JP5002930B2 - Method for producing low odor emulsion - Google Patents
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本発明は、乳化重合法により得られる重合体エマルションより揮発性有機化合物を効率よく除去して、低コストで低臭気のエマルションを製造する方法に関するものである。 The present invention relates to a method for producing a low-cost, low-odor emulsion by efficiently removing volatile organic compounds from a polymer emulsion obtained by an emulsion polymerization method.
スチレン、酢酸ビニル、アクリロニトリル、ブタジエン、アクリル酸エステル、メタクリル酸エステル（以下、アクリル酸エステルとメタクリル酸エステルを総称して（メタ）アクリル酸エステルという）等の単量体を水性媒体中で乳化重合法により共重合して得られる重合体エマルション（以下、単にエマルションという）は、塗料、接着剤、粘着剤等の原料として広く利用されている。
かかるエマルションには、通常未重合の単量体や重合中に発生する分解物を主成分とする揮発性有機化合物が微量含まれており、悪臭を発生して環境を汚染したり、毒性を有するため取り扱い作業者の健康問題を引き起こしたりしていた。
Monomers such as styrene, vinyl acetate, acrylonitrile, butadiene, acrylic acid ester, methacrylic acid ester (hereinafter collectively referred to as (meth) acrylic acid ester) are emulsified in an aqueous medium. A polymer emulsion (hereinafter simply referred to as an emulsion) obtained by copolymerization by a legal method is widely used as a raw material for paints, adhesives, pressure-sensitive adhesives, and the like.
Such an emulsion contains a trace amount of volatile organic compounds mainly composed of unpolymerized monomers and decomposition products generated during the polymerization, which generates a foul odor and pollutes the environment or has toxicity. For this reason, it causes health problems for workers.
エマルションから揮発性有機化合物を除去する方法としては、加圧水蒸気を吹き込み、水蒸気とともに揮発性有機化合物を追い出す方法（特許文献１、特許文献２）、段塔型ストリッパーの上部からエマルションを供給しながら下方から加圧水蒸気を供給する方法（特許文献３）、及びエチレン系共重合体より未重合単量体を除去する方法（特許文献４）等が提案されている。
特許文献１においては、揮発性有機化合物の含有量を低減させるために極めて長時間を要しており、具体的には各実施例においていずれも４８時間も要していた。また、特許文献２に記載の方法では、エマルション中の揮発性有機化合物の濃度を２００ｐｐｍ以下のように微量にすることは極めて困難であった。一方、特許文献３は特殊な除去装置を使用しなければならず汎用性に欠けていた。特許文献４は、揮発性有機物が常温でガス状のエチレン単量体（沸点が−１０３℃）、塩化ビニル単量体（−１４℃）であって、除去が極めて容易である。
本発明においては、沸点が５０℃以上の単量体からなるエマルションを、簡便な装置で長時間を掛けることなく処理して、該エマルション中の揮発性有機化合物の濃度が２００ｐｐｍ以下になる方法を提供することを課題にした。
In Patent Document 1, a very long time is required to reduce the content of the volatile organic compound, and specifically, each example requires 48 hours. In the method described in Patent Document 2, it is extremely difficult to make the concentration of the volatile organic compound in the emulsion as small as 200 ppm or less. On the other hand, Patent Document 3 had to use a special removing device and lacked versatility. In Patent Document 4, volatile organic substances are gaseous ethylene monomer (boiling point: −103 ° C.) and vinyl chloride monomer (−14 ° C.) at room temperature, and removal is extremely easy.
In the present invention, an emulsion comprising a monomer having a boiling point of 50 ° C. or higher is treated with a simple apparatus without taking a long time, and the concentration of the volatile organic compound in the emulsion is reduced to 200 ppm or less. It was an issue to provide.
本発明者らは、上記課題を解決するため鋭意検討した結果、本発明を完成するに至った。
すなわち、本発明は、
〔１〕沸点が５０℃以上からなる単量体を乳化重合することによって得られたエマルションを、加熱処理容器または熱交換器で予め６０〜９５℃に予備加熱をおこなった後、該エマルションを脱臭処理槽に連続的に供給し、同槽内に貯えられた該エマルションに加圧水蒸気を吹き込み、水蒸気とともに揮発性有機化合物を除去した後、供給速度と等速で該エマルションを抜き出すことを特徴とする低臭気エマルションの製造方法。
〔２〕脱臭処理槽に供給する前におけるエマルション中の揮発性有機化合物の濃度が５００ｐｐｍ以下である〔１〕に記載の低臭気エマルションの製造方法。
〔３〕加熱処理容器において、エマルションに加圧水蒸気を供給し、かつ該容器内を水が沸騰する圧力に維持して、水蒸気とともに揮発性有機化合物を予備的に除去する〔１〕乃至〔２〕のいずれかに記載の低臭気エマルションの製造方法。
〔４〕加熱処理容器において、該容器内の気相部の圧力を７〜８５ＫＰａにして、エマルションの脱泡をおこなうことを特徴にする〔１〕乃至〔３〕のいずれかに記載の低臭気エマルションの製造方法。
〔５〕脱臭処理槽において、４０〜９５℃かつ該槽内の気相部の圧力を水が沸騰する圧力に維持しながら加圧水蒸気を供給し、水蒸気とともに揮発性有機化合物を蒸発させることによりエマルションより揮発性有機化合物を除去する〔１〕乃至〔４〕のいずれかに記載の低臭気エマルションの製造方法。
〔６〕脱臭処理槽より抜き出した脱臭後のエマルション中の揮発性有機化合物の濃度が２００ｐｐｍ以下である〔１〕乃至〔５〕のいずれかに記載の低臭気エマルションの製造方法。
〔７〕脱臭処理槽におけるエマルションの滞留時間が１〜８時間である〔１〕乃至〔６〕のいずれかに記載の低臭気エマルションの製造方法。
〔８〕該エマルションが、酢酸ビニルを含む単量体成分を乳化重合することによって得られたものである〔１〕乃至〔７〕のいずれかに記載の低臭気エマルションの製造方法。
〔９〕該エマルションが、アクリル酸エステル及び／又はメタクリル酸エステルを含む単量体成分を乳化重合することによって得られたものである〔１〕乃至〔７〕のいずれかに記載の低臭気エマルションの製造方法。
である。
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention
[1] An emulsion obtained by emulsion polymerization of a monomer having a boiling point of 50 ° C. or higher is preliminarily heated to 60 to 95 ° C. in a heat treatment container or a heat exchanger, and then the emulsion is deodorized. Continuously supplied to a treatment tank, pressurized water vapor is blown into the emulsion stored in the tank, and after removing volatile organic compounds together with water vapor, the emulsion is extracted at a rate equal to the supply speed. A method for producing a low odor emulsion.
[2] The method for producing a low-odor emulsion according to [1], wherein the concentration of the volatile organic compound in the emulsion before being supplied to the deodorization treatment tank is 500 ppm or less.
[3] In the heat treatment container, pressurized water vapor is supplied to the emulsion, and the inside of the container is maintained at a pressure at which water boils to preliminarily remove the volatile organic compound together with the water vapor. [1] to [2] The manufacturing method of the low odor emulsion in any one of.
[4] The low odor according to any one of [1] to [3], wherein in the heat treatment container, the pressure of the gas phase portion in the container is set to 7 to 85 KPa to defoam the emulsion. Method for producing emulsion.
[5] Emulsion by supplying pressurized steam while evaporating a volatile organic compound together with water vapor in a deodorizing treatment tank while maintaining the pressure of the gas phase in the tank at 40 to 95 ° C. The method for producing a low odor emulsion according to any one of [1] to [4], further removing volatile organic compounds.
[6] The method for producing a low-odor emulsion according to any one of [1] to [5], wherein the concentration of the volatile organic compound in the emulsion after deodorization extracted from the deodorization treatment tank is 200 ppm or less.
[7] The method for producing a low odor emulsion according to any one of [1] to [6], wherein the emulsion residence time in the deodorization treatment tank is 1 to 8 hours.
[8] The method for producing a low odor emulsion according to any one of [1] to [7], wherein the emulsion is obtained by emulsion polymerization of a monomer component containing vinyl acetate.
[9] The low odor emulsion according to any one of [1] to [7], wherein the emulsion is obtained by emulsion polymerization of a monomer component containing an acrylate ester and / or a methacrylate ester. Manufacturing method.
It is.
本発明によれば、特殊な処理装置を用いることなく、処理時間が１０時間以内という短期間に、揮発性有機化合物の濃度が２００ｐｐｍ以下のエマルションを製造することができる。さらに、本発明によって製造されたエマルションは、臭気がほとんどないために環境問題や安全衛生問題に優れ、品質が良いのみならず、生産性や製造コスト面でも優れている。 According to the present invention, an emulsion having a volatile organic compound concentration of 200 ppm or less can be produced in a short period of time of 10 hours or less without using a special processing apparatus. Furthermore, since the emulsion produced by the present invention has almost no odor, it is excellent in environmental problems and safety and health problems, not only in quality but also in productivity and production cost.
本発明では、エマルションに対し、加熱処理容器または熱交換器で予め６０〜９５℃に予備加熱する工程（以下、工程（１）という）をおこなった後に、該エマルションを脱臭処理槽に連続的に供給し、同槽内に貯えられた該エマルションに加圧水蒸気を吹き込み、水蒸気とともに揮発性有機化合物を除去した後、供給速度と等速で該エマルションを抜き出す工程（以下、工程（２）という）をおこなう。
本発明で工程（１）をおこなう理由は、予備加熱していないエマルションを工程（２）に供給すると、該工程においてエマルションの凝集や皮張りが発生し、エマルションの安定性の低下や粒子径の増大、処理時間の増加、脱臭能力の減少等を引き起こすためである。
工程（１）における加熱には、加熱処理容器を用いたバッチ処理や、熱交換器を用いたライン加熱による連続処理を用いることができる。
加熱処理容器を使用する場合は、少なくとも攪拌機、温度計（熱電対）を備えることが好ましく、脱泡のための脱気装置を備えることがより好ましい。予備脱臭のための加圧水蒸気吹き込み口を備えることがさらに好ましい。
工程（１）で加熱したエマルション中の揮発性有機化合物の濃度は、工程（２）に供給する前において５００ｐｐｍ以下であることが、工程（２）で効率よく脱臭するために好ましい。さらに好ましくは３００ｐｐｍ以下である。
In the present invention, with respect to emulsion, the step of pre-heating in advance 60 to 95 ° C. In the heat treatment chamber or a heat exchanger (hereinafter, step (1) hereinafter) after subjected to continuously the emulsion to deodorization treatment tank Supplying and blowing pressurized steam into the emulsion stored in the same tank, removing the volatile organic compound together with the steam, and then extracting the emulsion at the same rate as the supply rate (hereinafter referred to as step (2)). Do it.
The reason for carrying out the step (1) in the present invention is that when an emulsion that has not been preheated is supplied to the step (2), the emulsion is agglomerated and skinned in the step, resulting in a decrease in emulsion stability and particle size. This is to cause an increase, an increase in processing time, a decrease in deodorizing ability, and the like.
For the heating in the step (1), a batch process using a heat treatment container or a continuous process using line heating using a heat exchanger can be used.
In the case of using a heat treatment container, it is preferable to include at least a stirrer and a thermometer (thermocouple), and more preferably to include a deaeration device for defoaming. It is further preferable to provide a pressurized steam blowing port for preliminary deodorization.
The concentration of the volatile organic compound in the emulsion heated in the step (1) is preferably 500 ppm or less before being supplied to the step (2) in order to efficiently deodorize in the step (2). More preferably, it is 300 ppm or less.
乳化重合で得られたエマルションが上記の濃度を超える場合は、加熱処理容器で予備脱臭するのが好ましい。 工程（１）における加熱処理容器での予備脱臭は、該容器にエマルションを仕込み、温度６０〜９５℃かつ圧力７〜８５ＫＰａで、該容器内を水が沸騰する状態に維持して、加圧水蒸気を供給することによりおこなう。エマルションに含まれる揮発性有機化合物は、供給された加圧水蒸気の量と釣り合う分だけ、過剰の水蒸気とともに容器外に排出される。その際、該容器内の気相部を排気ポンプにより排気して減圧にすることにより、揮発性有機化合物と水蒸気をスムーズに系外に除去できる。該容器と排気ポンプの中間にコンデンサーを設けることにより排気したガスを凝縮することが好ましい。該容器の気相部の具体的な圧力は７〜８５ＫＰａが好ましく、１２〜４８ＫＰａがより好ましい。 When the emulsion obtained by emulsion polymerization exceeds the above-mentioned concentration, it is preferable to preliminarily deodorize with a heat treatment container. In the preliminary deodorization in the heat treatment container in the step (1), the emulsion is charged in the container, and the water is boiled at a temperature of 60 to 95 ° C. and a pressure of 7 to 85 KPa. This is done by supplying. The volatile organic compound contained in the emulsion is discharged out of the container together with excess water vapor by an amount commensurate with the amount of pressurized water vapor supplied. At that time, the volatile organic compound and water vapor can be smoothly removed out of the system by exhausting the gas phase portion in the container with an exhaust pump and reducing the pressure. It is preferable to condense the exhausted gas by providing a condenser between the container and the exhaust pump. The specific pressure in the gas phase part of the container is preferably 7 to 85 KPa, more preferably 12 to 48 KPa.
工程（１）において、加熱処理用容器は加熱用ジャケットで加熱することが好ましい。その際、エマルションの温度を６０〜９５℃にすることが必要である。エマルションの温度が９５℃を超えると、エマルションの分散安定性が破壊され、該容器の壁面で著しい量の重合体皮膜が発生し、容器内温度のバラツキや攪拌不良を引き起こす。温度が４０℃未満では予備加熱が足りず、工程（２）に供給した後でトラブルが生じる。
工程（１）において、該容器で予備脱臭を同時におこなう場合でも、エマルションの温度を４０〜９５℃にすることが必要である。４０℃未満では揮発性有機化合物の除去効率が低下する。９５℃を超えると前記のようにエマルションの安定性が低下する。好ましい温度は５０〜８０℃である。
In the step (1), the heat treatment container is preferably heated with a heating jacket. At that time, it is necessary that the temperature of the emulsion to 60 to 95 ° C.. When the temperature of the emulsion exceeds 95 ° C., the dispersion stability of the emulsion is destroyed, and a significant amount of polymer film is generated on the wall surface of the container, causing variations in temperature in the container and poor stirring. If the temperature is lower than 40 ° C., the preheating is insufficient, and a trouble occurs after the supply to the step (2).
In the step (1), even when preliminary deodorization is simultaneously performed in the container, the temperature of the emulsion needs to be 40 to 95 ° C. If it is less than 40 degreeC, the removal efficiency of a volatile organic compound will fall. When it exceeds 95 ° C., the stability of the emulsion is lowered as described above. A preferred temperature is 50-80 ° C.
予備脱臭における加圧水蒸気の供給時間は３０分〜８時間が好ましく、１〜６時間がより好ましい。供給時間が８時間を越えるとエマルションの分散安定性が低下して凝集が起こる懸念が生じ、３０分未満ではエマルションが所定の温度に達せず、エマルション中の揮発性有機化合物が所定量まで低減されない懸念がある。
加圧水蒸気としては、圧力４９ＫＰａ（０．５Ｋｇ／ｃｍ２）〜１５０ＫＰａ（１．５Ｋｇ／ｃｍ2）、温度１２０〜１５０℃程度の水蒸気が好ましく使用できる。加圧水蒸気の量が多量になるとコストが高くなり、少量であると揮発性有機化合物の除去が困難になる。
The supply time of pressurized water vapor in the preliminary deodorization is preferably 30 minutes to 8 hours, more preferably 1 to 6 hours. If the supply time exceeds 8 hours, there is a concern that the dispersion stability of the emulsion is reduced and aggregation occurs, and if it is less than 30 minutes, the emulsion does not reach a predetermined temperature, and the volatile organic compounds in the emulsion are not reduced to a predetermined amount. There are concerns.
The pressurized steam, the pressure 49KPa (0.5Kg / cm 2) ~150KPa (1.5Kg / cm 2), temperature of 120 to 150 ° C. of about steam can be preferably used. When the amount of pressurized water vapor is large, the cost is high, and when it is small, it is difficult to remove volatile organic compounds.
本発明では、工程（１）で予備加熱をおこなったエマルションは、配管を通って工程（２）に送られる。
工程（１）で予備脱臭をおこなった場合は、そのまま工程（２）に送っても良いが、一旦エマルションを別の容器に貯蔵してから工程（２）に供給することも可能である。貯蔵によりエマルションの温度が低下する場合は、該エマルションを所定温度まで加熱して使用することができる。加熱は一時的に貯蔵した容器でおこなっても良いし、熱交換器を通過させることによりライン加熱をおこなっても良い。
かかる熱交換器としては、特に限定されないが、例えばプレート式熱交換器が挙げられる。
In the present invention, the emulsion preliminarily heated in step (1) is sent to step (2) through a pipe.
When preliminary deodorization is performed in step (1), it may be sent to step (2) as it is, but it is also possible to store the emulsion in a separate container and then supply it to step (2). When the temperature of the emulsion decreases due to storage, the emulsion can be used by heating to a predetermined temperature. Heating may be performed in a temporarily stored container, or line heating may be performed by passing through a heat exchanger.
Although it does not specifically limit as this heat exchanger, For example, a plate type heat exchanger is mentioned.
工程（１）では、加熱処理容器の気相部の圧力を７〜８５ＫＰａまで減圧して、エマルションの脱泡をおこなうことができる。かかる場合は攪拌することが好ましいが、過剰の攪拌は突沸等を招く。その際は消泡剤を適量使用しても良い。好ましい消泡剤としては、例えばサンノプコ（株）商品名ＳＮデフォーマーＰＣ等のポリエーテル系消泡剤およびシリコーン系消泡剤が挙げられる。予備脱臭をおこなう場合はその工程中で脱気するため、改めて脱泡する必要はない。 In the step (1), the pressure of the gas phase part of the heat treatment container can be reduced to 7 to 85 KPa to defoam the emulsion. In such a case, stirring is preferable, but excessive stirring causes bumping and the like. In that case, an appropriate amount of an antifoaming agent may be used. Preferable examples of the antifoaming agent include polyether antifoaming agents such as Sannopco Co., Ltd. trade name SN deformer PC and silicone antifoaming agents. When preliminary deodorization is performed, degassing is not necessary since it is deaerated during the process.
本発明の工程（２）では、工程（１）で加熱したエマルション（必要により予備脱臭もおこなったエマルション）を連続的に脱臭処理槽に供給し、加圧水蒸気により本格的な脱臭処理をおこないながら供給量と同量のエマルションを連続的に抜き出す。
以下に工程（２）の条件を具体的に述べる。
工程（２）において処理槽内に加圧水蒸気を導入する際には、槽内に溜められた該エマルション中に直接吹き込むことが好ましい。これによりエマルションの粒子を破壊せずに、該粒子中の揮発性有機化合物を効率よく除去することができる。
槽内に溜められた該エマルション中に加圧水蒸気を吹き込み、これによって分離した揮発性有機化合物及び供給分と等量の水蒸気を系外に除去する。このためには、処理槽には排気ポンプが備えてあり、該ポンプで処理槽の上部の気相部より排気して減圧にすることが好ましい。排気される揮発性有機化合物及び水蒸気の除去方法は、特に限定されないが、処理槽と排気ポンプの中間の位置に設けられるコンデーサーで凝縮して除去することが好ましい。
In step (2) of the present invention, the emulsion heated in step (1) (emulsion subjected to preliminary deodorization if necessary) is continuously supplied to the deodorization treatment tank and supplied while performing full-scale deodorization treatment with pressurized steam. The same amount of emulsion is continuously withdrawn.
The conditions for step (2) will be specifically described below.
In the step (2), when pressurized steam is introduced into the treatment tank, it is preferable to blow directly into the emulsion stored in the tank. Thereby, the volatile organic compound in the particles can be efficiently removed without destroying the particles of the emulsion.
Pressurized water vapor is blown into the emulsion stored in the tank, thereby removing the volatile organic compound and the water vapor in an amount equivalent to the supplied amount out of the system. For this purpose, the treatment tank is provided with an exhaust pump, and it is preferable to evacuate the gas from the gas phase part at the top of the treatment tank. The method for removing the volatile organic compound and water vapor to be exhausted is not particularly limited, but it is preferable to condense and remove with a condenser provided at a position between the treatment tank and the exhaust pump.
工程（２）において処理槽内のエマルションは、水蒸気処理の期間一定の温度を維持するために、加温用ジャケットで加熱される。かかる際の処理槽内の温度は４０〜９５℃にする。槽内温度が９５℃を超えると槽内壁面に大量の重合体皮膜が発生し、槽内の温度が不均一になって温度コントロールができなくなる。これによりエマルションの分散安定性が破壊されて品質低下や固形分低下を生ずる。槽内温度が４０℃未満であると、揮発性有機化合物の除去効率が低下して臭気を除くことができなくなる。好ましい温度は５０〜８０℃である。 In step (2), the emulsion in the treatment tank is heated with a heating jacket in order to maintain a constant temperature during the steam treatment. The temperature in the treatment tank at this time is 40 to 95 ° C. When the temperature in the tank exceeds 95 ° C., a large amount of polymer film is generated on the inner wall surface of the tank, the temperature in the tank becomes non-uniform, and the temperature cannot be controlled. As a result, the dispersion stability of the emulsion is destroyed, resulting in deterioration of quality and solid content. When the temperature in the tank is lower than 40 ° C., the removal efficiency of the volatile organic compound is lowered and the odor cannot be removed. A preferred temperature is 50-80 ° C.
本発明においては、前記のように、水蒸気処理中に処理槽内の気体を排気ポンプで系外に排気することにより、上記の槽内温度において槽内が飽和水蒸気圧すなわち槽内の水分が沸騰している状態となるようにすることが必要である。処理槽内の気相部の具体的な圧力は７ＫＰａ〜８５ＫＰａの範囲が好ましく、１２ＫＰａ〜４７ＫＰａの範囲がより好ましい。
この加圧水蒸気の好ましい割合は、該処理槽に供給するエマルション１００質量部に対し５〜６０質量部である。更に好ましい割合は、エマルション１００重量部に対し１５〜５０質量部である。加圧水蒸気としては、工程（１）の予備脱臭と同様に圧力４９ＫＰａ〜１５０ＫＰａ、温度１２０〜１５０℃程度の水蒸気が好ましく使用できる。
加圧水蒸気の量が多量になるとコストが高くなり実用的でなく、一方、加圧水蒸気の量が少なすぎると揮発性物質の除去が困難になる。
In the present invention, as described above, the gas in the treatment tank is exhausted out of the system by the exhaust pump during the steam treatment, so that the saturated water vapor pressure in the tank, that is, the water in the tank is boiled at the temperature in the tank. It is necessary to be in the state of being. The specific pressure in the gas phase part in the treatment tank is preferably in the range of 7 KPa to 85 KPa, more preferably in the range of 12 KPa to 47 KPa.
A desirable ratio of the pressurized steam is 5 to 60 parts by mass with respect to 100 parts by mass of the emulsion supplied to the treatment tank. A more desirable ratio is 15 to 50 parts by mass with respect to 100 parts by weight of the emulsion. As the pressurized steam, steam having a pressure of 49 KPa to 150 KPa and a temperature of about 120 to 150 ° C. can be preferably used as in the preliminary deodorization in the step (1).
If the amount of pressurized steam is large, the cost increases and is not practical. On the other hand, if the amount of pressurized steam is too small, it is difficult to remove volatile substances.
工程（２）において該処理槽の内容積に対してエマルションの供給量を選択することにより、エマルションの平均滞留時間（以下、滞留時間という）を適宜選択することができる。工程（２）におけるエマルションの滞留時間は１〜８時間が好ましく、より好ましくは２〜６時間である。滞留時間が８時間を越えるとエマルションの品質が低下する。一方、滞留時間が１時間未満では、揮発性有機化合物の除去が不十分になる。 By selecting the supply amount of the emulsion with respect to the internal volume of the treatment tank in the step (2), the average residence time of the emulsion (hereinafter referred to as residence time) can be appropriately selected. The emulsion residence time in step (2) is preferably 1 to 8 hours, more preferably 2 to 6 hours. When the residence time exceeds 8 hours, the quality of the emulsion deteriorates. On the other hand, when the residence time is less than 1 hour, the removal of the volatile organic compound becomes insufficient.
本発明においては、処理後におけるエマルション中の揮発性有機化合物の濃度が２００ｐｐｍ以下となるように水蒸気処理をおこなうのが好ましい。かかる処理によってもなお該エマルション中に残留する揮発性有機化合物の量はガスクロマトグラフィーを用いて分析することができる。該エマルション中の揮発性有機化合物の濃度は１５０ｐｐｍ以下がより好ましく、１００ｐｐｍ以下が更に好ましい。 In the present invention, the steam treatment is preferably performed so that the concentration of the volatile organic compound in the emulsion after the treatment is 200 ppm or less. The amount of volatile organic compounds still remaining in the emulsion after such treatment can be analyzed using gas chromatography. The concentration of the volatile organic compound in the emulsion is more preferably 150 ppm or less, and still more preferably 100 ppm or less.
工程（２）においても、発泡を抑えるために消泡剤を適量使用してもよい。かかる消泡剤は、工程（１）で使用した物と同一であっても異なっても良い。 Also in the step (2), an appropriate amount of an antifoaming agent may be used in order to suppress foaming. Such an antifoaming agent may be the same as or different from the one used in step (1).
本発明において揮発性有機化合物を除去する対象となるエマルションとしては、沸点が５０℃以上の単量体のみからなる単量体を乳化重合して得られるエマルションである。
本発明で使用する単量体としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチルおよび（メタ）アクリル酸２−エチルヘキシル等の（メタ）アクリル酸アルキル、（メタ）アクリル酸、スチレン、（メタ）アクリロニトリル、（メタ）アクリル酸２−ヒドロキシエチル、酢酸ビニル、マレイン酸エステル、バーサチック酸ビニルなどの高級ビニルエステル等のビニル単量体であって沸点が５０℃以上のものが例示される。
沸点が５０℃未満の単量体を使用する場合は、公知の方法によって脱臭が可能であるため、本発明の方法を使用する価値がない。
In the present invention, the emulsion to be a target for removing the volatile organic compound is an emulsion obtained by emulsion polymerization of a monomer having a boiling point of only 50 ° C. or more.
As the monomer used in the present invention, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, ( Vinyl monomer such as (meth) acrylic acid, styrene, (meth) acrylonitrile, 2-hydroxyethyl (meth) acrylate, vinyl acetate, maleate, vinyl versatate, etc. The above is exemplified.
When using a monomer having a boiling point of less than 50 ° C., it is not worth using the method of the present invention because it can be deodorized by a known method.
本発明のエマルションは、上記単量体を水性媒体中で乳化重合して得られる。
塗料、粘着剤、バインダーや接着剤等の塗装作業に使用される乳化重合体としては、ガラス転移温度が−８０℃〜８０℃の共重合体が使用される。光沢、接着性や塗工性が良い点から酢酸ビニルを含む単量体成分を乳化重合することによって得られたエマルションが好ましい。また、光沢、耐水性や耐候性が良い点から（メタ）アクリル酸エステルを含む単量体成分を乳化重合することによって得られたエマルションが好ましい。酢酸ビニルと（メタ）アクリル酸エステルの共重合体も接着性が良い点から使用可能である。
エマルションにおける固形分濃度は、１５〜７０質量％が好ましい。固形分が少ないと必要な重合体に対して処理に要するエマルションの量が多く生産効率が悪い。固形分が高すぎると揮発性有機化合物が除去し難い。エマルションの安定性と処理効率の点から、３０〜６０質量％がより好ましい。
エマルションに含まれる揮発性有機化合物としては、未重合単量体および重合中に加水分解等によって生成したアルコール類が挙げられる。
The emulsion of the present invention is obtained by emulsion polymerization of the above monomer in an aqueous medium.
A copolymer having a glass transition temperature of −80 ° C. to 80 ° C. is used as an emulsion polymer used in coating operations such as paints, pressure-sensitive adhesives, binders and adhesives. An emulsion obtained by emulsion polymerization of a monomer component containing vinyl acetate is preferred from the viewpoint of good gloss, adhesion and coating properties. Moreover, the emulsion obtained by carrying out emulsion polymerization of the monomer component containing a (meth) acrylic acid ester from a point with favorable glossiness, water resistance, and a weather resistance is preferable. A copolymer of vinyl acetate and (meth) acrylic acid ester can also be used because of its good adhesiveness.
The solid content concentration in the emulsion is preferably 15 to 70% by mass. If the solid content is small, the amount of emulsion required for the treatment with respect to the required polymer is large and the production efficiency is poor. If the solid content is too high, it is difficult to remove volatile organic compounds. 30-60 mass% is more preferable from the point of stability of emulsion and processing efficiency.
Examples of the volatile organic compound contained in the emulsion include unpolymerized monomers and alcohols generated by hydrolysis during polymerization.
以下、実施例および比較例を挙げて、本発明をさらに具体的に説明する。なお、以下における「部」は「質量部」を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples . In the following, “part” means “part by mass”.
・ 製造例
撹拌機、還流冷却器、滴下槽および温度計を装着した反応容器に、水６００部を投入し、８７℃に維持した。滴下槽には、水３００部、アルキルベンゼンスルホン酸ナトリウム４３部、メタクリル酸メチル１５０部、アクリル酸ブチル５００部、スチレン３４０部およびメタクリル酸１０部を投入し撹拌して乳化液を作成した。この乳化液と重合開始剤（過硫酸アンモニウム）５％水溶液６０部を、反応容器に４時間かけて連続滴下して乳化重合させた後、さらに１．５時間熟成した。熟成中には過硫酸アンモニウム５％水溶液を４０部添加し、固形分５０質量％のエマルションを得た。
該エマルションの揮発性有機化合物の含有量は９１０ｐｐｍ（ガスクロマトグラフ測定）であり、主な物質はアクリル酸ブチルおよびブタノールであった。
Production Example 600 parts of water was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, and maintained at 87 ° C. In the dropping tank, 300 parts of water, 43 parts of sodium alkylbenzenesulfonate, 150 parts of methyl methacrylate, 500 parts of butyl acrylate, 340 parts of styrene and 10 parts of methacrylic acid were added and stirred to prepare an emulsion. The emulsion and 60 parts of a polymerization initiator (ammonium persulfate) 5% aqueous solution were continuously dropped into a reaction vessel over 4 hours to effect emulsion polymerization, and then aged for 1.5 hours. During the ripening, 40 parts of a 5% aqueous solution of ammonium persulfate was added to obtain an emulsion having a solid content of 50% by mass.
The content of volatile organic compounds in the emulsion was 910 ppm (measured by gas chromatography), and the main substances were butyl acrylate and butanol.
・ 実施例１
製造例で得られたエマルション用いて水蒸気処理を行った。
加熱処理容器及び脱臭処理槽としては、撹拌機、排気装置、温度計を備えた３リットルの内容積を有するものを用いた。加熱処理容器に製造例で得たエマルションを一括して７５０ｇ仕込み、工程（１）の予備脱臭をおこなった（所定の温度と圧力で加圧水蒸気を吹き込み、容器内圧力が飽和水蒸気圧になるように排気装置を稼動させた水分を沸騰状態にさせた）。その後直ちに、エマルションを工程（２）の脱臭処理槽に連続的に供給し、加圧水蒸気で処理して本格脱臭の処理をおこない、処理後のエマルションを等量で抜き出した。なお、水蒸気に関しては、供給量と同量を槽外に排出し、コンデンサーで水に凝縮させて除去した。
工程（１）の予備脱臭及び工程（２）の本格脱臭における加熱水蒸気処理の条件（エマルションの滞留時間、水蒸気の供給量およびエマルション温度等）は表１、処理によって得られるエマルション中の揮発性有機化合物濃度は表２に記載のとおりである。
Example 1
Steam treatment was performed using the emulsion obtained in the production example.
As the heat treatment container and the deodorization treatment tank, those having an internal volume of 3 liters equipped with a stirrer, an exhaust device and a thermometer were used. 750 g of the emulsion obtained in the production example was charged all at once into the heat treatment container, and the preliminary deodorization in the step (1) was performed (pressurized steam was blown at a predetermined temperature and pressure so that the pressure inside the container became saturated steam pressure) The water that operated the exhaust system was brought to a boiling state). Immediately after that, the emulsion was continuously supplied to the deodorization treatment tank in the step (2) and treated with pressurized steam to carry out full-scale deodorization, and the treated emulsion was extracted in an equal amount. In addition, about water vapor | steam, the same quantity as supply amount was discharged | emitted out of the tank, and it condensed by water with the condenser and removed.
The conditions (emulsion residence time, supply amount of water vapor, emulsion temperature, etc.) of the heated steam treatment in the preliminary deodorization in the step (1) and the full-scale deodorization in the step (2) are shown in Table 1, volatile organics in the emulsion obtained by the treatment The compound concentrations are as shown in Table 2.
○実施例２
製造例で得られたエマルションを用い、工程（１）の予備脱臭時間および工程（２）の加圧水蒸気供給量を変える以外は実施例１と同様に処理をおこなった。処理条件は表１、処理によって得られたエマルション中の揮発性有機化合物の濃度は表２に記載のとおりである。
Example 2
Using the emulsion obtained in the production example, the treatment was performed in the same manner as in Example 1 except that the preliminary deodorization time in the step (1) and the pressurized steam supply amount in the step (2) were changed. The treatment conditions are shown in Table 1, and the concentration of the volatile organic compound in the emulsion obtained by the treatment is as shown in Table 2.
○実施例３
製造例で得られたエマルションを用い、工程（１）の予備脱臭時の水蒸気供給量、並びに工程（２）のエマルション供給量及び滞留時間を変更する以外実施例２と同様に処理をおこなった。処理条件は表１、処理によって得られるエマルション中の揮発性有機化合物の濃度は表２に記載のとおりである。
Example 3
Using the emulsion obtained in the production example, the treatment was performed in the same manner as in Example 2 except that the water vapor supply amount at the time of preliminary deodorization in step (1) and the emulsion supply amount and residence time in step (2) were changed. The treatment conditions are shown in Table 1, and the concentration of volatile organic compounds in the emulsion obtained by the treatment is as shown in Table 2.
○実施例４
製造例で得られたエマルションに更に過硫酸アンモニウム５％水溶液を４０部添加し、５時間熟成をおこなって、揮発性有機化合物の含有量が４５０ｐｐｍ（ガスクロマトグラフ測定）のエマルションを得た。主な揮発性有機化合物はアクリル酸ブチルおよびブタノールであった。
次いで、該エマルションを６７℃になるように攪拌しながら３時間加熱した後（予備脱臭はおこなわなかったがメタクリル酸メチルが微量減少した。）、工程（２）をおこなった。処理条件は表１、処理によって得られるエマルション中の揮発性有機化合物の濃度は表２に記載のとおりである。
Example 4
40 parts of a 5% aqueous solution of ammonium persulfate was further added to the emulsion obtained in the production example, and aging was performed for 5 hours to obtain an emulsion having a volatile organic compound content of 450 ppm (gas chromatographic measurement). The main volatile organic compounds were butyl acrylate and butanol.
Next, the emulsion was heated to 67 ° C. with stirring for 3 hours (preliminary deodorization was not performed, but methyl methacrylate was slightly reduced), and then step (2) was performed. The treatment conditions are shown in Table 1, and the concentration of volatile organic compounds in the emulsion obtained by the treatment is as shown in Table 2.
・ 比較例１
製造例の方法によって得られたエマルションを用いて、処理条件を変えて実施例１と同様な脱臭処理を行った。処理条件は表１に、エマルション中の揮発性有機化合物の濃度は表２に記載のとおりである。
実施例１との違いは、工程（１）のエマルション温度、容器内圧力及び水蒸気供給量、工程（２）の水蒸気供給量及びエマルション温度である。処理条件は表１に、エマルション中の揮発性有機化合物の濃度は表２に記載のとおりである。
Comparative example 1
Using the emulsion obtained by the method of the production example, the same deodorizing treatment as in Example 1 was performed under different treatment conditions. The treatment conditions are shown in Table 1, and the concentration of the volatile organic compound in the emulsion is as shown in Table 2.
Differences from Example 1 are the emulsion temperature, the pressure in the container and the water vapor supply amount in the step (1), the water vapor supply amount and the emulsion temperature in the step (2). The treatment conditions are shown in Table 1, and the concentration of the volatile organic compound in the emulsion is as shown in Table 2.
本発明によれば、人体に有害な揮発性有機化合物の含有量が少なく環境に優しくかつ安全であって、品質も良好なエマルションが安価かつ容易に得られる。かかるエマルションは、塗料や接着剤、粘着剤、繊維バインダー等の環境面、安全面、品質面に対する要求が厳しい用途に、広範囲に使用できる。
According to the present invention, an emulsion that is low in content of volatile organic compounds harmful to the human body, is environmentally friendly and safe, and has good quality can be easily obtained at low cost. Such an emulsion can be used in a wide range of applications such as paints, adhesives, pressure-sensitive adhesives, fiber binders, and the like that have strict requirements for environmental, safety, and quality.
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| JP5712918B2 (en) * | 2011-12-27 | 2015-05-07 | 東亞合成株式会社 | Method for producing aqueous copolymer emulsion |
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