromatic monocarboxylic acid ester of the present invention, R ¹ to R ⁵ are each independently and preferably a hydrogen atom or an alkyl group, all of which are benzoic acid or one of them (R ^{3 is} preferred) is an alkyl group, and the remainder is a hydrogen atom.

Examples of the alkyl group include those having 1 to 20 carbon atoms. Among them, those having 1 to 5 carbon atoms are more preferable, and methyl, ethyl, propyl, or isopropyl are more preferable. Examples of the alkoxy group include, for example, those having a carbon number of 1 to 20, among which those having a carbon number of 1 to 5 are more preferable, and methoxy, ethoxy, propoxy, or isopropoxy are Better.

(A) About sucrose carboxylate (II)

<Target object>

In the sucrose aromatic monocarboxylic acid ester (II) of the present invention, the halogen The content is 100 ppm or less. Examples of the halogen include fluorine, chlorine, bromine, and iodine, among which the influence of the content of chlorine is large.

The preferred content of halogen is preferably below 90 ppm, more preferably below 60 ppm, even more preferably below 30 ppm, and even more preferably below 20 ppm. The preferred content of chlorine is preferably 80 ppm or less, 55 ppm or less, 25 ppm or less, or 17 ppm or less.

Although the sucrose aromatic monocarboxylic acid ester (II-1) of the present invention has a small esterification ratio of the alcohol portion of the sucrose, that is, it can still show excellent thermal stability at a higher ratio such as a lower substituent. However, the proportion of the substituents below the hexa substituent is preferably 95% by weight or less, more preferably 85% by weight or less, more preferably 50% by weight or less, and even more preferably 10% by weight or less. In addition, the six substituents refer to those in which 6 of the 8 hydroxyl groups in total of sucrose are esterified with an aromatic monocarboxylic acid. In this specification, as long as it is about a sucrose aromatic monocarboxylic acid ester (II-1), it is convenient to say that the substituents below a hexa substituent are a low substituent.

Meanwhile, the sucrose aromatic monocarboxylic acid ester (II-1) of the present invention shows an average value of the ratio of esterification even in the alcohol portion of sucrose (hereinafter, referred to as "average ester substitution rate" or "average substitution rate" ) Hourly thermal stability is still excellent. The average ester substitution rate is preferably above 5.0, more preferably above 6.0, and even above 7.0.

The sucrose aromatic monocarboxylic acid ester (II-1) of the present invention preferably has a hue in a 50% toluene solution of 30 or less, more preferably 25 or less, and more preferably 15 or less. At the same time, the sucrose aromatic monocarboxylic acid ester (II-1) of the present invention preferably has a hue in a 50% toluene solution of 30 or less, preferably 25 or less, and 15 or less after heating at 110 ° C for 12 hours. Better. Modified as resin when hue exceeds 30 In the case of an agent, the appearance (hue) and optical transparency of the resin tend to decrease.

The sucrose aromatic monocarboxylic acid ester (II-2) of the present invention preferably has a high esterification ratio of the alcohol portion of sucrose. Specifically, the content of the substituents below the penta-substitution is 2.0% by weight or less. It is more preferably 1.0% by weight or less, more preferably 0.5% by weight or less, and even more preferably 0.3% by weight or less. In addition, the five substituents refer to those in which 5 of the 8 hydroxyl groups in total of sucrose are esterified with an aromatic monocarboxylic acid. In this specification, except for the sucrose aromatic monocarboxylic acid ester (II-2), for convenience, it means that the substituents below the penta-substituent are low-substituents, and the remaining substituents are high-substituents.

In addition, other preferable examples of the sucrose aromatic monocarboxylic acid ester (II-2) of the present invention include those having a content of not more than 5% by weight of a hexa-substituent.

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

The sucrose aromatic monocarboxylic acid ester (II-2) of the present invention preferably has a hue of 10 or less in a 50% toluene solution. At the same time, the sucrose aromatic monocarboxylic acid ester (II-2) of the present invention preferably has a hue in a 50% toluene solution of 30 or less, more preferably 25 or less, and 15 or less after heating at 160 ° C for 3 hours. Better. When the hue exceeds 30, when it is used as a resin modifier, the appearance (hue) and optical transparency of the resin tend to decrease.

<Manufacturing method>

(Halogen removal step)

The sucrose aromatic monocarboxylic acid ester (II) of the present invention may contain It is manufactured by a manufacturing method with a content of 100 ppm or less.

In the step of making the halogen content below 100 ppm, any method generally used in this field can be used as long as the purpose can be achieved. Specific examples of such methods can be, for example, sucrose and aromatic monocarboxylic acids. The esterified product obtained by the esterification reaction is further washed with water. The water washing can be carried out by a conventional method, and the implementation can be performed as follows: water is added to the mixture after the esterification reaction is completed, and the mixture is stirred while being heated in a hot water bath, and then the water phase is allowed to stand still to separate and then removed. The temperature of the hot water bath is preferably 40 to 60 ° C. When the temperature is lower than 40 ° C, the washing tends to be insufficient, and when the temperature is higher than 60 ° C, the ester decomposition tends to be promoted. The stirring is not particularly limited as long as it is a sufficient time for the halide ions and other halogen-containing compounds to move in the aqueous phase, but generally, it is sufficient to perform the stirring for about 30 minutes.

In the case of sucrose aromatic monocarboxylic acid esters (II-1), the number of washing times varies depending on the raw materials used and the reaction conditions of the esters. However, high-purity raw materials with low impurities (such as high-purity benzamidine chloride ( > 99.5%), etc.) In general, it is sufficient to perform it at 5 times.

In the case of sucrose aromatic monocarboxylic acid esters (II-2), the number of washing times may vary depending on the raw materials used and the reaction conditions of the esters. However, high-purity raw materials with low impurities (such as high-purity benzamidine chloride) are used. (> 99.5%), etc.), generally, it is sufficient to carry out 5 to 8 times.

In addition, in the present invention, the halogen content in the sucrose aromatic monocarboxylic acid ester (II) may be set to 100 ppm or less, and it is effective to use a raw material having a small halogen content in advance. Therefore, the esterifying agent is preferably a high-purity halogenated aromatic monocarboxylic acid. Examples of such high-purity halogenated aromatic monocarboxylic acids include high-purity benzamidine chloride (> 99.5%) (made by Kawaguchi Pharmaceutical Co., Ltd.) and the like.

As described above, after the step of reducing the halogen content in the sucrose aromatic monocarboxylic acid ester (II) to 100 ppm or less, the solvent used in the esterification reaction can also be removed by evaporation in a conventional manner to obtain the object of the present invention. . In this case, the halogen content can be adjusted to less than 100 ppm in advance. In the present invention, the solvent can be removed by ordinary evaporation without using special processing equipment (such as a thin film evaporation device). Get the object.

(Synthesis of Ester)

In the present invention, the esterification reaction of sucrose and an aromatic monocarboxylic acid can be carried out by a conventional method. For example, it can be produced according to the method for producing sucrose benzoate described in Japanese Patent Application Laid-Open No. 61-4839.

烷、四氫呋喃等之醚系溶劑；乙酸甲酯等之酯系溶劑；三級丁醇等之醇系溶劑均適於使用。 That is, the raw material is a sucrose and an aromatic monocarboxylic acid chloride, and is produced by an esterification reaction in the presence of a basic compound in a mixed solution of a hydrophilic solvent and water. Examples of hydrophilic solvents, such as ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone;

Ether solvents such as alkane and tetrahydrofuran; ester solvents such as methyl acetate; alcohol solvents such as tertiary butanol are suitable for use.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, trimethylamine, and triethylamine.

The mixing ratio of the hydrophilic solvent and water is preferably such that the water content of a uniform liquid layer containing both is 7 to 80%. The reason is that these hydrophilic solvents can dissolve the chlorides and esters of aromatic monocarboxylic acids in one of the raw materials, and the sucrose in the other side of the raw materials can not be dissolved at all or the reaction efficiency The idea is that when it cannot be dissolved to a practical degree, when mixed with water, which is a good solvent for sucrose, the mixed solution can be dissolved to a practical degree. Therefore, take advantage of hydrophilicity This property of the solvent can adjust the reaction rate of sucrose and aromatic monocarboxylic acid chlorides. As a result, the amount of sucrose / aromatic monocarboxylic acid chlorides added (molar ratio) can be used to produce low-substitution products. Esters with different ratios and average ester substitution rates. For example, when a large amount of sucrose is added with respect to the amount of the aromatic monocarboxylic acid chloride added, an esterified product having a relatively low proportion of low substituents or a relatively high average ester substitution rate can be obtained. Conversely, Relative to the amount of aromatic monocarboxylic acid chloride added, when the amount of sucrose added is small, an esterified product having a relatively high ratio of low substituents or a relatively low average ester substitution rate can be obtained.

In terms of the reaction method, sucrose and aromatic monocarboxylic acid chlorides can be dissolved or suspended in a mixed solution containing a hydrophilic solvent and water, and then the aromatic monocarboxylic acid chlorides can be made alkaline in an equal or slightly excess amount. Compounds are dropped into; or sucrose and basic compounds are dissolved or suspended in the mixed solution, and then the aromatic monocarboxylic acid chloride is dropped; or sucrose is dissolved or suspended in the mixed solution, and then the aromatic monocarboxylic acid chloride is dissolved. The compound and the basic compound are dripped simultaneously or alternately.

The reaction temperature is preferably -15 ° C to 100 ° C, and more preferably -10 ° C to 30 ° C. However, after all of the reaction raw materials have been dripped in, it may be heated at a high temperature range in order to further promote the completion of the reaction.

The pH value during the reaction is preferably maintained at a weak alkaline. On the other hand, under strong alkalinity (for example, depending on the reaction temperature, but at pH 13 or higher), the side reaction of the hydrolysis of the aromatic monocarboxylic acid is significant, so it is preferably carried out at a pH of 8 to 13.

The reaction time is not particularly limited as long as the reaction between the raw materials can be completed. The specific time depends on the amount of the raw material compound and various conditions, but in general, it is sufficient to operate for about 3 hours.

<Use>

The sucrose aromatic monocarboxylic acid ester (II) of the present invention can be used as a resin modifier, and in particular, it has the excellent characteristics of suppressing the coloration due to heating. Therefore, it can be used as a resin modifier that requires optical transparency.

The resin to which the sucrose aromatic monocarboxylic acid ester (II) of the present invention can be added includes non-crystalline resins such as ABS resin, polyvinyl chloride resin, epoxy resin, unsaturated polyester, etc. It is a crystalline resin such as crystalline polyester. The resin is appropriately selected depending on its use. At the same time, the resin to which the sucrose aromatic monocarboxylic acid ester (II) of the present invention is added may also be appropriately selected according to the type / use of the resin, and the ratio of the low substituent and the ester substitution rate.

The ABS resin is not particularly limited, and examples thereof include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, chlorinated polyethylene, and polyacrylic rubber (such as acrylic acid). Methyl ester, ethyl acrylate, butyl acrylate, etc.), rubbery polymers such as copolymers of acrylonitrile, styrene, acrylic acid, acrylamide, 2-chloroethyl vinyl ether, etc., acrylonitrile, benzene Species obtained by graft copolymerization of ethylene, α-methylstyrene, and methyl methacrylate, and other acrylonitrile-polybutadiene-styrene graft copolymers. ABS resin can be used alone or in combination of two or more.

The polyvinyl chloride resin is not particularly limited, and examples thereof include: a polymer resin for vinyl chloride alone, a chlorinated vinyl chloride resin, and one of all monomers obtained by copolymerization with a vinyl chloride monomer. More than one vinyl chloride copolymer resin (such as vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, etc.) obtained by random copolymerization or block copolymerization, or the above resins are grafted with functional groups such as hydroxyl groups Copolymerized resin and such functional groups react with reactive compounds The grafted species. Polyvinyl chloride resins can be used alone or in combination of two or more.

In terms of epoxy resin, there is no particular limitation, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic phenolic epoxy resin, and alkylphenol. Aromatic epoxy resins such as phenolic epoxy resins, phenolic biphenylarene epoxy resins, biphenol epoxy resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins, biphenyls Epoxy resins, anthracene epoxy resins, epoxides of condensation products of phenols and aromatic aldehydes with phenolic hydroxyl groups, triglycidyl isocyanate, alicyclic epoxy resins, etc. An epoxy resin may be used individually by 1 type, and may use 2 or more types together.

The unsaturated polyester resin is not particularly limited, and examples thereof include species synthesized by addition reaction or dehydration condensation reaction of an α, β-olefin-based unsaturated dicarboxylic acid or an anhydride thereof with a diol. It can also be used in combination with saturated dicarboxylic acids and aromatic dicarboxylic acids or their anhydrides or dicyclopentadiene reacted with carboxylic acids. Examples of the α, β-olefin-based unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides of these dicarboxylic acids. Examples of dicarboxylic acids that can be used in combination with such α, β-olefin unsaturated dicarboxylic acids include adipic acid, sebacic acid, succinic acid, phthalic anhydride, phthalic acid, and isobenzene Dicarboxylic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, etc. Among them, it is preferred to use a combination of α, β-olefin unsaturated dicarboxylic acid fumaric acid and dicarboxylic acid isophthalic acid. The unsaturated polyester resin may be used singly or in combination of two or more kinds.

As for the crystalline polyester resin, there is no particular limitation, and examples thereof include polyethyl terephthalate, poly-1,4-dibutyl terephthalate, and polynaphthalene-2,6-diethyl esters, polyethylene terephthalate, cyclohexane dimethanol, polyethylene diphenyl 4,4 '- 1,4-dicarboxylate, polybutylene terephthalate, polyethylene oxybenzoate, polybutylene terephthalate Crystalline polyesters such as -1,3-propane diester, poly (terephthalate) -1,6-hexane diester, etc., among which poly (ethylene terephthalate), poly (terephthalate) -1,4- Dibutyl ester and polynaphthalene-2,6-diethyl ester are preferred. The crystalline polyester resin may be used singly or in combination of two or more kinds.

At the same time, such resins can be added with various additives such as impact strength modifiers, stabilizers, slippers, fillers, pigments, foaming agents, ultraviolet stabilizers, etc., as necessary.

The proportion of the sucrose aromatic monocarboxylic acid ester (II) in the resin is preferably 1 to 40 parts, more preferably 1 to 30 parts, relative to 100 parts of the resin. If it is less than 1 part, the intended performance may not be obtained. If it is more than 40 parts, the possibility of overflow for long-term storage and the like may increase.

(B) About sucrose carboxylate (III)

<Target object>

The sucrose carboxylate (III) of the present invention has a furanal content of 50 ppm or less and a hydroxymethylfuranal (HMF: 5- (hydroxymethyl) -2-furanal) content of 500 ppm or less. Sucrose aromatic monocarboxylic acid ester. That is, in the above-mentioned specific sucrose aromatic monocarboxylic acid ester, the content of these two impurities is suppressed to be low. Therefore, when it is formulated as an extender in a 2-cyanoacrylate-based adhesive, the Odor of the adhesive composition. The content of furanaldehyde is preferably 5 ppm or less, and more preferably 0.5 ppm or less. On the other hand, the content of HMF is preferably 50 ppm or less, and more preferably 5 ppm or less.

In the sucrose aromatic monocarboxylic acid ester (III) of the present invention, the average value of the ratio of esterification of the alcohol portion of sucrose (hereinafter, referred to as "average degree of esterification"), It is preferably 6.0 or less, and more preferably 5.0 or less. When the average degree of esterification exceeds 6.0, there is a tendency to reduce the odor-reducing effect. 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>

(Refining step)

The sucrose aromatic monocarboxylic acid ester (III) of the present invention may be any one that can make furfural formaldehyde to be 50 ppm or less and HMF to be 500 ppm or less. It can be produced by any generally known method. Examples of such methods include: The sucrose and the aromatic monocarboxylic acid are refined by the esterification obtained by a general esterification reaction. This refining can be carried out only after furfuralaldehyde is 50 ppm or lower and then HMF is 500 ppm or lower. However, from the viewpoint of simplicity and efficiency, both can be set at the same concentration. The following is better.

The method of making both at the same concentration or less, that is, furan formaldehyde is 50 ppm or less and HMF is 500 ppm or less, can be obtained by the common esterification reaction of sucrose and aromatic monocarboxylic acid , Dissolved in organic solvents such as toluene, o-xylene, m-xylene, etc., 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, and more preferably 50% by weight or less. When this concentration exceeds 80% by weight, the viscosity will be extremely high, and therefore, it tends to be difficult to be suitable for a reduced-pressure concentration device. This organic solvent may be used individually by 1 type, and may use 2 or more types together.

Dried sucrose aromatic monocarboxylic acid ester (Ⅲ) in an organic solvent solution The drying means may be any method previously known in general, and specifically, for example, the solution may be contacted with a heating surface to evaporate and remove the solvent and the like. When in contact with the heating surface, the solution is preferably in a liquid film state with a thickness of less than 10 cm, more preferably less than 5 cm, more preferably less than 5 mm, and even more preferably less than 1 mm. When the thickness of the liquid film exceeds 10 cm, furan formaldehyde and HMF tend to increase during drying. On the other hand, the lower limit of the thickness of the liquid film is not particularly limited as long as it is a thickness that can be implemented, but the thinner the thickness, the more refined it will increase, and therefore it tends to be industrially inferior. In addition, the "thickness of the liquid film" of the organic solvent solution of the sucrose aromatic monocarboxylic acid ester specifically refers to the surface from the lower surface of the liquid film in contact with the heating surface to the upper surface The distance of the face.

Drying is preferably performed under reduced pressure. The conditions for drying under reduced pressure vary depending on various conditions such as the amount of raw materials used, the required drying efficiency, and the type of organic solvent used, but generally, the pressure is preferably 0.01KPa · abs or more. When the pressure does not reach 0.01KPa‧abs, the equipment tends to be expensive. On the other hand, the pressure is preferably below 15KPa‧abs, and more preferably below 4KPa‧abs. When the pressure exceeds 15KPa‧abs, the drying efficiency tends to decrease. At the same time, the temperature of the heating surface during drying (referred to as "heating temperature") is preferably 90 ° C or higher, and more preferably 100 ° C or higher. When the heating temperature is less than 90 ° C, the drying efficiency tends to decrease. On the other hand, the heating temperature is preferably 300 ° C or lower, more preferably 200 ° C or lower, and 160 ° C or lower. When the heating temperature exceeds 300 ° C, furanal and HMF tend to increase.

The solution of the organic solvent of sucrose aromatic monocarboxylic acid ester (Ⅲ) in contact with the heating surface can be used, for example, using a vacuum drum dryer or a vacuum belt dryer. Dryer, thin film evaporator, rapid evaporator, vacuum extruder, stirring tank and other equipment. This type of machine can be used alone, or the same or different machines can be used in combination of two or more. When used in combination of two or more types, it is better to use a link, especially a link in line, to improve the degree of refining. Specific examples of the connection include a thin film evaporator and a thin film evaporator, a rapid evaporator and a thin film evaporator, a stirring tank and a thin film evaporator, and a stirring tank and a vacuum extruder. In addition, when a steel tube type concentrating device is used (in the embodiment, a steel tube type concentrating rapid evaporator is used), the caliber of the pipe into which the organic solvent solution is introduced (the diameter of the pipe to be introduced) is regarded as the “liquid Film thickness. "

In terms of drying, it can be implemented in any batch or continuous mode, but furan formaldehyde and HMF tend to increase with the extension of heating time. Therefore, continuous mode that can suppress cumulative heating is preferred.

(Synthesis of Ester)

The sucrose aromatic monocarboxylic acid ester (III) as a raw material for the above-mentioned refining step (for convenience in this specification, it may be referred to as "crude sucrose aromatic monocarboxylic acid ester (III)" or "crude ester (III)". ), Can be produced by sucrose and aromatic monocarboxylic acid (I) in a conventional manner by an esterification reaction, and the esterification reaction can be carried out according to Japanese Patent Publication No. 61-4839 and Japanese Patent Publication No. 40-5688. The method for producing a sucrose benzoate described is carried out by reacting sucrose with a chloride of an aromatic monocarboxylic acid (I).

For example, when following the method described in Japanese Patent Application Laid-Open No. 61-4839, the operation can be carried out according to the content described in the item "(A) above about sucrose carboxylate (II)".

On the other hand, when following the method described in Japanese Patent Publication No. 40-5688, the esterification reaction can replace the other solvents with the hydrophilic solvent used in the method described in Japanese Patent Publication No. 61-4839, that is, One or more solvents selected from the group consisting of aromatic or substituted aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, and lower aliphatic ethers are subjected to operations. Among them, examples of aromatic or substituted aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, chlorinated benzene, and chlorinated toluene; examples of chlorinated aliphatic hydrocarbons include: two Methyl chloride, chloroform, carbon tetrachloride, tetrachloroethane and the like; examples of lower aliphatic ethers include diethyl ether, diisopropyl ether, and the like.

The reaction temperature may be -15 ° C to 100 ° C, and preferably -10 ° C to 30 ° C. The reaction time depends on various conditions, but generally it is sufficient to carry out the reaction in about 3 hours.

<Use>

The sucrose aromatic monocarboxylic acid ester (III) of the present invention can be used as an extender and an odor improver for a 2-cyanoacrylate-based adhesive. In terms of the constituents of the 2-cyanoacrylate-based adhesive, it can be, for example, methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, propyl 2-cyanoacrylate, butyl 2-cyanoacrylate, 2 -Allyl cyanoacrylate, methoxyethyl 2-cyanoacrylate, ethoxyethyl 2-cyanoacrylate, 2-chloroethyl 2-cyanoacrylate, cyclohexyl 2-cyanoacrylate Among the various 2-cyanoacrylates below, ethyl 2-cyanoacrylate is particularly preferred.

When preparing the adhesive composition, the amount of the 2-cyanoacrylate-based adhesive in the sucrose aromatic monocarboxylic acid ester (III) of the present invention is preferably 5 parts or more relative to 100 parts of the adhesive. It is more preferably 15 parts or more. When the blending amount is less than 5 parts, the effect of adding to the sucrose aromatic monocarboxylic acid ester (III) tends to be insufficient. On the other hand, the blending amount is preferably 60 parts or less, 30 parts The following is better. When the blending amount exceeds 60 parts, there is a tendency that the adhesion performance is lowered. However, when the ratio of the sucrose aromatic monocarboxylic acid ester (III) is extremely large, although the adhesion force is reduced, it is better in terms of the purpose of temporary adhesion. Therefore, the above upper limit is in the sucrose aromatic monocarboxylic acid. The blending ratio of the acid ester (III) is not limited.

In the adhesive composition of the present invention, in addition to the 2-cyanoacrylate-based adhesive component and the sucrose aromatic monocarboxylic acid ester (III) of the present invention, various additives used in the past, such as preservation stabilizers, Organic solvents, plasticizers, tackifiers (polymers), fillers, thixotropy improvers, heat resistance imparting agents, polarizers, adhesion enhancers, hardening accelerators, hardening inhibitors, colorants, Additives such as a carboxylic acid ester compound are appropriately added.

When the sucrose aromatic monocarboxylic acid ester (III) of the present invention is added to the 2-cyanoacrylate-based adhesive component, it can be easily dissolved in the 2-cyanoacrylate-based adhesive component at an arbitrary ratio, and It can show the excellent effect of hardly changing the fast adhesion, adhesion, stability, viscosity, etc. of the 2-cyanoacrylate-based joining component.

In this specification, the term "part" means "part by weight".

The "average substitution rate", "average ester substitution rate", and "average degree of esterification" in sucrose aromatic monocarboxylic acid esters all have the same meaning, and are obtained by proton nuclear magnetic resonance ( ¹ H-NMR) value.

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 analysis (LC-MS). Meanwhile, the content of halogen (ppm) is based on inductively coupled plasma emission spectrometry (ICP) Measured value.

The amounts of each "furanaldehyde" and "HMF" in the sucrose aromatic monocarboxylic acid ester (III) are determined by high-speed liquid chromatography (HPLC) and "toluene", and determined by gas chromatography (GC). The requested value.

Examples

Hereinafter, the present invention is described in detail with examples, but the present invention is not limited thereto.

<Raw materials used>

Sucrose: ≧ 99.9%, manufactured by Shin Kwang Sugar Co., Ltd.

Benzamidine chloride (1): high purity (> 99.5%), manufactured by Kawaguchi Pharmaceutical Co., Ltd.

Benzamidine chloride (2): general product> 99.0%, manufactured by Jiangsu Qiangsheng Chemical Co., Ltd.

(A) Sucrose aromatic monocarboxylic acid ester (II-1)

Synthesis

Example 1

<Sucrose benzoate (proportion below hexasubstituted: 93.5%)>

Firstly add 34.2 parts of sucrose and 70 parts of water to a 1L five-necked triangular flask equipped with a stirring rod, thermometer, condenser, dropping funnel, and pH electrode connected to a pH meter, and then dissolve them, and then cool to below 10 ° C in a water bath. At the same time, 100 parts of cyclohexanone containing 75.0 parts of benzamidine chloride (1) was slowly added. After that, it was maintained at a temperature below 20 ° C, and at the same time, 48.5 parts of a 48% caustic soda aqueous solution was added to the dropping funnel at a rate to maintain the pH at 10 to 11. After that, remove the water bath and continue stirring for 1 hour at room temperature of 20 to 30 ° C to complete the reaction. Then add a small amount Sodium carbonate and heating to convert the remaining traces of benzamidine chloride to sodium benzoate. After that, it was left to stand for about 30 minutes to separate the aqueous phase and remove it.

An additional 70 parts of water was added, and the temperature was raised to 40 to 50 ° C. in a hot water bath. After stirring for 30 minutes, it was left to stand for about 30 minutes to separate the water phase and then remove it. After repeating the same operation twice (total water washing times: 3 times), the temperature was raised to 120 ° C, and the solvent was removed by evaporation under reduced pressure to obtain the target sucrose benzoate.

After that, the average substitution rate, the ratio of each substituent, the ratio of the six or less substituents, and the content of the halogen were measured (the same is true for the objects of the following examples and comparative examples).

Example 2

<Sucrose benzoate (proportion below hexasubstituted: 83.5%)>

The same procedure as in Example 1 was performed except that 82.1 parts of benzamidine chloride (1) and 53.1 parts of a 48% caustic soda aqueous solution were washed four times, and the target sucrose benzoate was obtained.

Example 3

<Sucrose benzoate (Proportion below hexasubstituted: 49.8%)>

Except using 93.7 parts of benzamidine chloride (1) and 60.6 parts of a 48% caustic soda aqueous solution, and performing 2 operations with water washing twice, the same treatment as in Example 1 was performed to obtain the target sucrose benzoate.

Example 4

<Sucrose benzoate (proportion below hexasubstituted: 9.0%)>

The same procedure as in Example 1 was performed except that 106.7 parts of benzamidine chloride (1) and 69.0 parts of a 48% caustic soda aqueous solution were used and the operation was repeated 4 times with water washing. Target sucrose benzoate.

Comparative Example 1

<Sucrose benzoate (proportion below hexasubstituted: 9.0%)>

The target sucrose benzoate was obtained in the same manner as in Example 4 except that the number of washing operations was 1 operation.

Comparative Example 2

<Sucrose benzoate (proportion below hexa-substitution: 9.6%)>

The same procedure as in Example 4 was carried out except that the benzamidine chloride (2) was used in place of the benzamidine chloride (1) and the number of washing operations was 8 times to obtain the target sucrose benzoate.

Comparative Example 3

<Sucrose benzoate (proportion below hexa-substitution: 9.6%)>

The same procedure as in Comparative Example 2 was performed except that the operation was repeated three times with water washing to obtain the target sucrose benzoate.

Comparative Example 4

<Sucrose benzoate (proportion below hexasubstituted: 6.0%)>

The target sucrose benzoate was obtained in the same manner as in Example 1 except that 111.0 parts of benzamidine chloride (1) and 71.8 parts of a 48% caustic soda aqueous solution were not washed.

2. Evaluation

<Hue>

Then, 25 g of each of the esters obtained in the above Examples and Comparative Examples was determined for their hue in accordance with the method described in JIS K2421. That is, first dilute each sample to 50% with toluene. The hue of the diluent is recorded when visual comparison is performed. It is the value of the same APHA standard solution (Hawson coloring number: APHA).

<Hue stability>

In a test tube, 5 g of each of the esters obtained in the above Examples and Comparative Examples was added and heated in an oil bath at 110 ° C. for 12 hours. The hue of each of the samples thus obtained was determined by the same method as described in the above item <Hue>.

The results are shown in Tables 1 and 2.

As described in Table 1, in Examples 1 to 4 of the present invention, not only the hue of the product was excellent below APHA30, but after heating at 110 ° C for 12 hours, no change in hue (APHA) was observed. Shows high thermal stability. In contrast, as described in Table 2 above, in Comparative Examples 1 to 4, a large change in hue was observed before and after heating, and to the extent that the higher the halogen content, the larger the change was observed. tendency.

(B) Sucrose aromatic monocarboxylic acid ester (II-2)

Synthesis

Example 5

<Sucrose benzoate (proportion below penta-substitution: 0.2%)>

Firstly add 34.2 parts of sucrose and 70 parts of water to a 1L five-necked triangular flask equipped with a stirring rod, thermometer, condenser, dropping funnel, and pH electrode connected to a pH meter, and then dissolve them, and then cool to below 10 ° C in a water bath. And at the same time slowly add chlorinated 106.7 parts of benzamidine (1) and 100 parts of cyclohexanone. After that, while maintaining the temperature below 20 ° C., 69.0 parts of a 48% caustic soda aqueous solution was simultaneously added in a dropping funnel to maintain the pH at a rate of 10 to 11. After that, the water bath was removed and stirring was continued at room temperature of 20 to 30 ° C for 1 hour to complete the reaction. Then, a small amount of sodium carbonate was added and heated to convert the remaining traces of benzamidine chloride to sodium benzoate. After that, it was left to stand for about 30 minutes to separate the aqueous phase and remove it.

After that, another 70 parts of water was added, and the temperature was raised to 40 to 50 ° C. in a hot water bath. After stirring for 30 minutes, it was allowed to stand for about 30 minutes to separate the water phase and then remove it. After repeating the same operation 7 times (total number of washings: 8 times), the temperature was raised to 120 ° C., and the solvent was removed by evaporation under reduced pressure to obtain the target sucrose benzoate.

Then, the average substitution rate, the ratio of each substituent, the ratio of penta-substitution, and the content of halogen (the objective of the following examples and comparative examples are also the same).

Example 6

<Sucrose benzoate (proportion below penta-substitution: 0.0%)>

The same procedure as in Example 5 was carried out except that 113.8 parts of benzamidine chloride (1) and 73.6 parts of a 48% caustic soda aqueous solution were used, and the operation was repeated 5 times to obtain the target sucrose benzoate.

Comparative Example 5

<Sucrose benzoate (proportion below penta-substitution: 0.0%)>

The same procedure as in Example 6 was performed except that the operation was performed once with the number of washings, and the target sucrose benzoate was obtained.

After that, Examples 5 to 6 and Comparative Examples 1 to 3 and 5 were tested. The average substitution rate, the proportion of each substituent, the proportion of penta-substitution, and the content of halogen are determined.

2. Evaluation

<Hue>

Then, 25 g of each of the esters obtained in the above Examples and Comparative Examples was determined for their hue in accordance with the method described in JIS K2421. That is, each sample was first diluted to 50% with toluene, and the hue of the diluent was recorded as the value of the APHA standard solution judged to be the same when visually compared (Hawson coloration number: APHA).

<Hue stability>

In a test tube, 5 g of each of the esters obtained in the above Examples and Comparative Examples was added and heated in an oil bath at 160 ° C. for 3 hours. The hue of each of the samples thus obtained was determined by the same method as described in the above item <Hue>.

The results are shown in Table 3.

As described in Table 3, in Examples 5 and 6 of the present invention, not only the hue of the product was excellent below APHA10, but also no change in hue (APHA) was observed after heating at 160 ° C for 3 hours. Shows 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 was such that the higher the halogen content, the larger the change was observed.

(C) Sucrose aromatic monocarboxylic acid ester (III)

1. Synthesis of crude sucrose benzoate

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

First add 30.0 parts of sucrose and 70.0 parts of water to a 1L five-necked triangle flask equipped with a stirring rod, thermometer, condenser, dropping funnel, and pH electrode connected to a pH meter, and then dissolve them, and then cool to below 10 ° C in a water bath. At the same time, 100 parts of cyclohexanone containing 67.7 parts of benzamidine chloride (1) was slowly added. After that, while maintaining the temperature below 20 ° C., 42.9 parts of a 48% caustic soda aqueous solution was simultaneously added in a dropping funnel to maintain the pH at a rate of 10 to 11. After that, the water bath was removed and stirring was continued at room temperature of 20 to 30 ° C for 1 hour to complete the reaction. Then, a small amount of sodium carbonate was added and heated to convert the remaining traces of benzamidine chloride to sodium benzoate. After that, it was left to stand for about 30 minutes to separate the aqueous phase and remove it.

Another 100 parts of water was added, and the temperature was raised to 40 to 50 ° C. in a hot water bath. After stirring for 30 minutes, it was left to stand for about 30 minutes to separate the water phase and then remove it. Then, the solvent was removed by evaporation under reduced pressure to obtain the target compound (crude SB (1)).

Production Example 2 (crude sucrose benzoate (2) (average degree of esterification: 4.9))

A target compound (crude SB (2)) was obtained in the same manner as in Production Example 1 except that 50.0 parts of sucrose and 60.3 parts of benzamidine (1) chloride were used.

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

A target compound (crude SB (3)) was obtained in the same manner as in Production Example 1 except that 30.0 parts of sucrose and 55.4 parts of benzamidine (1) chloride were used.

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

A target compound (crude SB (4)) was obtained in the same manner as in Production Example 1 except that 30.0 parts of sucrose and 70.2 parts of benzamidine (1) chloride were used.

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

The target compound (crude SB (5)) was obtained in the same manner as in Production Example 1 except that 30.0 parts of sucrose and 59.1 parts of benzamidine chloride (1) were used.

2. Refining steps (removal of furan formaldehyde and HMF)

Example 7

First, the crude SB (1) obtained in the above was dissolved in toluene, and a toluene solution of 50% by weight of crude sucrose benzoate (crude SB) was prepared. Thereafter, the solution was subjected to a steel tube type rapid evaporator, and a 50% by weight crude SB toluene solution was flowed at 1.5 L / h, the thickness of the liquid film containing the solution in the machine was 10 cm, the pressure in the machine was 13 KPa‧abs, and the heating surface was Drying was carried out at a temperature of 130 ° C to obtain sucrose benzoate (1) (SB (1)). Then, SB (1) was measured for each of the amount of furanaldehyde (ppm), the amount of HMF (ppm), the amount of toluene (ppm), and the average degree of esterification.

Examples 8 to 14

A sucrose benzoate (2) to (8) (SB (2) to SB (8)) was obtained in the same manner as in Example 7 except that the corresponding raw material compound was treated in accordance with the conditions described in Table 4. For each species, the amount of impurities and the degree of esterification were measured.

Comparative Example 6

A sucrose benzoate (I) (SB (I)) was obtained in the same manner as in Example 7 except that the corresponding raw material compounds were treated in accordance with the conditions described in Table 4. Then determine the amount of impurities and the degree of esterification.

The results are shown in Table 4.

3. Manufacture of adhesive composition

Each of the SBs obtained in the above was used as an extender to prepare each adhesive composition. That is, with respect to 100 parts of ethyl 2-cyanoacrylate containing a small amount of a stabilizer (SO ₂ and hydroquinone), 30 parts of SB were each added and dissolved, and each of the adhesive compositions (1) to (8) was obtained. And the adhesive composition (I).

4. Performance evaluation of adhesive

(Promotion test)

Each adhesive composition was filled in a polyethylene container with a capacity of 20 mL, sealed, and then kept at 70 ° C. for 5 days. In Table 4, "normal state" shows the state before the test promotion, and "after the test" shows the state after the test promotion.

(Hardening time)

The hardening time was measured on a cold-rolled steel plate of 25 mm × 100 mm × 1.6 mm in accordance with JIS K-6861.

(Tensile peeling strength)

Tensile peel strength, based on polished and degreased 25mm × 100mm × A 1.6mm cold rolled steel sheet is overlapped with a contact area of 12.5mm × 25mm, and is measured by a tensile tester after 24 hours of hardening.

(Odor)

The odor was determined based on the following criteria when the sucrose benzoate was not added as the base material (C).

A: When the reduction of odor is significant

B: When odor reduction can be confirmed

C: When sucrose benzoate is not added

D: Conversely, when the odor increases

The results are shown in Table 4.

As described above, when the sucrose aromatic monocarboxylic acid ester (III) of the present invention is used as an extender, it hardly affects the hardening time and tensile peel strength, and can exhibit an excellent effect of significantly reducing odor.

Possibility of industrial use

The sucrose aromatic monocarboxylic acid ester (II) of the present invention also has excellent compatibility with amorphous resins and crystalline resins, and can improve its moldability, physical properties, flexibility, impact resistance, etc. On the other hand, it can suppress the excellent characteristics of coloring under heating, so it can be used as a modifier on resins, especially resins that require optical transparency.

The sucrose aromatic monocarboxylic acid ester (III) of the present invention can be used as an extender of a 2-cyanoacrylate-based adhesive, and has the excellent characteristic that the odor can be improved without reducing its bonding performance. Therefore, Can be used as an odor improvement / increase agent for this adhesive.

Claims (5)

A method for producing sucrose aromatic monocarboxylic acid ester, which is a method for producing sucrose aromatic monocarboxylic acid ester having a halogen content of 100 ppm or less. The sucrose aromatic monocarboxylic acid ester is sucrose and an aromatic compound represented by general formula (I). Esters of monocarboxylic acids:

(Wherein R ¹ to R ⁵ are each independently a group selected from a hydrogen atom, an alkyl group, and an alkoxy group) The production method includes using sucrose and high-purity benzamidine chloride having a purity of more than 99.5% to perform esterification And a step of removing halogen from the obtained esterified body by washing with water, so that the halogen content is 100 ppm or less, wherein the sucrose aromatic monocarboxylic acid ester has a content of less than six (including six) substituents and 5 to 95% by weight, wherein the average substitution rate of the sucrose aromatic monocarboxylic acid ester is 5.0 or more, and in the esterification step, 75.0 to 106.7 parts by weight are used relative to 34.2 parts by weight of sucrose. High-purity benzamidine chloride with a purity of more than 99.5%. The method for producing a sucrose aromatic monocarboxylic acid ester according to Item 1 of the scope of application, wherein the content of the penta-substituted or less substituted substance of the sucrose aromatic monocarboxylic acid ester is 2.0% by weight or less. Manufacture of sucrose aromatic monocarboxylic acid ester as described in the scope of patent application No. 2 The method wherein the average substitution rate of the sucrose aromatic monocarboxylic acid ester is 7.0 or more. A method for manufacturing a resin modifier, characterized in that the resin modifier comprises a sucrose aromatic monocarboxylic acid ester, which is formed by the steps described in item 1 of the aforementioned patent application scope. A method for manufacturing a resin modifier, characterized in that the resin modifier comprises a sucrose aromatic monocarboxylic acid ester, which is formed by including the steps as described in item 2 or 3 of the scope of patent application.