JPH06279734A - Production of hydrogenated rosin - Google Patents
Production of hydrogenated rosinInfo
- Publication number
- JPH06279734A JPH06279734A JP5068594A JP6859493A JPH06279734A JP H06279734 A JPH06279734 A JP H06279734A JP 5068594 A JP5068594 A JP 5068594A JP 6859493 A JP6859493 A JP 6859493A JP H06279734 A JPH06279734 A JP H06279734A
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- hydrogenation reaction
- hydrogenated rosin
- purification
- hydrogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は水素添加ロジンの製造
方法に関し、より詳細には、淡色であり、加熱安定性及
び耐候性に優れた水素添加ロジンの製造方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrogenated rosin, and more particularly to a method for producing a hydrogenated rosin which has a light color and is excellent in heating stability and weather resistance.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来よ
りロジンは、製紙用サイズ剤、ワニス、印刷インキ、合
成ゴム用乳化剤、ゴム又はプラスチック改質剤、粘接着
剤、バン創コウ等に使用されている。しかし、ロジンは
黄色ないし黄褐色に着色した外観を有し、加熱安定性及
び耐候性等が充分でない等の欠点を有している。BACKGROUND OF THE INVENTION Rosin has hitherto been used as a sizing agent for papermaking, a varnish, a printing ink, an emulsifier for synthetic rubber, a rubber or plastic modifier, a tacky adhesive, a bun-making agent, etc. It is used. However, rosin has a yellow or yellow-brown colored appearance, and has drawbacks such as insufficient heat stability and weather resistance.
【０００３】ロジンの欠点の一つである着色の原因とし
ては、 ロジンの主成分である樹脂酸として、共役二重結合を
有するアビエチン酸等の酸素吸収性が大きく、不安定な
樹脂酸が含まれていること、 ロジン中に高分子量物及び不ケン化物が含まれている
こと、 等が考えられている。One of the causes of coloration, which is one of the drawbacks of rosin, is a resin acid which is a main component of rosin and which includes an unstable resin acid such as abietic acid having a conjugated double bond, which has a large oxygen absorption property. It is considered that the rosin contains high molecular weight substances and unsaponifiable substances.
【０００４】そこで、上記着色の原因等に着目し、無色
かつ加熱安定性及び耐候性に優れたロジンを得るため
に、未精製ロジンを不均化する方法や未精製ロジンを不
均化して精製する方法等が提案されている。例えば、特
開昭63-186783号公報には原料としてロジン及び／又は
不均化ロジンを用い、それを精製して得られる精製物と
アルコールとをエステル化反応させ、更にこれを水素添
加反応させる方法が開示されている。また、特開昭64-8
5265号公報には原料として不均化ロジンを用い、これを
精製する工程と水素添加する工程を任意に行う方法が開
示されている。しかしながら、これらの方法により得ら
れるロジンは、従来のロジンに比べて外観、加熱安定性
及び耐候性に優れているけれども、なお一層の改良の余
地があり、更にこれらの方法には、製造面において、不
均化反応と水素添加反応の異種工程を用いるために別の
装置が必要である。又、水素添加反応を行うためには比
較的高い水素初圧が必要である等の欠点がある。Therefore, in order to obtain a rosin that is colorless and has excellent heat stability and weather resistance, paying attention to the cause of the above-mentioned coloring, a method of disproportionating the unpurified rosin or a method of disproportionating the unpurified rosin and purifying Methods for doing so have been proposed. For example, in JP-A-63-186783, a rosin and / or a disproportionated rosin is used as a raw material, a refined product obtained by purifying the rosin and an alcohol are subjected to an esterification reaction, and then this is subjected to a hydrogenation reaction. A method is disclosed. In addition, JP-A-64-8
Japanese Patent No. 5265 discloses a method in which a disproportionated rosin is used as a raw material, and a step of purifying this and a step of hydrogenating are optionally performed. However, the rosin obtained by these methods is superior in appearance, heating stability and weather resistance to conventional rosins, but there is still room for improvement. Separate equipment is required to use different steps of disproportionation reaction and hydrogenation reaction. In addition, there is a defect that a relatively high initial hydrogen pressure is required to carry out the hydrogenation reaction.
【０００５】この発明は上記のような問題点を鑑みてな
されたもので、淡色であり、加熱安定性及び耐候性に優
れ、更には製造面において複数の装置を必要とせず、低
い水素初圧で水素添加反応を行うことができるロジンの
製造方法を提供することを目的としている。The present invention has been made in view of the above problems, is light in color, has excellent heat stability and weather resistance, does not require a plurality of devices in terms of production, and has a low hydrogen initial pressure. It is an object of the present invention to provide a method for producing rosin, which can carry out the hydrogenation reaction with.
【０００６】[0006]
【課題を解決するための手段】この発明によれば、ロジ
ンを水素添加反応させて精製し、更にこれを水素添加反
応させることを特徴とする水素添加ロジンの製造方法が
提供される。この発明で原料として使用するロジンは、
ガムロジン、ウッドロジン、トール油ロジンの何れでも
よい。ロジンの主成分は、約90％が樹脂酸であり、その
他は不ケン化物等の中性成分である。樹脂酸のうち主成
分はアビエチン酸とその類縁体、例えばネオアビエチン
酸、ジヒドロアビエチン酸、テトラヒドロアビエチン
酸、ピマール酸、イソピマール酸等である。According to the present invention, there is provided a method for producing a hydrogenated rosin, which comprises subjecting a rosin to a hydrogenation reaction for purification, and further subjecting this to a hydrogenation reaction. The rosin used as a raw material in this invention is
Any of gum rosin, wood rosin and tall oil rosin may be used. About 90% of the main component of rosin is resin acid, and the other components are neutral components such as unsaponifiables. Among the resin acids, the main component is abietic acid and its analogs, such as neoabietic acid, dihydroabietic acid, tetrahydroabietic acid, pimaric acid, isopimaric acid.
【０００７】この発明の製造方法では、ロジンをまず水
素添加反応（第一次水素添加反応）させて、それから精
製し、更にその後水素添加反応（第二次水素添加反応）
させることが必須である。ロジンを水素添加する前に精
製すると、精製の際に生じるロジンの各種成分の分解物
が精製物中に混入するため、好ましくない。そこで、例
えば蒸留による精製前にロジンを水素添加して安定化す
れば、精製の際にロジンの各種成分が分解し、精製物中
に混入するのを防ぐことができる。In the production method of the present invention, rosin is first subjected to hydrogenation reaction (primary hydrogenation reaction), then purified, and then hydrogenation reaction (secondary hydrogenation reaction).
It is essential to let Purification before hydrogenation of rosin is not preferable because decomposition products of various components of rosin produced during purification are mixed in the purified product. Therefore, for example, by hydrogenating and stabilizing rosin before purification by distillation, various components of rosin can be prevented from decomposing during purification and being mixed in the purified product.
【０００８】この発明における水素添加反応は、公知の
方法で行うことができる。例えば水素添加触媒の存在
下、密閉容器中、水素ガス圧入下にて加熱することによ
って行うことができる。水素添加触媒としては、公知の
水素添加触媒の何れでも使用することができ、例えばパ
ラジウムカーボン、ロジウムカーボン、還元ニッケル、
ラネーニッケル、白金、酸化白金、ラネーコバルト等が
あげられ、パラジウムカーボンが一般的である。The hydrogenation reaction in the present invention can be carried out by a known method. For example, it can be carried out by heating under pressure of hydrogen gas in a closed container in the presence of a hydrogenation catalyst. As the hydrogenation catalyst, any known hydrogenation catalyst can be used, for example, palladium carbon, rhodium carbon, reduced nickel,
Raney nickel, platinum, platinum oxide, Raney cobalt and the like are mentioned, and palladium carbon is common.
【０００９】第一次水素添加反応において、加熱温度は
240〜280℃が適切であり、250〜260℃が好ましい。水素
添加触媒の使用量はロジンに対して0.05〜2.0重量％が
適切であり、0.1〜0.2重量％が好ましい。水素初圧は、
10〜50Kg/cm2が適切であり、20〜30Kg/cm2が好ましい。
また、反応時間は２〜８時間が適切であり、３〜５時間
が好ましい。In the primary hydrogenation reaction, the heating temperature is
240-280 ° C is suitable and 250-260 ° C is preferred. The amount of hydrogenation catalyst used is suitably 0.05 to 2.0% by weight, preferably 0.1 to 0.2% by weight, based on rosin. The initial hydrogen pressure is
10-50 Kg / cm 2 is suitable, 20-30 Kg / cm 2 is preferred.
The reaction time is appropriately 2 to 8 hours, preferably 3 to 5 hours.
【００１０】第二次水素添加反応においては、精製を介
在させることによって水素添加触媒を被毒する成分がほ
とんど除去されるため、第一次水素添加反応における反
応条件よりも、少ない触媒量、低い加熱温度及び水素初
圧でよい。従って、加熱温度は200〜260℃が適切であ
り、230〜250℃が好ましい。水素添加触媒の使用量はロ
ジンに対して0.01〜1.0重量％が適切であり、0.05〜0.2
重量％が好ましい。水素初圧は、10〜40Kg/cm2が適切で
あり、15〜30Kg/cm2が好ましい。また、反応時間は２〜
８時間が適切であり、３〜５時間が好ましい。In the secondary hydrogenation reaction, most of the components poisoning the hydrogenation catalyst are removed by interposing purification, so that the amount of catalyst is smaller and the amount is lower than that in the reaction conditions in the primary hydrogenation reaction. The heating temperature and the hydrogen initial pressure are sufficient. Therefore, the heating temperature is suitably 200 to 260 ° C, preferably 230 to 250 ° C. The amount of the hydrogenation catalyst used is appropriately 0.01 to 1.0% by weight with respect to rosin, 0.05 to 0.2
Weight percent is preferred. Hydrogen initial pressure is, 10~40Kg / cm 2 are suitable, 15~30Kg / cm 2 is preferred. The reaction time is 2 to
8 hours is suitable and 3-5 hours is preferred.
【００１１】次に、この発明の精製方法としては公知の
方法を用いることができる。例えば蒸留、再結晶、抽出
等があげられ、蒸留によって精製するのが好ましい。蒸
留により精製する場合には、例えば減圧蒸留、分子蒸
留、水蒸気蒸留等によって精製することができ、減圧蒸
留によって精製するのが好ましい。減圧蒸留により精製
する場合を例にとって説明すると、例えば公知の蒸留装
置を用いて窒素気流下で蒸留することができ、加熱温度
は200〜300℃が適切であり、圧力は１〜10mmHgの範囲か
ら蒸留時間等を考慮して適宜選択される。Next, a known method can be used as the purification method of the present invention. Examples thereof include distillation, recrystallization, extraction and the like, and purification by distillation is preferable. In the case of purification by distillation, it can be purified by, for example, vacuum distillation, molecular distillation, steam distillation, etc., and it is preferable to carry out purification by vacuum distillation. Explaining the case of purification by vacuum distillation as an example, for example, it can be distilled under a nitrogen stream using a known distillation apparatus, the heating temperature is appropriately 200 ~ 300 ° C., the pressure is from 1 to 10 mmHg range. It is appropriately selected in consideration of distillation time and the like.
【００１２】再結晶により精製する場合には、例えば水
素添加ロジンを良溶媒に溶解して飽和溶液をつくり、こ
れを冷却することによって再結晶させる方法や水素添加
ロジンを良溶媒に溶解し、ついで溶媒を留去して濃厚な
溶液とし、この溶液に貧溶媒を添加することによって再
結晶させる方法等を用いることができる。使用する良溶
媒としては、例えばベンゼン、トルエン、キシレン、ク
ロロホルム、低級アルコール、アセトン等のケトン類、
酢酸エチル等の酢酸低級アルキル類等があげられ、使用
する貧溶媒としては、例えばn-ヘキサン、n-ヘプタン、
シクロヘキサン、イソオクタン等があげられる。In the case of purification by recrystallization, for example, a hydrogenated rosin is dissolved in a good solvent to form a saturated solution and then cooled to recrystallize, or the hydrogenated rosin is dissolved in a good solvent, It is possible to use a method in which the solvent is distilled off to form a concentrated solution, and a poor solvent is added to this solution for recrystallization. Examples of the good solvent to be used include benzene, toluene, xylene, chloroform, lower alcohol, ketones such as acetone,
Examples include lower alkyl acetates such as ethyl acetate, and examples of the poor solvent used include n-hexane, n-heptane,
Examples include cyclohexane and isooctane.
【００１３】抽出により精製する場合には、例えば水素
添加ロジンにアルカリ水を加えて水素添加ロジンを溶解
し、アルカリ水に不溶性の不ケン化物等を有機溶媒によ
って抽出した後、水層を酸で中和することによって精製
することができる。In the case of purification by extraction, for example, alkaline water is added to hydrogenated rosin to dissolve the hydrogenated rosin, and unsaponifiable substances insoluble in alkaline water are extracted with an organic solvent, and then the aqueous layer is acidified. It can be purified by neutralization.
【００１４】[0014]
【作用】この発明によれば、ロジンを水素添加反応させ
て精製し、更にこれを水素添加反応させることによって
極めて淡色かつ安定な水素添加ロジンが得られる。この
発明の水素添加ロジンの製造方法においては、まずロジ
ンを水素添加（第一次水素添加反応）することにより、
ロジン中のすべての不飽和基及び酸化物が安定化され
る。即ち、まずロジンを水素添加することにより、ロジ
ンの成分中、不均化反応で安定化されるアビエチン酸系
樹脂酸（不均化して、アビエチン酸がデヒドロアビエチ
ン酸、ジヒドロアビエチン酸、テトラヒドロアビエチン
酸に変化して安定化する）はもとより不均化しないデキ
ストロピマル酸系樹脂酸やその他各種の構造不明の中性
体及びその酸化物又は過酸化物も水素添加され、不飽和
結合を有する成分の割合が減少し、安定化される。つま
り、水素添加反応することにより、不均化反応するより
もロジンはより安定化することになる。この第一次水素
添加反応により、ロジンの成分中、大部分のものが水素
添加され安定化する。According to the present invention, a very light-colored and stable hydrogenated rosin can be obtained by subjecting a rosin to a hydrogenation reaction for purification, and further subjecting this to a hydrogenation reaction. In the method for producing hydrogenated rosin of the present invention, first, by hydrogenating rosin (primary hydrogenation reaction),
All unsaturated groups and oxides in the rosin are stabilized. That is, first by hydrogenating rosin, in the components of rosin, abietic acid-based resin acid stabilized by disproportionation reaction (disproportionated, abietic acid is dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid The ratio of the components having unsaturated bonds, which are not disproportionated, but also dextropimaric acid resin acid and other various neutral substances of unknown structure and their oxides or peroxides are hydrogenated. Is reduced and stabilized. That is, the hydrogenation reaction stabilizes the rosin more than the disproportionation reaction. By this primary hydrogenation reaction, most of the components of rosin are hydrogenated and stabilized.
【００１５】次に、精製することにより、ロジン中に含
有する微量金属、重金属等の着色要因になるものが除去
され、更には、水素添加触媒を被毒する成分が除去され
る。この発明の製造方法では、ロジンをまず水素添加し
て安定化した後、精製することにより、精製によるロジ
ンの各種成分の分解が抑制され、精製物中への分解物の
混入が抑制される。Next, by refining, trace metals, heavy metals, etc. contained in rosin, which become coloring factors, are removed, and further components which poison the hydrogenation catalyst are removed. In the production method of the present invention, the rosin is first hydrogenated and stabilized, and then purified, whereby the decomposition of various components of the rosin due to the purification is suppressed, and the mixture of the decomposed products in the purified product is suppressed.
【００１６】更に、精製によって水素添加触媒を被毒す
る成分を除去した後、水素添加（第二次水素添加反応）
することにより、ロジン中のすべての不飽和基及び酸化
物が完全に水素添加され、安定化される。この発明の製
造法では水素添加反応を二回行うため、得られる水素添
加ロジンは不飽和結合を有するものの割合が非常に少な
いものとなる。Further, after removing components poisoning the hydrogenation catalyst by purification, hydrogenation (secondary hydrogenation reaction)
By doing so, all unsaturated groups and oxides in the rosin are completely hydrogenated and stabilized. Since the hydrogenation reaction is performed twice in the production method of the present invention, the ratio of the hydrogenated rosin obtained has an unsaturated bond is very small.
【００１７】従って、この発明の製造方法によって得ら
れる水素添加ロジンは、その外観が淡色（ほぼ無色に近
い色調、少なくともハーゼン50）であり、加熱安定性及
び耐候性に優れたものとなる。このようにして得られる
水素添加ロジンは、製紙用サイズ剤、ワニス、印刷イン
キ、合成ゴム用乳化剤、ゴム又はプラスチック改質剤、
粘接着剤、バン創コウ等として好適に使用され、これら
用途における最終製品の価値を向上することになる。ま
た、この発明の水素添加ロジンの製造方法では、水素添
加反応を二回行うため、同一装置を使用すればよく、か
つ水素添加反応の水素初圧も低くてよい等の利点があ
る。Therefore, the hydrogenated rosin obtained by the production method of the present invention has a light appearance (a color tone close to colorless, at least Hazen 50), and is excellent in heating stability and weather resistance. The hydrogenated rosin thus obtained is a papermaking size, varnish, printing ink, synthetic rubber emulsifier, rubber or plastic modifier,
It is preferably used as an adhesive, a bun-making cloth, etc., and improves the value of the final product in these applications. Further, in the method for producing a hydrogenated rosin of the present invention, since the hydrogenation reaction is carried out twice, there is an advantage that the same apparatus may be used and the initial hydrogen pressure of the hydrogenation reaction may be low.
【００１８】[0018]
【実施例】この発明の水素添加ロジンの製造方法及び得
られた水素添加ロジンの外観、加熱安定性及び耐候性を
実施例で説明する。 実施例１ 以下の第一次水素添加反応、精製、第二次水素添加反応
に付することによって水素添加ロジンを製造した。 (1) 第一次水素添加反応 酸価170、軟化点（JIS K 5902に規定する環球法により
測定）74℃、色調ガードナー６の未精製中国産ガムロジ
ン300gと触媒として５％パラジウムカーボン（含水率50
％）0.5gを１リットル容量の振とう式オートクレーブに
仕込み、系内の酸素を除去した後、系内を水素で30Kg/c
m2に加圧して250℃まで昇温し、同温度で４時間水素添
加反応を行い、酸価162、軟化点72℃、色調ガードナー
２の水素添加ロジン295gを得た。 (2) 精製（減圧蒸留） 第一次水素添加反応によって得られた水素添加ロジン29
0gを500ml蒸留フラスコに入れ、窒素気流下、3mmHgの減
圧下で表１に示す条件にて蒸留を行った。得られた初
留、主留及び後留における酸価及び収率（％）を求め、
蒸留条件とともに表１に示した。EXAMPLES The method for producing a hydrogenated rosin of the present invention and the appearance, heating stability and weather resistance of the obtained hydrogenated rosin will be described in Examples. Example 1 A hydrogenated rosin was produced by subjecting to the following primary hydrogenation reaction, purification, and secondary hydrogenation reaction. (1) Primary hydrogenation reaction Acid value 170, softening point (measured by ring and ball method stipulated in JIS K 5902) 74 ℃, color tone Gardner 6 unpurified Chinese gum rosin 300g and 5% palladium carbon (water content) 50
%) 0.5g was charged into a shaker autoclave with a capacity of 1 liter, oxygen in the system was removed, and then 30Kg / c of hydrogen was added to the system.
The pressure was raised to m 2 and the temperature was raised to 250 ° C., and the hydrogenation reaction was carried out at the same temperature for 4 hours to obtain 295 g of hydrogenated rosin having an acid value of 162, a softening point of 72 ° C. and a color tone Gardner 2. (2) Purification (vacuum distillation) Hydrogenated rosin 29 obtained by primary hydrogenation reaction
0 g was put in a 500 ml distillation flask and distilled under a nitrogen stream under a reduced pressure of 3 mmHg under the conditions shown in Table 1. The acid value and yield (%) in the obtained initial distillate, main distillate and post-distillate are calculated,
Table 1 shows the distillation conditions.
【００１９】[0019]
【表１】 得られた主留を次の第二次水素添加反応に付した。 (3) 第二次水素添加反応 前記精製工程で得られた主留中の水素添加ロジン200gと
５％パラジウムカーボン（含水率50％）0.1gを１リット
ル容量の振とう式オートクレーブに仕込み、系内の酸素
を除去した後、系内を水素で20Kg/cm2に加圧して250℃
まで昇温し、同温度で４時間水素添加反応を行い、酸価
175、軟化点85℃、色調ハーゼンカラー20の水素添加ロ
ジン195gを得た。[Table 1] The obtained main distillate was subjected to the following secondary hydrogenation reaction. (3) Secondary hydrogenation reaction 200 g of hydrogenated rosin in the main distillate obtained in the above-mentioned purification step and 0.1 g of 5% palladium carbon (water content 50%) were charged into a shaking autoclave having a volume of 1 liter, and a system was prepared. After removing oxygen in the system, pressurize the system with hydrogen to 20 Kg / cm 2 and 250 ℃.
Up to 4 hours, hydrogenation reaction at the same temperature for 4 hours, acid value
175 g of hydrogenated rosin having a softening point of 85 ° C. and a Hazen color of 20 was obtained.
【００２０】比較例１ 以下の不均化反応、精製、水素添加反応に付することに
よって水素添加ロジンを製造した。 (1) 不均化反応 酸価170、軟化点74℃、色調ガードナー６の未精製中国
産ガムロジン500gと触媒として５％パラジウムカーボン
（含水率50％）0.2gを１ｌフラスコに入れ、窒素気流
下、280℃で４時間攪拌して不均化反応を行い、酸価15
8、軟化点76.5℃、色調ガードナー８の不均化ロジン485
gを得た。 (2) 精製（減圧蒸留） 不均化反応によって得られた不均化ロジン450gを１ｌ蒸
留フラスコに入れ、窒素気流下、3mmHgの減圧下で実施
例１の(2)精製（減圧蒸留）と同じ条件にて蒸留を行っ
た。得られた初留、主留及び後留における酸価及び収率
（％）を求め、蒸留条件とともに表２に示した。Comparative Example 1 A hydrogenated rosin was produced by subjecting to the following disproportionation reaction, purification and hydrogenation reaction. (1) Disproportionation reaction Acid value 170, softening point 74 ° C, color tone Gardner 6 500g unpurified Chinese gum rosin and 0.2g of 5% palladium carbon (water content 50%) as a catalyst were put in a 1 liter flask, and under nitrogen flow. Stir at 280 ℃ for 4 hours to carry out disproportionation reaction.
8, softening point 76.5 ℃, color tone Gardner 8 disproportionated rosin 485
got g. (2) Purification (vacuum distillation) 450 g of disproportionated rosin obtained by the disproportionation reaction was placed in a 1 liter distillation flask, and (2) Purification (vacuum distillation) of Example 1 was performed under a reduced pressure of 3 mmHg under a nitrogen stream. Distillation was performed under the same conditions. The acid value and yield (%) in the obtained initial distillate, main distillate and post-distillate were determined and are shown in Table 2 together with the distillation conditions.
【００２１】[0021]
【表２】 得られた主留を次の水素添加反応に付した。 (3) 水素添加反応 前記精製工程で得られた主留中の不均化ロジン200gと５
％パラジウムカーボン（含水率50％）0.4gを１リットル
容量の振とう式オートクレーブに仕込み、系内の酸素を
除去した後、系内を水素で50Kg/cm2に加圧して 255℃ま
で昇温し、同温度で３時間水素添加反応を行い、酸価17
4.2 、軟化点84℃、色調ハーゼンカラー60の水素添加ロ
ジン195gを得た。[Table 2] The obtained main distillate was subjected to the following hydrogenation reaction. (3) Hydrogenation reaction 200 g of the disproportionated rosin in the main distillate obtained in the above purification step and 5
0.4 g of% palladium carbon (water content 50%) was charged into a shaking autoclave with a volume of 1 liter, oxygen in the system was removed, and then the system was pressurized to 50 kg / cm 2 with hydrogen and heated to 255 ° C. Then, the hydrogenation reaction is carried out at the same temperature for 3 hours to give an acid value of 17
4.2, 195 g of hydrogenated rosin having a softening point of 84 ° C. and a Hazen color of 60 was obtained.
【００２２】上記実施例１及び比較例１において得られ
た水素添加ロジンの外観、加熱安定性及び耐候性は以下
の方法で測定した。加熱安定性及び耐候性試験の結果を
表３に示した。The appearance, heating stability and weather resistance of the hydrogenated rosins obtained in Example 1 and Comparative Example 1 were measured by the following methods. The results of the heat stability and weather resistance tests are shown in Table 3.
【００２３】[0023]
【表３】 [Table 3]
【００２４】測定方法１（外観試験） ＡＳＴＭデジグネーションＤ1686-61及びＤ1544-58 Ｔ
に準ず。 測定方法２（加熱安定性試験） 内径1.5cm、高さ15cmの試験管に、実施例１及び比較例
１において得られた水素添加ロジン10gを入れ、蓋をし
ないで180℃の循風乾燥機に静置し、経時的色調（ガー
ドナー）の変化を観察した。 測定方法３（耐候性試験） 60〜100メッシュの粒度に揃えた実施例１及び比較例１
において得られた水素添加ロジン2.0gを内径5.8cm、高
さ１cmの軟膏缶に入れ、400Wの水銀灯を40cmの距離から
15時間照射したときの重量増加（酸素吸収量）を化学天
秤で測定した。また、照射０時間後及び24時間後の色調
（ガードナー）の変化を観察した。色調は50％トルエン
溶液での変化を観察した。Measurement Method 1 (Appearance Test) ASTM Designation D1686-61 and D1544-58 T
According to Measuring Method 2 (Heating Stability Test) 10 g of the hydrogenated rosin obtained in Example 1 and Comparative Example 1 was placed in a test tube having an inner diameter of 1.5 cm and a height of 15 cm, and a circulating air drier at 180 ° C. without a lid. The sample was allowed to stand still and the change in color tone (Gardner) with time was observed. Measurement method 3 (weather resistance test) Example 1 and comparative example 1 in which the particle size was 60 to 100 mesh
2.0g of hydrogenated rosin obtained in 1 was placed in an ointment can with an inner diameter of 5.8cm and a height of 1cm, and a 400W mercury lamp was used from a distance of 40cm.
The weight increase (oxygen absorption) after irradiation for 15 hours was measured by an analytical balance. In addition, changes in color tone (Gardner) after 0 hour and 24 hours after irradiation were observed. The color tone was observed to change with a 50% toluene solution.
【００２５】[0025]
【発明の効果】この発明によれば、ロジンを水素添加反
応させて精製し、更にこれを水素添加反応させることに
よって、外観が淡色（ほぼ無色に近い色調、少なくとも
ハーゼン50）であり、加熱安定性及び耐候性に優れた水
素添加ロジンを得ることができる。つまり、この発明の
水素添加ロジンの製造方法においては、水素添加反応を
二回行うため、ロジン中のすべての不飽和基及び酸化物
を完全に水素添加して安定化することができ、不飽和結
合を有するものの割合が非常に少ない水素添加ロジンを
得ることができる。従って、このようにして得られる水
素添加ロジンは、製紙用サイズ剤、ワニス、印刷イン
キ、合成ゴム用乳化剤、ゴム又はプラスチック改質剤、
粘接着剤、バン創コウ等として好適に使用することがで
き、これら用途における最終製品の価値を向上すること
ができる。また、この発明の水素添加ロジンの製造方法
では、水素添加反応を二回行うために同一装置の使用が
可能であり、複数の装置を必要とせず、かつ低い水素初
圧で水素添加反応を行うことができる。EFFECTS OF THE INVENTION According to the present invention, rosin is subjected to hydrogenation reaction to be purified, and further subjected to hydrogenation reaction to give a pale appearance (color tone close to colorless, at least Hazen 50) and heat stability. It is possible to obtain a hydrogenated rosin having excellent properties and weather resistance. That is, in the method for producing a hydrogenated rosin of the present invention, since the hydrogenation reaction is performed twice, it is possible to completely hydrogenate and stabilize all unsaturated groups and oxides in the rosin. A hydrogenated rosin having a very small proportion of bonds can be obtained. Therefore, the hydrogenated rosin thus obtained is a papermaking size, varnish, printing ink, synthetic rubber emulsifier, rubber or plastic modifier,
It can be suitably used as a tacky adhesive, a bun maker, etc., and can enhance the value of the final product in these applications. Further, in the method for producing hydrogenated rosin of the present invention, it is possible to use the same apparatus for performing the hydrogenation reaction twice, and it is possible to perform the hydrogenation reaction at a low initial hydrogen pressure without requiring a plurality of apparatuses. be able to.
Claims (1)
にこれを水素添加反応させることを特徴とする水素添加
ロジンの製造方法。1. A method for producing hydrogenated rosin, which comprises subjecting rosin to hydrogenation reaction for purification, and further subjecting this to hydrogenation reaction.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5068594A JP2790404B2 (en) | 1993-03-26 | 1993-03-26 | Method for producing hydrogenated rosin |
| CN94102152A CN1052500C (en) | 1993-03-26 | 1994-02-28 | Process for preparing hydrogenated rosin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5068594A JP2790404B2 (en) | 1993-03-26 | 1993-03-26 | Method for producing hydrogenated rosin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06279734A true JPH06279734A (en) | 1994-10-04 |
| JP2790404B2 JP2790404B2 (en) | 1998-08-27 |
Family
ID=13378279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5068594A Expired - Lifetime JP2790404B2 (en) | 1993-03-26 | 1993-03-26 | Method for producing hydrogenated rosin |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2790404B2 (en) |
| CN (1) | CN1052500C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259897A (en) * | 1995-03-22 | 1996-10-08 | Arakawa Chem Ind Co Ltd | Production of light-color rosin metal salt |
| JPH10219227A (en) * | 1997-01-31 | 1998-08-18 | Arakawa Chem Ind Co Ltd | Tack-imparting resin emulsion and aqueous tacky agent composition |
| JP2009527599A (en) * | 2006-02-22 | 2009-07-30 | フィドゥス インターナショナル インコーポレイティッド | Tackifier solution |
| KR20110109890A (en) * | 2010-03-30 | 2011-10-06 | 아라까와 가가꾸 고교 가부시끼가이샤 | Flux for solder and solder composition |
| JP2011202054A (en) * | 2010-03-26 | 2011-10-13 | Arakawa Chem Ind Co Ltd | Tackifier for styrenic block copolymer, tackifier resin, and adhesive composition containing styrenic block copolymer |
| CN103627324A (en) * | 2013-11-28 | 2014-03-12 | 广东科茂林产化工股份有限公司 | Preparation method of hydrogenated rosin without crystallization tendency |
| US11261277B2 (en) | 2017-09-25 | 2022-03-01 | Lg Chem, Ltd. | Method of preparing graft copolymer, graft copolymer, and thermoplastic resin molded article |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060200C (en) * | 1998-07-16 | 2001-01-03 | 中国科学院广州化学研究所 | Catalytic esterification method of rosin |
| CN1089353C (en) * | 1998-08-13 | 2002-08-21 | 广西壮族自治区苍梧县松脂厂 | Process for preparing hydrogenated rosin |
| CN1317347C (en) * | 2004-09-27 | 2007-05-23 | 广西大学 | Water-white hydrogenating rosin production |
| BR102014025671B1 (en) * | 2014-10-15 | 2022-07-12 | Socer Rb Indústria E Comércio Ltda. | PROCESS FOR OBTAINING HYDROGENATED RESIN GUM |
| CN109694653B (en) * | 2017-10-23 | 2021-04-02 | 湖南长岭石化科技开发有限公司 | Production method of highly hydrogenated rosin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145668A (en) * | 1988-11-28 | 1990-06-05 | Harima Chem Inc | Production of hydrogenated rosin |
| JPH03115480A (en) * | 1989-09-29 | 1991-05-16 | Arakawa Chem Ind Co Ltd | Manufacture of colorless glycidyl ester of rosin |
| JPH03277675A (en) * | 1990-03-27 | 1991-12-09 | Arakawa Chem Ind Co Ltd | Manufacture of colorless rosin compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1011512B (en) * | 1988-11-14 | 1991-02-06 | 金华市工业科学研究所 | Modifying process for rosin |
-
1993
- 1993-03-26 JP JP5068594A patent/JP2790404B2/en not_active Expired - Lifetime
-
1994
- 1994-02-28 CN CN94102152A patent/CN1052500C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145668A (en) * | 1988-11-28 | 1990-06-05 | Harima Chem Inc | Production of hydrogenated rosin |
| JPH03115480A (en) * | 1989-09-29 | 1991-05-16 | Arakawa Chem Ind Co Ltd | Manufacture of colorless glycidyl ester of rosin |
| JPH03277675A (en) * | 1990-03-27 | 1991-12-09 | Arakawa Chem Ind Co Ltd | Manufacture of colorless rosin compound |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259897A (en) * | 1995-03-22 | 1996-10-08 | Arakawa Chem Ind Co Ltd | Production of light-color rosin metal salt |
| JPH10219227A (en) * | 1997-01-31 | 1998-08-18 | Arakawa Chem Ind Co Ltd | Tack-imparting resin emulsion and aqueous tacky agent composition |
| JP2009527599A (en) * | 2006-02-22 | 2009-07-30 | フィドゥス インターナショナル インコーポレイティッド | Tackifier solution |
| JP2011202054A (en) * | 2010-03-26 | 2011-10-13 | Arakawa Chem Ind Co Ltd | Tackifier for styrenic block copolymer, tackifier resin, and adhesive composition containing styrenic block copolymer |
| KR20110109890A (en) * | 2010-03-30 | 2011-10-06 | 아라까와 가가꾸 고교 가부시끼가이샤 | Flux for solder and solder composition |
| JP2011224652A (en) * | 2010-03-30 | 2011-11-10 | Arakawa Chem Ind Co Ltd | Flux for solder and solder composition |
| CN103627324A (en) * | 2013-11-28 | 2014-03-12 | 广东科茂林产化工股份有限公司 | Preparation method of hydrogenated rosin without crystallization tendency |
| CN103627324B (en) * | 2013-11-28 | 2015-09-09 | 广东科茂林产化工股份有限公司 | A kind of preparation method of nodeless mesh trend staybelite |
| US11261277B2 (en) | 2017-09-25 | 2022-03-01 | Lg Chem, Ltd. | Method of preparing graft copolymer, graft copolymer, and thermoplastic resin molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2790404B2 (en) | 1998-08-27 |
| CN1093728A (en) | 1994-10-19 |
| CN1052500C (en) | 2000-05-17 |
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