JP4793519B2 - Method for producing colorless polymerized rosin - Google Patents
Method for producing colorless polymerized rosin Download PDFInfo
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- JP4793519B2 JP4793519B2 JP2001001100A JP2001001100A JP4793519B2 JP 4793519 B2 JP4793519 B2 JP 4793519B2 JP 2001001100 A JP2001001100 A JP 2001001100A JP 2001001100 A JP2001001100 A JP 2001001100A JP 4793519 B2 JP4793519 B2 JP 4793519B2
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- rosin
- purified
- polymerized rosin
- colorless
- polymerized
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Description
【0001】
【発明の属する技術分野】
本発明は、無色重合ロジンの製造法に関する。
【0002】
【従来の技術】
ガムロジン、ウッドロジンまたはトール油ロジンから得られる重合ロジンや当該重合ロジンのエステル化物は、顔料分散性、相溶性、粘・接着力などの特性に優れているため、印刷インキ、塗料、粘・接着剤、フラックスなどの広範な分野においてバインダーや添加剤として賞用されている。しかしながら、これらの外観は、一般的に黄色〜褐色であり、ガードナー色数で7〜10程度である。このような色調の劣る重合ロジン等を前記用途に使用した場合には、印刷インキや塗料の色相が変化したり、粘・接着剤として黄味を帯び、それらの商品価値を低減させる不利がある。
【0003】
そのため、これら用途において、無色の重合ロジンやそのエステル化物の開発要請がある。しかしながら、本出願人の知る限りでは、このような問題点を解決できる無色ロジンは未だに開発上市されていないのが実情である。
【0004】
【発明が解決しようとする課題】
本発明は、従来の重合ロジンが有する諸特性を保持し、しかも当該色調を顕著に改善した無色の重合ロジンを与えることのできる、新規な製造法を提供することを目的とする。
【0005】
【課題を解決するための手段】
本発明者は、従来の重合ロジンに見られる前記課題に鑑み、鋭意研究を重ねた結果、原料ロジンとして特定のロジンを使用して重合を行い、次いで水素化することにより、上記課題を解決しうる無色の重合ロジンを収得しうることを見出し、本発明を完成するに至った。
【0006】
すなわち、本発明は、精製ロジンを重合してなる精製重合ロジン(1)を水素化することを特徴とする無色重合ロジンの製造法に関する。
【0007】
【発明の実施の形態】
本発明では、第一に、出発原料であるロジンとして、精製ロジン(精製ガムロジン、精製ウッドロジン、精製トール油ロジン)を使用することが必須である。ここで精製とは、出発原料である未精製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、および該ロジンにもともと含まれている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200〜300℃、圧力130〜1300Pa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。更に前記精製は未精製ロジンをアルカリ水を用いてアルカリ水溶液となし、生じた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、精製ロジンを得ることもできる。
【0008】
本発明では、前記の精製ロジンを重合して、精製重合ロジン(1)を得る工程が必須とされる。かかる重合反応の条件は、格別に限定されるものではなく、従来公知の条件から適宜に選択して決定される。たとえば、精製ロジンを硫酸、フッ化水素、塩化亜鉛、塩化アルミニウム、四塩化チタン、スチレン−ジビニルベンゼン共重合体スルホン化物等の触媒を含むトルエン、キシレン、ハロゲン化炭化水素等の溶媒中、温度40〜160℃程度で、1〜10時間程度反応させる方法等があげられる。当該重合反応が終了した後、必要に応じて、当該重合反応物から使用した溶剤、触媒および未反応精製ロジン並びに分解物を除去することにより、精製重合ロジン(1)を得ることができる。触媒除去方法としては、たとえば水洗、ろ過などを採用でき、未反応精製ロジンおよび分解物の除去方法としては、減圧蒸留を採用できる。上記のようにして得られる精製重合ロジン(1)の色調(ガードナー色数)は、4〜7程度であり、この水準では無色や淡色とは言い難いものである。
【0009】
こうして得られる精製重合ロジン(1)は、一般的に、未反応物としての精製ロジン(単量体)、これが二量化したダイマー成分、更にはダイマー成分より大きい分子量を持つ成分などから構成された混合物である。精製重合ロジン(1)中の重合物の含有率は、重合反応時の反応温度、反応時間、触媒種、および重合反応物から未反応精製ロジンを除去する条件等により異なるため、所望の重合ロジン含有率となるよう反応条件等を適宜に選択できる。本発明で用いる精製重合ロジン(1)中の重合物含有率は、格別の限定はされず、最終的に得られる無色重合ロジンの用途に応じて決定すればよい。通常は10〜85重量%程度、好ましくは20〜80重量%である。
【0010】
本発明の製造法では、前記で得られた精製重合ロジン(1)を水素化することが必須とされる。該水素化反応に際しては、公知の水素化反応条件を適宜に選択できる。即ち、水素化触媒の存在下に通常1〜25MPa、好ましくは5〜20MPaの水素加圧下で、精製重合ロジン(1)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、ルテニウムカーボン、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、各種公知のものを例示しうる。特に好ましくはパラジウム、ロジウム、ルテニウムまたは白金系触媒である。該触媒の使用量は、精製重合ロジン(1)に対して通常0.01〜5重量%、好ましくは0.01〜2.0重量%であり、反応温度は100〜300℃、好ましくは150〜290℃である。
【0011】
本製造法により得られた無色重合ロジンは、色調(ガードナー色数)が1以下、ハーゼン色数で300〜30程度、好ましくは200〜30であり、軟化点は90〜150℃程度、好ましくは95〜145℃であり、重量平均分子量(ポリスチレン換算)は350〜650程度、好ましくは400〜600であり、酸価は130〜160mgKOH/g程度、好ましくは135〜150mgKOH/gである。また、無色重合ロジン中の重合物含有率は、通常は10〜85重量%程度、好ましくは20〜80重量%とされる。なお、精製重合ロジン(1)を水素化しても、重合物含有率それ自体は、水素化の前後でほとんど変化しない。
【0012】
なお、本発明の製造法で得られた無色重合ロジンには、適宜にフェノール系酸化防止剤、リン系酸化防止剤、紫外線吸収剤など各種の添加剤を添加することができる。無色重合ロジンは、そのままの形態で、または適宜に溶媒中に分散させたディスパージョンやエマルジョンの形態で、前記の如き各種用途に好適に使用できる。
【0013】
【発明の効果】
本発明によれば、従来の重合ロジンの特性(顔料分散性、相溶性、粘・接着性など)を保持し、しかもその色調および加熱時の色調安定性を顕著に改善した、無色の重合ロジンを提供できる。
【0014】
【実施例】
以下に実施例及び比較例をあげて本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。尚、各例中、%は重量基準である。
【0015】
実施例1
(1)精製
酸価170.0mgKOH/g、軟化点78℃、色調ガードナー6の未精製ロジン(中国産ガムロジン)を窒素シール下に400Paの減圧下で蒸留し、表1に示す主留を精製ロジンとした。当該精製ロジンは、酸価178.4mgKOH/g、軟化点88℃、色調(ガードナー色数)3の一般恒数を有する。
【0016】
【表1】
【0017】
(2)重合反応
温度計、攪拌機、窒素導入管および減圧装置を備えた反応装置に、(1)で得られた精製ロジン700g、キシレン700g、および触媒(三菱化学(株)製イオン交換樹脂、商品名「ダイアイオンHPK165」)280gを仕込み、窒素気流下85℃で8時間、重合反応を行なった。反応生成物から触媒をろ別した後、液温200℃未満、減圧度1300Paの条件下でキシレンを留去した後、更に液温200〜275℃、減圧度400Paの条件下で精製ロジンの分解物及び未反応精製ロジン計250gを留去して、酸価134.7mgKOH/g、軟化点145℃、色調(ガードナー色数)5の精製重合ロジン430gを得た。GPC測定により、当該精製重合ロジン中の重合物含有率は74.8%、単量体(未反応精製ロジン)は23.8%、分解物は1.4%であることが認められた。
【0018】
(3)水素化反応
ついでオートクレーブ反応装置に、(2)で得た精製重合ロジン150g、水素化触媒として5%パラジウムカーボン(含水率50%)1.5g、およびシクロヘキサン150gを仕込み、系内の酸素を除去した後、系内を水素にて10MPaに加圧後、撹拌下に260℃まで昇温して、同温度で3時間水素化反応を行ない、酸価138.8mgKOH/g、軟化点142℃、色調(ハーゼン色数)80の無色重合ロジンを得た。GPC測定により、当該無色重合ロジン中の重合物含有率は72.2%、単量体(未反応精製ロジンの水素化物)は25.7%、分解物は2.1%であることが認められた。
【0019】
実施例2
実施例1(2)において、イオン交換樹脂280gに代えて塩化亜鉛17.5gを用い、かつ反応条件を140℃で7時間に変更した他は、同様にして重合反応を行なった。反応生成物のキシレン溶液1417gを温水500gで洗浄した後、濃塩酸7gおよび温水500gを加えて洗浄した。更に各500gの温水にて2回洗浄した後、減圧下にキシレンを留去した。更にロジンの分解物及び未反応精製ロジン(計200g)を留去して、酸価135.3mgKOH/g、軟化点146℃、色調(ガードナー色数)5の精製重合ロジン471gを得た。GPC測定により、当該精製重合ロジン中の重合物含有率は71.3%、単量体(精製ロジン)は27.2%、分解物は1.6%であることが認められた。ついで、実施例1(3)と同一条件で水素化反応を行い、酸価145.2mgKOH/g、軟化点140℃、色調(ハーゼン色数)60の無色重合ロジンを得た。GPC測定により、当該無色重合ロジン中の重合物含有率は70.3%、単量体(精製ロジンの水素化物)は27.7%、分解物は2.0%であることが認められた。
【0020】
比較例1(未精製重合ロジンの水素化物)
酸価170.0mgKOH/g、軟化点78℃、色調ガードナー6の未精製ロジン(中国産ガムロジン)を使用し、実施例1(2)と同様の条件で重合反応と後処理を行った後、実施例1(3)と同様の条件で水素化反応を行い、更に触媒の除去を行なうことにより、未精製重合ロジンの水素化物を得た。当該水素化物は、酸価136.5mgKOH/g、軟化点139℃、色調(ガードナー色数)5であった。
【0021】
比較例2(未精製重合ロジンの水素化物)
酸価170.0mgKOH/g、軟化点78℃、色調ガードナー6の未精製ロジン(中国産ガムロジン)を使用し、実施例2と同様の条件で重合反応と後処理を行った後、実施例と同様の条件で水素化反応を行い、更に触媒の除去を行なうことにより、未精製重合ロジンの水素化物を得た。当該水素化物は、酸価138.3mgKOH/g、軟化点140℃、色調(ガードナー色数)4であった。
【0022】
比較例3(精製重合ロジンの不均化物)
温度計、攪拌機、窒素導入管を備えた反応装置に、実施例1(2)で得た精製重合ロジン150g、不均化触媒として5%パラジウムカーボン(含水率50%)1.5g、を仕込み、窒素気流下に260℃で3時間不均化反応を行った。当該反応生成物は、酸価138.5mgKOH/g、軟化点140℃、色調(ガードナー色数)6であった。
【0023】
(性能評価)
各実施例および比較例にて得た各種の重合ロジンを以下の条件にて性能評価した。結果は表2に示す。
(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(ガードナー色数)の変化を観察した。
【0024】
【表2】
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a colorless polymerized rosin.
[0002]
[Prior art]
Polymerized rosin obtained from gum rosin, wood rosin or tall oil rosin and esterified products of the polymerized rosin are excellent in properties such as pigment dispersibility, compatibility, viscosity and adhesive strength, so printing inks, paints, and adhesives It is used as a binder and additive in a wide range of fields such as flux. However, these appearances are generally yellow to brown and have a Gardner color number of about 7 to 10. When such a polymer rosin having a poor color tone is used for the above-mentioned purposes, there is a disadvantage that the hue of printing ink or paint changes, or yellowish as a sticky / adhesive agent, reducing their commercial value. .
[0003]
Therefore, there is a demand for development of colorless polymerized rosin and its esterified products in these applications. However, to the best of the applicant's knowledge, colorless rosin that can solve such problems has not yet been developed and marketed.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel production method that can provide a colorless polymerized rosin that retains various properties of a conventional polymerized rosin and that significantly improves the color tone.
[0005]
[Means for Solving the Problems]
In light of the above-mentioned problems found in conventional polymerized rosins, the present inventor has solved the above problems by conducting polymerization using a specific rosin as a raw material rosin, and then hydrogenating it. The inventors have found that a colorless polymerized rosin can be obtained, and have completed the present invention.
[0006]
That is, the present invention relates to a method for producing a colorless polymerized rosin characterized by hydrogenating a purified polymerized rosin (1) obtained by polymerizing a purified rosin.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, first, it is essential to use purified rosin (refined gum rosin, purified wood rosin, purified tall oil rosin) as the starting material rosin. Here, purification means removal of a high-molecular-weight product thought to be generated from the peroxide contained in the unpurified rosin that is the starting material, and unsaponifiable matter originally contained in the rosin. . Specifically, operations such as distillation, recrystallization and extraction may be performed, and industrial purification is preferred. In the case of distillation, it is usually selected appropriately in consideration of the distillation time from a temperature range of 200 to 300 ° C. and a pressure of 130 to 1300 Pa. In the case of recrystallization, for example, unpurified rosin is dissolved in a good solvent, and then the solvent is distilled off to form a concentrated solution, and a poor solvent is added to this solution. Examples of good solvents include ketones such as benzene, toluene, xylene, chloroform, lower alcohol, and acetone, and acetates such as ethyl acetate. Examples of poor solvents include n-hexane, n-heptane, cyclohexane, and isooctane. Can be mentioned. Further, in the purification, an unpurified rosin can be made into an alkaline aqueous solution using alkaline water, and the insoluble unsaponified product produced can be extracted with an organic solvent, and then the aqueous layer can be neutralized to obtain a purified rosin.
[0008]
In the present invention, the step of polymerizing the purified rosin to obtain the purified polymerized rosin (1) is essential. The conditions for the polymerization reaction are not particularly limited, and are determined by appropriately selecting from conventionally known conditions. For example, the purified rosin is heated in a solvent such as toluene, xylene, halogenated hydrocarbon, etc. containing a catalyst such as sulfuric acid, hydrogen fluoride, zinc chloride, aluminum chloride, titanium tetrachloride, sulfonated styrene-divinylbenzene copolymer, temperature 40 The method etc. which are made to react for about 1 to 10 hours at about -160 degreeC are mention | raise | lifted. After the polymerization reaction is completed, the purified polymerized rosin (1) can be obtained by removing the solvent, catalyst, unreacted purified rosin and decomposition products from the polymerized reaction product, if necessary. As the catalyst removal method, for example, washing with water, filtration and the like can be employed, and as a method for removing unreacted purified rosin and decomposition products, vacuum distillation can be employed. The color tone (Gardner color number) of the purified polymerized rosin (1) obtained as described above is about 4 to 7, and at this level, it is difficult to say colorless or light color.
[0009]
The purified polymerized rosin (1) thus obtained is generally composed of a purified rosin (monomer) as an unreacted substance, a dimer component obtained by dimerization thereof, and a component having a molecular weight larger than that of the dimer component. It is a mixture. The content of the polymer in the purified polymerized rosin (1) varies depending on the reaction temperature, reaction time, catalyst type, conditions for removing unreacted purified rosin from the polymerized product, etc. Reaction conditions and the like can be appropriately selected so as to achieve the content. The polymer content in the purified polymerized rosin (1) used in the present invention is not particularly limited, and may be determined according to the use of the finally obtained colorless polymerized rosin. Usually, it is about 10 to 85% by weight, preferably 20 to 80% by weight.
[0010]
In the production method of the present invention, it is essential to hydrogenate the purified polymerized rosin (1) obtained above. In the hydrogenation reaction, known hydrogenation reaction conditions can be appropriately selected. That is, the purification polymerization rosin (1) is heated in the presence of a hydrogenation catalyst under a hydrogen pressure of usually 1 to 25 MPa, preferably 5 to 20 MPa. Examples of the hydrogenation catalyst include various known catalysts such as supported catalysts such as palladium carbon, rhodium carbon, ruthenium carbon, and platinum carbon, metal powders such as nickel and platinum, and iodides such as iodine and iron iodide. Particularly preferred are palladium, rhodium, ruthenium or platinum based catalysts. The amount of the catalyst used is usually 0.01 to 5% by weight, preferably 0.01 to 2.0% by weight, based on the purified polymerized rosin (1), and the reaction temperature is 100 to 300 ° C., preferably 150. ~ 290 ° C.
[0011]
The colorless polymerized rosin obtained by this production method has a color tone (Gardner color number) of 1 or less, a Hazen color number of about 300 to 30, preferably 200 to 30, and a softening point of about 90 to 150 ° C., preferably It is 95-145 degreeC, a weight average molecular weight (polystyrene conversion) is about 350-650, Preferably it is 400-600, and an acid value is about 130-160 mgKOH / g, Preferably it is 135-150 mgKOH / g. The content of the polymer in the colorless polymerized rosin is usually about 10 to 85% by weight, preferably 20 to 80% by weight. Even when the purified polymerized rosin (1) is hydrogenated, the polymer content itself hardly changes before and after the hydrogenation.
[0012]
In addition, various additives, such as a phenolic antioxidant, a phosphorus antioxidant, and an ultraviolet absorber, can be appropriately added to the colorless polymerized rosin obtained by the production method of the present invention. The colorless polymerized rosin can be suitably used for various uses as described above in the form as it is or in the form of a dispersion or emulsion appropriately dispersed in a solvent.
[0013]
【The invention's effect】
According to the present invention, a colorless polymerized rosin that retains the properties (pigment dispersibility, compatibility, viscosity / adhesiveness, etc.) of conventional polymerized rosin and that has significantly improved its color tone and color tone stability upon heating. Can provide.
[0014]
【Example】
EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples. In each example,% is based on weight.
[0015]
Example 1
(1) Purified acid value 170.0 mgKOH / g, softening point 78 ° C., color Gardner 6 unpurified rosin (Chinese gum rosin) was distilled under a vacuum of 400 Pa under a nitrogen seal to purify the main fractions shown in Table 1. Rosin. The purified rosin has a general constant of an acid value of 178.4 mg KOH / g, a softening point of 88 ° C., and a color tone (Gardner color number) of 3.
[0016]
[Table 1]
[0017]
(2) In a reactor equipped with a polymerization reaction thermometer, a stirrer, a nitrogen introduction tube and a decompression device, 700 g of the purified rosin obtained in (1), 700 g of xylene, and a catalyst (an ion exchange resin manufactured by Mitsubishi Chemical Corporation) 280 g of a trade name “Diaion HPK165”) was charged, and a polymerization reaction was performed at 85 ° C. for 8 hours under a nitrogen stream. After the catalyst is filtered off from the reaction product, xylene is distilled off under conditions of a liquid temperature of less than 200 ° C. and a reduced pressure of 1300 Pa, and then the purified rosin is decomposed under the conditions of a liquid temperature of 200 to 275 ° C. and a reduced pressure of 400 Pa. The total amount of the product and 250 g of unreacted purified rosin was distilled off to obtain 430 g of purified polymerized rosin having an acid value of 134.7 mgKOH / g, a softening point of 145 ° C., and a color tone (Gardner color number) of 5. GPC measurement showed that the polymer content in the purified polymerized rosin was 74.8%, the monomer (unreacted purified rosin) was 23.8%, and the decomposed product was 1.4%.
[0018]
(3) Hydrogenation reaction Then, 150 g of the purified polymerized rosin obtained in (2), 1.5 g of 5% palladium carbon (water content 50%) and 150 g of cyclohexane were charged into the autoclave reaction apparatus. After removing oxygen, the system was pressurized to 10 MPa with hydrogen, heated to 260 ° C. with stirring, and subjected to a hydrogenation reaction at the same temperature for 3 hours. An acid value of 138.8 mgKOH / g, a softening point A colorless polymerized rosin having a color tone (Hazen color number) of 80 ° C. at 142 ° C. was obtained. By GPC measurement, it was confirmed that the content of the polymer in the colorless polymerized rosin was 72.2%, the monomer (hydride of unreacted purified rosin) was 25.7%, and the decomposition product was 2.1%. It was.
[0019]
Example 2
In Example 1 (2), a polymerization reaction was carried out in the same manner except that 17.5 g of zinc chloride was used instead of 280 g of the ion exchange resin and the reaction conditions were changed to 140 ° C. for 7 hours. After washing 1417 g of the xylene solution of the reaction product with 500 g of warm water, 7 g of concentrated hydrochloric acid and 500 g of warm water were added for washing. Further, after washing twice with 500 g of warm water, xylene was distilled off under reduced pressure. Further, rosin decomposition products and unreacted purified rosin (total 200 g) were distilled off to obtain 471 g of purified polymerized rosin having an acid value of 135.3 mg KOH / g, a softening point of 146 ° C., and a color tone (Gardner color number) of 5. GPC measurement showed that the polymer content in the purified polymerized rosin was 71.3%, the monomer (purified rosin) was 27.2%, and the decomposed product was 1.6%. Then, a hydrogenation reaction was performed under the same conditions as in Example 1 (3) to obtain a colorless polymerized rosin having an acid value of 145.2 mgKOH / g, a softening point of 140 ° C., and a color tone (Hazen color number) of 60. The GPC measurement showed that the content of the polymer in the colorless polymerized rosin was 70.3%, the monomer (purified rosin hydride) was 27.7%, and the decomposition product was 2.0%. .
[0020]
Comparative example 1 (hydride of unpurified polymerized rosin)
After using an unpurified rosin (Chinese gum rosin) having an acid value of 170.0 mgKOH / g, a softening point of 78 ° C., and a color tone Gardner 6, the polymerization reaction and post-treatment were performed under the same conditions as in Example 1 (2). A hydrogenation reaction was carried out under the same conditions as in Example 1 (3), and the catalyst was further removed to obtain a hydride of unpurified polymerized rosin. The hydride had an acid value of 136.5 mgKOH / g, a softening point of 139 ° C., and a color tone (Gardner color number) of 5.
[0021]
Comparative Example 2 (Unrefined Polymerized Rosin Hydride)
An unpurified rosin (Chinese gum rosin) having an acid value of 170.0 mgKOH / g, a softening point of 78 ° C., and a color tone of Gardner 6 was used and subjected to a polymerization reaction and a post-treatment under the same conditions as in Example 2. By performing a hydrogenation reaction under the same conditions and further removing the catalyst, an unpurified polymerized rosin hydride was obtained. The hydride had an acid value of 138.3 mgKOH / g, a softening point of 140 ° C., and a color tone (Gardner color number) of 4.
[0022]
Comparative Example 3 (Purified Polymerized Rosin Disproportionate)
A reactor equipped with a thermometer, a stirrer, and a nitrogen introduction tube was charged with 150 g of the purified polymerized rosin obtained in Example 1 (2) and 1.5 g of 5% palladium carbon (water content 50%) as a disproportionation catalyst. The disproportionation reaction was performed at 260 ° C. for 3 hours under a nitrogen stream. The reaction product had an acid value of 138.5 mgKOH / g, a softening point of 140 ° C., and a color tone (Gardner color number) of 6.
[0023]
(Performance evaluation)
Various polymerized rosins obtained in each Example and Comparative Example were evaluated for performance under the following conditions. The results are shown in Table 2.
(Heating stability)
10 g of a sample was put in a test tube having an inner diameter of 1.5 cm and a height of 15 cm, and left to stand in a circulating dryer at 200 ° C. without a lid, and the change in color tone (Gardner color number) over time was observed.
[0024]
[Table 2]
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JP2008231373A (en) * | 2007-03-23 | 2008-10-02 | Arakawa Chem Ind Co Ltd | Method of manufacturing hydrogenated polymerized rosin ester |
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CN104231938A (en) * | 2013-06-24 | 2014-12-24 | 王荷琴 | Processing method of rosin |
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