JP6789375B2 - 高吸水性樹脂の製造方法およびこのような方法で得られた高吸水性樹脂 - Google Patents
高吸水性樹脂の製造方法およびこのような方法で得られた高吸水性樹脂 Download PDFInfo
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- JP6789375B2 JP6789375B2 JP2019506089A JP2019506089A JP6789375B2 JP 6789375 B2 JP6789375 B2 JP 6789375B2 JP 2019506089 A JP2019506089 A JP 2019506089A JP 2019506089 A JP2019506089 A JP 2019506089A JP 6789375 B2 JP6789375 B2 JP 6789375B2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Description
本出願は、2017年6月30日付韓国特許出願第10−2017−0083849号および2018年6月20日付韓国特許出願第10−2018−0071073号に基づいた優先権の利益を主張し、当該韓国特許出願の文献に開示されたすべての内容は本明細書の一部として組み含まれる。
前記含水ゲル重合体に対してゲル粉砕する段階;
前記ゲル粉砕された含水ゲル重合体を乾燥し、含水ゲル重合体の乾燥物を粉砕および分級してベース樹脂粉末を形成する段階;および
表面架橋剤の存在下で、前記ベース樹脂粉末を熱処理しながら表面架橋して高吸水性樹脂粒子を形成する段階を含み、
前記含水ゲル重合体の乾燥物の分級後、微粉末を回収する段階;
前記微粉末を粉末形態の高分子バインダーの存在下で再造粒して微分再造粒体を提供する段階;および
前記微分再造粒体を前記乾燥前の含水ゲル重合体と混合する段階;をさらに含む、高吸水性樹脂の製造方法を提供する。
前記ベース樹脂粉末上に形成されており、前記第1架橋重合体が表面架橋剤を媒介として追加架橋された第2架橋重合体を含む表面架橋層を含み、
生理食塩水(0.9重量%塩化ナトリウム水溶液)に対する30分間の遠心分離保水能(CRC)が30g/g乃至45g/gである、高吸水性樹脂を提供する。
CRC(g/g)={[W2(g)−W1(g)−W0(g)]/W0(g)}
W0(g)は、微分再造粒体の初期重量(g)であり、
W1(g)は、微分再造粒体を入れない不織布封筒を常温で生理食塩水に30分間含浸した後、遠心分離機を用いて250Gで3分間脱水した後に測定した重量であり、
W2(g)は、微分再造粒体を入れた不織布封筒を常温で生理食塩水に30分間含浸した後、遠心分離機を用いて250Gで3分間脱水した後に測定した重量である。
R1−COOM1
R1は、不飽和結合を含む炭素数2乃至5のアルキルグループであり、
M1は、水素原子、1価または2価金属、アンモニウム基または有機アミン塩である。
高吸水性樹脂の製造装置としては、重合工程、含水ゲル粉砕工程、乾燥工程、粉砕工程、分級工程、表面架橋工程、冷却工程、分級工程および各工程を連結する輸送工程から構成される連続製造装置を用いた。
含水ゲル重合体形成段階
アクリル酸100重量部に内部架橋剤としてポリエチレングリコールジアクリレート(重量平均分子量:〜500g/mol)0.7重量部(7000ppm)とアリルメタクリレート0.015重量部(150ppm)および光開始剤としてIRGACURE 819 0.01重量部を混合して単量体溶液を製造した。次に、前記単量体溶液を定量ポンプで連続供給し、同時に24重量%水酸化ナトリウム水溶液160重量部を連続的にラインミキシングして単量体水溶液を製造した。この時、中和熱により上昇した温度を40℃に調節した。また、4重量%過硫酸ナトリウム水溶液6重量部を連続的にラインミキシングした後、両端に土手を備えた平面状の重合ベルトを有する連続重合機に連続的に供給した。その後、1分間UVを照射し、2分間追加的に熱重量を実施して含水ゲル重合体を製造した。このような含水ゲル重合体の含水率は45重量%に確認された。
含水ゲル重合体粉砕段階
前記含水ゲル重合体を平均大きさが約300mm以下になるようにカッターで1次切断した後、微分再造粒体と共に粉砕機(chopper)に投入して2次粉砕した。ここで、前記微分再造粒体は、以下の段階5で製造した微分再造粒体を用い、投入比率は含水ゲル重合体100重量部を基準に20重量部を混合した。
ゲル粉砕された含水ゲル重合体の乾燥段階
次に、前記段階2で粉砕された含水ゲル重合体を上下に風量の転移が可能な乾燥機で乾燥させた。乾燥された粉の含水量が約2%以下になるように180℃のホットエアー(hot air)を15分間下方から上方へ流れるようにし、再び15分間上方から下方へ流れるようにして前記含水ゲル重合体を均一に乾燥させた。
ベース樹脂粉末形成段階
前記段階3で乾燥された含水ゲル重合体を粉砕機で粉砕した後、分級して150乃至850μm大きさのベース樹脂を得た。
微分再造粒体提供段階(含水率0%微分再造粒)
前記分級を通じて150μm未満の粒径を有する重合体粒子である微分を回収した後、混合機に入れてPEO粉末(Mw=100,000g/mol)と共に無溶媒下で乾燥混合した。前記PEO粉末は、全体微粉末100重量部を基準にその含有量を変更しながら用いた。つまり、前記PEO粉末は、それぞれ1、5、10、15、25、50、75および100重量部使用し、実施例1乃至8に区分した。前記混合機は攪拌手段と温度調節手段が備えられたものを用いた。
高吸水性樹脂粒子形成段階
以降、前記段階4で製造したベース樹脂100重量部を、水4重量部、エチレンカーボネート1重量部を混合した架橋剤溶液と混合した後、180℃で40分間表面架橋反応させた。そして、得られた生成物を冷却させた後、分級して粒径が150乃至850μmである表面架橋された高吸水性樹脂を得た。
前記段階5の微分再造粒工程において、熱処理温度を180℃に変更したことを除き、実施例8と同様な方法で高吸水性樹脂を製造した。
前記段階5の微分再造粒工程において、微分と水を混合した後、再造粒を行い、別途の乾燥機で微分再造粒体の水分乾燥工程を行ったことを除き、実施例1と同様な方法で高吸水性樹脂を製造した。
前記段階5の微分再造粒工程において、微分100重量部を基準にポリプロピレングリコール水溶液を10g(含水率10%)を用いたことを除き、実施例1と同様な方法で高吸水性樹脂を製造した。
段階5の微分再造粒工程において、熱処理を180℃で、9分間行うことを除き、実施例1と同様な方法で行って高吸水性樹脂を製造した。
前記実施例8および9の微分再造粒体に対して、走査電子顕微鏡写真を用いて平均粒径を測定して図1に示した。
実施例1乃至8の微分再造粒体に対して、次の表1の方法で粉砕および分級した後、再造粒効率とCRCを測定して表2に結果を示した。
Hammer mill(粉砕条件:650rpm、torque値4到達時まで粉砕
Ball mill(粉砕条件:300rpm、20分、ceramic ballを10個使用)
3段分類:再造粒効率=(#30上の量+#30〜50の量)/全体微分量*100
7段分類:再造粒効率=(#20〜30の量+#30〜40の量+#40〜50の量+#50〜70の量+#70〜100の量)/全体微分量*100
比較例1乃至2の微分再造粒体に対して、一般的な方法で再造粒効率、CRC、水吸水速度を測定した。その結果は表3に示した。
実施例1および比較例2で製造した各高吸水性樹脂のCRCを次の方法で測定および評価した。
欧州不織布産業協会(European Disposables and Nonwovens Association、EDANA)規格EDANA WSP 241.3により無荷重下吸水倍率による遠心分離保水能(CRC)を測定した。高吸水性樹脂W0’(g、約0.2g)を不織布製の封筒に均一に入れて密封(seal)した後、常温に0.9重量%の塩化ナトリウム水溶液の生理食塩水に浸水させた。30分後に封筒を遠心分離機を利用して250Gで3分間水分を除去した後に封筒の質量W2’(g)を測定した。また、高吸水性樹脂を利用せずに同一の操作をした後、その時の質量W1’(g)を測定した。このように得られた各質量を利用して次の計算式4により高吸水性樹脂のCRC(g/g)を算出して保水能を確認した。
CRC(g/g)={[W2’(g)−W1’(g)−W0’(g)]/W0’(g)}
Claims (8)
- 内部架橋剤の存在下で、少なくとも一部が中和された酸性基を有する水溶性エチレン系不飽和単量体を架橋重合して第1架橋重合体を含む含水ゲル重合体を形成する段階;
前記含水ゲル重合体に対してゲル粉砕する段階;
前記ゲル粉砕された含水ゲル重合体を乾燥し、含水ゲル重合体の乾燥物を粉砕および分級してベース樹脂粉末を形成する段階;および
表面架橋剤の存在下で、前記ベース樹脂粉末を熱処理しながら表面架橋して高吸水性樹脂粒子を形成する段階を含み、
前記含水ゲル重合体の乾燥物の分級後、微粉末を回収する段階;
前記微粉末を粉末形態の高分子バインダーの存在下で再造粒して微粉末の再造粒体を提供する段階;および
前記微粉末の再造粒体を前記乾燥前の含水ゲル重合体と混合する段階;
をさらに含み、
前記微粉末の再造粒体を提供する段階は、150μm未満の平均粒径を有する微粉末および粉末形態の高分子バインダーを無溶媒下で乾燥混合した後、熱処理を通じて微粉末を再造粒する段階を含み、
前記熱処理は、105乃至180℃で10分乃至20分間行い、
前記粉末形態の高分子バインダーは、重量平均分子量が100,000乃至600,000g/molの重量平均分子量を有するポリエチレンオキシド粉末を用いる、高吸水性樹脂の製造方法。 - 前記粉末形態の高分子バインダーは、微粉末100重量部に対して、1乃至100重量部の量で用いる、請求項1に記載の高吸水性樹脂の製造方法。
- 前記微粉末の再造粒体は、前記乾燥前の含水ゲル重合体100重量部を基準に10乃至30重量部の含有量で混合する、請求項1に記載の高吸水性樹脂の製造方法。
- 前記ゲル粉砕する段階において、含水ゲル重合体は、少なくとも1回以上の粉砕段階を行う、請求項1に記載の高吸水性樹脂の製造方法。
- 前記水溶性エチレン系不飽和単量体は、アクリル酸、メタクリル酸、無水マレイン酸、フマル酸、クロトン酸、イタコン酸、2−アクリロイルエタンスルホン酸、2−メタクリロイルエタンスルホン酸、2−(メタ)アクリロイルプロパンスルホン酸、または2−(メタ)アクリルアミド−2−メチルプロパンスルホン酸の陰イオン性単量体とその塩;(メタ)アクリルアミド、N−置換(メタ)アクリレート、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレートまたはポリエチレングリコール(メタ)アクリレートの非イオン系親水性含有単量体;および(N,N)−ジメチルアミノエチル(メタ)アクリレートまたは(N,N)−ジメチルアミノプロピル(メタ)アクリルアミドのアミノ基含有不飽和単量体とその四級化物;からなる群より選択された1種以上を含む、請求項1に記載の高吸水性樹脂の製造方法。
- 前記第1架橋重合体は、トリメチルロールプロパントリ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ブタンジオールジ(メタ)アクリレート、ブチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、ヘキサンジオールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ジペンタエリスリトールペンタアクリレート、グリセリントリ(メタ)アクリレートおよびペンタエリスリトールテトラアクリレートからなる群より選択されたポリオールのポリ(メタ)アクリレート系第1内部架橋剤;およびアリル(メタ)アクリレート系第2内部架橋剤の存在下で、前記単量体が架橋重合された高分子を含む、請求項1に記載の高吸水性樹脂の製造方法。
- 前記内部架橋剤は、ポリオールのポリ(メタ)アクリレート系第1内部架橋剤およびアリル(メタ)アクリレート系第2内部架橋剤を含み、
前記第1内部架橋剤は、前記内部架橋剤および単量体を含む単量体組成物の100重量部に対して0.4重量部乃至1重量部の含有量で含まれ、前記第2内部架橋剤は、前記単量体組成物の100重量部に対して0.008重量部乃至0.5重量部の含有量で含まれる、請求項1に記載の高吸水性樹脂の製造方法。 - 前記表面架橋剤は、アルキレンカーボネート系化合物または多価アルコール系化合物を含む、請求項1に記載の高吸水性樹脂の製造方法。
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