TW201335172A - Sucrose aromatic monocarboxylate - Google Patents

Sucrose aromatic monocarboxylate Download PDF

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TW201335172A
TW201335172A TW102103067A TW102103067A TW201335172A TW 201335172 A TW201335172 A TW 201335172A TW 102103067 A TW102103067 A TW 102103067A TW 102103067 A TW102103067 A TW 102103067A TW 201335172 A TW201335172 A TW 201335172A
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monocarboxylic acid
aromatic monocarboxylic
acid ester
sucrose
sucrose aromatic
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TW102103067A
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TWI615399B (en
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Ichihiro Maeda
Keiichi Fujise
Shunichiro Hata
Hiroyuki Kurahashi
Satoshi Izuno
Akira Matsuo
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Dai Ichi Kogyo Seiyaku Co Ltd
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Priority claimed from JP2012035379A external-priority patent/JP6178042B2/en
Priority claimed from JP2012094637A external-priority patent/JP2013221021A/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/08Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00Processes for the preparation of sugar derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/15Heterocyclic compounds having oxygen in the ring
    • C08K5/151Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545Six-membered rings

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Abstract

The present invention provides an ester of sucrose and aromatic monocarboxylic acid represented by the general formula (I): wherein R1 to R5 are independently a group selected from hydrogen atom, an alkyl group and an alkoxy group, and a content of certain impurities in the ester is small. This ester having a small content of halogen has good miscibility with an amorphous resin and a crystalline resin, improves mold-processability, physical properties, flexibility, impact resistance, etc. of these resins, and is useful as a resin modifier having good thermal stability and good resistance to coloring due to heat. This ester having a small content of furfural and hydroxymethyl furfural is useful as an odor improving and extending agent which can improve odor without lowering adhesion of 2-cyano acrylate adhesive.

Description

蔗糖芳香族單羧酸酯 Sucrose aromatic monocarboxylate

本發明關於特定雜質含量少的蔗糖芳香族單羧酸酯,特別為關於鹵素含量少的蔗糖芳香族單羧酸酯,以及呋喃甲醛(furfural)及羥甲基呋喃甲醛(hydroxyl methyl furfural)含量少的蔗糖芳香族單羧酸酯。 The present invention relates to a sucrose aromatic monocarboxylic acid ester having a small specific impurity content, particularly to a sucrose aromatic monocarboxylic acid ester having a small halogen content, and a small amount of furfural and hydroxyl methyl furfural. Sucrose aromatic monocarboxylate.

本發明之鹵素含量少的樣態(本發明之第一樣態),為關於與非結晶性樹脂或結晶性樹脂的相溶性優異,並可提升其成形加工性、物性、柔軟性、耐衝擊性等,作為樹脂改質劑的蔗糖芳香族單羧酸酯,可抑制因加熱之著色的熱安定性良好的蔗糖芳香族單羧酸酯。 The aspect of the present invention having a small halogen content (the first aspect of the present invention) is excellent in compatibility with an amorphous resin or a crystalline resin, and can improve moldability, physical properties, flexibility, and impact resistance. A sucrose aromatic monocarboxylic acid ester which is a resin modifier, and a sucrose aromatic monocarboxylic acid ester which is excellent in thermal stability due to heating and coloring can be suppressed.

本發明之呋喃甲醛及羥甲基呋喃甲醛含量少的樣態(本發明之第二樣態),為關於2-氰基丙烯酸酯系接著劑之增量劑,更詳細言之,為不會使該接著劑之接著性能降低而可改善臭氣之蔗糖芳香族單羧酸酯,由包含該酯作為臭氣改善增量劑所形成的2-氰基丙烯酸酯系接著劑,以及該酯之製造方法。 The aspect of the invention wherein the content of furaldehyde and hydroxymethylfurfural is small (the second aspect of the invention) is an extender for a 2-cyanoacrylate-based adhesive, and more specifically, A sucrose aromatic monocarboxylic acid ester which can improve odor by lowering the adhesive performance of the adhesive, a 2-cyanoacrylate-based adhesive comprising the ester as an odor improving extender, and the ester Production method.

在樹脂改質劑方面,蔗糖衍生物如蔗糖苯甲酸酯已為一般所知,且已知可改善非結晶性樹脂如ABS樹脂、聚 氯乙烯樹脂、環氧樹脂、不飽和聚酯樹脂等之成形加工性、物性,及改善晶形聚酯的柔軟性、耐衝擊性(專利文獻1至3)。 In the case of a resin modifier, a sucrose derivative such as sucrose benzoate is generally known, and it is known to improve a non-crystalline resin such as ABS resin, poly The moldability and physical properties of a vinyl chloride resin, an epoxy resin, an unsaturated polyester resin, and the like, and the softness and impact resistance of the crystalline polyester are improved (Patent Documents 1 to 3).

然而,由於蔗糖苯甲酸酯係蔗糖之衍生物,在作為改質劑添加時,由該些樹脂所形成的製品的色相或色相的熱安定性成為課題。亦即,蔗糖苯甲酸酯一般係使用有機溶劑所製造,但首先在其製造過程中,去除有機溶劑之加熱步驟中,會發生著色之情形。更具體言之,蔗糖苯甲酸酯之熔點為80~90℃,在其製造過程中將所使用的有機溶劑去除時,一般情形必須以100℃以上或更好是110℃以上加熱,但在此如100℃以上的加熱條件下,將使蔗糖苯甲酸酯的著色進行。因此,著色的程度有隨蔗糖苯甲酸酯中酯化度低的成分的比例增加,或平均酯取代率降低變得更為顯著的傾向。又,如果以特殊的處理設備(如薄膜蒸發裝置)設法使處理時間縮短,雖然可藉由有機溶劑去除時降低蔗糖苯甲酸酯的熱履歷,儘可能地抑制著色,但在將蔗糖苯甲酸酯加入樹脂後,該樹脂因加工、成形時的熱履歷而發生著色的問題。 However, since the sucrose benzoate-based sucrose derivative is added as a modifier, the thermal stability of the hue or hue of the product formed from these resins is a problem. That is, sucrose benzoate is generally produced by using an organic solvent, but first, in the heating process in which the organic solvent is removed during the manufacturing process, coloring occurs. More specifically, the sucrose benzoate has a melting point of 80 to 90 ° C. When the organic solvent used is removed during the production process, it is generally necessary to heat at 100 ° C or higher or better at 110 ° C or higher. Thus, the coloring of the sucrose benzoate proceeds under heating conditions of 100 ° C or higher. Therefore, the degree of coloration tends to increase as the ratio of the component having a lower degree of esterification in the sucrose benzoate increases, or the decrease in the average ester substitution rate becomes more remarkable. Moreover, if a special processing device (such as a thin film evaporation device) is tried to shorten the processing time, although the heat history of the sucrose benzoate can be reduced by removing the organic solvent, the coloring is suppressed as much as possible, but the sucrose benzene is added. When the acid ester is added to the resin, the resin is colored due to the heat history during processing and molding.

因此,以蔗糖苯甲酸酯作為要求光學透明性的樹脂之改質劑,並非可令人滿意者。 Therefore, it is not satisfactory to use sucrose benzoate as a modifier for a resin requiring optical transparency.

另一方面,2-氰基丙烯酸酯系接著劑具有不論對木材、塑料、金屬之大部分材料的接著力均大且可用於異種材料間之接著,而且又可以秒速接著的特性。該接著劑雖然比其他廣泛使用之接著劑高價,但由於具有如上所述之大優點,其使用量仍在年年穩定地增加。 On the other hand, the 2-cyanoacrylate-based adhesive has a large adhesion force to most materials such as wood, plastic, and metal, and can be used for the subsequent connection between dissimilar materials, and can be followed by a second speed. Although this adhesive is more expensive than other widely used adhesives, its use amount is steadily increasing year by year because of its great advantages as described above.

2-氰基丙烯酸酯系接著劑,為使成本減低及臭氣改 善之目的,可使用蔗糖苯甲酸酯作為增量劑(專利文獻4)。然而,在臭氣之改善方面,仍非可令人滿意者。 2-cyanoacrylate-based adhesive for cost reduction and odor change For the purpose of goodness, sucrose benzoate can be used as an extender (Patent Document 4). However, in terms of improvement in odor, it is still not satisfactory.

【先前技術文獻】 [Previous Technical Literature]

專利文獻 Patent literature

【專利文獻1】日本專利特開昭52-81362號公報 [Patent Document 1] Japanese Patent Laid-Open No. 52-81362

【專利文獻2】日本專利特公昭62-15582號公報 [Patent Document 2] Japanese Patent Publication No. Sho 62-15582

【專利文獻3】日本專利特開平6-255274號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 6-255274

【專利文獻4】日本專利特開平5-222340號公報 [Patent Document 4] Japanese Patent Laid-Open No. Hei 5-222340

在第一樣態中,本發明提供與非結晶性樹脂或結晶性樹脂的相溶性優異、可提升其成形加工性、物性、柔軟性、耐衝擊性等、有效作為樹脂改質劑之蔗糖芳香族單羧酸酯,且可抑制加熱之著色,而熱安定性良好。 In the first aspect, the present invention provides an sucrose aroma which is excellent in compatibility with an amorphous resin or a crystalline resin, and which can improve moldability, physical properties, flexibility, impact resistance, and the like, and is effective as a resin modifier. The monocarboxylic acid ester can suppress the coloring of heating and has good thermal stability.

在第二樣態中,本發明係提供蔗糖芳香族單羧酸酯,為對2-氰基丙烯酸酯系接著劑,在使其增量時亦不會使接著性能降低,並且,又可使臭氣改善。 In the second aspect, the present invention provides a sucrose aromatic monocarboxylic acid ester which is a 2-cyanoacrylate based adhesive which does not cause an increase in the adhesion property when it is increased, and The odor is improved.

本發明人等,對解決關於第一樣態之上述課題而刻意進行研究之結果,發現可藉由抑低蔗糖芳香族單羧酸酯中鹵素之含量,而抑制受累積加熱時之著色,經過再三之檢討而完成本發明。 The inventors of the present invention have deliberately studied the above-mentioned problems in the first aspect, and found that the color of the halogen in the sucrose aromatic monocarboxylic acid ester can be suppressed to suppress the coloration during the cumulative heating. The invention is completed by a review of the third.

亦即,本發明係關於:蔗糖、與通式(I)所示之芳香族單羧酸之酯 【化1】 (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: sucrose, an ester of an aromatic monocarboxylic acid represented by the formula (I) [Chemical 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 halogen content thereof is 100 ppm or less of the sucrose aromatic monocarboxylic acid ester (II).

前述蔗糖芳香族單羧酸酯(Ⅱ),以六取代體以下之取代體的含量為5重量%以上(蔗糖芳香族單羧酸酯(Ⅱ-1))較佳。 The content of the sucrose aromatic monocarboxylic acid ester (II) is preferably 5% by weight or more (sucrose aromatic monocarboxylic acid ester (II-1)).

前述蔗糖芳香族單羧酸酯(Ⅱ-1),又以平均取代率為5.0以上較佳。 The sucrose aromatic monocarboxylic acid ester (II-1) preferably has an average substitution ratio of 5.0 or more.

前述蔗糖芳香族單羧酸酯(Ⅱ-1),又以在50%甲苯溶液中之色相為APHA30以下較佳。 The sucrose aromatic monocarboxylic acid ester (II-1) is preferably a color phase of APHA 30 or less in a 50% toluene solution.

前述蔗糖芳香族單羧酸酯(Ⅱ-1),又以在110℃、12小時加熱後在50%甲苯溶液中之色相為APHA30以下更佳。 The sucrose aromatic monocarboxylic acid ester (II-1) is further preferably a PHA of 50% or less in a 50% toluene solution after heating at 110 ° C for 12 hours.

同時,本發明,亦為關於包含前述蔗糖芳香族單羧酸酯(Ⅱ-1)之樹脂改質劑。 Meanwhile, the present invention also relates to a resin modifier comprising the sucrose aromatic monocarboxylic acid ester (II-1).

又,本發明,亦為關於在蔗糖芳香族單羧酸酯(Ⅱ)中,五取代體以下之取代體的含量為2.0重量%以下的蔗糖芳香族單羧酸酯(蔗糖芳香族單羧酸酯(Ⅱ-2))。 In addition, the present invention is also a sucrose aromatic monocarboxylic acid ester (sucrose aromatic monocarboxylic acid) in which the content of the substituted substituent of the sucrose aromatic monocarboxylic acid ester (II) is 2.0% by weight or less. Ester (II-2)).

前述蔗糖芳香族單羧酸酯(Ⅱ-2),以平均取代率為7.0以上較佳。 The sucrose aromatic monocarboxylic acid ester (II-2) preferably has an average substitution ratio of 7.0 or more.

前述蔗糖芳香族單羧酸酯(Ⅱ-2),亦以在50%甲苯溶液中之色相為APHA10以下較佳。 The sucrose aromatic monocarboxylic acid ester (II-2) is also preferably a color phase of APHA 10 or less in a 50% toluene solution.

前述蔗糖芳香族單羧酸酯(Ⅱ-2),又以在160℃、3小時加熱後在50%甲苯溶液中之色相為APHA30以下更佳。 The sucrose aromatic monocarboxylic acid ester (II-2) is more preferably a color phase of APHA 30 or less in a 50% toluene solution after heating at 160 ° C for 3 hours.

同時,本發明,亦為關於包含前述蔗糖芳香族單羧酸酯(Ⅱ-2)之樹脂改質劑。 Meanwhile, the present invention is also directed to a resin modifier comprising the aforementioned sucrose aromatic monocarboxylic acid ester (II-2).

又,本發明,亦為關於蔗糖芳香族單羧酸酯之製造方法,係可抑制著色之蔗糖芳香族單羧酸酯(Ⅱ)的製造方法,並包含使鹵素之含量為100ppm以下的步驟。 Further, the present invention 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 a step of containing a halogen content of 100 ppm or less.

上述可抑制著色之蔗糖芳香族單羧酸酯(Ⅱ),亦以在50%甲苯溶液中之色相為APHA30以下的蔗糖芳香族單羧酸酯(Ⅱ-1)較佳,同時,又以在50%甲苯溶液中之色相為APHA10以下的蔗糖芳香族單羧酸酯(Ⅱ-2)更佳。 The above-mentioned sucrose aromatic monocarboxylic acid ester (II) capable of suppressing coloration is preferably a sucrose aromatic monocarboxylic acid ester (II-1) having a hue of 50 or less in a 50% toluene solution, and at the same time The sucrose aromatic monocarboxylic acid ester (II-2) having a hue of 50% or less in the toluene solution of APHA 10 or less is more preferable.

同時,本發明人等,對解決關於第二樣態之上述課題刻意進行研究之結果,發現可藉由抑低蔗糖芳香族單羧酸酯中特定之雜質(呋喃甲醛及羥甲基呋喃甲醛)的含量,在作為2-氰基丙烯酸酯系接著劑之增量劑時,不會使接著性能降低而改善臭氣,經過再三之檢討而完成本發明。 Meanwhile, the inventors of the present invention have deliberately studied the above-mentioned problems concerning the second aspect, and found that the specific impurities (furfural and hydroxymethylfurfural) in the sucrose aromatic monocarboxylic acid ester can be suppressed. When the content is an extender of a 2-cyanoacrylate-based adhesive, the odor is not improved by lowering the adhesion performance, and the present invention has been completed through repeated review.

亦即,本發明係關於:蔗糖與通式(I)所示之芳香族單羧酸之酯 【化2】 (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 with an aromatic monocarboxylic acid represented by the general formula (I) [Chemical 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 furfural content of 50 ppm or less and a hydroxymethylfurfural content of 500 ppm or less Carboxylic ester (III).

前述蔗糖芳香族單羧酸酯(Ⅲ),以平均酯化度為6.0以下較佳。 The sucrose aromatic monocarboxylic acid ester (III) preferably has an average degree of esterification of 6.0 or less.

同時,本發明,亦為關於2-氰基丙烯酸酯系接著劑,其中包含前述蔗糖芳香族單羧酸酯(Ⅲ)為臭氣改善/增量劑。 Meanwhile, the present invention also relates to a 2-cyanoacrylate-based adhesive comprising the sucrose aromatic monocarboxylic acid ester (III) as an odor improving/extending agent.

又,本發明,亦為關於蔗糖芳香族單羧酸酯(Ⅲ)的製造方法,係呋喃甲醛含量50ppm以下且羥甲基呋喃甲醛含量500ppm以下之蔗糖芳香族單羧酸酯(Ⅲ)的製造方法,而該蔗糖芳香族單羧酸酯(Ⅲ),包含蔗糖、與通式(I)所示之芳香族單羧酸之酯 (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。 Further, the present invention relates to a process for producing a sucrose aromatic monocarboxylic acid ester (III), which is a process for producing a sucrose aromatic monocarboxylic acid ester (III) having a furaldehyde content of 50 ppm or less and a hydroxymethylfurfural content of 500 ppm or less. a method, wherein the sucrose aromatic monocarboxylate (III) comprises sucrose, an ester of an aromatic monocarboxylic acid represented by the 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), and an organic solvent solution of the sucrose aromatic monocarboxylic acid ester (III) is a liquid having a thickness of 10 cm or less. It is dried in contact with the heating surface in the state of the film.

前述之乾燥,以減壓乾燥為佳。 The above drying is preferably carried out under reduced pressure.

前述之減壓乾燥,以在機內壓力0.01至15KPa.abs、加熱溫度90至300℃之條件下實施為佳。 The above-mentioned drying under reduced pressure, in the machine pressure of 0.01 to 15KPa. It is preferred to carry out the conditions of abs and heating temperature of 90 to 300 °C.

前述之減壓乾燥,以使用選自:真空式滾筒乾燥機、真空式帶式乾燥機、薄膜蒸發器、急速蒸發器及真空式擠壓機,之1種或2種以上之機械實施為佳。 The above-mentioned vacuum drying is preferably carried out using one or two or more types selected from the group consisting of a vacuum drum dryer, a vacuum belt dryer, a thin film evaporator, a rapid evaporator, and a vacuum extruder. .

本發明相關之第一樣態,蔗糖芳香族單羧酸酯(Ⅱ),併有與非結晶性樹脂及結晶性樹脂的相溶性優異,並可改善其成形加工性、物性、柔軟性、耐衝擊性等,另一方面又可抑制加熱之著色的優異特長。因此,可作為要求光學透明性之樹脂的改質劑。 In the first aspect of the present invention, the sucrose aromatic monocarboxylic acid ester (II) is excellent in compatibility with the amorphous resin and the crystalline resin, and can improve moldability, physical properties, flexibility, and resistance. Impact, etc., on the other hand, can suppress the excellent characteristics of the color of heating. Therefore, it can be used as a modifier of the resin which requires optical transparency.

同時,本發明之蔗糖芳香族單羧酸酯(Ⅱ-1),顯示即使在蔗糖之醇部分的酯化之比例小時,亦即,在低取代體之比例較高時,仍可表現熱安定性良好的特性之特點。 Meanwhile, the sucrose aromatic monocarboxylic acid ester (II-1) of the present invention exhibits thermal stability even when the ratio of esterification of the alcohol portion of sucrose is small, that is, when the proportion of the low substituent is high. Characteristics of good sexual characteristics.

又,本發明之蔗糖芳香族單羧酸酯(Ⅱ-2),蔗糖之醇部分酯化之比例較高,亦即,由於低取代體之比例較低,因此顯示熱安定性優異的特性。 Further, the sucrose aromatic monocarboxylic acid ester (II-2) of the present invention has a high ratio of esterification of the sucrose to the alcohol, that is, since the ratio of the low substituent is low, it exhibits excellent thermal stability.

同時,本發明之製造方法,係以此種顯示優良特性的蔗糖芳香族單羧酸酯(Ⅱ),在不使用特殊之處理設備(如薄膜蒸發裝置)下,可簡便地製造,因此在製造之成本面等工業方面優異。 Meanwhile, the production method of the present invention is such that the sucrose aromatic monocarboxylic acid ester (II) exhibiting excellent characteristics can be easily produced without using a special treatment device (such as a thin film evaporation device), and thus is manufactured. The cost aspect is excellent in industry.

本發明相關之第二樣態,蔗糖芳香族單羧酸酯 (Ⅲ),併有可作為2-氰基丙烯酸酯系接著劑之增量劑,並可在不會降低接著性能下改善臭氣之優異的特性。因此,可使用作為該接著劑之臭氣改善/增量劑。 A second aspect related to the present invention, a sucrose aromatic monocarboxylic acid ester (III), and an extender which can be used as a 2-cyanoacrylate-based adhesive, and which can improve the excellent characteristics of the odor without lowering the adhesion property. Therefore, an odor improving/extending agent as the adhesive can be used.

又,以本發明之製造方法,對顯示此種優良特性的蔗糖芳香族單羧酸酯(Ⅲ),可容易且有效地製造,因此有工業方面之優點。 Moreover, the sucrose aromatic monocarboxylic acid ester (III) exhibiting such excellent characteristics can be easily and efficiently produced by the production method of the present invention, and therefore has industrial advantages.

本發明中,目的物之蔗糖芳香族單羧酸酯方面,如上所述,係存在蔗糖芳香族單羧酸酯(Ⅱ-1)、(Ⅱ-2)及(Ⅲ),在單獨地稱為「蔗糖芳香族單羧酸酯」時,視其文脈,係包含其任意者,同時亦具有包含及可能包含其所有者之意。 In the present invention, the sucrose aromatic monocarboxylic acid ester of the object is as described above, and the sucrose aromatic monocarboxylic acid esters (II-1), (II-2) and (III) are present separately. "Sucrose aromatic monocarboxylic acid ester", depending on its context, contains any of them and also contains and may contain its owner.

本發明蔗糖芳香族單羧酸酯之芳香族單羧酸(I)中,R1至R5,以各獨立,而為氫原子或烷基較佳,全部為氫原子之苯甲酸或其一種(以R3較佳)為烷基,其餘為氫原子者更佳。 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 a hydrogen atom or an alkyl group is preferred, and all of them are hydrogen atoms of benzoic acid or a kind thereof. (It is preferred that R 3 is an alkyl group), and the remainder is preferably a hydrogen atom.

烷基之例,可例舉如:碳數為1至20者,其中,又以碳數為1至5者更佳,甲基、乙基、丙基或異丙基又更佳。烷氧基之例,可例舉如:碳數為1至20者,其中,又以碳數為1至5者更佳,甲氧基、乙氧基、丙氧基或異丙氧基又更佳。 The alkyl group may, for example, be a carbon number of from 1 to 20, and more preferably a carbon number of from 1 to 5, more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. Examples of the alkoxy group include those having a carbon number of 1 to 20, and more preferably a carbon number of 1 to 5, and a methoxy group, an ethoxy group, a propoxy group or an isopropoxy group. Better.

(A)關於蔗糖羧酸酯(Ⅱ) (A) About sucrose carboxylate (II)

<目的物> <object>

本發明之蔗糖芳香族單羧酸酯(Ⅱ)中,鹵素之 含量為100ppm以下。鹵素之例,可例舉如:氟、氯、溴、碘等,其中,以氯之含量的影響為大。 In the sucrose aromatic monocarboxylic acid ester (II) of the present invention, halogen The content is 100 ppm or less. Examples of the halogen include fluorine, chlorine, bromine, and iodine, and the influence of the chlorine content is large.

鹵素之較佳之含量,以90ppm以下為佳,60ppm以下更佳,30ppm以下又更佳,20ppm以下再更佳。氯之較佳之含量,以80ppm以下為佳,55ppm以下更佳,25ppm以下又更佳,17ppm以下再更佳。 The preferred content of the halogen is preferably 90 ppm or less, more preferably 60 ppm or less, still more preferably 30 ppm or less, and still more preferably 20 ppm or less. The preferred content of chlorine is preferably 80 ppm or less, more preferably 55 ppm or less, still more preferably 25 ppm or less, and still more preferably 17 ppm or less.

本發明之蔗糖芳香族單羧酸酯(Ⅱ-1),雖然在蔗糖之醇部分酯化之比例小時,亦即,在如低取代體之比例較高之下,仍可顯示優良之熱安定性,但六取代體以下之取代體的比例,以如:95重量%以下為佳,85重量%以下更佳,50重量%以下又更佳,10重量%以下再更佳。又,其中之六取代體,係指蔗糖之合計的8個羥基中之6個羥基受芳香族單羧酸所酯化者。本說明書中,只要為關於蔗糖芳香族單羧酸酯(Ⅱ-1)者,方便上,均稱六取代體以下之取代體為低取代體。 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 small, that is, at a higher ratio such as a low substituent. The ratio of the substituents of the hexamethylene or less is preferably 95% by weight or less, more preferably 85% by weight or less, still more preferably 50% by weight or less, still more preferably 10% by weight or less. Further, the six-substituted form thereof means that six of the eight hydroxyl groups in the total of sucrose are esterified by an aromatic monocarboxylic acid. In the present specification, as long as it is a sucrose aromatic monocarboxylic acid ester (II-1), it is convenient to say that the hexasubstituted or lower substituent is a low substituent.

同時,本發明之蔗糖芳香族單羧酸酯(Ⅱ-1),顯示即使在蔗糖之醇部分之酯化的比例之平均值(以下,稱為「平均酯取代率」或「平均取代率」)小時熱安定性仍優良的特徵,平均酯取代率以如5.0以上為佳,6.0以上更佳,7.0以上又更佳。 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". The characteristics of the hourly heat stability are still excellent, and the average ester substitution rate is preferably 5.0 or more, more preferably 6.0 or more, and still more preferably 7.0 or more.

本發明之蔗糖芳香族單羧酸酯(Ⅱ-1),以在50%甲苯溶液中之色相為30以下為佳,25以下更佳,15以下又更佳。同時,本發明之蔗糖芳香族單羧酸酯(Ⅱ-1),以在110℃、12小時加熱後,在50%甲苯溶液中之色相為30以下為佳,25以下更佳,15以下又更佳。在色相超過30時在作為樹脂改質 劑時,會有使該樹脂之外觀(色相)、光學透明性降低之傾向。 The sucrose aromatic monocarboxylic acid ester (II-1) of the present invention preferably has a hue of 30 or less in a 50% toluene solution, more preferably 25 or less, and still more preferably 15 or less. Meanwhile, the sucrose aromatic monocarboxylic acid ester (II-1) of the present invention preferably has a hue of 30 or less in a 50% toluene solution after heating at 110 ° C for 12 hours, more preferably 25 or less, and 15 or less. Better. Modification as a resin when the hue exceeds 30 In the case of the agent, the appearance (hue) and optical transparency of the resin tend to be lowered.

本發明之蔗糖芳香族單羧酸酯(Ⅱ-2),亦以蔗糖之醇部分之酯化的比例高為佳,具體地,以五取代體以下之取代體的含量為2.0重量%以下為佳,1.0重量%以下更佳,0.5重量%以下又更佳,0.3重量%以下再更佳。又,其中之五取代體,係指蔗糖之合計之8個羥基中的5個羥基受芳香族單羧酸所酯化者。本說明書中,除與蔗糖芳香族單羧酸酯(Ⅱ-2)相關,方便上,係指五取代體以下之取代體為低取代體,其餘之取代體為高取代體。 The sucrose aromatic monocarboxylic acid ester (II-2) of the present invention preferably has a higher ratio of esterification of the alcohol portion of sucrose, and specifically, the content of the substituent having a pentoxide or less is 2.0% by weight or less. Preferably, it is more preferably 1.0% by weight or less, more preferably 0.5% by weight or less, still more preferably 0.3% by weight or less. Further, the five-substituent thereof means that five of the eight hydroxyl groups in the total of sucrose are esterified by an aromatic monocarboxylic acid. In the present specification, in addition to the sucrose aromatic monocarboxylic acid ester (II-2), it is convenient that the substituent below the pentasubstituted body is a low substituent, and the remaining substituents are high substituents.

又,本發明蔗糖芳香族單羧酸酯(Ⅱ-2)其他之較佳例,可舉如六取代體以下之含量未達5重量%者。 Further, in another preferred embodiment of the sucrose aromatic monocarboxylic acid ester (II-2) of the present invention, the content of the hexa-substituted or less is less than 5% by weight.

本發明之蔗糖芳香族單羧酸酯(Ⅱ-2),以蔗糖之醇部分酯化的比例之平均值(以下,稱為「平均酯取代率」或「平均取代率」)大者為佳,具體地,以平均酯取代率,在如:7.0以上為佳,7.3以上更佳。 The sucrose aromatic monocarboxylic acid ester (II-2) of the present invention is preferably an average of the ratio of partial esterification of the sucrose alcohol (hereinafter referred to as "average ester substitution ratio" or "average substitution ratio"). Specifically, the average ester substitution ratio is preferably, for example, 7.0 or more, and more preferably 7.3 or more.

本發明之蔗糖芳香族單羧酸酯(Ⅱ-2),以在50%甲苯溶液中之色相為10以下為佳。同時,本發明之蔗糖芳香族單羧酸酯(Ⅱ-2),以在160℃、3小時加熱後,在50%甲苯溶液中之色相為30以下為佳,25以下更佳,15以下又更佳。在色相超過30時在作為樹脂改質劑時,會有使該樹脂之外觀(色相)、光學透明性降低之傾向。 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. Meanwhile, the sucrose aromatic monocarboxylic acid ester (II-2) of the present invention preferably has a hue of 30 or less in a 50% toluene solution after heating at 160 ° C for 3 hours, more preferably 25 or less, and 15 or less. Better. When the hue is more than 30, when it is used as a resin modifier, the appearance (hue) and optical transparency of the resin tend to be lowered.

<製法> <Method>

(鹵素去除步驟) (halogen removal step)

本發明之蔗糖芳香族單羧酸酯(Ⅱ),可以包含使鹵素之 含量在100ppm以下之步驟的製造方法,進行製造。 The sucrose aromatic monocarboxylic acid ester (II) of the present invention may comprise a halogen The production method is carried out in a production method in which the content is 100 ppm or less.

使鹵素之含量在100ppm以下之步驟,只要可達到該目的,一般在該領域所使用之任何方法均可使用,此類方法之具體之例,可如:以藉由蔗糖與芳香族單羧酸之酯化反應所得之酯化物,再藉由水洗進行。該水洗可以常法實施,其實施可如:在酯化反應終了後之混合物中,加入水,並在熱水浴之同時加以攪拌,之後靜置使水相分離,再將其去除。熱水浴之溫度,以40至60℃為佳。在40℃以下時會有洗淨不足之傾向,在60℃以上時則會有促進酯分解之傾向。該攪拌,只要為水相中,可使鹵化物離子及其他含鹵素化合物移動之充分的時間即可並無特別之限定,但一般,以30分鐘程度進行即已充分。 The step of bringing the halogen content to 100 ppm or less, as long as the object can be attained, any method generally used in the field can be used, and specific examples of such a method can be, for example, by using sucrose and an aromatic monocarboxylic acid. The esterified product obtained by the esterification reaction is further washed with water. The water washing can be carried out in a usual manner, and it can be carried out, for example, by adding water to the mixture after the end of the esterification reaction, and stirring while stirring in a hot water bath, and then standing to separate the aqueous phase and then removing it. The temperature of the hot water bath is preferably 40 to 60 ° C. When it is 40 ° C or less, there is a tendency that the cleaning is insufficient, and when it is 60 ° C or more, the decomposition of the ester tends to be promoted. The stirring is not particularly limited as long as it is sufficient to move the halide ions and other halogen-containing compounds in the aqueous phase, but it is generally sufficient to carry out the reaction for 30 minutes.

蔗糖芳香族單羧酸酯(Ⅱ-1)方面,水洗之次數,視使用之原料、酯之反應條件等而不同,但在使用雜質少之高純度原料(如高純度氯化苯甲醯(>99.5%)等)時,一般,以5次程度進行即已充分。 In the case of the sucrose aromatic monocarboxylic acid ester (II-1), the number of times of washing differs depending on the raw materials used and the reaction conditions of the ester, but a high-purity raw material having low impurities (such as high-purity benzyl benzamidine (such as high purity) is used. When it is >99.5%), etc., it is sufficient to carry out it in five times.

蔗糖芳香族單羧酸酯(Ⅱ-2)方面,水洗之次數,亦視使用之原料、酯之反應條件等而不同,但在使用雜質少之高純度原料(如高純度氯化苯甲醯(>99.5%)等)時,一般,以5至8次程度進行即已充分。 In the case of the sucrose aromatic monocarboxylic acid ester (II-2), the number of times of washing differs depending on the raw materials used and the reaction conditions of the ester, but a high-purity raw material having a small amount of impurities (such as high-purity chlorinated benzamidine) is used. (>99.5%), etc., generally, it is sufficient to carry out 5 to 8 times.

又,本發明中,亦可使蔗糖芳香族單羧酸酯(Ⅱ)中鹵素之含量在100ppm以下,即預先使用鹵素含量少之原料亦為有效。因此,酯化劑,以使用高純度鹵化芳香族單羧酸為佳。該類高純度鹵化芳香族單羧酸之例,可舉如:高純度氯化苯甲醯(>99.5%)(川口藥品公司製造)等。 Further, in the present invention, the content of the halogen in the sucrose aromatic monocarboxylic acid ester (II) may be 100 ppm or less, that is, it is also effective to use a raw material having a small halogen content in advance. Therefore, the esterifying agent is preferably a halogenated aromatic monocarboxylic acid having a high purity. Examples of such high-purity halogenated aromatic monocarboxylic acids include high-purity chlorinated benzamidine (>99.5%) (manufactured by Kawaguchi Pharmaceutical Co., Ltd.).

在如上述,在經過使蔗糖芳香族單羧酸酯(Ⅱ)中鹵素之含量在100ppm以下之步驟後,酯化反應中所使用之溶劑亦可以常法蒸發去除,而得到本發明之目的物。在該情形時,可將鹵素之含量預先調至100ppm以下,在本發明中,即不須以特殊之處理設備(如薄膜蒸發裝置)等,而可以常法蒸發去除溶劑,在抑制著色下,得到目的物。 As described above, after the step of allowing the content of the halogen in the sucrose aromatic monocarboxylic acid ester (II) to be 100 ppm or less, the solvent used in the esterification reaction can also be removed by usual evaporation to obtain the object of the present invention. . In this case, the content of the halogen can be adjusted to 100 ppm or less in advance. In the present invention, the solvent can be removed by evaporation in a conventional manner without special processing equipment (such as a thin film evaporation apparatus). Get the target.

(酯之合成) (ester synthesis)

本發明中,蔗糖與芳香族單羧酸之酯化反應,可以常法實施,如可依照特開昭61-4839號中所記載之蔗糖苯甲酸酯的製造方法,進行製造。 In the present invention, the esterification reaction of sucrose with an aromatic monocarboxylic acid can be carried out in a conventional manner, and can be produced, for example, according to the method for producing sucrose benzoate described in JP-A-61-4839.

亦即,以原料之蔗糖與芳香族單羧酸之氯化物,在親水性溶劑與水之混合液中,在鹼性化合物之存在下,藉由酯化反應而製造。親水性溶劑之例,如:丙酮、甲基乙基酮、環己酮等之酮系溶劑;二烷、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, a raw material of sucrose and a chloride of an aromatic monocarboxylic acid are produced by a esterification reaction in a mixture of a hydrophilic solvent and water in the presence of a basic compound. Examples of hydrophilic solvents, such as ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; An ether solvent such as an alkane or tetrahydrofuran; an ester solvent such as methyl acetate; and an alcohol solvent such as a tertiary alcohol such as butanol are preferably used.

鹼性化合物之例,可舉如:氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、氨水、三甲基胺、三乙基胺等。 Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, aqueous ammonia, trimethylamine, and triethylamine.

親水性溶劑與水混合之比例,以可使含兩者之均一液層的含水率為7至80%為佳。其緣由,係由於此等親水性溶劑,可溶解原料中一方之芳香族單羧酸的氯化物及生成物之酯,在原料之另一方之蔗糖,係單獨時完全無法溶解或由反應效率之觀點為無法以實用程度溶解時,與蔗糖之良溶劑之水混合時,可使該混合液以實用程度溶解蔗糖。因此,利用親水性 溶劑之此種性質,可調節蔗糖與芳香族單羧酸氯化物的反應速率,結果,即可依照蔗糖/芳香族單羧酸之氯化物的添加量(莫耳比),製造低取代體之比例及平均酯取代率不同之酯。例如,相對於芳香族單羧酸氯化物之添加量使蔗糖之添加量為多量時,可得到低取代體之比例相對地較低或平均酯取代率相對地較高之酯化物,相反地,相對於芳香族單羧酸氯化物之添加量在蔗糖之添加量少時,則可得到低取代體之比例相對地較高或平均酯取代率相對地較低之酯化物。 The ratio of the hydrophilic solvent to water is such that the water content of the uniform liquid layer containing both is preferably from 7 to 80%. The reason is that these hydrophilic solvents can dissolve the chloride of the aromatic monocarboxylic acid in one of the raw materials and the ester of the product, and the sucrose in the other side of the raw material cannot be dissolved at all or by the reaction efficiency. When the viewpoint is such that it cannot be dissolved to a practical degree, it can be mixed with water of a good solvent of sucrose to dissolve the sucrose to a practical degree. Therefore, the use of hydrophilicity Such a property of the solvent can adjust the reaction rate of sucrose and the aromatic monocarboxylic acid chloride, and as a result, a low-substituted product can be produced according to the amount of the sucrose/aromatic monocarboxylic acid chloride added (mol ratio). Esters with different ratios and average ester substitution rates. For example, when the amount of the sucrose added is a large amount relative to the amount of the aromatic monocarboxylic acid chloride added, an ester compound having a relatively low proportion of the low substituent or a relatively high average ester substitution ratio can be obtained, and conversely, When the amount of the sucrose added is small relative to the amount of the aromatic monocarboxylic acid chloride added, an ester compound having a relatively low proportion of the low substituent or a relatively low average ester substitution ratio can be obtained.

反應之方法方面,可在含親水性溶劑與水之混合液中,將蔗糖及芳香族單羧酸氯化物溶解或懸浮,再將芳香族單羧酸氯化物以等量或稍為過量之鹼性化合物滴入;或將蔗糖及鹼性化合物溶解或懸浮在混合液中,再將芳香族單羧酸氯化物滴入;或者將蔗糖溶解或懸浮在混合液中,再將芳香族單羧酸氯化物與鹼性化合物同時或交替滴入。 In the method of the reaction, the sucrose and the aromatic monocarboxylic acid chloride may be dissolved or suspended in a mixture containing a hydrophilic solvent and water, and the aromatic monocarboxylic acid chloride is equimolar or slightly excessively alkaline. The compound is added dropwise; or the sucrose and the basic compound are dissolved or suspended in the mixed solution, and the aromatic monocarboxylic acid chloride is dropped; or the sucrose is dissolved or suspended in the mixed solution, and the aromatic monocarboxylic acid chloride is further added. The compound and the basic compound are dropped simultaneously or alternately.

反應溫度,以採用-15℃至100℃為佳,-10℃至30℃更佳。但,亦可在全部之反應原料滴入完了後,為再促進反應之完成,再於高溫範圍下加熱。 The reaction temperature is preferably -15 ° C to 100 ° C, more preferably -10 ° C to 30 ° C. However, after all of the reaction raw materials have been dropped, the reaction may be further accelerated and then heated in a high temperature range.

反應中之pH值以維持在弱鹼性為佳。另一方面,在強鹼性下(如視乎反應溫度等,但在pH13以上等),由於芳香族單羧酸的水解之副反應顯著,因此,以如在pH8至13程度進行為佳。 The pH in the reaction is preferably maintained at a weak alkalinity. On the other hand, under strong alkali (for example, depending on the reaction temperature or the like, but at a pH of 13 or higher, etc.), since the side reaction of the hydrolysis of the aromatic monocarboxylic acid is remarkable, it is preferably carried out at a pH of from 8 to 13.

反應時間方面,只要原料之間之反應可完全反應完成即可並無特別之限定。具體之時間,係依照原料化合物之量及各種條件,但一般,以3小時程度操作即已充分。 The reaction time is not particularly limited as long as the reaction between the raw materials can be completely completed. The specific time is based on the amount of the raw material compound and various conditions, but in general, it is sufficient to operate at a level of about 3 hours.

<用途> <Use>

本發明之蔗糖芳香族單羧酸酯(Ⅱ),可作為樹脂改質劑,特別,兼具有可抑制加熱之著色的優異特點,因此可作為要求光學透明性的樹脂之改質劑使用。 The sucrose aromatic monocarboxylic acid ester (II) of the present invention can be used as a resin modifier, and particularly has an excellent feature of suppressing coloring by heating. Therefore, it can be used as a modifier for a resin requiring optical transparency.

可添加本發明之蔗糖芳香族單羧酸酯(Ⅱ)之樹脂,可舉如:ABS樹脂、聚氯化乙烯樹脂、環氧樹脂、不飽和聚酯等之非結晶性樹脂,此外亦可舉例為晶形聚酯等之結晶性樹脂。樹脂可視其用途適當地選擇。同時,添加本發明之蔗糖芳香族單羧酸酯(Ⅱ)之樹脂,亦可視樹脂之種類/用途,以低取代體之比例及酯取代率,適當選擇相應者。 The resin of the sucrose aromatic monocarboxylic acid ester (II) of the present invention may be added, and examples thereof include amorphous resins such as ABS resin, polyvinyl chloride resin, epoxy resin, and unsaturated polyester, and examples thereof It is a crystalline resin such as a crystalline polyester. The resin can be appropriately selected depending on its use. Meanwhile, the resin to which the sucrose aromatic monocarboxylic acid ester (II) of the present invention is added may be appropriately selected depending on the type/use of the resin, the ratio of the low substituent, and the ester substitution ratio.

ABS樹脂方面,並無特別之限定,可例舉如:聚丁二烯、苯乙烯-丁二烯共聚物、丙烯腈-丁二烯共聚物、氯化聚乙烯、聚丙烯酸系橡膠(如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯等)、及以丙烯腈、苯乙烯、丙烯酸、丙烯醯胺、2-氯乙基乙烯基醚等之共聚物等橡膠狀聚合物、以丙烯腈、苯乙烯、α-甲基苯乙烯、甲基丙烯酸甲酯等接枝共聚所得之物種,以及,其他之丙烯腈-聚丁二烯-苯乙烯系之接枝共聚物等。ABS樹脂,可以1種單獨使用,亦可以2種以上併用。 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). a rubbery polymer such as a methyl ester, ethyl acrylate or butyl acrylate, or a copolymer such as acrylonitrile, styrene, acrylic acid, acrylamide or 2-chloroethyl vinyl ether, or acrylonitrile or benzene. A species obtained by graft copolymerization of ethylene, α-methylstyrene, methyl methacrylate or the like, and other acrylonitrile-polybutadiene-styrene graft copolymers. The ABS resin may be used alone or in combination of two or more.

聚氯化乙烯樹脂方面,並無特別之限定,可舉如:氯化乙烯單獨之聚合樹脂、氯化之氯化乙烯樹脂、以在與氯化乙烯單體共聚所得之所有單體中之1種以上經過無規共聚或嵌段共聚所得之氯化乙烯共聚樹脂(如乙酸乙烯酯-氯化乙烯共聚物、乙烯-氯化乙烯共聚物等)、或上述樹脂以羥基等之官能基接枝共聚所得之樹脂及此類官能基與反應性化合物反應 所接枝聚合之物種。聚氯化乙烯樹脂,可以1種單獨使用,亦可以2種以上併用。 The polyvinyl chloride resin is not particularly limited, and examples thereof include a vinyl chloride alone polymer resin, a chlorinated vinyl chloride resin, and one of all monomers obtained by copolymerization with a vinyl chloride monomer. The above-mentioned vinyl chloride copolymer resin obtained by random copolymerization or block copolymerization (such as vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, etc.) or the above resin is grafted with a functional group such as a hydroxyl group Copolymerization of the resin and reaction of such functional groups with reactive compounds The species polymerized by grafting. The polyvinyl chloride resin may be used alone or in combination of two or more.

環氧樹脂方面,亦無特別之限定,可舉如:雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、酚系酚醛型環氧樹脂、烷基酚系酚醛型環氧樹脂、酚系聯苯芳烷環氧樹脂等之芳烷型環氧樹脂、聯苯酚型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂、聯苯型環氧樹脂、蒽型環氧樹脂、酚類與具有酚性羥基之芳香族醛之縮合物的環氧化物、三聚異氰酸三環氧丙酯、脂環式環氧樹脂等。環氧樹脂,可以1種單獨使用,亦可以2種以上併用。 The epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic novolac epoxy resin, and alkylphenol. Aralkyl type epoxy resin such as phenolic epoxy resin or phenolic biphenyl aralkyl epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl An epoxy resin, a fluorene type epoxy resin, an epoxide of a condensate of a phenol and an aromatic aldehyde having a phenolic hydroxyl group, a triglycidyl isocyanate, an alicyclic epoxy resin or the like. The epoxy resin may be used alone or in combination of two or more.

不飽和聚酯樹脂方面,亦無特別之限定,可舉如:以α,β-烯烴系不飽和二羧酸或其酸酐與二醇之加成反應或脫水縮合反應所合成之物種。同時亦可以與飽和二羧酸及芳香族二羧酸或其酸酐或者羧酸所反應之二環戊二烯等併用。α,β-烯烴系不飽和二羧酸之例,可舉如:順丁烯二酸、反丁烯二酸、伊康酸、檸康酸及此等二羧酸之酸酐。可與此類α,β-烯烴系不飽和二羧酸併用之二羧酸之例,可舉如:已二酸、癸二酸、琥珀酸、苯二甲酸酐、鄰苯二甲酸、異苯二甲酸、對苯二甲酸、四氫苯二甲酸、四氯苯二甲酸等。其中,以α,β-烯烴系不飽和二羧酸之反丁烯二酸、及二羧酸之異苯二甲酸併用較佳。不飽和聚酯樹脂可以1種單獨使用,亦可以2種以上併用。 The unsaturated polyester resin is not particularly limited, and examples thereof include a compound synthesized by an addition reaction or a dehydration condensation reaction of an α,β-olefin-based unsaturated dicarboxylic acid or an acid anhydride thereof with a diol. At the same time, it may be used in combination with a dicarboxylic acid or an aromatic dicarboxylic acid or an anhydride thereof or a dicyclopentadiene which is reacted with a carboxylic acid. Examples of the α,β-olefin-based unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and anhydrides of such dicarboxylic acids. Examples of the dicarboxylic acid which can be used in combination with such an α,β-olefin-based unsaturated dicarboxylic acid include adipic acid, sebacic acid, succinic acid, phthalic anhydride, phthalic acid, and isophthalic acid. Dicarboxylic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, and the like. Among them, fumaric acid of an α,β-olefin-based unsaturated dicarboxylic acid and isophthalic acid of a dicarboxylic acid are preferably used in combination. The unsaturated polyester resin may be used alone or in combination of two or more.

晶形聚酯樹脂方面,亦無特別之限定,可舉如:聚對苯二甲酸二乙酯、聚對苯二甲酸-1,4-二丁酯、聚萘二甲酸-2,6-二乙酯、聚對苯二甲酸環己烷二甲醇酯、聚二苯基-4,4'- 二羧酸-1,4-丁二酯、聚乙烯氧基苯甲酸酯、聚對苯二甲酸-1,3-丙二酯、聚對苯二甲酸-1,6-己二酯等之晶形聚酯,其中,以聚對苯二甲酸二乙酯、聚對苯二甲酸-1,4-二丁酯、聚萘二甲酸-2,6-二乙酯較佳。晶形聚酯樹脂可以1種單獨使用,亦可以2種以上併用。 The crystalline polyester resin is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate-1,4-dibutyl ester, and polynaphthalene dicarboxylic acid-2,6-diethyl. Ester, poly(cyclohexanedimethylene terephthalate), polydiphenyl-4,4 ' -dicarboxylic acid-1,4-butane diester, polyvinyloxybenzoate, polyterephthalic acid a crystalline polyester such as 1,3-propane diester or poly(terephthalic acid-1,6-hexanediester), wherein polyethylene terephthalate or polyterephthalic acid-1,4- Dibutyl ester and polyethylene naphthalate-2,6-diethyl ester are preferred. The crystal polyester resin may be used alone or in combination of two or more.

同時,此類樹脂,視其必要,亦可添加:衝擊強度改質劑、安定劑、滑劑、填充劑、顏料、發泡劑、紫外線安定劑等之各種添加劑。 At the same time, such resins may be added, as necessary, various additives such as impact strength modifiers, stabilizers, slip agents, fillers, pigments, foaming agents, ultraviolet stabilizers, and the like.

本發明之蔗糖芳香族單羧酸酯(Ⅱ)在樹脂中調配之比例,相對於樹脂100份,以1至40份為佳,1至30份更佳。在未達1份時,會有無法得到目的性能之傾向,在高於40份時,則會使長期保存等之溢流的可能性提高。 The proportion of the sucrose aromatic monocarboxylic acid ester (II) of the present invention to be blended in the resin is preferably from 1 to 40 parts, more preferably from 1 to 30 parts, per 100 parts by weight of the resin. When the amount is less than one part, the intended performance may not be obtained, and when it is more than 40 parts, the possibility of overflow for long-term storage or the like may be increased.

(B)關於蔗糖羧酸酯(Ⅲ) (B) About sucrose carboxylate (III)

<目的物> <object>

本發明之蔗糖羧酸酯(Ⅲ),呋喃甲醛含量為50ppm以下且羥甲基呋喃甲醛(HMF:5-(羥甲基)-2-呋喃甲醛)含量為500ppm以下,即係上述的特定之蔗糖芳香族單羧酸酯。亦即,在上述特定之蔗糖芳香族單羧酸酯中,係將此二種雜質之含量抑低,因此在作為增量劑調配在2-氰基丙烯酸酯系接著劑時,可顯著改善該接著劑組成物之臭氣。呋喃甲醛之含量,以5ppm以下為佳,0.5ppm以下更佳。另一方面,HMF之含量,以50ppm以下為佳,5ppm以下更佳。 The sucrose carboxylate (III) of the present invention has a furaldehyde content of 50 ppm or less and a hydroxymethylfurfural (HMF: 5-(hydroxymethyl)-2-furancarbaldehyde) content of 500 ppm or less, which is the specific one described above. Sucrose aromatic monocarboxylate. That is, in the above specific sucrose aromatic monocarboxylic acid ester, the content of the two kinds of impurities is suppressed, so that when the 2-cyanoacrylate-based adhesive is formulated as an extender, the effect can be remarkably improved. The odor of the composition of the agent. The content of furaldehyde 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.

本發明之蔗糖芳香族單羧酸酯(Ⅲ)中,蔗糖之醇部分的酯化之比例的平均值(以下,稱為「平均酯化度」), 以6.0以下為佳,5.0以下更佳。在平均酯化度超過6.0時會有降低臭氣減低效果的傾向。另一方面,平均酯化度又以3.0以上為佳,4.5以上更佳。在平均酯化度未達3.0時,會有減低接著性的傾向。 In the sucrose aromatic monocarboxylic acid ester (III) of the present invention, the average value of the esterification ratio of the alcohol portion of sucrose (hereinafter referred to as "average degree of esterification"), It is preferably 6.0 or less, and 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, more preferably 4.5 or more. When the average degree of esterification is less than 3.0, there is a tendency to reduce the adhesion.

<製法> <Method>

(精製步驟) (refining step)

本發明之蔗糖芳香族單羧酸酯(Ⅲ),只要為可使呋喃甲醛為50ppm以下且HMF為500ppm以下者即可,可使用任何一般已知之方法製造,該類方法之例,可如:以蔗糖與芳香族單羧酸藉由一般酯化反應所得到之酯化物予以精製。該精製,可先單使呋喃甲醛為50ppm以下之後,再使HMF為500ppm以下實施,或與此相反亦可,但由簡便性及效率性之觀點而言,以使兩者同時在設定之濃度以下為佳。 The sucrose aromatic monocarboxylic acid ester (III) of the present invention may be any one which can be furfural-formaldehyde 50 ppm or less and HMF 500 ppm or less, and can be produced by any generally known method. Examples of such a method are as follows: The esterified product obtained by a general esterification reaction of sucrose and an aromatic monocarboxylic acid is purified. This purification may be carried out after the furaldehyde is 50 ppm or less, and then the HMF is 500 ppm or less, or vice versa, but from the viewpoint of simplicity and efficiency, both of them are at the set concentration. The following is better.

使兩者同時在設定之濃度以下,亦即,使呋喃甲醛在50ppm以下且使HMF在500ppm以下之方法,可如將蔗糖與芳香族單羧酸藉由一般之酯化反應所得到的酯化物,溶解在甲苯、鄰二甲苯、間二甲苯等之有機溶劑中,再將該溶液,加以乾燥。有機溶劑中酯化物之濃度,以10重量%以上為佳,30重量%以上更佳。在該濃度未達10重量%時,在工業上無效率。另一方面,該濃度以80重量%以下為佳,50重量%以下更佳。該濃度,在超過80重量%時將使黏度極高,因此會有不易適合減壓濃縮裝置之傾向。該有機溶劑,可以1種單獨使用,亦可以2種以上混合使用。 When the two are simultaneously below the set concentration, that is, the furaldehyde is 50 ppm or less and the HMF is 500 ppm or less, an esterified product obtained by a general esterification reaction between sucrose and an aromatic monocarboxylic acid can be used. It is dissolved in an organic solvent such as toluene, o-xylene or m-xylene, and the solution is dried. The concentration of the esterified product in the organic solvent is preferably 10% by weight or more, 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% by weight, the viscosity is extremely high, so that it tends to be difficult to be suitable for a reduced pressure concentrating device. These organic solvents may be used alone or in combination of two or more.

將蔗糖芳香族單羧酸酯(Ⅲ)之有機溶劑溶液乾 燥之手段,可利用先前一般已知之任何方法,具體地,可如:將該溶液,與加熱面接觸,使溶劑等蒸發去除。在與加熱面接觸時,該溶液以在厚度10cm以下之液膜狀態接觸為佳,5cm以下更佳,5mm以下又更佳,1mm以下又再更佳。在該液膜之厚度超過10cm時,會有乾燥中使呋喃甲醛及HMF增加之傾向。另一方面,該液膜之厚度的下限值方面只要為可能實施之厚度即可並無特別之限定,但厚度越薄單其精製成本即會增加,因此有工業方面不佳之傾向。又,其中,所謂蔗糖芳香族單羧酸酯之有機溶劑溶液的「液膜之厚度」,具體地,係指由與加熱面接觸之該液膜之下方之面,至對側之面之上方之面的距離。 Drying the organic solvent solution of sucrose aromatic monocarboxylate (III) For the means of drying, any method generally known in the past can be used. Specifically, the solution can be brought into contact with a heating surface to evaporate and remove a solvent or the like. When it comes into contact with the heating surface, the solution is preferably contacted in a liquid film state having a thickness of 10 cm or less, more preferably 5 cm or less, more preferably 5 mm or less, and still more preferably 1 mm or less. When the thickness of the liquid film exceeds 10 cm, furfural 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 carried out. However, the thinner the thickness, the higher the purification cost, and the lower the industrial tendency. In addition, the "thickness of the liquid film" of the organic solvent solution of the sucrose aromatic monocarboxylic acid ester specifically means the surface below the liquid film which is in contact with the heating surface, and is above the opposite side. The distance between the faces.

乾燥,以在減壓下實施減壓乾燥為佳。減壓乾燥的條件,視原料之使用量、要求之乾燥效率、使用之有機溶劑的種類等之各條件而改變,但一般,壓力以0.01KPa.abs以上為佳。在壓力未達0.01KPa.abs時會有設備須高價的傾向。另一方面,壓力又以15KPa.abs以下為佳,4KPa.abs以下更佳。在壓力超過15KPa.abs時會有使乾燥效率降低之傾向。同時,乾燥中之加熱面的溫度(稱為「加熱溫度」。),以90℃以上為佳,100℃以上更佳。加熱溫度未達90℃時會有使乾燥效率降低之傾向。另一方面,加熱溫度,又以300℃以下為佳,200℃以下更佳,160℃以下又更佳。加熱溫度超過300℃時會有使呋喃甲醛及HMF增加之傾向。 Drying is preferably carried out under reduced pressure under reduced pressure. The conditions for drying under reduced pressure vary depending on the conditions of the amount of the raw materials used, the required drying efficiency, the type of the organic solvent to be used, and the like, but generally, the pressure is 0.01 KPa. Above abs is better. The pressure is less than 0.01KPa. There is a tendency for equipment to be expensive when abs. On the other hand, the pressure is again 15KPa. Abs below is better, 4KPa. Abs below is better. At pressures above 15KPa. When abs, there is a tendency to lower the drying efficiency. Meanwhile, the temperature of the heating surface in the drying (referred to as "heating temperature") is preferably 90 ° C or more, more preferably 100 ° C or more. When 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 ° C or less, more preferably 200 ° C or less, and even more preferably 160 ° C or less. When the heating temperature exceeds 300 ° C, furfural and HMF tend to increase.

蔗糖芳香族單羧酸酯(Ⅲ)之有機溶劑之溶液,與加熱面之接觸,可如使用真空式滾筒乾燥機、真空式帶式乾 燥機、薄膜蒸發器、急速蒸發器、真空式擠壓機、攪拌槽等機器實施。此類機器,可單獨使用,亦可以相同或不同之機器以二種以上組合使用。在以二種以上組合使用時,以連結,特別以直列連結,可使精製之程度提高因此更佳。連結之具體例,可舉如以薄膜蒸發器與薄膜蒸發器連結、以急速蒸發器與薄膜蒸發器連結、以攪拌槽與薄膜蒸發器連結、以攪拌槽與真空式擠壓機連結等。又,在使用鋼管式濃縮型裝置時(在實施例中,係使用鋼管式濃縮型急速蒸發器),可以導入有機溶劑溶液的配管之口徑(導入配管徑),視為有機溶劑溶液的「液膜之厚度」。 A solution of an organic solvent of sucrose aromatic monocarboxylate (III), in contact with a heating surface, such as a vacuum drum dryer or a vacuum belt dryer Machines such as dryers, thin film evaporators, rapid evaporators, vacuum extruders, and stirred tanks are used. Such machines may be used singly or in combination of two or more kinds of the same or different machines. When it is used in combination of two or more kinds, it is preferable to increase the degree of purification by linking, particularly in-line. Specific examples of the connection include a thin film evaporator connected to a thin film evaporator, a quick evaporator connected to a thin film evaporator, a stirring tank connected to a thin film evaporator, and a stirring tank connected to a vacuum extruder. In addition, when a steel pipe type concentrated type device is used (in the embodiment, a steel pipe type concentrated type rapid evaporator) is used, the diameter of the pipe into which the organic solvent solution can be introduced (introduction pipe diameter) can be regarded as the "liquid of the organic solvent solution". The thickness of the film."

乾燥方面,可以任何批式或連續式之任意樣態實施,但隨加熱時間之延長亦有使呋喃甲醛及HMF增加之傾向,因此以可抑制累積加熱之連續式為佳。 In terms of drying, it can be carried out in any batch or continuous form, but the furfural formaldehyde and HMF tend to increase as the heating time is extended. Therefore, it is preferred to continue the continuous heating.

(酯之合成) (ester synthesis)

作為上述精製步驟之原料的蔗糖芳香族單羧酸酯(Ⅲ)(本說明書中,方便上,可稱為「粗蔗糖芳香族單羧酸酯(Ⅲ)」或「粗酯(Ⅲ)」。),可以蔗糖、與芳香族單羧酸(I),以常法,藉由酯化反應製造,該酯化反應,可如依照特開昭61-4839號及特公昭40-5688號中所記載之蔗糖苯甲酸酯之製造方法,以蔗糖與芳香族單羧酸(I)之氯化物,進行反應實施。 The sucrose aromatic monocarboxylic acid ester (III) which is a raw material of the above-mentioned purification step (in the present specification, it may be referred to as "crude sucrose aromatic monocarboxylic acid ester (III)" or "crude ester (III)". And sucrose, and an aromatic monocarboxylic acid (I) can be produced by an esterification reaction in a usual manner, and the esterification reaction can be carried out according to JP-A-61-4839 and JP-A-40-5688. The method for producing sucrose benzoate described above is carried out by reacting sucrose with a chloride of an aromatic monocarboxylic acid (I).

例如,在依照特開昭61-4839號中所記載之方法時,可依照「上述(A)關於蔗糖羧酸酯(Ⅱ)」項中所說明之內容,實施操作。 For example, in the method described in JP-A-61-4839, the operation can be carried out in accordance with the contents described in the above section (A) on sucrose carboxylic acid ester (II).

另一方面,在依照特公昭40-5688號中所記載之方法時,酯化反應,可以上述特開昭61-4839號中所記載之方法所使用之親水性溶劑,取代其他之溶劑,即選自芳香族或取代之芳香族烴、氯化脂族烴、低級脂族醚之1種或2種以上的溶劑,實施操作。其中,芳香族或取代之芳香族烴之例,可舉如:苯、甲苯、二甲苯、乙基苯、氯化苯、氯化甲苯等;氯化脂族烴之例,可舉如:二氯甲烷、氯仿、四氯化碳、四氯乙烷等;低級脂族醚之例,可舉如:二乙基醚、二異丙基醚等。 On the other hand, in the method described in Japanese Patent Publication No. 40-5688, the esterification reaction can be carried out by using the hydrophilic solvent used in the method described in JP-A-61-4839, that is, other solvents, that is, One or two or more solvents selected from the group consisting of aromatic or substituted aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, and lower aliphatic ethers are operated. Examples of the aromatic or substituted aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, chlorinated benzene, and chlorinated toluene; and examples of the chlorinated aliphatic hydrocarbons include: Methyl chloride, chloroform, carbon tetrachloride, tetrachloroethane, etc.; examples of the lower aliphatic ethers include diethyl ether and diisopropyl ether.

反應溫度,可採用-15℃至100℃,而以-10℃至30℃較佳。反應時間,視乎各種條件,但一般,以3小時程度進行即已充分。 The reaction temperature can 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 at a level of 3 hours.

<用途> <Use>

本發明之蔗糖芳香族單羧酸酯(Ⅲ),可作為2-氰基丙烯酸酯系接著劑之增量劑及臭氣改善劑使用。2-氰基丙烯酸酯系接著劑之接著成分方面,可以如:2-氰基丙烯酸甲酯、2-氰基丙烯酸乙酯、2-氰基丙烯酸丙酯、2-氰基丙烯酸丁酯、2-氰基丙烯酸烯丙酯、2-氰基丙烯酸甲氧基乙酯、2-氰基丙烯酸乙氧基乙酯、2-氰基丙烯酸-2-氯乙酯、2-氰基丙烯酸環己酯之下之各種2-氰基丙烯酸酯,特別,以2-氰基丙烯酸乙酯為佳。 The sucrose aromatic monocarboxylic acid ester (III) of the present invention can be used as an extender of a 2-cyanoacrylate-based adhesive and an odor improving agent. The second component of the cyanoacrylate-based adhesive may be, for example, methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, propyl 2-cyanoacrylate or butyl 2-cyanoacrylate, 2 - allyl cyanoacrylate, methoxyethyl 2-cyanoacrylate, ethoxyethyl 2-cyanoacrylate, 2-chloroethyl 2-cyanoacrylate, cyclohexyl 2-cyanoacrylate The various 2-cyanoacrylates below, in particular, ethyl 2-cyanoacrylate are preferred.

在調製接著劑組成物時,本發明之蔗糖芳香族單羧酸酯(Ⅲ)中,2-氰基丙烯酸酯系接著劑之調配量,相對於接著劑100份,以5份以上為佳,15份以上更佳,該調配量在未達5份時會有在蔗糖芳香族單羧酸酯(Ⅲ)中添加的效果不足之傾向。另一方面,該調配量,又以60份以下為佳,30份 以下更佳。在該調配量超過60份時會有使接著性能降低之傾向。但,在蔗糖芳香族單羧酸酯(Ⅲ)之比例極端大時雖會使接著力降低,但在暫時性接著之目的方面卻更佳,因此上述之上限值,在蔗糖芳香族單羧酸酯(Ⅲ)之調配比例上並無限定。 In the preparation of 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 based on 100 parts of the adhesive. More preferably, 15 parts or more, and when the 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 or less, 30 parts. The following is better. When the amount is more than 60 parts, the subsequent performance tends to be lowered. However, when the ratio of the sucrose aromatic monocarboxylic acid ester (III) is extremely large, the adhesion is lowered, but it is preferable for the purpose of temporary continuation. Therefore, the above upper limit is in the sucrose aromatic monocarboxylic acid. The proportion of the acid ester (III) is not limited.

本發明之接著劑組成物中,在2-氰基丙烯酸酯系接著劑成分及本發明之蔗糖芳香族單羧酸酯(Ⅲ)之外,以已往使用之各種添加劑,如以保存安定劑、有機溶劑、可塑劑、增黏劑(聚合物類)、填充劑、流變性(thixotropy)改良劑、耐熱性賦予劑、降極性劑、接著強化劑、硬化促進劑、硬化抑制劑、著色劑、羧酸酯化合物等之添加劑適當添加。 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 conventionally used, such as a preservation stabilizer, Organic solvent, plasticizer, tackifier (polymer), filler, thixotropy improver, heat resistance imparting agent, polar modifier, adhesion enhancer, hardening accelerator, hardening inhibitor, colorant, An additive such as a carboxylate compound is appropriately added.

以本發明之蔗糖芳香族單羧酸酯(Ⅲ),在2-氰基丙烯酸酯系接著成分中添加時,可以任意之比例容易地在2-氰基丙烯酸酯系接著成分中溶解,且其中,可顯示幾乎不使2-氰基丙烯酸酯系接著成分之快速接著性、接著力、安定性、黏度等變化之優異作用。 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 in an arbitrary ratio, and It can exhibit an excellent effect of almost no change in the fast adhesion, adhesion, stability, viscosity, and the like of the 2-cyanoacrylate-based component.

本說明書中,單稱為「份」時,為「重量份」之意。 In this manual, the term "parts" is the meaning of "parts by weight".

蔗糖芳香族單羧酸酯中之「平均取代率」、「平均酯取代率」及「平均酯化度」,均具有相同之意味,而係以質子核磁共振(1H-NMR)求得之值。 The "average substitution rate", "average ester substitution rate" and "average esterification degree" in the sucrose aromatic monocarboxylic acid ester have the same meaning, and are obtained by proton nuclear magnetic resonance ( 1 H-NMR). value.

蔗糖芳香族單羧酸酯(Ⅱ)中,在「低取代體」之比例計算時之各取代體之比例,係以液相層析質量分析(LC-MS)所求之值。同時,鹵素之含量(ppm),係以感應耦合電漿質譜分析(inductively coupled plasma emission spectrometry)(ICP) 所測定之值。 In the sucrose aromatic monocarboxylic acid ester (II), the ratio of each substituent in the calculation of the ratio of "lower substituent" is a value obtained by liquid chromatography mass spectrometry (LC-MS). At the same time, the halogen content (ppm) is determined by inductively coupled plasma emission spectrometry (ICP). The value measured.

蔗糖芳香族單羧酸酯(Ⅲ)中各「呋喃甲醛」、及「HMF」之量係以高速液相層析(HPLC),「甲苯」之量,係以氣相層析(GC),所求之值。 The amount of each "furaldehyde" and "HMF" in the sucrose aromatic monocarboxylic acid ester (III) is determined by high-speed liquid chromatography (HPLC), and the amount of "toluene" is gas chromatography (GC). The value sought.

實施例 Example

以下再以實施例詳細說明本發明,但本發明並不單限定於此。 Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto.

<使用之原料> <Materials used>

蔗糖:≧99.9%,新光製糖公司製造 Sucrose: 99.9%, manufactured by Sunbeam Sugar Co., Ltd.

氯化苯甲醯(1):高純度品(>99.5%),川口藥品公司製造 Benzoyl chloride (1): high purity product (>99.5%), manufactured by Kawaguchi Pharmaceutical Co., Ltd.

氯化苯甲醯(2):普通品>99.0%,Jiangsu Qiangsheng Chemical Co.,Ltd.製造 Benzoquinone chloride (2): General product > 99.0%, manufactured by Jiangsu Qiangsheng Chemical Co., Ltd.

(A)蔗糖芳香族單羧酸酯(Ⅱ-1) (A) sucrose aromatic monocarboxylate (II-1)

1.合成 Synthetic

實施例1 Example 1

<蔗糖苯甲酸酯(六取代體以下之比例:93.5%)> <sucrose benzoate (proportion of hexa-substituent: 93.5%)>

先在具備攪拌棒、溫度計、冷凝器、滴液漏斗、連接pH計之pH電極的1L五口三角瓶中加入蔗糖34.2份及水70份並使其溶解後,再以水浴冷卻至10℃以下並同時徐徐加入含氯化苯甲醯(1)75.0份之環己酮100份。之後,再保持於20℃以下之溫度,並同時將48%苛性鈉水溶液48.5份以滴液漏斗而以保持pH於10至11之速度加入。之後移去水浴並在20至30℃之室溫下繼續攪拌1小時熟成而完成反應後,再加入少量 之碳酸鈉並加熱,使餘存微量之氯化苯甲醯轉換為苯甲酸鈉。其後,再靜置約30分鐘,使水相分離,並將其去除。 First, add 34.2 parts of sucrose and 70 parts of water to a 1 L five-necked triangular flask equipped with a stir bar, a thermometer, a condenser, a dropping funnel, and a pH electrode connected to a pH meter, and then dissolve it in water, and then cool to 10 ° C or less in a water bath. At the same time, 100 parts of cyclohexanone containing 75.0 parts of benzylguanidinium chloride (1) was slowly added. Thereafter, it was kept at a temperature of 20 ° C or lower, and at the same time, 48.5 parts of a 48% aqueous sodium caustic solution was added as a dropping funnel at a rate to maintain the pH at 10 to 11. Then remove the water bath and continue stirring at room temperature of 20 to 30 ° C for 1 hour to complete the reaction, then add a small amount. The sodium carbonate is heated and the remaining trace amount of benzamidine chloride is converted to sodium benzoate. Thereafter, it was allowed to stand for another 30 minutes to separate the aqueous phase and remove it.

再另外加入水70份,並以熱水浴昇溫至40至50℃,經過攪拌30分鐘後,再靜置約30分鐘,使水相分離,再將其去除。在相同操作重複2次後(合計水洗次數:3次),將其昇溫至120℃,並於減壓下蒸發去除溶劑,而得到目標之蔗糖苯甲酸酯。 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, the mixture was allowed to stand for another 30 minutes to separate the aqueous phase and then removed. After repeating the same operation twice (total number of washings: 3 times), the temperature was raised to 120 ° C, and the solvent was evaporated under reduced pressure to obtain the desired sucrose benzoate.

之後再測定其平均取代率、各取代體之比例及六取代體以下之比例、以及鹵素之含量(以下之實施例及比較例之目的物亦相同)。 Thereafter, the average substitution ratio, the ratio of each substituent, the ratio of the hexasubstituted body or less, and the halogen content were measured (the same applies to the following examples and comparative examples).

實施例2 Example 2

<蔗糖苯甲酸酯(六取代體以下之比例:83.5%)> <Sucrose benzoate (proportion of hexa-substituent: 83.5%)>

除以氯化苯甲醯(1)82.1份及48%苛性鈉水溶液53.1份,並以水洗次數4次操作以外與實施例1同樣處理,而得到目標之蔗糖苯甲酸酯。 The target sucrose benzoate was obtained by the same treatment as in Example 1 except that 82.1 parts of benzamidine chloride (1) and 53.1 parts of a 48% aqueous solution of caustic soda were used, and the number of times of washing was four times.

實施例3 Example 3

<蔗糖苯甲酸酯(六取代體以下之比例:49.8%)> <Sucrose benzoate (proportion of hexa-substituent: 49.8%)>

除以氯化苯甲醯(1)93.7份及48%苛性鈉水溶液60.6份,並以水洗次數2次操作以外與實施例1同樣處理,而得到目標之蔗糖苯甲酸酯。 The target sucrose benzoate was obtained by the same treatment as in Example 1 except that 93.7 parts of benzamidine chloride (1) and 60.6 parts of a 48% aqueous solution of caustic soda were used in the same manner as the number of times of washing.

實施例4 Example 4

<蔗糖苯甲酸酯(六取代體以下之比例:9.0%)> <Sucrose benzoate (proportion of hexa-substituent: 9.0%)>

除以氯化苯甲醯(1)106.7份及48%苛性鈉水溶液69.0份,並以水洗次數4次操作以外與實施例1同樣處理,而得到 目標之蔗糖苯甲酸酯。 The same treatment as in Example 1 was carried out except that 106.7 parts of benzamidine chloride (1) and 69.0 parts of a 48% caustic soda solution were treated in the same manner as in the case of four times of washing. Target sucrose benzoate.

比較例1 Comparative example 1

<蔗糖苯甲酸酯(六取代體以下之比例:9.0%)> <Sucrose benzoate (proportion of hexa-substituent: 9.0%)>

除以水洗次數1次操作以外與實施例4同樣處理,而得到目標之蔗糖苯甲酸酯。 The same treatment as in Example 4 was carried out except that the number of times of washing was one operation, and the intended sucrose benzoate was obtained.

比較例2 Comparative example 2

<蔗糖苯甲酸酯(六取代體以下之比例:9.6%)> <Sucrose benzoate (proportion of hexa-substituent: 9.6%)>

除取代氯化苯甲醯(1)使用氯化苯甲醯(2),並以水洗次數8次操作以外與實施例4同樣處理,而得到目標之蔗糖苯甲酸酯。 The target sucrose benzoate was obtained by treating in the same manner as in Example 4 except that the chlorinated benzamidine (1) was used as the substituted benzamidine chloride (1) and the number of times of washing was 8 times.

比較例3 Comparative example 3

<蔗糖苯甲酸酯(六取代體以下之比例:9.6%)> <Sucrose benzoate (proportion of hexa-substituent: 9.6%)>

除以水洗次數3次操作以外與比較例2同樣處理,而得到目標之蔗糖苯甲酸酯。 The same treatment as in Comparative Example 2 was carried out except that the number of times of washing was three times, and the intended sucrose benzoate was obtained.

比較例4 Comparative example 4

<蔗糖苯甲酸酯(六取代體以下之比例:6.0%)> <Sucrose benzoate (proportion of hexa-substituent: 6.0%)>

除使用氯化苯甲醯(1)111.0份及48%苛性鈉水溶液71.8份,並不進行水洗以外與實施例1同樣處理,而得到目標之蔗糖苯甲酸酯。 The target sucrose benzoate was obtained by the same treatment as in Example 1 except that 111.0 parts of benzamidine chloride (1) and 71.8 parts of a 48% aqueous solution of caustic soda were used without washing with water.

2.評估 2. Evaluation

<色相> <hue>

之後對上述實施例及比較例中所得之各酯25g,依照JIS K2421中記載之方法,判定其色相。亦即,先將各樣品以甲苯稀釋為50%,該稀釋液之色相,係記錄在以目視比較時,判斷 為相同之APHA標準液的數值(哈生著色數:APHA)。 Then, 25 g of each ester obtained in the above examples and comparative examples was judged to have a hue according to the method described in JIS K2421. That is, each sample is first diluted to 50% with toluene, and the hue of the diluted solution is recorded when visually compared. It is the value of the same APHA standard solution (Harbin coloring number: APHA).

<色相安定性> <hue stability>

在試管中,加入上述實施例及比較例中所得之各酯5g,並於110℃之油浴中加熱12小時。再對如此得到之各樣品,以與上述<色相>項中所記載之相同方法,判定其色相。 5 g of each ester obtained in the above Examples and Comparative Examples was placed in a test tube, and heated in an oil bath at 110 ° C for 12 hours. Further, each of the samples thus obtained was judged to have a hue in the same manner as described in the above-mentioned <hue>.

其結果如表1及表2所示。 The results are shown in Tables 1 and 2.

如表1中之記載,本發明之實施例1至4中,製品不只色相均為APHA30以下而優良,在之後在110℃下加熱12小時之後,亦未觀察到色相(APHA)方面之變化,顯示為高熱安定性。相對於此,如上述表2中之記載,在比較例1至4中,加熱前後,可觀察到色相之變化大,且其程度,在鹵素含量越高時,可觀察到變化有越大之傾向。 As shown in Table 1, in Examples 1 to 4 of the present invention, the product was excellent in not only the color hue of APHA 30 or less, but also after the heating at 110 ° C for 12 hours, no change in the hue (APHA) was observed. Shown as high heat stability. On the other hand, as described in the above Table 2, in Comparative Examples 1 to 4, the change in hue was observed to be large before and after heating, and the degree was changed as the halogen content was higher. tendency.

(B)蔗糖芳香族單羧酸酯(Ⅱ-2) (B) sucrose aromatic monocarboxylate (II-2)

1.合成 Synthetic

實施例5 Example 5

<蔗糖苯甲酸酯(五取代體以下之比例:0.2%)> <Sucrose benzoate (ratio of pentasubstituted body: 0.2%)>

先在具備攪拌棒、溫度計、冷凝器、滴液漏斗、連接pH計之pH電極的1L五口三角瓶中加入蔗糖34.2份及水70份並使其溶解後,再以水浴冷卻至10℃以下並同時徐徐加入含氯化 苯甲醯(1)106.7份之環己酮100份。之後,再保持於20℃以下之溫度,並同時將48%苛性鈉水溶液69.0份以滴液漏斗而以保持pH於10至11之速度加入。之後移去水浴並在20至30℃之室溫下繼續攪拌1小時熟成而完成反應後,再加入少量之碳酸鈉並將其加熱,使餘存微量之氯化苯甲醯轉換為苯甲酸鈉。其後,再靜置約30分鐘,使水相分離,並將其去除。 First, add 34.2 parts of sucrose and 70 parts of water to a 1 L five-necked triangular flask equipped with a stir bar, a thermometer, a condenser, a dropping funnel, and a pH electrode connected to a pH meter, and then dissolve it in water, and then cool to 10 ° C or less in a water bath. And slowly add chlorination Benzoquinone (1) 106.7 parts of cyclohexanone 100 parts. Thereafter, it was kept at a temperature of 20 ° C or lower, and at the same time, 69.0 parts of a 48% aqueous sodium hydroxide solution was added as a dropping funnel at a rate to maintain the pH at 10 to 11. Thereafter, the water bath was removed and stirring was continued for 1 hour at room temperature of 20 to 30 ° C to complete the reaction, and then a small amount of sodium carbonate was added and heated to convert the remaining trace amount of benzamidine chloride to sodium benzoate. Thereafter, it was allowed to stand for another 30 minutes to separate the aqueous phase and remove it.

之後再另外加入水70份,並以熱水浴昇溫至40至50℃,經過攪拌30分鐘後,靜置約30分鐘,使水相分離,再將其去除。在相同操作重複7次後(合計水洗次數:8次),再昇溫至120℃,並於減壓下蒸發去除溶劑,而得到目標之蔗糖苯甲酸酯。 Thereafter, 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, the mixture was allowed to stand for about 30 minutes to separate the aqueous phase and then removed. After the same operation was repeated 7 times (total number of washings: 8 times), the temperature was further raised to 120 ° C, and the solvent was evaporated under reduced pressure to obtain the desired sucrose benzoate.

之後再測定其平均取代率、各取代體之比例及五取代體以下之比例、以及鹵素之含量(以下之實施例及比較例之目的物亦相同)。 Thereafter, the average substitution ratio, the ratio of each substituent, the ratio of the pentasubstituted body or less, and the halogen content were measured (the same applies to the following examples and comparative examples).

實施例6 Example 6

<蔗糖苯甲酸酯(五取代體以下之比例:0.0%)> <Sucrose benzoate (proportion below pentasubstituted: 0.0%)>

除以氯化苯甲醯(1)113.8份及48%苛性鈉水溶液73.6份,並以水洗次數5次操作以外與實施例5同樣處理,而得到目標之蔗糖苯甲酸酯。 The target sucrose benzoate was obtained by the same treatment as in Example 5 except that 113.8 parts of benzamidine chloride (1) and 73.6 parts of a 48% aqueous solution of caustic soda were used, and the number of times of washing was 5 times.

比較例5 Comparative Example 5

<蔗糖苯甲酸酯(五取代體以下之比例:0.0%)> <Sucrose benzoate (proportion below pentasubstituted: 0.0%)>

除以水洗次數1次操作以外與實施例6同樣處理,而得到目標之蔗糖苯甲酸酯。 The same treatment as in Example 6 was carried out except that the number of times of washing was one operation, and the intended sucrose benzoate was obtained.

之後再對實施例5至6及比較例1至3、5,各測 定其平均取代率、各取代體之比例及五取代體以下之比例、以及鹵素之含量。 Then, for each of Examples 5 to 6 and Comparative Examples 1 to 3, 5, each test The average substitution ratio, the ratio of each substituent, the ratio below the pentasubstituted, and the halogen content are determined.

2.評估 2. Evaluation

<色相> <hue>

之後對上述實施例及比較例中所得之各酯25g,依照JIS K2421中記載之方法,判定其色相。亦即,先將各樣品以甲苯稀釋為50%,該稀釋液之色相,係記錄在以目視比較時,判斷為相同之APHA標準液的數值(哈生著色數:APHA)。 Then, 25 g of each ester obtained in the above examples and comparative examples was judged to have a hue according to the method described in JIS K2421. That is, each sample was first diluted to 50% with toluene, and the hue of the diluted solution was recorded as the value of the APHA standard solution (Harbin coloring number: APHA) which was judged to be the same when visually compared.

<色相安定性> <hue stability>

在試管中,加入上述實施例及比較例中所得之各酯5g,並於160℃之油浴中加熱3小時。再對如此得到之各樣品,以與上述<色相>項中所記載之相同方法,判定其色相。 5 g of each ester obtained in the above Examples and Comparative Examples was placed in a test tube, and heated in an oil bath at 160 ° C for 3 hours. Further, each of the samples thus obtained was judged to have a hue in the same manner as described in the above-mentioned <hue>.

其結果如表3所示。 The results are shown in Table 3.

如表3中之記載,本發明之實施例5及6中,製品不只色相均為APHA10以下而優良,且在之後在160℃下加熱3小時之後,亦未觀察到色相(APHA)之變化,顯示為高熱安定性。相對於此,在比較例1至3及5中,加熱前後,可觀察到色相之變化大,且其程度,在鹵素含量越高時,可觀察到變化有越大之傾向。 As shown in Table 3, in Examples 5 and 6 of the present invention, the product was excellent not only in the hue of APHA 10 or less, but also after the heating at 160 ° C for 3 hours, and no change in the hue (APHA) was observed. Shown as high heat stability. On the other hand, in Comparative Examples 1 to 3 and 5, the change in hue was observed to be large before and after heating, and the degree of change was observed to be higher as the halogen content was higher.

(C)蔗糖芳香族單羧酸酯(Ⅲ) (C) sucrose aromatic monocarboxylate (III)

1.粗蔗糖苯甲酸酯之合成 1. Synthesis of crude sucrose benzoate

製造例1(粗蔗糖苯甲酸酯(1)(平均酯化度:5.5)) Production Example 1 (crude sucrose benzoate (1) (average degree of esterification: 5.5))

先在具備攪拌棒、溫度計、冷凝器、滴液漏斗、連接pH計之pH電極的1L五口三角瓶中加入蔗糖30.0份及水70.0份並使其溶解後,再以水浴冷卻至10℃以下並同時徐徐加入含氯化苯甲醯(1)67.7份之環己酮100份。之後,再保持於20℃以下之溫度,並同時將48%苛性鈉水溶液42.9份以滴液漏斗而以保持pH於10至11之速度加入。之後移去水浴並在20至30℃之室溫下繼續攪拌1小時熟成而完成反應後,再加入少量之碳酸鈉並將其加熱,使餘存微量之氯化苯甲醯轉換為苯甲酸鈉。其後,再靜置約30分鐘,使水相分離,並將其去除。 First, add 30.0 parts of sucrose and 70.0 parts of water to a 1 L five-necked triangular flask equipped with a stir bar, a thermometer, a condenser, a dropping funnel, and a pH electrode connected to a pH meter, and then dissolve it in a water bath to below 10 ° C. At the same time, 100 parts of cyclohexanone containing 67.7 parts of benzamidine chloride (1) was slowly added. Thereafter, the temperature was kept at 20 ° C or lower, and at the same time, 42.9 parts of a 48% aqueous sodium caustic solution was added as a dropping funnel at a rate to maintain the pH at 10 to 11. Thereafter, the water bath was removed and stirring was continued for 1 hour at room temperature of 20 to 30 ° C to complete the reaction, and then a small amount of sodium carbonate was added and heated to convert the remaining trace amount of benzamidine chloride to sodium benzoate. Thereafter, it was allowed to stand for another 30 minutes to separate the aqueous phase and remove it.

另外再加入水100份,並以熱水浴昇溫至40至50℃,經過攪拌30分鐘後,再靜置約30分鐘,使水相分離,再將其去除。之後於減壓下蒸發去除溶劑,而得到目標化合物(粗SB(1))。 Further, 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, the mixture was allowed to stand for another 30 minutes to separate the aqueous phase and then removed. Thereafter, the solvent was evaporated under reduced pressure to give the title compound (crude SB (1)).

製造例2(粗蔗糖苯甲酸酯(2)(平均酯化度:4.9)) Production Example 2 (crude sucrose benzoate (2) (average degree of esterification: 4.9))

除使用蔗糖50.0份及氯化苯甲醯(1)60.3份以外與製造例1同樣處理,而得到目標化合物(粗SB(2))。 The 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 chloride (1) were used.

製造例3(粗蔗糖苯甲酸酯(3)(平均酯化度:4.5)) Production Example 3 (crude sucrose benzoate (3) (average degree of esterification: 4.5))

除使用蔗糖30.0份及氯化苯甲醯(1)55.4份以外與製造例1同樣處理,而得到目標化合物(粗SB(3))。 The 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 benzyl sulfonium chloride (1) were used.

製造例4(粗蔗糖苯甲酸酯(4)(平均酯化度:5.7)) Production Example 4 (crude sucrose benzoate (4) (average degree of esterification: 5.7))

除使用蔗糖30.0份及氯化苯甲醯(1)70.2份以外與製造例1同樣處理,而得到目標化合物(粗SB(4))。 The 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 chloride (1) were used.

製造例5(粗蔗糖苯甲酸酯(5)(平均酯化度:4.8)) Production Example 5 (crude sucrose benzoate (5) (average degree of esterification: 4.8))

除使用蔗糖30.0份及氯化苯甲醯(1)59.1份以外與製造例1同樣處理,而得到目標化合物(粗SB(5))。 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.精製步驟(呋喃甲醛及HMF之去除) 2. Refining step (removal of furaldehyde and HMF)

實施例7 Example 7

先將上述中所得之粗SB(1)溶解於甲苯中,調配成50重量%之粗蔗糖苯甲酸酯(粗SB)的甲苯溶液。之後將該溶液,以鋼管式濃縮型急速蒸發器,將50重量%之粗SB甲苯溶液在流量1.5L/h、機內含該溶液之液膜厚度10cm、機內壓力13KPa.abs及加熱面溫度130℃之條件下,進行乾燥,而得到蔗糖苯甲酸酯(1)(SB(1))。之後對SB(1),對其呋喃甲醛量(ppm)、HMF量(ppm)、甲苯量(ppm)及平均酯化度,各進行測定。 The crude SB (1) obtained above was dissolved in toluene to prepare a toluene solution of 50% by weight of crude sucrose benzoate (crude SB). Then, the solution was a steel tube type concentrated type rapid evaporator, 50% by weight of crude SB toluene solution at a flow rate of 1.5 L / h, the liquid film thickness of the solution containing the solution is 10 cm, the internal pressure of 13 KPa. The abs and the heating surface temperature were dried at 130 ° C to obtain sucrose benzoate (1) (SB (1)). Then, for SB (1), the amount of furaldehyde (ppm), the amount of HMF (ppm), the amount of toluene (ppm), and the average degree of esterification were measured.

實施例8至14 Examples 8 to 14

除對應原料化合物,依照表4所記載之條件以外,與實施例7同樣處理,而得到蔗糖苯甲酸酯(2)至(8)(SB(2)至SB(8))。再對各物種,測定其雜質之量及酯化度。 The sucrose benzoate (2) to (8) (SB(2) to SB(8)) were 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 for each species.

比較例6 Comparative Example 6

除對應原料化合物,依照表4所記載之條件以外,與實施例7同樣處理,而得到蔗糖苯甲酸酯(I)(SB(I))。再測定其雜質之量及酯化度。 The sucrose benzoate (I) (SB(I)) was obtained in the same manner as in Example 7 except that the corresponding starting compound was obtained according to the conditions described in Table 4. The amount of impurities and the degree of esterification were measured.

其結果如表4所示。 The results are shown in Table 4.

3.接著劑組成物之製造 3. Manufacture of adhesive composition

使用上述中所得之各SB作為增量劑,調製各接著劑組成物。亦即,相對於含少量安定劑(SO2及氫醌)之2-氰基丙烯酸乙酯100份,各添加SB30份並將其溶解,而各得到接著劑組成物(1)至(8)及接著劑組成物(I)。 Each of the SB compositions obtained above was used as an extender to prepare each of the adhesive compositions. That is, 30 parts of SB is added and dissolved in 100 parts of ethyl 2-cyanoacrylate containing a small amount of stabilizer (SO 2 and hydroquinone), and each of the adhesive compositions (1) to (8) is obtained. And an adhesive composition (I).

4.接著劑之性能評估 4. Performance evaluation of the adhesive

(促進試驗) (promoting the test)

將各接著劑組成物,填充於容量20mL之聚乙烯製容器並將其密封,再於70℃下保持5日。在表4中,「常態」所示為促進試驗實施前之狀態,「試驗後」所示為促進試驗實施後之狀態。 Each of the adhesive compositions was filled in a polyethylene container having a capacity of 20 mL, sealed, and kept at 70 ° C for 5 days. In Table 4, "normal" indicates the state before the test is carried out, and "after the test" indicates the state after the test is promoted.

(硬化時間) (hardening time)

硬化時間,係以25mm×100mm×1.6mm之冷輾鋼板,依照JIS K-6861測定。 The hardening time was measured by a cold-rolled steel sheet of 25 mm × 100 mm × 1.6 mm in accordance with JIS K-6861.

(抗拉剝離強度) (tensile peel strength)

抗拉剝離強度,係以經過磨光、脫脂之25mm×100mm× 1.6mm冷輾鋼板,以接觸面積12.5mm×25mm重疊,經過24小時硬化後再以抗拉試驗機測定。 Tensile peel strength is 25mm × 100mm after polishing and degreasing × 1.6mm cold-twisted steel plate, with a contact area of 12.5mm × 25mm overlap, after 24 hours hardening and then measured by a tensile tester.

(臭氣) (odor)

臭氣,係以未添加蔗糖苯甲酸酯時為基材(C),並依照以下基準判定。 The odor was determined as the base material (C) when sucrose benzoate was not added, and was determined according to the following criteria.

A:臭氣之減少顯著時 A: When the reduction of odor is significant

B:可確定臭氣減少時 B: When the odor is reduced

C:未添加蔗糖苯甲酸酯時 C: When sucrose benzoate is not added

D:相反地臭氣增強時 D: Conversely, when the odor is enhanced

其結果如表4所示。 The results are shown in Table 4.

如上所述,在使用本發明之蔗糖芳香族單羧酸酯(Ⅲ)為增量劑時,對硬化時間及抗拉剝離強度幾乎無影響,而可發揮顯著地減少臭氣的優異效果。 As described above, when the sucrose aromatic monocarboxylic acid ester (III) of the present invention is used as an extender, the hardening time and the tensile peel strength are hardly affected, and an excellent effect of remarkably reducing odor can be exhibited.

產業上利用之可能性 Industrial use possibility

本發明之蔗糖芳香族單羧酸酯(Ⅱ),同時併具與非結晶性樹脂及結晶性樹脂的相溶性優異,而可使其成形加工性、物性、柔軟性、耐衝擊性等改善,另一方面,又可抑制加熱之著色的優異特點,因此可使用在樹脂,特別是要求光學透明性之樹脂上,作為改質劑。 The sucrose aromatic monocarboxylic acid ester (II) of the present invention has excellent compatibility with a non-crystalline resin and a crystalline resin, and can improve moldability, physical properties, flexibility, impact resistance, and the like. On the other hand, since the excellent characteristics of the color of heating can be suppressed, it can be used as a modifier in a resin, particularly a resin requiring optical transparency.

本發明之蔗糖芳香族單羧酸酯(Ⅲ),可作為2-氰基丙烯酸酯系接著劑之增量劑,而併具不使其接著性能減低而可使臭氣改善之優異特點,因此可作為該接著劑之臭氣改善/增量劑使用。 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 an excellent characteristic that the odor can be improved without lowering the subsequent performance. It can be used as an odor improving/extending agent for the adhesive.

Claims (19)

一種蔗糖芳香族單羧酸酯,為蔗糖與通式(I)所示之芳香族單羧酸之酯,其鹵素含量為100ppm以下 (式中,R1至R5各自獨立為選自氫原子、烷基及烷氧基之基)。 A sucrose aromatic monocarboxylic acid ester which is an ester of sucrose and an aromatic monocarboxylic acid represented by the formula (I), and has a halogen content of 100 ppm or less. (wherein R 1 to R 5 are each independently a group selected from a hydrogen atom, an alkyl group, and an alkoxy group). 如申請專利範圍第1項所述之蔗糖芳香族單羧酸酯,其中,該蔗糖芳香族單羧酸酯的六取代體以下的取代體之含量為5重量%以上。 The sucrose aromatic monocarboxylic acid ester according to claim 1, wherein the sucrose aromatic monocarboxylic acid ester has a content of a hexa-substituted or lower substituent of 5% by weight or more. 如申請專利範圍第1或2項所述之蔗糖芳香族單羧酸酯,其中,該蔗糖芳香族單羧酸酯的平均取代率為5.0以上。 The sucrose aromatic monocarboxylic acid ester according to claim 1 or 2, wherein the sucrose aromatic monocarboxylic acid ester has an average substitution ratio of 5.0 or more. 如申請專利範圍第1至3項之任一項所述之蔗糖芳香族單羧酸酯,其中,該蔗糖芳香族單羧酸酯在50%甲苯溶液中的色相為APHA 30以下。 The sucrose aromatic monocarboxylic acid ester according to any one of claims 1 to 3, wherein the sucrose aromatic monocarboxylic acid ester has a hue of at least APHA 30 in a 50% toluene solution. 如申請專利範圍第1至4之任一項所述之蔗糖芳香族單羧酸酯,其中,該蔗糖芳香族單羧酸酯在110℃、12小時加熱後在50%甲苯溶液中的色相為APHA 30以下。 The sucrose aromatic monocarboxylic acid ester according to any one of claims 1 to 4, wherein the hue of the sucrose aromatic monocarboxylic acid ester in a 50% toluene solution after heating at 110 ° C for 12 hours is Below APHA 30. 一種樹脂改質劑,由包含如前述申請專利範圍第1至5項任一項所述之蔗糖芳香族單羧酸酯所構成。 A resin modifier comprising the sucrose aromatic monocarboxylic acid ester according to any one of the preceding claims. 一種蔗糖芳香族單羧酸酯之製造方法,其為抑制著色之蔗糖芳香族單羧酸酯的製造方法,由包含使鹵素的含量為100ppm以下之步驟所構成。 A method for producing a sucrose aromatic monocarboxylic acid ester, which is a method for producing a sucrose aromatic monocarboxylic acid ester which inhibits coloration, and comprises a step of containing a halogen content of 100 ppm or less. 如申請專利範圍第1項所述之蔗糖芳香族單羧酸酯,其中,該蔗糖芳香族單羧酸酯的五取代體以下之取代體的含量為2.0重量%以下。 The sucrose aromatic monocarboxylic acid ester of the sucrose aromatic monocarboxylic acid ester, wherein the sucrose aromatic monocarboxylic acid ester has a content of a substituent of less than 2.0% by weight. 如申請專利範圍第8項所述之蔗糖芳香族單羧酸酯,其中,該蔗糖芳香族單羧酸酯的平均取代率為7.0以上。 The sucrose aromatic monocarboxylic acid ester according to claim 8, wherein the sucrose aromatic monocarboxylic acid ester has an average substitution ratio of 7.0 or more. 如申請專利範圍第8或9項所述之蔗糖芳香族單羧酸酯,其中,該蔗糖芳香族單羧酸酯在50%甲苯溶液中之色相為APHA10以下。 The sucrose aromatic monocarboxylic acid ester according to claim 8 or 9, wherein the sucrose aromatic monocarboxylic acid ester has a hue of less than or equal to APHA 10 in a 50% toluene solution. 如申請專利範圍第8至11項任一項所述之蔗糖芳香族單羧酸酯,其中,該蔗糖芳香族單羧酸酯在160℃、3小時加熱後在50%甲苯溶液中之色相為APHA30以下。 The sucrose aromatic monocarboxylic acid ester according to any one of claims 8 to 11, wherein the hue of the sucrose aromatic monocarboxylic acid ester in a 50% toluene solution after heating at 160 ° C for 3 hours is Below APHA30. 一種樹脂改質劑,由包含如申請專利範圍第8至11項任一項所述之蔗糖芳香族單羧酸酯所構成。 A resin modifier comprising the sucrose aromatic monocarboxylic acid ester according to any one of claims 8 to 11. 一種蔗糖芳香族單羧酸酯,其為蔗糖與通式(I)所示之芳香族單羧酸之酯,其呋喃甲醛之含量為50ppm以下,且羥甲基呋喃甲醛之含量為500ppm以下【化5】 (式中,R1至R5各自獨立為選自氫原子、烷基及烷氧基之基)。 A sucrose aromatic monocarboxylic acid ester which is an ester of sucrose and an aromatic monocarboxylic acid represented by the formula (I), wherein the content of furaldehyde is 50 ppm or less, and the content of hydroxymethylfurfural is 500 ppm or less. 5 (wherein R 1 to R 5 are each independently a group selected from a hydrogen atom, an alkyl group, and an alkoxy group). 如申請專利範圍第13項所述之蔗糖芳香族單羧酸酯,其中,該蔗糖芳香族單羧酸酯的平均酯化度為6.0以下。 The sucrose aromatic monocarboxylic acid ester according to claim 13, wherein the sucrose aromatic monocarboxylic acid ester has an average degree of esterification of 6.0 or less. 一種2-氰基丙烯酸酯系接著劑,由包含如申請專利範圍第13或14項所述之蔗糖芳香族單羧酸酯為臭氣改善增量劑所構成。 A 2-cyanoacrylate-based adhesive comprising the sucrose aromatic monocarboxylic acid ester as described in claim 13 or 14 as an odor improving extender. 一種蔗糖芳香族單羧酸酯之製造方法,其為呋喃甲醛含量50ppm以下且羥甲基呋喃甲醛含量500ppm以下之蔗糖芳香族單羧酸酯之製造方法,該蔗糖芳香族單羧酸酯為蔗糖與通式(I)所示之芳香族單羧酸之酯 (式中,R1至R5各自獨立為選自氫原子、烷基及烷氧基之基),該蔗糖芳香族單羧酸酯之製造方法包含使該蔗糖芳香族單 羧酸酯的有機溶劑溶液,以厚度10cm以下的液膜之狀態,與加熱面接觸、乾燥。 A method for producing a sucrose aromatic monocarboxylic acid ester, which is a method for producing a sucrose aromatic monocarboxylic acid ester having a furaldehyde content of 50 ppm or less and a hydroxymethylfurfural content of 500 ppm or less, wherein the sucrose aromatic monocarboxylic acid ester is sucrose Ester with aromatic monocarboxylic acid represented by 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), and the method for producing the sucrose aromatic monocarboxylic acid ester comprises an organic compound of the sucrose aromatic monocarboxylic acid ester The solvent solution is brought into contact with the heating surface in a state of a liquid film having a thickness of 10 cm or less, and dried. 如申請專利範圍第16項所述之蔗糖芳香族單羧酸酯之製造方法,其中,前述乾燥為減壓乾燥。 The method for producing a sucrose aromatic monocarboxylic acid ester according to claim 16, wherein the drying is dried under reduced pressure. 如申請專利範圍第17項所述之蔗糖芳香族單羧酸酯之製造方法,其中,前述之減壓乾燥為在壓力0.01~15KPa.abs、加熱溫度90~300℃之條件下實施。 The method for producing a sucrose aromatic monocarboxylic acid ester according to claim 17, wherein the drying under reduced pressure is at a pressure of 0.01 to 15 KPa. Abs, heating temperature of 90 ~ 300 ° C conditions. 如申請專利範圍第17或18項所述之蔗糖芳香族單羧酸酯之製造方法,其中,前述之減壓乾燥為使用選自真空式滾筒乾燥機、真空式帶式乾燥機、薄膜蒸發器、急速蒸發器及真空式擠壓機之1種或2種以上之機械實施。 The method for producing a sucrose aromatic monocarboxylic acid ester according to claim 17 or 18, wherein the vacuum drying is performed using a vacuum drum dryer, a vacuum belt dryer, and a thin film evaporator. One or more types of mechanical implementations of a rapid evaporator and a vacuum extruder.
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