JPH0711194A - Production of colorless rosin ester - Google Patents

Production of colorless rosin ester

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Publication number
JPH0711194A
JPH0711194A JP18004393A JP18004393A JPH0711194A JP H0711194 A JPH0711194 A JP H0711194A JP 18004393 A JP18004393 A JP 18004393A JP 18004393 A JP18004393 A JP 18004393A JP H0711194 A JPH0711194 A JP H0711194A
Authority
JP
Japan
Prior art keywords
rosin
rosin ester
dehydrogenation
color tone
reaction
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
Application number
JP18004393A
Other languages
Japanese (ja)
Other versions
JP3371985B2 (en
Inventor
Masao Maeda
正雄 前田
Koji Yamada
幸治 山田
Hiroshi Koba
寛 木場
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arakawa Chemical Industries Ltd
Original Assignee
Arakawa Chemical Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Arakawa Chemical Industries Ltd filed Critical Arakawa Chemical Industries Ltd
Priority to JP18004393A priority Critical patent/JP3371985B2/en
Publication of JPH0711194A publication Critical patent/JPH0711194A/en
Application granted granted Critical
Publication of JP3371985B2 publication Critical patent/JP3371985B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Abstract

PURPOSE:To produce a colorless rosin ester markedly improved in the properties such as color tone, odor and stability as compared with a conventional known rosin ester. CONSTITUTION:This process for producing a colorless rosin ester comprises esterifying purified hydrogenated rosin with an alcohol and hydrogenating the reactional product in the presence of a dehydrogenation catalyst. Another process for producing a colorless rosin ester wherein the esterification of the purified hydrogenerated rosin with an alcohol and the dehydrogenation of the reactional product in the presence of a dehydrogenation catalyst are performed simultaneously. Thus, rosin esters markedly improved in the properties such as color tone, odor and stability can be obtained.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、無色、無臭かつ安定性
の優れたロジンエステルの製造法に関する。
TECHNICAL FIELD The present invention relates to a method for producing a rosin ester which is colorless, odorless and excellent in stability.

【0002】[0002]

【従来の技術】従来よりロジンエステルは、粘接着剤用
のタッキファイヤー、ゴム類や各種プラスチック類の改
質剤、トラフィックッペイント用原材料、チューインガ
ム基材等の各種用途に使用されている。しかし、該ロジ
ンエステルは、その外観が黄色ないし黄褐色に着色して
おり、しかも臭気や加熱安定性、耐候性(以下、安定性
という)等の点で満足しうるものではなかった。
2. Description of the Related Art Rosin esters have hitherto been used in various applications such as tackifiers for adhesives, modifiers for rubbers and various plastics, raw materials for traffic paints, chewing gum base materials and the like. However, the rosin ester is colored yellow to yellowish brown in its appearance, and is not satisfactory in terms of odor, heat stability, weather resistance (hereinafter referred to as stability) and the like.

【0003】該ロジンエステルの上記欠点を解消するた
めに、出発原料として熱安定性に優れた不均化ロジンや
水添ロジンを使用することによりえられる不均化ロジン
エステルや水添ロジンエステルも市販されているが、い
ずれも色調、安定性等の点で不充分である。
In order to solve the above-mentioned drawbacks of the rosin ester, a disproportionated rosin ester or a hydrogenated rosin ester obtained by using a disproportionated rosin or a hydrogenated rosin having excellent thermal stability as a starting material is also used. Although they are commercially available, they are all insufficient in terms of color tone and stability.

【0004】特公昭45−33771号公報及び特公昭
49−20599号公報にはロジンまたはロジン系化合
物を特定の有機硫黄化合物により不均化する方法が記載
されているが、この方法によりえられた不均化ロジンも
色調、臭気、安定性の点で不充分である。
JP-B-45-33771 and JP-B-49-20599 describe a method of disproportionating a rosin or a rosin-based compound with a specific organic sulfur compound, which was obtained by this method. Disproportionated rosin is also insufficient in terms of color tone, odor and stability.

【0005】特開昭55−9605号公報には安定性に
優れたロジンエステルの製造法として、不均化ロジンを
精製することにより、原料ロジン中に含まれる高分子量
物及び不ケン化物等を除去した後、えられた精製不均化
ロジンとアルコールとをエステル化する方法が記載され
ている。しかし、この方法でえられたロジンエステルは
従来のロジンエステルに比べて淡色かつ安定であるもの
の、該エステル化工程において着色するとともに、加熱
着色に対する安定性も満足しうるものではなく尚改良の
余地がある。
As a method for producing a highly stable rosin ester, JP-A-55-9605 discloses a method of purifying disproportionated rosin to obtain high molecular weight substances and unsaponifiable substances contained in raw rosin. After removal, a method for esterifying the obtained purified disproportionated rosin with alcohol is described. However, although the rosin ester obtained by this method is lighter and more stable than the conventional rosin ester, it is colored in the esterification step and the stability against heat coloring is not satisfactory, and there is still room for improvement. There is.

【0006】更に、特開昭59−230072号公報に
は、淡色かつ安定性良好なロジンエステルの製造方法と
して、不均化能力と淡色化能力を併有する特定の有機硫
黄化合物の共存下に蒸留精製ロジンをアルコールでエス
テル化する方法が記載されているが、この方法によりえ
られたロジンエステルもいまだ色調、安定性の点で不満
足であり、しかも有機硫黄化合物に起因して加熱時の硫
黄臭が強いという問題がある。
Further, JP-A-59-230072 discloses a method for producing a rosin ester having a light color and good stability, which is distilled in the presence of a specific organic sulfur compound having both disproportionation ability and lightening ability. A method of esterifying purified rosin with alcohol has been described, but the rosin ester obtained by this method is still unsatisfactory in terms of color tone and stability, and the sulfur odor during heating due to the organic sulfur compound is still present. There is a problem that is strong.

【0007】このように、従来のいずれのロジンエステ
ルも色調、臭気、安定性のすべての性能を同時に満足し
うるものではなく、同用途で使用される水添石油樹脂に
比較して到底競合しうるものではなかった。
[0007] As described above, none of the conventional rosin esters can simultaneously satisfy all the performances of color tone, odor and stability, and they compete with each other in comparison with hydrogenated petroleum resins used for the same purpose. It wasn't profitable.

【0008】[0008]

【発明が解決しようとする課題】本発明者らは、上記の
如き実状に鑑み、従来公知のロジンエステルの色調、臭
気、安定性の諸性能を更に改良したロジンエステルを、
比較的廉価に提供しうる新規製造法を開発することを目
的として鋭意検討を行った。
In view of the above-mentioned circumstances, the present inventors have proposed a rosin ester which has been further improved in the color tone, odor and stability of the conventionally known rosin ester.
An intensive study was conducted for the purpose of developing a new manufacturing method that can be provided at a relatively low price.

【0009】[0009]

【課題を解決するための手段】上記課題に鑑みて、本発
明者らは出発原料たる原料ロジン種、精製操作、エステ
ル化及び脱水素化反応などの各種条件に着目することに
よって前記諸性能を改良すべく検討を行なった結果、特
定の原料ロジンを使用し、更にこれを精製し、ついで特
定の反応工程を経由せしめることにより、前記課題を解
決して、本目的に合致する優れた諸性能を有するロジン
エステルを収得しうる新規製造法を見い出した。
In view of the above-mentioned problems, the present inventors have focused on various conditions such as a starting material rosin species as a starting material, a refining operation, an esterification and a dehydrogenation reaction to achieve the above-mentioned various performances. As a result of studies to improve, by using a specific raw material rosin, further purifying it, and then passing it through a specific reaction step, the above-mentioned problems were solved, and various excellent performances meeting this objective were obtained. We have found a new process for obtaining a rosin ester having

【0010】すなわち本発明は、精製水素化ロジンを
(以下、ロジン(A)という)とアルコールをエステル
化反応させ、ついで脱水素化触媒存在下に脱水素化反応
させることを特徴とする無色ロジンエステルの製造法に
係る。更に本発明は、ロジン(A)とアルコールをエス
テル化するに際し、脱水素化触媒存在下に脱水素化反応
を同時進行させることを特徴とする無色ロジンエステル
の製造法に係る。
That is, the present invention is a colorless rosin characterized in that a purified hydrogenated rosin (hereinafter referred to as rosin (A)) is subjected to an esterification reaction with an alcohol, and then subjected to a dehydrogenation reaction in the presence of a dehydrogenation catalyst. It relates to a method for producing an ester. Further, the present invention relates to a method for producing a colorless rosin ester, which comprises simultaneously advancing a dehydrogenation reaction in the presence of a dehydrogenation catalyst when esterifying a rosin (A) and an alcohol.

【0011】本発明は、酸化防止剤、着色防止剤等の何
らの安定化剤を添加することなく、外観がほぼ無色であ
り、加熱時の臭気や安定性の点に優れたロジンエステル
を提供することのできる新規な製造法に関するものであ
り、該方法によってえられるロジンエステルは、従来の
ロジンエステルの諸性能から由来して形成された固定観
念を一掃するものであり、淡色樹脂として代表される水
添石油樹脂と比較して何らの遜色もないものである。し
かもロジン誘導体である特徴(即ち、各種ポリマ−との
幅広い相容性)を保持している。
The present invention provides a rosin ester which is almost colorless in appearance and has excellent odor and stability when heated without adding any stabilizer such as an antioxidant and a coloring inhibitor. The rosin ester obtained by the method is one that eliminates the stereotype formed from the various properties of conventional rosin esters, and is represented by a light-colored resin. Compared with hydrogenated petroleum resin, it is in no way inferior. Moreover, it retains the characteristic of being a rosin derivative (that is, having a wide compatibility with various polymers).

【0012】本発明においては、最終的に得られるロジ
ンエステルの色調、安定性などの点から、出発原料とし
て以下の特定ロジン化合物であるロジン(A)を必須使
用する。ロジン(A)とは、未精製水素化ロジンを精製
処理してなるものである。即ち、アビエチン酸、パラス
トリン酸、ネオアビエチン酸、ピマール酸、イソピマー
ル酸、デヒドロアビエチン酸等の樹脂酸を主成分とする
ガムロジン、ウッドロジン、トール油ロジンを部分的に
または完全に水素化反応したのち、これを更に精製して
得られるものをいう。
In the present invention, rosin (A) which is the following specific rosin compound is essentially used as a starting material from the viewpoints of color tone, stability and the like of the rosin ester finally obtained. The rosin (A) is obtained by purifying an unpurified hydrogenated rosin. That is, after a partial or complete hydrogenation reaction of gum rosin, wood rosin, or tall oil rosin containing abietic acid, parastophosphoric acid, neoabietic acid, pimaric acid, isopimaric acid, resin acid such as dehydroabietic acid as a main component, and wood oil rosin, It is obtained by further purifying this.

【0013】該水素化反応に際しては、公知の水素化反
応条件を適宜選択できる。即ち、水素化触媒の存在下に
通常10〜200Kg/cm2 、好ましくは50〜15
0Kg/cm2 の水素加圧下で、未精製ロジンを加熱す
ることにより行なう。水素化触媒としては、パラジウム
カーボン、ロジウムカーボン、白金カーボンなどの担持
触媒、ニッケル、白金等の金属粉末、ヨウ素、ヨウ化鉄
等のヨウ化物等の各種公知のものを例示しうる。該触媒
の使用量は、ロジンに対して通常0.01〜5重量%、
好ましくは0.01〜1.0重量%であり、反応温度は
100〜300℃、好ましくは150〜290℃であ
る。前記の精製とは水素化前のロジンや水素化後のロジ
ンに含まれていた過酸化物から生起したと考えられる高
分子量物、及び該ロジンにもともと含まれていた不ケン
化物を除去することを意味する。具体的には蒸留、再結
晶、抽出等の操作を行なえばよく、工業的には蒸留によ
る精製が好ましい。蒸留による場合は、通常は温度20
0〜300℃、圧力1〜10mmHgの範囲から蒸留時
間を考慮して適宜選択される。再結晶の場合は例えば未
精製水素化ロジンを良溶媒に溶解し、ついで溶媒を留去
して濃厚な溶液となし、この溶液に貧溶媒を添加するこ
とにより行なうことができる。良溶媒としてはベンゼ
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エステ
ル類等が挙げられ、貧溶媒としてはn−ヘキサン、n−
ヘプタン、シクロヘキサン、イソオクタン等が挙げられ
る。更には、未精製水素化ロジンをアルカリ水を用いて
アルカリ水溶液となし、不溶性の不ケン化物を有機溶媒
により抽出したのち水層を中和してもよく、これにより
ロジン(A)をうることもできる。
In the hydrogenation reaction, known hydrogenation reaction conditions can be appropriately selected. That is, it is usually 10 to 200 Kg / cm 2 , preferably 50 to 15 in the presence of a hydrogenation catalyst.
It is carried out by heating the crude rosin under a hydrogen pressure of 0 Kg / cm 2 . As the hydrogenation catalyst, various known catalysts such as supported catalysts such as palladium carbon, rhodium carbon and platinum carbon, metal powders such as nickel and platinum, iodide such as iodine and iron iodide can be exemplified. The amount of the catalyst used is usually 0.01 to 5% by weight based on rosin,
It is preferably 0.01 to 1.0% by weight, and the reaction temperature is 100 to 300 ° C, preferably 150 to 290 ° C. The above-mentioned purification is to remove a high molecular weight substance considered to be generated from a peroxide contained in a rosin before hydrogenation or a rosin after hydrogenation, and an unsaponifiable substance originally contained in the rosin. Means Specifically, operations such as distillation, recrystallization and extraction may be performed, and purification by distillation is industrially preferable. If distilled, a temperature of 20
It is appropriately selected from the range of 0 to 300 ° C. and the pressure of 1 to 10 mmHg in consideration of the distillation time. Recrystallization can be performed, for example, by dissolving crude hydrogenated rosin in a good solvent, distilling off the solvent to form a concentrated solution, and adding a poor solvent to this solution. Examples of good solvents include ketones such as benzene, toluene, xylene, chloroform, lower alcohols and acetone, and acetic acid esters such as ethyl acetate, and examples of poor solvents include n-hexane and n-hexane.
Heptane, cyclohexane, isooctane and the like can be mentioned. Furthermore, the crude hydrogenated rosin may be made into an alkaline aqueous solution using alkaline water, the insoluble unsaponifiable matter may be extracted with an organic solvent, and then the aqueous layer may be neutralized, thereby obtaining rosin (A). You can also

【0014】本発明では、ロジン(A)とアルコールを
エステル化した後、該エステル化物(C)を脱水素触媒
の存在下に脱水素化反応行させる方法(以下、第1方法
という)、またはロジン(A)とアルコールを脱水素触
媒の存在下にエステル化と脱水素化反応を同時進行させ
る方法(以下、第2方法という)を採用することによ
り、目的物を収得できる。
In the present invention, a method of esterifying a rosin (A) with an alcohol and then carrying out a dehydrogenation reaction of the esterified product (C) in the presence of a dehydrogenation catalyst (hereinafter referred to as the first method), or By adopting a method in which the esterification and the dehydrogenation reaction proceed simultaneously in the presence of a dehydrogenation catalyst for rosin (A) and alcohol (hereinafter referred to as the second method), the target product can be obtained.

【0015】第1方法におけるエステル化反応では、通
常の条件をそのまま採用でき、例えば、不活性ガス気流
下に原料ロジン(A)と以下のようなアルコール(B)
を通常150〜300℃に加熱し、生成水を系外に除去
することにより行なえばよい。アルコール(B)の具体
例としては、n−オクチルアルコール、2−エチルヘキ
シルアルコール、デシルアルコール、ラウリルアルコー
ルのような1価アルコール;エチレングリコール、ジエ
チレングリコール、プロピレングリコール、ネオペンチ
ルグリコール等の2価アルコール;グリセリン、トリメ
チロールエタン、トリメチロールプロパン、シクロヘキ
サンジメタノール等の3価アルコール;ペンタエリスリ
トール、ジグリセリン等の4価アルコールが挙げられ
る。尚、反応に際しては、必ずしもエステル化触媒を必
要としないが、反応時間の短縮のために酢酸、パラトル
エンスルホン酸等の酸触媒、水酸化カルシウム等のアル
カリ金属の水酸化物、酸化カルシウム、酸化マグネシウ
ム等の金属酸化物等を使用することもできる。
In the esterification reaction in the first method, the usual conditions can be employed as they are, for example, the raw material rosin (A) and the following alcohol (B) under an inert gas stream.
Is usually heated to 150 to 300 ° C. and the produced water is removed to the outside of the system. Specific examples of the alcohol (B) include monohydric alcohols such as n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol and lauryl alcohol; dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and neopentyl glycol; glycerin. , Trimethylolethane, trimethylolpropane, cyclohexanedimethanol and other trihydric alcohols; pentaerythritol, diglycerin and other tetrahydric alcohols. The reaction does not necessarily require an esterification catalyst, but in order to reduce the reaction time, acetic acid, an acid catalyst such as p-toluenesulfonic acid, an alkali metal hydroxide such as calcium hydroxide, calcium oxide, or an oxide. It is also possible to use a metal oxide such as magnesium.

【0016】第1方法では、エステル化物(C)を脱水
素化する最終工程に付することにより目的物を収得でき
る。該脱水素化反応条件は、特に制限はされず通常の条
件を採用できる。例えば前記ロジン(A)を脱水素化触
媒の存在下、密閉容器中で水素初圧が10Kg/cm2
未満、好ましくは5Kg/cm2 未満、反応温度が10
0〜300℃、好ましくは200〜280℃の範囲で加
熱すればよい。脱水素化反応であるため実質的には水素
は不必要であるが、前記のように生成水素を過酸化物の
還元に利用する意図から、水素初圧を10Kg/cm2
未満としたものであり、生成水素の自圧により、または
若干水素を外部より供給することにより圧力調整すれば
良い。上記脱水素化触媒としては特に制限なく各種公知
のものが使用できるが、好ましくはパラジウム系、ロジ
ウム系、白金系の触媒を例示できる。該触媒は通常シリ
カ、カーボンなどの担体に担持して使用される。また該
触媒の使用量はエステル化物(C)に対して通常0.0
1〜5重量%程度、好ましくは0.02〜2重量%とさ
れる。なお、脱水素化反応に際しては、シクロヘキサ
ン、デカリンなどの脂環族炭化水素か、トルエン、キシ
レンなどの芳香族炭化水素を溶媒として適宜使用するこ
とができる。
In the first method, the desired product can be obtained by subjecting it to the final step of dehydrogenating the esterified product (C). The dehydrogenation reaction conditions are not particularly limited and usual conditions can be adopted. For example, in the presence of a dehydrogenation catalyst, the rosin (A) has a hydrogen initial pressure of 10 kg / cm 2 in a closed container.
Less, preferably less than 5 Kg / cm 2 , reaction temperature 10
The heating may be performed in the range of 0 to 300 ° C, preferably 200 to 280 ° C. Hydrogen is essentially unnecessary because it is a dehydrogenation reaction, but the initial hydrogen pressure is set to 10 kg / cm 2 in order to utilize the produced hydrogen for the reduction of peroxide as described above.
However, the pressure may be adjusted by the self-pressure of the produced hydrogen or by slightly supplying hydrogen from the outside. As the above dehydrogenation catalyst, various known catalysts can be used without particular limitation, but palladium-based, rhodium-based, and platinum-based catalysts are preferred. The catalyst is usually used by supporting it on a carrier such as silica or carbon. The amount of the catalyst used is usually 0.0 with respect to the esterified product (C).
It is about 1 to 5% by weight, preferably 0.02 to 2% by weight. In the dehydrogenation reaction, an alicyclic hydrocarbon such as cyclohexane or decalin or an aromatic hydrocarbon such as toluene or xylene can be appropriately used as a solvent.

【0017】前記第2方法による場合には、エステル化
と脱水素化反応が同時進行するため、製造工程が簡略化
され、製品コストの低減効果が図れる点で第1方法より
優れるが、本質的にはエステル化、脱水素化反応それ自
体は異なるものではない。したがって、第2方法におい
ても、エステル化、脱水素化反応ともに第1方法におけ
るのと同一条件を採用できるが、エステル化反応で生じ
る生成水の系外への除去容易性の点から、大気圧付近で
第2方法を進行させるのが好ましい。また該反応時に
は、得られるロジンエステルの色調低下を防止するため
に不活性ガス気流下、好ましくは水素気流下に行うのが
好ましい。
In the case of the second method, the esterification and dehydrogenation reactions proceed at the same time, which is superior to the first method in that the manufacturing process can be simplified and the product cost can be reduced. The esterification and dehydrogenation reactions themselves are not different. Therefore, in the second method as well, the same conditions as in the first method can be adopted for both the esterification and dehydrogenation reactions, but from the viewpoint of easy removal of the water produced in the esterification reaction to the outside of the system, the atmospheric pressure is used. It is preferable to proceed the second method in the vicinity. Further, during the reaction, in order to prevent the color tone of the obtained rosin ester from being lowered, it is preferable to carry out the reaction under an inert gas stream, preferably under a hydrogen stream.

【0018】上記第1方法および第2方法で得られる無
色ロジンエステル中の樹脂酸組成は、水素供給圧により
若干変化するが、通常はアビエチン酸1%未満、テトラ
ヒドロ体10〜50重量%、ジヒドロ体10〜40重量
%、デヒドロアビエチン酸20〜60重量%となる。ま
た、その過酸化物価は通常1以下となる。
The resin acid composition in the colorless rosin ester obtained by the first method and the second method slightly changes depending on the hydrogen supply pressure, but it is usually less than 1% of abietic acid, 10 to 50% by weight of tetrahydro compound, and dihydro. The body is 10 to 40% by weight, and dehydroabietic acid is 20 to 60% by weight. The peroxide value is usually 1 or less.

【0019】なお、未精製水素化ロジンを出発原料とし
て使用した場合には、上記第1、第2方法を経由しても
本発明の目的物を収得することはできない。
When unpurified hydrogenated rosin is used as a starting material, the target product of the present invention cannot be obtained even through the first and second methods.

【0020】本発明の製造法に従えば、本質的にハーゼ
ン色調レベルの極めて淡色なロジンエステルを収得でき
るが、更に必要により、本発明の各製造段階において安
定剤、例えば公知各種の有機リン系化合物を添加できる
ことはもとよりである。
According to the production method of the present invention, an extremely light-colored rosin ester having essentially a Hazen color tone level can be obtained, but if necessary, a stabilizer such as various known organophosphorus compounds can be used in each production step of the present invention. It goes without saying that compounds can be added.

【0021】本発明の方法でえられたロジンエステル
は、その外観がほとんど無色に近い色調をしており、し
かも加熱時の臭気、安定、相溶性等の諸性能に優れてい
るため、感圧性接着剤またはホットメルト接着剤用のタ
ッキファイヤー、ゴム類や各種プラスチック類の改質
剤、トラフィックペイント用原材料、チューインガム基
材、インキ・塗料の改質剤等として好適に使用でき、こ
れら用途における最終製品の商品価値を向上しうる。
The rosin ester obtained by the method of the present invention has an almost colorless color tone in appearance, and is excellent in various properties such as odor upon heating, stability and compatibility, so that it is pressure sensitive. It can be suitably used as a tackifier for adhesives or hot melt adhesives, a modifier for rubbers and various plastics, a raw material for traffic paints, a chewing gum base material, a modifier for inks and paints, etc. It can improve the commercial value of the product.

【0022】[0022]

【発明の効果】本発明により、従来公知のロジンエステ
ルに比較して色調、臭気、安定性等の諸性能を顕著に改
良したロジンエステルを比較的廉価に提供しうる。
Industrial Applicability According to the present invention, it is possible to provide a rosin ester which is remarkably improved in various properties such as color tone, odor and stability as compared with conventionally known rosin esters at a relatively low cost.

【0023】[0023]

【実施例】以下、実施例及び比較例をあげて本発明方法
を更に詳しく説明するが、本発明がこれらに限定されな
いことはもとよりである。
EXAMPLES The method of the present invention will be described in more detail below with reference to examples and comparative examples, but it goes without saying that the present invention is not limited to these.

【0024】実施例1 (1)水素化反応 3リットルのオートクレーブに酸価171、軟化点76
℃、色調ガードナー6の未精製中国産ガムロジン100
0gと水素化触媒として5%パラジウムカーボン(含水
率50%)2gを仕込み、系内の酸素を除去した後、系
内を水素にて100Kg/cm2 に加圧後、撹拌下に2
60℃まで昇温し、同温度で3時間水素化反応を行な
い、酸価167、軟化点74℃、色調ガードナー5の未
精製水素化ロジンをえた。 (2)精製 前記未精製水素化ロジンを窒素シール下に3mmHgの
減圧下で蒸留し、酸価175.2、軟化点83℃、色調
ガードナー2の一般恒数を有する表1に示す主留を精製
水素化ロジンとした。
Example 1 (1) Hydrogenation reaction An acid value of 171 and a softening point of 76 in a 3 liter autoclave.
℃, unrefined Chinese gum rosin 100 with color Gardner 6
0 g and 2 g of 5% palladium carbon (water content 50%) as a hydrogenation catalyst were charged to remove oxygen in the system, and the system was pressurized to 100 Kg / cm 2 with hydrogen, and then 2 with stirring.
The temperature was raised to 60 ° C., and hydrogenation reaction was carried out at the same temperature for 3 hours to obtain an unpurified hydrogenated rosin having an acid value of 167, a softening point of 74 ° C. and a color tone Gardner 5. (2) Purification The unpurified hydrogenated rosin was distilled under a nitrogen blanket under a reduced pressure of 3 mmHg to give a main distillate shown in Table 1 having an acid value of 175.2, a softening point of 83 ° C., and a general constant of color tone Gardner 2. It was purified hydrogenated rosin.

【0025】[0025]

【表1】 [Table 1]

【0026】(3)エステル化 前記蒸留でえられた酸価175.2、軟化点83℃、色
調ガードナー2の精製水素化ロジン500gを1リット
ルのフラスコに取り、窒素シール下に180℃に昇温
し、溶融撹拌下に200℃でグリセリン58gを加えた
のち270℃まで昇温し、同温度で12時間エステル化
反応を行ない、酸価7.0、軟化点95℃、色調ガード
ナー3の精製水素化ロジンエステルをえた。
(3) Esterification 500 g of purified hydrogenated rosin having an acid value of 175.2, a softening point of 83 ° C. and a color tone Gardner 2 obtained by the above distillation was placed in a 1 liter flask and heated to 180 ° C. under a nitrogen seal. After heating and adding 58 g of glycerin at 200 ° C. under melting and stirring, the temperature was raised to 270 ° C., and the esterification reaction was carried out at the same temperature for 12 hours to obtain an acid value of 7.0, a softening point of 95 ° C., and a color tone of Gardner 3. A hydrogenated rosin ester was obtained.

【0027】(4)脱水素化 前記(3)でえられた精製水素化ロジンエステル200
gと5%パラジウムカーボン0.4gを1リットル振と
う式オートクレーブに仕込み、系内の酸素を除去した
後、系内を水素にて0.5Kg/cm2 に加圧し270
℃まで昇温し、同温度で3時間脱水素化反応を行ない、
酸価8.5、軟化点96℃、色調ガードナー1以下(ハ
ーゼンカラー100)のロジンエステルをえた。
(4) Dehydrogenation Purified hydrogenated rosin ester 200 obtained in (3) above
g and 0.4 g of 5% palladium carbon were charged into a 1 liter shaking autoclave to remove oxygen in the system, and the system was pressurized to 0.5 Kg / cm 2 with hydrogen to 270
The temperature is raised to ℃, and the dehydrogenation reaction is performed at the same temperature for 3 hours.
A rosin ester having an acid value of 8.5, a softening point of 96 ° C. and a color tone of Gardner 1 or less (Hazen color 100) was obtained.

【0028】実施例2 (1)水素化反応 実施例1(1)において、5%パラジウム(含水率50
%)を0.7gに変えた他は実施例1(1)と同様に水
素化反応を行ない、酸価169、軟化点75℃、色調ガ
ードナー6の未精製水素化ロジンをえた。 (2)精製 前記未精製水素化ロジンを実施例1(2)と同一条件で
減圧蒸留し、酸価175.5、軟化点85.5℃、色調
ガードナー2−3の一般恒数を有する表2に示す主留を
精製水素化ロジンとした。
Example 2 (1) Hydrogenation reaction In Example 1 (1), 5% palladium (water content 50
(%) Was changed to 0.7 g to carry out hydrogenation reaction in the same manner as in Example 1 (1) to obtain an unpurified hydrogenated rosin having an acid value of 169, a softening point of 75 ° C. and a color tone Gardner 6. (2) Purification The unpurified hydrogenated rosin was distilled under reduced pressure under the same conditions as in Example 1 (2) to give an acid value of 175.5, a softening point of 85.5 ° C., and a table having a general constant of color tone Gardner 2-3. The main distillate shown in 2 was purified hydrogenated rosin.

【0029】[0029]

【表2】 [Table 2]

【0030】(3)エステル化 前記蒸留でえられた酸価175.5、軟化点85.5
℃、色調ガードナー2〜3の精製水素化ロジン500g
を用いたほかは実施例1の(3)に従い、酸価6.5、
軟化点95℃、色調ガードナー4の精製水素化ロジンエ
ステルをえた。 (4)脱水素化 前記(3)でえられた精製水素化ロジンエステル200
gと5%パラジウムカーボン0.4gを1リットル振と
う式オートクレーブに仕込み、系内の酸素を除去した
後、系内を水素にて0.5Kg/cm2 に加圧し270
℃まで昇温し、同温度で3時間脱水素化反応を行ない、
酸価8.0、軟化点97℃、色調ガードナー1以下(ハ
ーゼンカラー100)のロジンエステルをえた。
(3) Esterification The acid value obtained by the distillation is 175.5 and the softening point is 85.5.
C., 500 g of purified hydrogenated rosin with color tone Gardner 2-3
According to (3) of Example 1 except that the acid value was 6.5,
A purified hydrogenated rosin ester having a softening point of 95 ° C. and a color tone of Gardner 4 was obtained. (4) Dehydrogenation Purified hydrogenated rosin ester 200 obtained in (3) above
g and 0.4 g of 5% palladium carbon were charged into a 1 liter shaking autoclave to remove oxygen in the system, and the system was pressurized to 0.5 Kg / cm 2 with hydrogen to 270
The temperature is raised to ℃, and the dehydrogenation reaction is performed at the same temperature for 3 hours.
A rosin ester having an acid value of 8.0, a softening point of 97 ° C. and a color tone of Gardner 1 or less (Hazen color 100) was obtained.

【0031】実施例3 実施例1の(2)でえた精製水素化ロジン500gを1
リットルのフラスコに取り、窒素シール下に180℃に
昇温し、溶融撹拌下に200℃でグリセリン43g及び
ジエチレングリコール33gを加えたのち270℃まで
昇温し、同温度で12時間エステル化反応を行ない、酸
価3.4、軟化点75.0℃、色調ガードナー3の精製
水素化ロジンエステルをえた。ついで、該精製水素化ロ
ジンエステル200gを実施例1の(4)と同様にして
脱水素化反応を行ない、酸価7.6、軟化点74℃、色
調ガードナー1以下(ハーゼンカラー60)のロジンエ
ステルをえた。
Example 3 500 g of the purified hydrogenated rosin obtained in (2) of Example 1
Transfer to a liter flask, raise the temperature to 180 ° C. under a nitrogen blanket, add 43 g of glycerin and 33 g of diethylene glycol at 200 ° C. under melting and stirring, then raise the temperature to 270 ° C., and perform the esterification reaction at the same temperature for 12 hours. A purified hydrogenated rosin ester having an acid value of 3.4, a softening point of 75.0 ° C. and a color tone of Gardner 3 was obtained. Then, 200 g of the purified hydrogenated rosin ester was subjected to a dehydrogenation reaction in the same manner as in (4) of Example 1 to give a rosin having an acid value of 7.6, a softening point of 74 ° C., and a color tone of Gardner 1 or less (Hazen color 60). I got an ester.

【0032】実施例4 実施例1の(2)でえた精製水素化ロジン500g、お
よび脱水素化触媒として5%パラジウムカーボン(含水
率50%)2gを1リットルのフラスコに取り、水素シ
ール下に180℃に昇温し、溶融撹拌下に200℃でグ
リセリン58gを加えたのち270℃まで昇温し、同温
度で12時間エステル化反応と脱水素化反応を同時に行
ない、酸価3.7、軟化点96℃、色調ガードナー1以
下(ハーゼンカラー150)のロジンエステルをえた。
Example 4 500 g of the purified hydrogenated rosin obtained in (2) of Example 1 and 2 g of 5% palladium carbon (water content 50%) as a dehydrogenation catalyst were placed in a 1 liter flask and sealed under hydrogen. The temperature was raised to 180 ° C., 58 g of glycerin was added at 200 ° C. under melting and stirring, and then the temperature was raised to 270 ° C., the esterification reaction and the dehydrogenation reaction were simultaneously carried out for 12 hours at the same temperature, and the acid value was 3.7. A rosin ester having a softening point of 96 ° C. and a color tone of Gardner 1 or less (Hazen color 150) was obtained.

【0033】比較例1 実施例1の(1)でえた未精製水素化ロジン500gを
用いたほかは、実施例1の(3)に従い、酸価4.5、
軟化点93℃、色調ガードナー8の未精製水素化ロジン
エステルをえた。ついで該未精製水素化ロジンエステル
200gを実施例1の(4)と同様にして脱水素化反応
を行ない、酸価8.5、軟化点95℃、色調ガードナー
6のロジンエステルをえた。
Comparative Example 1 An acid value of 4.5 was obtained according to (3) of Example 1 except that 500 g of the unpurified hydrogenated rosin obtained in (1) of Example 1 was used.
A crude hydrogenated rosin ester having a softening point of 93 ° C. and a color tone of Gardner 8 was obtained. Then, 200 g of the unpurified hydrogenated rosin ester was subjected to a dehydrogenation reaction in the same manner as in (4) of Example 1 to obtain a rosin ester having an acid value of 8.5, a softening point of 95 ° C. and a color tone Gardner 6.

【0034】比較例2 実施例1の(1)でえた未精製水素化ロジン500gを
用いたほかは、実施例4に従い、酸価4.0、軟化点9
6℃、色調ガードナー7のロジンエステルをえた。
Comparative Example 2 According to Example 4, except that 500 g of the unpurified hydrogenated rosin obtained in (1) of Example 1 was used, the acid value was 4.0 and the softening point was 9
A rosin ester having a color tone of Gardner 7 was obtained at 6 ° C.

【0035】諸性能の測定方法は以下の通りである。結
果は表4および表5に示す。 (ロジン中の樹脂酸組成)脱水素化反応前後の各ロジン
エステルを加水分解し、該加水分解物をASTMD30
08−82に準拠してガスクロマトグラフィー測定し
た。 (加熱安定性)内径1.5cm、高さ15cmの試験管
にサンプル10gを入れ、蓋をしないまま200℃の循
風乾燥器に静置して経時による色調(ガ−ドナ−)の変
化を観察した。 (耐候性)60〜100メッシュの粒度に揃えた樹脂
2.0gを内径5.6cm、高さ1cmの軟膏缶に入
れ、400W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)及び色調(ガ−ドナ
−)の変化を観察した。尚、色調は50%トルエン溶液
での評価による。
The methods of measuring various performances are as follows. The results are shown in Tables 4 and 5. (Resin Acid Composition in Rosin) Each rosin ester before and after the dehydrogenation reaction is hydrolyzed, and the hydrolyzate is treated with ASTM D30.
Gas chromatography measurement was performed according to 08-82. (Heating stability) 10 g of the sample was put into a test tube having an inner diameter of 1.5 cm and a height of 15 cm, and the sample was allowed to stand in a circulating air dryer at 200 ° C. without a lid to change the color tone (gardner) with time. I observed. (Weather resistance) 2.0 g of resin having a uniform particle size of 60 to 100 mesh was placed in an ointment can having an inner diameter of 5.6 cm and a height of 1 cm, and a weight increase (oxygen absorption when a 400 W mercury lamp was irradiated from a distance of 40 cm for 15 hours) The amount and the color tone (gardner) were observed. The color tone is evaluated by a 50% toluene solution.

【0036】[0036]

【表4】 [Table 4]

【0037】[0037]

【表5】 [Table 5]

Claims (6)

【特許請求の範囲】[Claims] 【請求項1】 精製水素化ロジンとアルコールをエステ
ル化反応させ、ついで脱水素化触媒存在下に脱水素化反
応させることを特徴とする無色ロジンエステルの製造
法。
1. A process for producing a colorless rosin ester, which comprises subjecting a purified hydrogenated rosin and an alcohol to an esterification reaction, and then performing a dehydrogenation reaction in the presence of a dehydrogenation catalyst.
【請求項2】 精製水素化ロジンとアルコールをエステ
ル化するに際し、脱水素化触媒存在下に脱水素化反応を
同時進行させることを特徴とする無色ロジンエステルの
製造法。
2. A process for producing a colorless rosin ester, which comprises simultaneously advancing a dehydrogenation reaction in the presence of a dehydrogenation catalyst when esterifying a purified hydrogenated rosin with an alcohol.
【請求項3】 脱水素化触媒がパラジウム、ロジウムま
たは白金系触媒である請求項1記載の製造法。
3. The method according to claim 1, wherein the dehydrogenation catalyst is a palladium, rhodium or platinum-based catalyst.
【請求項4】 脱水素化触媒がパラジウム、ロジウムま
たは白金系触媒である請求項2記載の製造法。
4. The method according to claim 2, wherein the dehydrogenation catalyst is a palladium, rhodium or platinum-based catalyst.
【請求項5】 脱水素化反応において、反応圧力が10
Kg/cm2 未満である請求項1記載の製造法。
5. A reaction pressure of 10 in the dehydrogenation reaction.
The method according to claim 1, wherein the production method is less than Kg / cm 2 .
【請求項6】 エステル化と脱水素化反応を同時進行さ
せる際、反応圧力が10Kg/cm2 未満である請求項
2記載の製造法。
6. The production method according to claim 2 , wherein the reaction pressure is less than 10 kg / cm 2 when the esterification and dehydrogenation reactions are simultaneously advanced.
JP18004393A 1993-06-25 1993-06-25 Method for producing colorless rosin ester Expired - Lifetime JP3371985B2 (en)

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Application Number Priority Date Filing Date Title
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001316330A (en) * 2000-05-09 2001-11-13 Arakawa Chem Ind Co Ltd Method for producing colorless rosin ester
US9940852B2 (en) 2013-09-27 2018-04-10 Kranton Chemical, LLC Rosin esters and compositions thereof
US9951254B2 (en) 2013-09-27 2018-04-24 Arizona Chemical Company, Llc Compositions containing ethylene polymers
US10011740B2 (en) 2013-09-27 2018-07-03 Kraton Chemical, Llc Rosin esters and compositions thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2851396A4 (en) * 2012-05-18 2016-01-06 Arakawa Chem Ind Base resin for soldering flux, soldering flux and solder paste
KR101868052B1 (en) * 2016-05-09 2018-06-18 주식회사 엘에스켐코리아 Method for preparing rosin ester composition, rosin ester composition and cosmetic composition comprising the rosin ester composition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001316330A (en) * 2000-05-09 2001-11-13 Arakawa Chem Ind Co Ltd Method for producing colorless rosin ester
US9940852B2 (en) 2013-09-27 2018-04-10 Kranton Chemical, LLC Rosin esters and compositions thereof
US9951254B2 (en) 2013-09-27 2018-04-24 Arizona Chemical Company, Llc Compositions containing ethylene polymers
US10011740B2 (en) 2013-09-27 2018-07-03 Kraton Chemical, Llc Rosin esters and compositions thereof
US10336922B2 (en) 2013-09-27 2019-07-02 Kraton Chemical, Llc Compositions containing ethylene polymers

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