JPH08283201A - Hydroxyisobutyric ester improved in storage stability - Google Patents
Hydroxyisobutyric ester improved in storage stabilityInfo
- Publication number
- JPH08283201A JPH08283201A JP10717295A JP10717295A JPH08283201A JP H08283201 A JPH08283201 A JP H08283201A JP 10717295 A JP10717295 A JP 10717295A JP 10717295 A JP10717295 A JP 10717295A JP H08283201 A JPH08283201 A JP H08283201A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- acid ester
- hydroxyisobutyric acid
- hydroxyisobutyric
- hydroxyisobutyrate
- 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
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は貯蔵安定性の改善された
ヒドロキシイソ酪酸エステルに関するものであり、この
ヒドロキシイソ酪酸エステルは、金属部品、電子部品な
どの洗浄剤や塗料、接着剤などの溶剤などの幅広い用途
に有用なものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydroxyisobutyric acid ester having improved storage stability. The hydroxyisobutyric acid ester is a solvent such as a cleaning agent for metal parts, electronic parts, paints and adhesives. It is useful for a wide range of applications such as.
【０００２】[0002]
【従来の技術およびその問題点】ヒドロキシイソ酪酸エ
ステルは洗浄剤、溶剤、合成原料として有用な化合物で
ある。しかし、従来用いられているヒドロキシイソ酪酸
エステルは長期間の貯蔵中に分解、変色するという現象
が発生し、金属部品、電子部品などの精密洗浄用途や塗
料、接着剤などの溶剤用途などに使用する場合の大きな
問題点となっている。2. Description of the Related Art Hydroxyisobutyric acid ester is a compound useful as a detergent, a solvent, and a synthetic raw material. However, the conventionally used hydroxyisobutyric acid ester decomposes and discolors during long-term storage, and is used for precision cleaning applications such as metal parts and electronic parts, and solvent applications such as paints and adhesives. It becomes a big problem when doing.
【０００３】また、ヒドロキシイソ酪酸エステルを貯蔵
するに際し、工業用に一般に用いられる炭素鋼、ブリキ
などを材質とする容器中に貯蔵する場合、これらの金属
をも腐食してしまう現象がみられる。このような金属材
料の腐食を防止するために、例えば腐食防止剤の添加と
いった対策がとられているが、これでも完全に腐食を防
ぐことは困難である。Further, when the hydroxyisobutyric acid ester is stored, when it is stored in a container made of carbon steel, tinplate or the like, which is generally used for industry, there is a phenomenon that these metals are also corroded. In order to prevent such corrosion of the metal material, measures such as addition of a corrosion inhibitor have been taken, but even with this, it is difficult to completely prevent corrosion.
【０００４】このような事から貯蔵中に分解、変色する
ことのない貯蔵安定性の優れたヒドロキシイソ酪酸エス
テルの登場が工業的に強く要望されている。Under these circumstances, industrially, there is a strong demand for the appearance of a hydroxyisobutyric acid ester which does not decompose or discolor during storage and is excellent in storage stability.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上記
問題点を解決し、分解、変色することのない貯蔵安定性
の優れたヒドロキシイソ酪酸エステルを提供することに
ある。An object of the present invention is to solve the above problems and provide a hydroxyisobutyric acid ester which is free from decomposition and discoloration and is excellent in storage stability.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、ヒドロキ
シイソ酪酸エステルの貯蔵安定性について鋭意検討した
結果、ヒドロキシイソ酪酸エステルの分解、変色は、ヒ
ドロキシイソ酪酸エステルに含まれている不純物中の酸
成分により引き起こされていることを見いだした。Means for Solving the Problems As a result of intensive studies on the storage stability of hydroxyisobutyric acid ester, the present inventors have found that the decomposition and discoloration of hydroxyisobutyric acid ester are caused by the impurities contained in hydroxyisobutyric acid ester. It was found that it is caused by the acid component of.
【０００７】さらに、ヒドロキシイソ酪酸エステルの製
造において使用される酸成分が製品ヒドロキシイソ酪酸
エステル中に不純物として混入している場合には、酸成
分が混入していない場合に比して、ヒドロキシイソ酪酸
エステルの分解、変色が著しく促進されることが判明し
た。Further, when the acid component used in the production of hydroxyisobutyric acid ester is mixed as an impurity in the product hydroxyisobutyric acid ester, the hydroxyisobutyric acid ester is compared with the case where no acid component is mixed. It was found that the decomposition and discoloration of butyric acid ester were significantly accelerated.
【０００８】すなわち、ヒドロキシイソ酪酸エステルの
貯蔵中の分解、変色といった貯蔵安定性の悪さの原因
が、ヒドロキシイソ酪酸エステルに含まれる不純物中の
酸成分によるものであること、そしてその酸成分の含有
量を一定量以下にすることにより上記目的が達成できる
ことを見出し、本発明を完成させるに至った。That is, the cause of poor storage stability such as decomposition and discoloration of hydroxyisobutyric acid ester during storage is due to the acid component in impurities contained in hydroxyisobutyric acid ester, and the content of the acid component. The inventors have found that the above object can be achieved by controlling the amount to be a certain amount or less, and have completed the present invention.
【０００９】本発明は、一般式［１］または［２］で表
されるヒドロキシイソ酪酸エステルにおいて、 （前記各式中、Ｒは炭素数１〜４のアルキル基を表す）
当該ヒドロキシイソ酪酸エステル中の酸成分の含有量を
０．５重量％以下に調整することを特徴とする貯蔵安定
性の改善されたヒドロキシイソ酪酸エステルに関する。The present invention provides a hydroxyisobutyric acid ester represented by the general formula [1] or [2], (In the above formulas, R represents an alkyl group having 1 to 4 carbon atoms)
It relates to hydroxyisobutyric acid ester having improved storage stability, characterized in that the content of the acid component in the hydroxyisobutyric acid ester is adjusted to 0.5% by weight or less.
【００１０】以下、本発明を詳細に説明する。本発明に
おけるヒドロキシイソ酪酸エステルとしては、α−ヒド
ロキシイソ酪酸メチル、α−ヒドロキシイソ酪酸エチ
ル、α−ヒドロキシイソ酪酸プロピル、α−ヒドロキシ
イソ酪酸ブチルなどのα−ヒドロキシイソ酪酸アルキル
エステル（一般式［１］に相当）、β−ヒドロキシイソ
酪酸メチル、β−ヒドロキシイソ酪酸エチル、β−ヒド
ロキシイソ酪酸プロピル、β−ヒドロキシイソ酪酸ブチ
ルなどのβ−ヒドロキシイソ酪酸アルキルエステル（一
般式［２］に相当）が挙げられるが、これらに限定され
るものではない。Hereinafter, the present invention will be described in detail. As the hydroxyisobutyric acid ester in the present invention, α-hydroxyisobutyric acid alkyl ester such as α-hydroxyisobutyric acid methyl ester, α-hydroxyisobutyric acid ethyl ester, α-hydroxyisobutyric acid propyl ester and butyl α-hydroxyisobutyric acid ester (general formula [ 1)), β-hydroxyisobutyric acid alkyl ester such as methyl β-hydroxyisobutyrate, ethyl β-hydroxyisobutyrate, propyl β-hydroxyisobutyrate and butyl β-hydroxyisobutyrate (corresponding to general formula [2] ), But is not limited thereto.
【００１１】ヒドロキシイソ酪酸エステルの製造法は従
来から種々知られているが、硫酸、塩酸、強酸性イオン
交換樹脂等の触媒存在下でのヒドロキシイソ酪酸のエス
テル化反応、シアンヒドリンのアルコリシス反応、ヒド
ロキシイソ酪酸アミドとギ酸エステルとの交換反応など
による製造法が一般的である。なお、本発明のヒドロキ
シイソ酪酸エステルは上記方法によって製造されたもの
に限定されるものではなく、いずれの方法によって得ら
れたヒドロキシイソ酪酸エステルも本発明の対象となり
うる。Various methods for producing hydroxyisobutyric acid ester have been known so far, but esterification reaction of hydroxyisobutyric acid in the presence of a catalyst such as sulfuric acid, hydrochloric acid or strongly acidic ion exchange resin, alcoholysis reaction of cyanohydrin, hydroxy A general method is a production method such as an exchange reaction of isobutyric acid amide and formic acid ester. The hydroxyisobutyric acid ester of the present invention is not limited to the one produced by the above method, and a hydroxyisobutyric acid ester obtained by any method can be the subject of the present invention.
【００１２】ヒドロキシイソ酪酸エステルを製造する場
合、通常の製造方法では製品ヒドロキシイソ酪酸エステ
ル中への若干の酸成分の混入は避けられない。例えば、
酸触媒存在下でのヒドロキシイソ酪酸のエステル化反応
やシアンヒドリンのアルコリシス反応の場合、必然的に
反応液中にヒドロキシイソ酪酸や反応に用いた酸触媒な
どの酸成分が多量に残存してしまい、後に行う蒸留精製
工程においてもヒドロキシイソ酪酸エステルと完全に分
離することは困難であり、製品ヒドロキシイソ酪酸エス
テル中に酸成分が混入してしまう。また、シアンヒドリ
ンの水和によるヒドロキシイソ酪酸アミドを経由する方
法の場合、水和時の副反応により生じたヒドロキシイソ
酪酸などが製品中に混入してしまう。In the case of producing hydroxyisobutyric acid ester, it is inevitable that a slight amount of an acid component is mixed into the product hydroxyisobutyric acid ester by a usual production method. For example,
In the case of esterification reaction of hydroxyisobutyric acid or alcoholysis reaction of cyanohydrin in the presence of an acid catalyst, a large amount of acid components such as hydroxyisobutyric acid and the acid catalyst used for the reaction inevitably remain in the reaction solution, It is difficult to completely separate it from the hydroxyisobutyric acid ester even in the subsequent distillation and purification step, and the acid component is mixed in the product hydroxyisobutyric acid ester. Further, in the case of the method of passing through hydroxyisobutyric acid amide by hydration of cyanohydrin, hydroxyisobutyric acid and the like generated by a side reaction during hydration are mixed in the product.
【００１３】ヒドロキシイソ酪酸エステル中に不純物と
して存在する酸成分としては、ヒドロキシイソ酪酸エス
テル製造時において使用される硫酸、塩酸、硝酸、リン
酸、酢酸、プロピオン酸、ベンゼンスルホン酸、トルエ
ンスルホン酸、安息香酸などの無機酸あるいは有機酸
類、またはヒドロキシイソ酪酸エステル製造時の酸性副
生物であるメタクリル酸、ヒドロキシイソ酪酸、アルコ
キシイソ酪酸などである。これら酸成分はヒドロキシイ
ソ酪酸エステルの製造法によっても異なるが、通常の製
法では１重量％程度の混入が避けられない。ヒドロキシ
イソ酪酸エステルの貯蔵中における分解、変色を防止す
るためには、ヒドロキシイソ酪酸エステルに含まれる酸
成分を０．５重量％以下にすることが必要である。好ま
しくは０．３重量％以下、特に好ましくは０．１重量％
以下にするのがよい。Acid components present as impurities in hydroxyisobutyric acid ester include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, propionic acid, benzenesulfonic acid, toluenesulfonic acid, which are used in the production of hydroxyisobutyric acid ester. Examples thereof include inorganic acids such as benzoic acid or organic acids, or methacrylic acid, hydroxyisobutyric acid, alkoxyisobutyric acid, which are acidic by-products in the production of hydroxyisobutyric acid ester. These acid components differ depending on the production method of hydroxyisobutyric acid ester, but in the usual production method, mixing of about 1% by weight cannot be avoided. In order to prevent decomposition and discoloration of the hydroxyisobutyric acid ester during storage, it is necessary to make the acid component contained in the hydroxyisobutyric acid ester 0.5% by weight or less. Preferably 0.3% by weight or less, particularly preferably 0.1% by weight
The following is recommended.
【００１４】ヒドロキシイソ酪酸エステル中への酸成分
を低減する方法としては、いろいろな方法により行うこ
とができる。例えば、反応液中の酸成分を塩基にて中和
した後に蒸留精製工程に供しヒドロキシイソ酪酸エステ
ルを得る方法がある。いかなる方法にせよヒドロキシイ
ソ酪酸エステル中の酸成分の含有量を０．５重量％以下
に調整することが重要である。Various methods can be used to reduce the acid component in the hydroxyisobutyric acid ester. For example, there is a method in which the acid component in the reaction solution is neutralized with a base and then subjected to a distillation purification step to obtain hydroxyisobutyric acid ester. Whatever method is used, it is important to adjust the content of the acid component in the hydroxyisobutyric acid ester to 0.5% by weight or less.
【００１５】ヒドロキシイソ酪酸エステルの酸成分含有
量はできるだけ少ないほうが好ましいが、実質的に０重
量％とするには極めて過酷な操作条件を必要とし、必然
的に大幅なコストアップとなり経済的ではない。そのた
め、ヒドロキシイソ酪酸エステル中の酸成分含有量の下
限値としては０．００１重量％程度でよい。It is preferable that the content of the acid component of hydroxyisobutyric acid ester is as low as possible. However, in order to achieve substantially 0% by weight, extremely harsh operating conditions are required, and the cost is inevitably increased, which is not economical. . Therefore, the lower limit of the content of the acid component in the hydroxyisobutyric acid ester may be about 0.001% by weight.
【００１６】[0016]
【実施例】以下、実施例を示して本発明をさらに具体的
に説明するが、本発明は以下の実施例に何ら限定される
ものではない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.
【００１７】実施例１、２および比較例１、２ 表１に示す酸成分を含有するα−ヒドロキシイソ酪酸メ
チル５０ｋｇを直径５０ｃｍ、高さ８０ｃｍの炭素鋼製
(SS-41) ドラム内に密封して、貯蔵温度を１５〜３０℃
に保ち、直射日光に当たらないようにして１年間保存し
た。この間、３ヶ月ごとに内容物を取り出して、内容物
の外観観察、純度分析、およびドラム材質の外観観察を
行った。結果を表１に示す。Examples 1 and 2 and Comparative Examples 1 and 2 50 kg of methyl α-hydroxyisobutyrate containing the acid component shown in Table 1 was made of carbon steel having a diameter of 50 cm and a height of 80 cm.
(SS-41) Sealed in a drum and stored at 15-30 ℃
And stored for 1 year without exposing to direct sunlight. During this period, the contents were taken out every 3 months, and the appearance of the contents was observed, the purity was analyzed, and the appearance of the drum material was observed. The results are shown in Table 1.
【００１８】[0018]
【表１】 [Table 1]
【００１９】実施例３、４および比較例３、４ 表２に示す酸成分を含有するα−ヒドロキシイソ酪酸エ
チル１５ｋｇを１８リットル石油缶（ブリキ製）内に密
封して、貯蔵温度を１５〜３０℃に保ち、直射日光に当
たらないようにして６ヶ月間保存した。６ヶ月後内容物
を取り出して、内容物の外観観察、純度分析、および石
油缶材質の外観観察を行った。結果を表２に示す。Examples 3 and 4 and Comparative Examples 3 and 4 15 kg of ethyl α-hydroxyisobutyrate containing the acid component shown in Table 2 was sealed in an 18 liter petroleum can (made by tinplate) and the storage temperature was 15 to. It was kept at 30 ° C and stored for 6 months so as not to be exposed to direct sunlight. After 6 months, the contents were taken out, and the appearance of the contents was observed, the purity was analyzed, and the appearance of the petroleum can material was observed. Table 2 shows the results.
【００２０】[0020]
【表２】 [Table 2]
【００２１】実施例５、６および比較例５、６ 表３に示す酸成分を含有するβ−ヒドロキシイソ酪酸メ
チルを実施例１と同様に１年間貯蔵した後、その１００
ｇ中に、はんだ (Sn-37Pb)付けを施したプリント配線基
板（銅張積層板）を２０℃で所定時間（１０分間および
１時間）浸漬した。浸漬後、２−プロパノールによる１
分間のリンス洗浄、熱風乾燥を行った後、金属部分（は
んだ、銅）を目視により観察した。結果を表３に示す。Examples 5 and 6 and Comparative Examples 5 and 6 Methyl β-hydroxyisobutyrate containing the acid components shown in Table 3 was stored for 1 year in the same manner as in Example 1, and then 100
A printed wiring board (copper clad laminate) to which solder (Sn-37Pb) was applied was immersed in g at 20 ° C. for a predetermined time (10 minutes and 1 hour). After dipping, 1 with 2-propanol
After rinsing for 1 minute and hot air drying, the metal parts (solder, copper) were visually observed. The results are shown in Table 3.
【００２２】[0022]
【表３】 [Table 3]
【００２３】[0023]
【発明の効果】従来用いられているヒドロキシイソ酪酸
エステルは貯蔵中に分解、変色してしまうという問題を
有していた。これに対して、本発明によるヒドロキシイ
ソ酪酸エステルは、貯蔵中の分解、変色を著しく抑制す
ることができ、かつ金属部品、電子部品などの精密洗浄
用途や塗料、接着剤などの溶剤用途などへの使用が容易
になった。The previously used hydroxyisobutyric acid ester has the problem that it decomposes and changes color during storage. On the other hand, the hydroxyisobutyric acid ester according to the present invention can significantly suppress decomposition and discoloration during storage, and can be used for precision cleaning applications such as metal parts and electronic parts, and solvent applications such as paints and adhesives. Is easier to use.
Claims (2)
れるヒドロキシイソ酪酸エステルにおいて、 （前記各式中、Ｒは炭素数１〜４のアルキル基を表
す。）当該ヒドロキシイソ酪酸エステル中の酸成分の含
有量を０．５重量％以下に調整することを特徴とする貯
蔵安定性の改善されたヒドロキシイソ酪酸エステル。1. In the hydroxyisobutyric acid ester represented by the general formula [1] or the general formula [2], (In each of the above formulas, R represents an alkyl group having 1 to 4 carbon atoms.) Storage stability characterized in that the content of the acid component in the hydroxyisobutyric acid ester is adjusted to 0.5% by weight or less. Improved hydroxyisobutyrate.
ドロキシイソ酪酸メチル、α−ヒドロキシイソ酪酸エチ
ル、α−ヒドロキシイソ酪酸プロピル、α−ヒドロキシ
イソ酪酸ブチル、β−ヒドロキシイソ酪酸メチル、β−
ヒドロキシイソ酪酸エチル、β−ヒドロキシイソ酪酸プ
ロピルおよびβ−ヒドロキシイソ酪酸ブチルから選ばれ
たものである請求項１記載の貯蔵安定性の改善されたヒ
ドロキシイソ酪酸エステル。2. The hydroxyisobutyric acid ester is methyl α-hydroxyisobutyrate, ethyl α-hydroxyisobutyrate, propyl α-hydroxyisobutyrate, butyl α-hydroxyisobutyrate, methyl β-hydroxyisobutyrate, β-hydroxyisobutyrate.
The hydroxyisobutyric acid ester with improved storage stability according to claim 1, which is selected from ethyl hydroxyisobutyrate, propyl β-hydroxyisobutyrate and butyl β-hydroxyisobutyrate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10717295A JP4116104B2 (en) | 1995-04-07 | 1995-04-07 | Hydroxyisobutyric acid ester with improved storage stability |
| KR1019950030372A KR100367534B1 (en) | 1994-09-14 | 1995-09-14 | Solvent composition containing oxyisobutyric acid ester with improved stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10717295A JP4116104B2 (en) | 1995-04-07 | 1995-04-07 | Hydroxyisobutyric acid ester with improved storage stability |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007140487A Division JP2007284798A (en) | 2007-05-28 | 2007-05-28 | Method for cleaning metallic component and/or electronic component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08283201A true JPH08283201A (en) | 1996-10-29 |
| JP4116104B2 JP4116104B2 (en) | 2008-07-09 |
Family
ID=14452313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10717295A Expired - Lifetime JP4116104B2 (en) | 1994-09-14 | 1995-04-07 | Hydroxyisobutyric acid ester with improved storage stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4116104B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010001219A (en) * | 2008-06-18 | 2010-01-07 | Mitsubishi Rayon Co Ltd | METHOD FOR PRODUCING alpha-HYDROXY ACID ESTER |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6760299B2 (en) | 2015-10-02 | 2020-09-23 | 三菱瓦斯化学株式会社 | High-purity carboxylic acid ester and its manufacturing method |
-
1995
- 1995-04-07 JP JP10717295A patent/JP4116104B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010001219A (en) * | 2008-06-18 | 2010-01-07 | Mitsubishi Rayon Co Ltd | METHOD FOR PRODUCING alpha-HYDROXY ACID ESTER |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4116104B2 (en) | 2008-07-09 |
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