JPWO2019159779A1 - ディップ成形体の製造方法 - Google Patents
ディップ成形体の製造方法 Download PDFInfo
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- JPWO2019159779A1 JPWO2019159779A1 JP2020500429A JP2020500429A JPWO2019159779A1 JP WO2019159779 A1 JPWO2019159779 A1 JP WO2019159779A1 JP 2020500429 A JP2020500429 A JP 2020500429A JP 2020500429 A JP2020500429 A JP 2020500429A JP WO2019159779 A1 JPWO2019159779 A1 JP WO2019159779A1
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- Prior art keywords
- dip
- dip molding
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- acid
- water content
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
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Abstract
Description
前記ディップ成形型の表面に形成された前記ディップ成形層の水分含有量を1〜30重量%に調整する水分含有量調整工程と、
前記水分含有量の調整を行った後、前記ディップ成形型の表面に形成された前記ディップ成形層のうち一部を、前記ディップ成形型から剥離するビーディング加工を行うビーディング加工工程と、を備えるディップ成形体の製造方法が提供される。
本発明の製造方法において、前記水分含有量調整工程が、前記ディップ成形型の表面に形成された前記ディップ成形層に対し、20〜100℃、1〜20分の条件で加熱する工程であることが好ましい。
本発明の製造方法において、前記水分含有量調整工程が、前記ディップ成形型の表面に形成された前記ディップ成形層に対し、40〜80℃、1〜20分の条件で加熱する工程であることが好ましい。
本発明の製造方法において、前記金属化合物(B)が、アルミニウム化合物であることが好ましい。
カルボキシル基含有共役ジエン系ゴム(A)のラテックスと、水溶性の金属化合物(B)とを含有するラテックス組成物を、ディップ成形型を用いて、ディップ成形することにより、ディップ成形型の表面にディップ成形層を形成するディップ成形工程と、
前記ディップ成形型の表面に形成された前記ディップ成形層の水分含有量を1〜30重量%に調整する水分含有量調整工程と、
前記水分含有量の調整を行った後、前記ディップ成形型の表面に形成された前記ディップ成形層のうち一部を、前記ディップ成形型から剥離するビーディング加工を行うビーディング加工工程と、を備えるものである。
まず、本発明の製造方法に用いられる、ラテックス組成物について説明する。
本発明の製造方法に用いられる、ラテックス組成物は、カルボキシル基含有共役ジエン系ゴム(A)のラテックスと、水溶性の金属化合物(B)とを含有する。
共役ジエン単量体およびエチレン性不飽和カルボン酸単量体と共重合可能なその他のエチレン性不飽和単量体としては、たとえば、上述したカルボキシル基含有ニトリルゴム(a1)のラテックスと同様のものが挙げられる。カルボキシル基含有共役ジエンゴム(a3)中における、その他のエチレン性不飽和単量体により形成されるその他の単量体単位の含有割合は、好ましくは10重量%以下であり、より好ましくは5重量%以下、さらに好ましくは3重量%以下である。
次いで、本発明のディップ成形体の製造方法について、説明する。
本発明のディップ成形体の製造方法は、
カルボキシル基含有共役ジエン系ゴム(A)のラテックスと、水溶性の金属化合物(B)とを含有するラテックス組成物を、ディップ成形型を用いて、ディップ成形することにより、ディップ成形型の表面にディップ成形層を形成するディップ成形工程と、
前記ディップ成形型の表面に形成された前記ディップ成形層の水分含有量を1〜30重量%に調整する水分含有量調整工程と、
前記水分含有量の調整を行った後、前記ディップ成形型の表面に形成された前記ディップ成形層のうち一部を、前記ディップ成形型から剥離するビーディング加工を行うビーディング加工工程と、を備えるものである。
本発明の製造方法におけるディップ成形工程は、カルボキシル基含有共役ジエン系ゴム(A)のラテックスと、水溶性の金属化合物(B)とを含有するラテックス組成物を、ディップ成形型を用いて、ディップ成形することにより、ディップ成形型の表面にディップ成形層を形成する工程である。
凝固剤は、通常、水、アルコール、またはそれらの混合物の溶液として使用する。凝固剤濃度は、通常、5〜50重量%、好ましくは10〜35重量%である。
本発明の製造方法における水分含有量調整工程は、上記ディップ成形工程において得られた、ディップ成形型の表面に形成されたディップ成形層の水分含有量を1〜30重量%に調整する工程である。
ディップ成形層の水分含有量(単位:重量%)=〔{水分除去前のディップ成形層の重量(G1)−水分除去後のディップ成形層の重量(G2)}/水分除去前のディップ成形層の重量(G1)〕×100
本発明のビーディング加工工程は、上記水分含有量調整工程において水分含有量の調整を行ったディップ成形層のうち一部を、ディップ成形型から剥離するビーディング加工を行う工程である。
実施例および比較例にて作製した、水分含有量調整後のディップ成形層について、次の方法により水分含有量の測定を行った。すなわち、まず、ディップ成形層を一部サンプリングし、サンプリングしたディップ成形層の重量(G1)を精秤した。次いで、ディップ成形層を120℃、30分の条件で加熱することで水分を除去することで、水分除去後のディップ成形層を得た。そして、水分除去後のディップ成形層の重量(G2)を測定し、これらの測定結果より、下記式にしたがって、ディップ成形層の水分含有量を求めた。
ディップ成形層の水分含有量(単位:重量%)=〔{水分除去前のディップ成形層の重量(G1)−水分除去後のディップ成形層の重量(G2)}/水分除去前のディップ成形層の重量(G1)〕×100
実施例および比較例にて作製した、水分含有量調整後のディップ成形層について、手袋型から脱型する前の段階において、万能型引張試験器にてディップ成形層と手袋型との間における180°剥離試験を実施することで、ディップ成形層と手袋型との間のピール強度を測定した。剥離速度は500mm/分とした。ピール強度が小さいほど、ディップ成形層と手袋型との密着力が低く、ビーディングが巻きやすく、ビーディング加工性に優れると判断できる。
実施例および比較例にて作製した、水分含有量調整後のディップ成形層について、手袋型から脱型する前の段階において、手袋型に密着しているディップ成形層の端の部分を巻き上げるビーディング巻き操作を、手作業にて実施し、以下の基準で評価を行った。
なし:5回以内の巻き上げ操作で所望のビーディング巻き操作が完了した。
有り:所望のビーディング巻き操作が完了するまでに、6回以上の巻き上げ操作が必要であったか、あるいは、ビーディング巻き操作が全くできなかった。
攪拌機付きの耐圧重合反応容器に、1,3−ブタジエン63部、アクリロニトリル34部、メタクリル酸3部、連鎖移動剤としてt−ドデシルメルカプタン0.25部、脱イオン水132部、ドデシルベンゼンスルホン酸ナトリウム3部、β−ナフタリンスルホン酸ホルマリン縮合物ナトリウム1部、過硫酸カリウム0.3部、およびエチレンジアミン四酢酸ナトリウム0.005部を仕込み、重合温度を37℃に保持して重合を開始した。そして、重合転化率が70%になった時点で、重合温度を43℃に昇温し、継続して重合転化率が95%になるまで反応させ、その後、重合停止剤としてジメチルジチオカルバミン酸ナトリウム0.1部を添加して重合反応を停止した。そして、得られた共重合体のラテックスから、未反応単量体を減圧にして留去した後、固形分濃度とpHとを調整することで、固形分濃度40重量%、pH8.0のカルボキシル基含有ニトリルゴム(a1−1)のラテックスを得た。
<ラテックス組成物の調製>
まず、二酸化チタン(TiO2)4.5部、β−ナフタリンスルホン酸ホルマリン縮合物ナトリウム塩0.3部、水酸化カリウム0.0015部、および水4.5部を混合することで、二酸化チタン分散液を調製した。そして、混合容器中において、製造例1で得られたカルボキシル基含有ニトリルゴム(a1−1)のラテックス250部(カルボキシル基含有ニトリルゴム(a1−1)換算で100部)に、アルミン酸ナトリウム0.5部、ソルビトール0.75部、グリコール酸ナトリウム0.75部を水溶させた混合水溶液を加えた。次いで、これに、カルボキシル基含有ニトリルゴム(a1−1)100部に対して、二酸化チタンの添加量が1.5部となるように、上記にて調製した二酸化チタン分散液を添加した。そして、脱イオン水を加えて、固形分濃度を30重量%に調整することで、ラテックス組成物を得た。
硝酸カルシウム30部、ノニオン性乳化剤であるポリエチレングリコールオクチルフェニルエーテル0.05部および水70部を混合することにより、凝固剤水溶液を調製した。次いで、この凝固剤水溶液に、予め70℃に加温したセラミック製手袋型(表面が粗面化されたセラミック製手袋型)を5秒間浸漬し、引上げた後、温度70℃、10分間の条件で乾燥して、凝固剤を手袋型に付着させた。そして、凝固剤を付着させた手袋型を、上記にて得られたラテックス組成物に10秒間浸漬し、引上げた後、50℃の温水に90秒間浸漬して、水溶性不純物を溶出させて、手袋型にディップ成形層を形成した。
実施例1と同様にして得られたラテックス組成物を用い、同様にして、手袋型にディップ成形層を形成した。次いで、ディップ成形層を形成した手袋型について、手袋型から脱型する前の段階において、温度30℃にて、5分間の条件にて乾燥することで、ディップ成形層の水分含有量の調整を行った。得られた水分含有量調整後のディップ成形層の水分含有量を、上記方法にしたがって測定したところ、水分含有量は25重量%であった。そして、このようにして得られた水分含有量調整後のディップ成形層について、上記方法にしたがって、ディップ成形層と手袋型との間のピール強度の測定、および、ディップ成形層のビーディング巻き不良の評価を行った。結果を表1に示す。
実施例1と同様にして得られたラテックス組成物を用い、同様にして、手袋型にディップ成形層を形成した。次いで、ディップ成形層を形成した手袋型について、手袋型から脱型する前の段階において、温度15℃にて、5分間の条件にて乾燥することで、ディップ成形層の水分含有量の調整を行った。得られた水分含有量調整後のディップ成形層の水分含有量を、上記方法にしたがって測定したところ、水分含有量は50重量%であった。そして、このようにして得られた水分含有量調整後のディップ成形層について、上記方法にしたがって、ディップ成形層と手袋型との間のピール強度の測定、および、ディップ成形層のビーディング巻き不良の評価を行った。結果を表1に示す。
実施例1と同様にして得られたラテックス組成物を用い、同様にして、手袋型にディップ成形層を形成した。次いで、ディップ成形層を形成した手袋型について、手袋型から脱型する前の段階において、温度125℃にて、5分間の条件にて乾燥することで、ディップ成形層の水分含有量の調整を行った。得られた水分含有量調整後のディップ成形層の水分含有量を、上記方法にしたがって測定したところ、水分含有量は0重量%であった。そして、このようにして得られた水分含有量調整後のディップ成形層について、上記方法にしたがって、ディップ成形層と手袋型との間のピール強度の測定、および、ディップ成形層のビーディング巻き不良の評価を行った。結果を表1に示す。
また、ディップ成形層の水分含有量が1重量%未満である場合には、ディップ成形型との密着性が高く、ビーディング加工性に劣り、ビーディング巻き操作ができないものであった(比較例2)。
Claims (5)
- カルボキシル基含有共役ジエン系ゴム(A)のラテックスと、水溶性の金属化合物(B)とを含有するラテックス組成物を、ディップ成形型を用いて、ディップ成形することにより、ディップ成形型の表面にディップ成形層を形成するディップ成形工程と、
前記ディップ成形型の表面に形成された前記ディップ成形層の水分含有量を1〜30重量%に調整する水分含有量調整工程と、
前記水分含有量の調整を行った後、前記ディップ成形型の表面に形成された前記ディップ成形層のうち一部を、前記ディップ成形型から剥離するビーディング加工を行うビーディング加工工程と、を備えるディップ成形体の製造方法。 - 前記ビーディング加工を行った後、前記ディップ成形層を架橋させる架橋工程と、
架橋後の前記ディップ成形層を、前記ディップ成形型から脱型させる脱型工程とをさらに備える請求項1に記載のディップ成形体の製造方法。 - 前記水分含有量調整工程が、前記ディップ成形型の表面に形成された前記ディップ成形層に対し、20〜100℃、1〜20分の条件で加熱する工程である請求項1または2に記載のディップ成形体の製造方法。
- 前記水分含有量調整工程が、前記ディップ成形型の表面に形成された前記ディップ成形層に対し、40〜80℃、1〜20分の条件で加熱する工程である請求項1〜3のいずれかに記載のディップ成形体の製造方法。
- 前記金属化合物(B)が、アルミニウム化合物である請求項1〜4のいずれかに記載のディップ成形体の製造方法。
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