WO2023067676A1 - Method for producing film molded article - Google Patents

Method for producing film molded article Download PDF

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Publication number
WO2023067676A1
WO2023067676A1 PCT/JP2021/038531 JP2021038531W WO2023067676A1 WO 2023067676 A1 WO2023067676 A1 WO 2023067676A1 JP 2021038531 W JP2021038531 W JP 2021038531W WO 2023067676 A1 WO2023067676 A1 WO 2023067676A1
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Prior art keywords
film
mold
latex composition
molded article
producing
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PCT/JP2021/038531
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French (fr)
Japanese (ja)
Inventor
良太 奥西
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白石カルシウム株式会社
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Application filed by 白石カルシウム株式会社 filed Critical 白石カルシウム株式会社
Priority to JP2022506032A priority Critical patent/JP7033242B1/en
Priority to PCT/JP2021/038531 priority patent/WO2023067676A1/en
Publication of WO2023067676A1 publication Critical patent/WO2023067676A1/en

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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
    • B29C41/02—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

Definitions

  • the present invention relates to a method for forming a film forming body using a film forming mold.
  • Various film molded products such as gloves, balloons, and sacks are manufactured as products that utilize the elasticity and conformability of rubber films.
  • Such film molded articles are required to have not only stretchability and conformability but also various properties depending on the application.
  • rubber gloves are used to protect workers' hands from the chemicals they handle. , heat resistance is required.
  • Rubber gloves made of chlorosulfonated polyethylene (CSM) are excellent in chemical resistance and heat resistance and are suitable as work gloves.
  • Patent Document 1 describes a composition for dipping a glove mold prepared by dissolving 100 parts by weight of CSM solid rubber in 350 parts by weight of a solvent.
  • Patent Document 2 describes a CSM latex obtained by colloidally dispersing CSM in water by the action of an emulsifier as a composition for dipping a glove mold.
  • JP-A-5-230702 Japanese Patent Application Laid-Open No. 2011-32590
  • Patent Document 1 Because the composition described in Patent Document 1 uses a large amount of solvent, it has a large impact on the environment. Patent Document 2 describes that even if a glove is made using CSM latex, it may not form a normal film on the surface of the mold. Patent Document 2 describes that the reason for this is that the CSM latex adhered to the surface of the mold flows before it dries.
  • an object of the present invention is to provide a method for producing a film forming body that has a small environmental load and excellent film-forming properties.
  • One aspect of the present invention is a method for producing a film molded product.
  • the method for producing the film molded body comprises: an attaching step of attaching a solution containing calcium ions to the surface of the film-forming mold; After the attaching step, a dipping step of dipping the membrane mold in a latex composition comprising a latex of chlorosulfonated polyethylene and sodium alginate; and a molding step of pulling up the film-forming mold from the latex composition and molding the film-forming body on the surface of the film-forming mold.
  • the number average molecular weight of the sodium alginate is preferably 400,000 to 3,000,000.
  • the latex composition preferably further contains at least one of carboxymethylcellulose, polyvinyl alcohol, and sodium polyacrylate.
  • the immersion time of the film forming mold in the immersion step is 60 to 120 seconds.
  • the method for manufacturing the film molded body further comprises a demolding step of removing the film molded body from the film molding mold, In the demolding step, it is preferable that the film molded body formed on the surface of the film forming mold is washed with water.
  • the above-mentioned method for manufacturing a film compact has a small environmental load and is excellent in film-forming properties.
  • the method for manufacturing a film molded article of the present embodiment includes an adhesion step, an immersion step, and a forming step.
  • the attachment step is a step of attaching a solution containing a calcium salt to the surface of the film forming mold (hereinafter simply referred to as the mold).
  • the mold preferably has a shape corresponding to the shape of the film molded product.
  • a mold used to produce a glove which is an example of a film molded product, imitates the shape of a human hand (including the portion from the wrist to the fingertips, and may further include the arm portion corresponding to the sleeve). It is an object, for example a ceramic or metal monolith.
  • the solution containing calcium ions is preferably an aqueous solution in which a water-soluble calcium salt is dissolved.
  • the calcium salt is preferably calcium nitrate or calcium chloride, particularly preferably calcium nitrate.
  • the solution containing calcium ions has the action of reacting with sodium alginate in the later-described latex composition to gel and solidify the latex composition.
  • a solution containing calcium ions is also referred to herein as a coagulant.
  • the concentration of calcium salt in the coagulant is preferably 5-50%. If the concentration of the calcium salt is less than 5%, it will be difficult to obtain a sufficient effect of gelling the latex composition.
  • % means % by weight. Adhesion of the coagulant to the mold is performed, for example, by dipping or coating.
  • the immersion step is a step of immersing the mold in a latex composition containing chlorosulfonated polyethylene (CSM) latex and sodium alginate after the adhesion step.
  • CSM latex is an emulsion of CSM microparticles dispersed in water. The fine particles of CSM are contained in the latex at, for example, 30-60%.
  • Sodium alginate has the function of rapidly reacting with calcium ions and gelling the latex composition.
  • the flow of the latex composition adhering to the mold is suppressed, and dripping is suppressed, thereby forming a good film on the surface of the mold. That is, the method for producing a film molded article of the present embodiment is excellent in film formability.
  • sodium alginate is a component that can increase the viscosity of the latex composition. Therefore, when the mold is pulled up from the latex composition, a large amount of the latex composition adheres to the mold, and the thickness of the film forming the film molded product can be effectively increased. If the latex composition does not contain sodium alginate, gelation due to reaction with calcium ions will not occur. not formed. In addition, it becomes difficult to increase the film thickness of the film.
  • the concentration of sodium alginate in the latex composition is preferably 0.1-1.0%, more preferably 0.4-0.6%. If the concentration of sodium alginate is lower than the above range, the latex composition may not be sufficiently gelled. Also, the viscosity of the latex composition may not be increased sufficiently. If the concentration of sodium alginate is higher than the above range, a large amount of unvulcanized gel remains on the surface of the film formed on the surface of the mold, which may make it difficult to remove the molded film from the mold.
  • Sodium alginate is preferably 0.3 to 4.0 parts by weight, more preferably 1.0 to 2.0 parts by weight, based on 100 parts by weight of the CSM latex.
  • the latex composition preferably further contains acid acceptors such as magnesium oxide and zinc oxide, and vulcanizing agents such as polyamines and polyols.
  • the latex composition preferably further contains an antifoaming agent in order to obtain a film molded product with few air bubbles.
  • the amount of the antifoaming agent added is, for example, 0.2 to 0.8 parts by weight per 100 parts by weight of the CSM latex in the latex composition.
  • the molding step is a step of pulling up the mold from the latex composition and molding the film molding on the surface of the mold.
  • the heat treatment is preferably carried out in an atmosphere of 60 to 160°C, more preferably 70 to 120°C, for preferably 30 to 180 minutes, more preferably 60 to 120 minutes.
  • the heat treatment for producing the gloves is preferably carried out with the mold pulled up from the latex composition, with the part of the mold corresponding to the fingertips facing up.
  • the mold pulled up from the latex composition is immersed in a mixture of different types of latex such as chloroprene rubber (CR) or nitrile rubber (NBR) (latex composition of other rubber).
  • CR chloroprene rubber
  • NBR nitrile rubber
  • An immersion treatment may also be performed.
  • the above-described method for producing a film-formed article can produce a film-formed article having a small environmental load, excellent film-forming properties, and excellent chemical resistance, heat resistance, weather resistance, and the like.
  • the film molded article has the properties of CSM such as elasticity, conformability, and flexibility, and is suitable for gloves, balloons, sacks, syringes, tubes, sleeve covers, shoe covers, and the like.
  • the film thickness of the film forming the film molded article obtained by the method for producing the film molded article of the present embodiment is preferably 0.1 to 2.0 mm, more preferably 0.20 to 0.50 mm.
  • a film thickness within the above range is preferable when the molded film is a glove, a finger cot, or the like.
  • the film thickness of the film forming the film forming article is preferably 1.0 to 2.0 mm.
  • the method for manufacturing the film molded body of the embodiment further includes a heating step.
  • the heating step is a step of heating the mold so that the mold to which the coagulant is attached is dry before the dipping step.
  • the mold to which the coagulant is adhered can be dried quickly before the dipping step, improving the productivity of the film molded product. Since the coagulant is dry, the effect of gelling the latex composition can be obtained uniformly on the surface of the mold, and the occurrence of unevenness in the film thickness of the film forming the molded film can be suppressed.
  • the heating process is preferably performed after the adhesion process, but it is also preferable to perform it before the adhesion process, and it is also preferable to perform it before and after the adhesion process.
  • the mold is preferably heated to 60-80°C. When the temperature is lower than 60°C, the coagulant cannot be dried quickly, and it is difficult to improve the productivity of the film forming product. If the temperature exceeds 80°C, the temperature of the mold during the dipping step is too high, the viscosity of the latex composition in contact with the mold decreases, and the amount of the latex composition adhering to the mold decreases. It tends to be thin.
  • the method for manufacturing a film molded article of the embodiment further includes a cooling step of cooling the mold heated in the heating step before the immersion step.
  • the viscosity of the latex composition in contact with the mold is reduced during the dipping step, preventing the amount of the latex composition adhering to the mold from decreasing and effectively increasing the film thickness of the molded film. can.
  • Cooling of the mold is carried out until the mold is preferably at room temperature (eg 25° C.). Cooling of the mold is preferably carried out by allowing the mold to cool without blowing air or the like, in order to avoid unevenness in the film thickness.
  • the viscosity at 25° C. measured according to JIS Z8803:2011 using a rotational viscometer at a rotational speed of 6 rpm is preferably 500 to 20000 mPa ⁇ s, more preferably 2000 to 15000 mPa ⁇ s. is s.
  • the viscosity measured in the same manner as above except that the rotation speed is 60 rpm is preferably 100 to 5000 mPa ⁇ s, more preferably 500 to 4000 mPa ⁇ s.
  • the number average molecular weight of sodium alginate is preferably 200,000 to 3,000,000, more preferably 500,000 to 2,000,000.
  • sodium alginate having such a molecular weight it is easy to adjust the viscosity of the latex composition within the range described above, so that a large amount of the latex composition adheres to the pulled up mold, and the film formed on the surface of the mold is thin. The film thickness can be effectively increased.
  • molecular weight refers to that measured using a gel permeation chromatography (GPC) method.
  • the latex composition preferably further contains at least one of carboxymethylcellulose, polyvinyl alcohol, and sodium polyacrylate in addition to sodium alginate. These substances have the function of increasing the viscosity of the latex composition, can further increase the viscosity of the latex composition, and contribute to increasing the film thickness of the coating.
  • the total concentration of these substances in the latex composition is preferably 0.1-1.0%, more preferably 0.3-0.7%.
  • the temperature of the latex composition is preferably maintained at 30°C or lower, more preferably 10 to 25°C, in order to increase the thickness of the film.
  • the temperature of the latex composition is preferably maintained at 30°C or lower, more preferably 10 to 25°C, in order to increase the thickness of the film.
  • the immersion time of the mold in the immersion step is preferably 30 to 180 seconds, more preferably 60 to 120 seconds. If the immersion time is shorter than the above range, gelation in the latex composition in which the mold is immersed will be insufficient, making it difficult to suppress dripping after the mold is pulled out. If the immersion time is longer than the above range, it is difficult to improve the productivity of the film-formed product.
  • the method for manufacturing a film molded product of the present embodiment further includes a demolding step.
  • the demolding step is a step of removing the film molded body from the mold.
  • the film formed on the surface of the mold is washed with water.
  • unvulcanized hardened gel remaining on the surface of the film can be washed off, and the flexibility of the CSM film can be exhibited to facilitate demolding.
  • the water washing of the film molded product can be performed, for example, by immersing the film molded product together with the mold in water.
  • the immersion time is preferably 60-120 seconds.
  • air bubbling of water is preferred in order to promote dissolution of the unvulcanized gel in water. Since the unvulcanized gel easily dissolves in water, there is no need to rub the surface of the film by hand in water.
  • composition means the latex composition.
  • the latex composition contains 0.5% of the "components in the composition” shown in the table, and in Example 4, further, “other components in the composition” shown in the table Contains 0.25%.
  • coagulant means the solution that adheres to the surface of the mold prior to the dipping step.
  • cooling before immersion means that the mold to which the coagulant was adhered was subjected to heat treatment for drying, and then allowed to cool to room temperature (25°C) before the immersion step. . In the examples where "cooling before immersion” was “none”, the immersion step was performed within 60 seconds after the mold was dried by heating.
  • Releasability was rated as A when the glove could be removed from the mold without washing with water, and B when the glove could be removed from the mold by washing with water. A was evaluated as excellent in demoldability, and B and C were evaluated as poor demoldability. The glove was washed with water by immersing the glove together with the mold in water for 120 seconds and gently rocking the glove during that time.
  • the film thickness is measured using a micrometer at 5 or more points on the obtained glove, and is shown in the range of the maximum and minimum values of the measured values.
  • films with a minimum film thickness of 0.2 mm or more were evaluated as having a sufficient film thickness, and films with a minimum film thickness of less than 0.2 mm were evaluated as having an insufficient film thickness.
  • Example 1 From the comparison between Example 1 and Comparative Examples 1 and 2, by immersing the mold to which the solution containing calcium ions was adhered in the latex composition containing sodium alginate, excellent film-forming properties and releasability, and sufficient It can be seen that a film molded article having a thickness can be obtained.
  • Comparative Example 1 ⁇ -carrageenan in the composition solidified, resulting in poor workability.
  • the film thickness was insufficient and demolding was difficult. The film thickness did not change even when the film-formed article was produced in the same manner with a longer immersion time.
  • Example 1 From the comparison between Example 1 and Comparative Example 3, it was found that by including sodium alginate in the latex composition and calcium ions in the coagulant, a film molded article having excellent film-forming properties and releasability and a sufficient thickness was obtained. is obtained.
  • Comparative Example 3 sodium alginate in the coagulant gelled, but dripping occurred and no latex composition film was formed. Therefore, evaluation of releasability and measurement of film thickness could not be performed.
  • Comparative Examples 1 and 2 and Examples 1 to 5 a film was formed on all the immersed portions of the mold.
  • Example 1 and 3 and Example 2 From the comparison between Examples 1 and 3 and Example 2, it can be seen that the thickness of the film increases when the number average molecular weight of sodium alginate is 1,500,000 or more. From the comparison between Example 1 and Example 4, it can be seen that the film thickness of the film increases when the latex composition contains a predetermined substance. From the comparison between Example 1 and Example 5, it can be seen that the thickness of the film increases by cooling the heated mold before the immersion step.

Abstract

This method for producing a film molded article according to an embodiment comprises: an attachment step in which a solution including calcium ions is attached to the surface of a mold for film molding; an immersion step in which the mold for film molding is dipped in a latex composition, containing a chlorosulfonated polyethylene latex and a sodium alginate, after the attachment step; and a molding step in which the mold for film molding is pulled up out of the latex composition and the film molded article is molded on the surface of the mold for film molding.

Description

膜成形体の製造方法METHOD FOR MANUFACTURING FILM MOLDED BODY
　本発明は、膜成形用型を用いて膜成形体を成形する方法に関する。 The present invention relates to a method for forming a film forming body using a film forming mold.
　ゴムの膜が備える伸縮性や追従性を利用した製品として、手袋、風船、サック等の種々の膜成形体が製造されている。このような膜成形体には、伸縮性及び追従性だけでなく、用途に応じて、種々の特性が求められている。例えば、化学品を取り扱う化学工場などにおいて、取り扱う化学物質から作業者の手を保護するために用いられるゴム手袋には、高濃度の強酸や強アルカリ、有機溶剤等に侵食されない高い耐薬品性や、耐熱性が要求される。クロロスルホン化ポリエチレン（ＣＳＭ）製のゴム手袋は、耐薬品性、耐熱性に優れており、作業用手袋として適している。 Various film molded products such as gloves, balloons, and sacks are manufactured as products that utilize the elasticity and conformability of rubber films. Such film molded articles are required to have not only stretchability and conformability but also various properties depending on the application. For example, in chemical factories that handle chemicals, rubber gloves are used to protect workers' hands from the chemicals they handle. , heat resistance is required. Rubber gloves made of chlorosulfonated polyethylene (CSM) are excellent in chemical resistance and heat resistance and are suitable as work gloves.
　膜成形体を作製する方法として、ゴムを含む液状の組成物に型を浸漬し、引き上げて乾燥させる浸漬法と呼ばれる方法が知られている。特許文献１には、手袋の型を浸漬させる組成物として、ＣＳＭの固形ゴム１００重量部を３５０重量部の溶剤に溶かして調製したものが記載されている。特許文献２には、手袋の型を浸漬させる組成物として、ＣＳＭを乳化剤の作用によって水中にコロイド状に分散させたＣＳＭのラテックスが記載されている。 As a method for producing a film molded body, a method called an immersion method is known in which a mold is immersed in a liquid composition containing rubber, pulled out and dried. Patent Document 1 describes a composition for dipping a glove mold prepared by dissolving 100 parts by weight of CSM solid rubber in 350 parts by weight of a solvent. Patent Document 2 describes a CSM latex obtained by colloidally dispersing CSM in water by the action of an emulsifier as a composition for dipping a glove mold.
特開平５－２３０７０２号公報JP-A-5-230702 特開２０１１－３２５９０号公報Japanese Patent Application Laid-Open No. 2011-32590
　特許文献１に記載の組成物には、多量の溶剤が用いられているので、環境への負荷が大きい。特許文献２には、ＣＳＭのラテックスを用いて手袋を作製しても、型の表面に正常な皮膜を形成できない場合があることが記載されている。その原因として、型の表面に付着させたＣＳＭのラテックスが、乾燥するまでの間に流動してしまうことが特許文献２には記載されている。 Because the composition described in Patent Document 1 uses a large amount of solvent, it has a large impact on the environment. Patent Document 2 describes that even if a glove is made using CSM latex, it may not form a normal film on the surface of the mold. Patent Document 2 describes that the reason for this is that the CSM latex adhered to the surface of the mold flows before it dries.
　そこで、本発明は、環境負荷が小さく、成膜性に優れた膜成形体の製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for producing a film forming body that has a small environmental load and excellent film-forming properties.
　本発明の一態様は、膜成形体の製造方法である。
　前記膜成形体の製造方法は、
　膜成形用型の表面に、カルシウムイオンを含む溶液を付着させる付着工程と、
　前記付着工程の後、前記膜成形用型を、クロロスルホン化ポリエチレンのラテックスと、アルギン酸ナトリウムとを含むラテックス組成物に浸す浸漬工程と、
　前記膜成形用型を前記ラテックス組成物から引き上げ、前記膜成形用型の表面に前記膜成形体を成形する成形工程と、を備える。 One aspect of the present invention is a method for producing a film molded product.
The method for producing the film molded body comprises:
an attaching step of attaching a solution containing calcium ions to the surface of the film-forming mold;
After the attaching step, a dipping step of dipping the membrane mold in a latex composition comprising a latex of chlorosulfonated polyethylene and sodium alginate;
and a molding step of pulling up the film-forming mold from the latex composition and molding the film-forming body on the surface of the film-forming mold.
　前記浸漬工程の前に、前記溶液を付着させた前記膜成形用型を加熱し、乾燥させる乾燥工程をさらに備える、ことが好ましい。 It is preferable to further include a drying step of heating and drying the film forming mold to which the solution is attached before the immersion step.
　前記浸漬工程の前に、前記加熱工程において加熱した前記膜成形用型を冷却する冷却工程をさらに備える、ことが好ましい。 It is preferable to further include a cooling step for cooling the film forming mold heated in the heating step before the immersion step.
　前記アルギン酸ナトリウムの数平均分子量は４０万～３００万である、ことが好ましい。 The number average molecular weight of the sodium alginate is preferably 400,000 to 3,000,000.
　前記ラテックス組成物は、カルボキシメチルセルロース、ポリビニルアルコール、及びポリアクリル酸ナトリウムの少なくとも１つをさらに含む、ことが好ましい。 The latex composition preferably further contains at least one of carboxymethylcellulose, polyvinyl alcohol, and sodium polyacrylate.
　前記浸漬工程における前記膜成形用型の浸漬時間は６０～１２０秒である、ことが好ましい。 It is preferable that the immersion time of the film forming mold in the immersion step is 60 to 120 seconds.
　前記膜成形体の製造方法は、前記膜成形体を前記膜成形用型から取り外す脱型工程をさらに備え、
　前記脱型工程では、前記膜成形用型の表面に成形された前記膜成形体の水洗を行う、ことが好ましい。 The method for manufacturing the film molded body further comprises a demolding step of removing the film molded body from the film molding mold,
In the demolding step, it is preferable that the film molded body formed on the surface of the film forming mold is washed with water.
　上述の膜成形体の製造方法は、環境負荷が小さく、成膜性に優れている。 　The above-mentioned method for manufacturing a film compact has a small environmental load and is excellent in film-forming properties.
　以下、実施形態の膜成形体の製造方法について説明する。
　本実施形態の膜成形体の製造方法は、付着工程と、浸漬工程と、成形工程と、を備える。 A method for manufacturing a film molded article according to the embodiment will be described below.
The method for manufacturing a film molded article of the present embodiment includes an adhesion step, an immersion step, and a forming step.
　付着工程は、膜成形用型（以降、単に型という）の表面に、カルシウム塩を含む溶液を付着させる工程である。型は、膜成形体の形状と対応する形状を有するものが好ましく用いられる。膜成形体の一例である手袋の作製に用いられる型は、人の手（手首から指先にかけての部分を含む。袖と対応する腕の部分をさらに含む場合がある。）の形状を模った物体であり、例えばセラミックや金属の一体成型品である。カルシウムイオンを含む溶液は、好ましくは水溶性のカルシウム塩が溶解した水溶液である。カルシウム塩は、好ましくは、硝酸カルシウム、塩化カルシウムであり、特に好ましくは硝酸カルシウムである。カルシウムイオンを含む溶液は、後述するラテックス組成物中のアルギン酸ナトリウムと反応し、ラテックス組成物をゲル化し、凝固させる作用を有する。本明細書では、カルシウムイオンを含む溶液を、凝固剤ともいう。凝固剤中のカルシウム塩の濃度は、好ましくは５～５０％である。カルシウム塩の濃度が５％未満であると、ラテックス組成物をゲル化させる作用が十分に得られ難い。本明細書において％は、重量％を意味する。型への凝固剤の付着は、例えば、浸漬や塗布により行われる。 The attachment step is a step of attaching a solution containing a calcium salt to the surface of the film forming mold (hereinafter simply referred to as the mold). The mold preferably has a shape corresponding to the shape of the film molded product. A mold used to produce a glove, which is an example of a film molded product, imitates the shape of a human hand (including the portion from the wrist to the fingertips, and may further include the arm portion corresponding to the sleeve). It is an object, for example a ceramic or metal monolith. The solution containing calcium ions is preferably an aqueous solution in which a water-soluble calcium salt is dissolved. The calcium salt is preferably calcium nitrate or calcium chloride, particularly preferably calcium nitrate. The solution containing calcium ions has the action of reacting with sodium alginate in the later-described latex composition to gel and solidify the latex composition. A solution containing calcium ions is also referred to herein as a coagulant. The concentration of calcium salt in the coagulant is preferably 5-50%. If the concentration of the calcium salt is less than 5%, it will be difficult to obtain a sufficient effect of gelling the latex composition. As used herein, % means % by weight. Adhesion of the coagulant to the mold is performed, for example, by dipping or coating.
　浸漬工程は、付着工程の後、型を、クロロスルホン化ポリエチレン（ＣＳＭ）のラテックスと、アルギン酸ナトリウムとを含むラテックス組成物に浸す工程である。ＣＳＭのラテックスは、ＣＳＭの微粒子を水中に分散させたエマルションである。ＣＳＭの微粒子は、ラテックス中、例えば、３０～６０％含まれる。ＣＳＭのラテックスを膜成形体の原料とすることで、耐薬品性、耐熱性、耐候性等に優れた膜成形体が得られる。また、ＣＳＭのラテックスを膜成形体の原料とすることで、有機溶剤にＣＳＭの固形ゴムを溶かしたものを原料として用いる場合と比べ、環境への負荷が小さい。 The immersion step is a step of immersing the mold in a latex composition containing chlorosulfonated polyethylene (CSM) latex and sodium alginate after the adhesion step. CSM latex is an emulsion of CSM microparticles dispersed in water. The fine particles of CSM are contained in the latex at, for example, 30-60%. By using the latex of CSM as a raw material for the film molded product, a film molded product having excellent chemical resistance, heat resistance, weather resistance, etc. can be obtained. In addition, by using the CSM latex as the raw material of the film molded product, the load on the environment is smaller than when using a CSM solid rubber dissolved in an organic solvent as the raw material.
　アルギン酸ナトリウムは、カルシウムイオンと速やかに反応し、ラテックス組成物をゲル化させる機能を有する。アルギン酸ナトリウムがラテックス組成物に含まれていることで、型に付着したラテックス組成物の流動が抑制され、液だれが抑制されることにより、型の表面に良好な皮膜が形成される。すなわち、本実施形態の膜成形体の製造方法は、成膜性に優れる。また、アルギン酸ナトリウムは、ラテックス組成物の粘度を高めることができる成分である。そのため、ラテックス組成物から型を引き上げたときに、型に多くのラテックス組成物が付着し、膜成形体をなす皮膜の膜厚を効果的に厚くすることができる。ラテックス組成物にアルギン酸ナトリウムが含まれていないと、カルシウムイオンとの反応によるゲル化が起きないので、ラテックス組成物の粘度を高くしても、液だれを抑えることができず、良好な皮膜が形成されない。また、皮膜の膜厚を厚くすることが困難となる。 　Sodium alginate has the function of rapidly reacting with calcium ions and gelling the latex composition. By containing sodium alginate in the latex composition, the flow of the latex composition adhering to the mold is suppressed, and dripping is suppressed, thereby forming a good film on the surface of the mold. That is, the method for producing a film molded article of the present embodiment is excellent in film formability. Also, sodium alginate is a component that can increase the viscosity of the latex composition. Therefore, when the mold is pulled up from the latex composition, a large amount of the latex composition adheres to the mold, and the thickness of the film forming the film molded product can be effectively increased. If the latex composition does not contain sodium alginate, gelation due to reaction with calcium ions will not occur. not formed. In addition, it becomes difficult to increase the film thickness of the film.
　ラテックス組成物中のアルギン酸ナトリウムの濃度は、好ましくは０．１～１．０％であり、より好ましくは０．４～０．６％である。アルギン酸ナトリウムの濃度が上記範囲より低いと、ラテックス組成物を十分にゲル化させることができない恐れがある。また、ラテックス組成物の粘度を十分に高められない場合がある。アルギン酸ナトリウムの濃度が上記範囲より高いと、型の表面に形成された皮膜の表面に多量の未加硫ゲルが残ることによって、膜成形体の脱型が困難となる場合がある。アルギン酸ナトリウムは、ＣＳＭのラテックス１００重量部に対し、好ましくは０．３～４．０重量部であり、より好ましくは１．０～２．０重量部である。 The concentration of sodium alginate in the latex composition is preferably 0.1-1.0%, more preferably 0.4-0.6%. If the concentration of sodium alginate is lower than the above range, the latex composition may not be sufficiently gelled. Also, the viscosity of the latex composition may not be increased sufficiently. If the concentration of sodium alginate is higher than the above range, a large amount of unvulcanized gel remains on the surface of the film formed on the surface of the mold, which may make it difficult to remove the molded film from the mold. Sodium alginate is preferably 0.3 to 4.0 parts by weight, more preferably 1.0 to 2.0 parts by weight, based on 100 parts by weight of the CSM latex.
　ラテックス組成物は、酸化マグネシウム、酸化亜鉛等の受酸剤や、ポリアミン、ポリオール等の加硫剤をさらに含むことが好ましい。また、ラテックス組成物は、気泡の少ない膜成形体を得るため、消泡剤をさらに含むことが好ましい。消泡剤の添加量は、ラテックス組成物中、ＣＳＭラテックス１００重量部に対し、例えば０．２～０．８重量部である。 The latex composition preferably further contains acid acceptors such as magnesium oxide and zinc oxide, and vulcanizing agents such as polyamines and polyols. In addition, the latex composition preferably further contains an antifoaming agent in order to obtain a film molded product with few air bubbles. The amount of the antifoaming agent added is, for example, 0.2 to 0.8 parts by weight per 100 parts by weight of the CSM latex in the latex composition.
　成形工程は、型をラテックス組成物から引き上げ、型の表面に膜成形体を成形する工程である。型に付着したラテックス組成物を乾燥させ、ＣＳＭを加硫させるため、成形工程では、加熱処理を行うことが好ましい。加熱処理は、好ましくは６０～１６０℃、より好ましくは７０～１２０℃の雰囲気下、好ましくは３０～１８０分間、より好ましくは６０～１２０分間行われる。ＣＳＭが加硫することで、型の表面に膜成形体となる皮膜が形成される。手袋を作製する場合の加熱処理は、ラテックス組成物から引き上げた型を、指先と対応する型の部分を上にして行われるのが好ましい。
　成形工程では、加熱処理を行う前に、ラテックス組成物から引き上げた型を、クロロプレンゴム（ＣＲ）やニトリルゴム（ＮＢＲ）等の異種ラテックスの配合液（他のゴムのラテックス組成物）に浸漬する浸漬処理をさらに行ってもよい。このような成形工程を行うことにより、膜成形体であるＣＳＭゴムの層及び他のゴムの層が積層された複層構造の膜製品が得られる。 The molding step is a step of pulling up the mold from the latex composition and molding the film molding on the surface of the mold. In order to dry the latex composition adhering to the mold and vulcanize the CSM, it is preferable to carry out heat treatment in the molding process. The heat treatment is preferably carried out in an atmosphere of 60 to 160°C, more preferably 70 to 120°C, for preferably 30 to 180 minutes, more preferably 60 to 120 minutes. By vulcanizing the CSM, a film is formed on the surface of the mold as a film forming product. The heat treatment for producing the gloves is preferably carried out with the mold pulled up from the latex composition, with the part of the mold corresponding to the fingertips facing up.
In the molding step, before the heat treatment, the mold pulled up from the latex composition is immersed in a mixture of different types of latex such as chloroprene rubber (CR) or nitrile rubber (NBR) (latex composition of other rubber). An immersion treatment may also be performed. By carrying out such a molding process, a membrane product having a multi-layer structure in which a layer of CSM rubber, which is a membrane molded body, and another layer of rubber are laminated is obtained.
　以上の膜成形体の製造方法は、環境負荷が小さく、成膜性に優れ、耐薬品性、耐熱性、耐候性等に優れた膜成形体を製造することができる。膜成形体は、ＣＳＭが有する伸縮性、追従性、柔軟性等の特性を備えており、手袋、風船、サック、スポイト、チューブ、袖カバー、シューズカバー等として好適である。
　また、本実施形態の膜成形体の製造方法では、ポリビニルメチルエーテル、ポリアルキレングリコール、ポリエーテルポリオール等のいわゆる感熱化剤をラテックス組成物に含ませる必要がなく、したがって、浸漬工程の前に型を予め加熱（予熱）する必要がない。 The above-described method for producing a film-formed article can produce a film-formed article having a small environmental load, excellent film-forming properties, and excellent chemical resistance, heat resistance, weather resistance, and the like. The film molded article has the properties of CSM such as elasticity, conformability, and flexibility, and is suitable for gloves, balloons, sacks, syringes, tubes, sleeve covers, shoe covers, and the like.
In addition, in the method for producing a film molded product of the present embodiment, it is not necessary to include so-called heat sensitizers such as polyvinyl methyl ether, polyalkylene glycol, and polyether polyol in the latex composition. does not need to be preheated (preheated).
　本実施形態の膜成形体の製造方法により得られる膜成形体をなす皮膜の膜厚は、好ましくは０．１～２．０ｍｍであり、より好ましくは０．２０～０．５０ｍｍである。上記範囲の膜厚は、膜成形体が手袋、指サック等である場合に好ましい。また、一方で、膜成形体をなす皮膜の膜厚は、膜成形体がシューズカバー等である場合に、好ましくは１．０～２．０ｍｍである。 The film thickness of the film forming the film molded article obtained by the method for producing the film molded article of the present embodiment is preferably 0.1 to 2.0 mm, more preferably 0.20 to 0.50 mm. A film thickness within the above range is preferable when the molded film is a glove, a finger cot, or the like. On the other hand, when the film forming article is a shoe cover or the like, the film thickness of the film forming the film forming article is preferably 1.0 to 2.0 mm.
　実施形態の膜成形体の製造方法は、加熱工程をさらに備えることが好ましい。加熱工程は、浸漬工程の前に、凝固剤が付着した型が乾燥するよう、型を加熱する工程である。型を加熱することにより、浸漬工程の前に、凝固剤が付着した型を速く乾燥させることができ、膜成形体の生産性が向上する。凝固剤が乾燥していることにより、ラテックス組成物をゲル化させる効果が型の表面において均一に得られ、膜成形体をなす皮膜の膜厚にムラが発生することを抑えられる。 It is preferable that the method for manufacturing the film molded body of the embodiment further includes a heating step. The heating step is a step of heating the mold so that the mold to which the coagulant is attached is dry before the dipping step. By heating the mold, the mold to which the coagulant is adhered can be dried quickly before the dipping step, improving the productivity of the film molded product. Since the coagulant is dry, the effect of gelling the latex composition can be obtained uniformly on the surface of the mold, and the occurrence of unevenness in the film thickness of the film forming the molded film can be suppressed.
　加熱工程は、付着工程の後に行うことが好ましいが、付着工程の前に行うことも好ましく、付着工程の前後のそれぞれにおいて行うことも好ましい。型は、好ましくは６０～８０℃に加熱される。６０℃未満であると、凝固剤を速く乾燥させることができず、膜成形体の生産性を向上させ難い。８０℃を超えると、浸漬工程を行う際の型の温度が高すぎて、型と接するラテックス組成物の粘度が下がり、型に付着するラテックス組成物の量が少なくなるので、膜成形体の膜厚が薄くなりやすい。 The heating process is preferably performed after the adhesion process, but it is also preferable to perform it before the adhesion process, and it is also preferable to perform it before and after the adhesion process. The mold is preferably heated to 60-80°C. When the temperature is lower than 60°C, the coagulant cannot be dried quickly, and it is difficult to improve the productivity of the film forming product. If the temperature exceeds 80°C, the temperature of the mold during the dipping step is too high, the viscosity of the latex composition in contact with the mold decreases, and the amount of the latex composition adhering to the mold decreases. It tends to be thin.
　膜成形体の生産性を確保する観点からは、浸漬工程の前に、加熱工程により加熱した型の冷却を行わないことが好ましいが、一方で、加熱工程により加熱された型を、浸漬工程の前に、冷却することも好ましい。すなわち、実施形態の膜成形体の製造方法は、浸漬工程の前に、加熱工程において加熱した型を冷却する冷却工程をさらに備えることが好ましい。これにより、浸漬工程の際に、型と接するラテックス組成物の粘度が下がり、型に付着するラテックス組成物の量が少なくなることを抑え、膜成形体の膜厚を効果的に厚くすることができる。型の冷却は、型が、好ましくは室温（例えば２５℃）になるまで行われる。型の冷却は、膜厚のムラが生じるのを避けるため、送風等を行うことなく、放冷により行うことが好ましい。 From the viewpoint of ensuring the productivity of the film molded article, it is preferable not to cool the mold heated in the heating step before the immersion step. Cooling is also preferred before. That is, it is preferable that the method for manufacturing a film molded article of the embodiment further includes a cooling step of cooling the mold heated in the heating step before the immersion step. As a result, the viscosity of the latex composition in contact with the mold is reduced during the dipping step, preventing the amount of the latex composition adhering to the mold from decreasing and effectively increasing the film thickness of the molded film. can. Cooling of the mold is carried out until the mold is preferably at room temperature (eg 25° C.). Cooling of the mold is preferably carried out by allowing the mold to cool without blowing air or the like, in order to avoid unevenness in the film thickness.
　ラテックス組成物の粘度に関して、回転速度を６ｒｐｍとして回転粘度計を用いてＪＩＳ　Ｚ８８０３：２０１１に従い、測った２５℃での粘度は、好ましくは５００～２００００ｍＰａ・ｓであり、より好ましくは２０００～１５０００ｍＰａ・ｓである。また、回転速度を６０ｒｐｍとした点を除いて上記と同様に測った粘度は、好ましくは１００～５０００ｍＰａ・ｓであり、より好ましくは５００～４０００ｍＰａ・ｓである。ラテックス組成物の粘度が上記範囲に調整されていることにより、型の表面に形成される皮膜の膜厚を厚くし、膜厚を調節しやすくなる。ラテックス組成物の粘度は、アルギン酸ナトリウムの配合量や分子量の調整、所定の物質の添加等により調整できる。 Regarding the viscosity of the latex composition, the viscosity at 25° C. measured according to JIS Z8803:2011 using a rotational viscometer at a rotational speed of 6 rpm is preferably 500 to 20000 mPa·s, more preferably 2000 to 15000 mPa·s. is s. The viscosity measured in the same manner as above except that the rotation speed is 60 rpm is preferably 100 to 5000 mPa·s, more preferably 500 to 4000 mPa·s. By adjusting the viscosity of the latex composition within the above range, the film thickness of the film formed on the surface of the mold is increased and the film thickness can be easily adjusted. The viscosity of the latex composition can be adjusted by adjusting the blending amount and molecular weight of sodium alginate, adding a predetermined substance, and the like.
　アルギン酸ナトリウムの数平均分子量は２０万～３００万であることが好ましく、５０万～２００万であることがより好ましい。このような分子量を持つアルギン酸ナトリウムによれば、ラテックス組成物の粘度を上述の範囲に調節しやすいので、引き上げた型に付着するラテックス組成物の量が多く、型の表面に形成される皮膜の膜厚を効果的に厚くすることができる。本明細書において分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）法を用いて測定したものをいう。 The number average molecular weight of sodium alginate is preferably 200,000 to 3,000,000, more preferably 500,000 to 2,000,000. With sodium alginate having such a molecular weight, it is easy to adjust the viscosity of the latex composition within the range described above, so that a large amount of the latex composition adheres to the pulled up mold, and the film formed on the surface of the mold is thin. The film thickness can be effectively increased. As used herein, molecular weight refers to that measured using a gel permeation chromatography (GPC) method.
　ラテックス組成物は、アルギン酸ナトリウムに加え、カルボキシメチルセルロース、ポリビニルアルコール、及びポリアクリル酸ナトリウムの少なくとも１つをさらに含むことが好ましい。これらの物質は、ラテックス組成物の粘度を高める機能を有し、ラテックス組成物の粘度をさらに高めることができ、皮膜の膜厚を厚くすることに貢献する。ラテックス組成物中のこれらの物質の合計の濃度は、好ましくは０．１～１．０％であり、より好ましくは０．３～０．７％である。 The latex composition preferably further contains at least one of carboxymethylcellulose, polyvinyl alcohol, and sodium polyacrylate in addition to sodium alginate. These substances have the function of increasing the viscosity of the latex composition, can further increase the viscosity of the latex composition, and contribute to increasing the film thickness of the coating. The total concentration of these substances in the latex composition is preferably 0.1-1.0%, more preferably 0.3-0.7%.
　浸漬工程では、皮膜の膜厚を厚くするため、ラテックス組成物の温度を３０℃以下に維持することが好ましく、１０～２５℃に維持することがより好ましい。この温度範囲に維持することで、ラテックス組成物の粘度を高め、皮膜の膜厚を厚くする効果を向上させることができる。 In the immersion step, the temperature of the latex composition is preferably maintained at 30°C or lower, more preferably 10 to 25°C, in order to increase the thickness of the film. By maintaining the temperature within this range, it is possible to increase the viscosity of the latex composition and improve the effect of increasing the film thickness of the film.
　浸漬工程における型の浸漬時間は３０～１８０秒であることが好ましく、６０～１２０秒であることがより好ましい。浸漬時間が上記範囲より短いと、型を浸漬したラテックス組成物中でのゲル化が不十分となり、引き上げた後の液だれを抑制し難くなる。浸漬時間が上記範囲より長いと、膜成形体の生産性を向上させ難い。 The immersion time of the mold in the immersion step is preferably 30 to 180 seconds, more preferably 60 to 120 seconds. If the immersion time is shorter than the above range, gelation in the latex composition in which the mold is immersed will be insufficient, making it difficult to suppress dripping after the mold is pulled out. If the immersion time is longer than the above range, it is difficult to improve the productivity of the film-formed product.
　本実施形態の膜成形体の製造方法は、さらに、脱型工程を備えることが好ましい。脱型工程は、膜成形体を型から取り外す工程である。脱型工程では、型の表面に成形された膜成形体の水洗を行う。これにより、皮膜の表面に残った未加硫の固くなったゲルを洗い落とすことができ、ＣＳＭの皮膜が持つ柔軟性が発揮され、容易に脱型を行える。膜成形体の水洗は、例えば、膜成形体を型ごと、水に浸漬することにより行うことができる。浸漬時間は、好ましくは６０～１２０秒間である。水洗の際、未加硫のゲルの水への溶解を促すため、水をエアバブリングすることが好ましい。未加硫のゲルは、水に容易に溶けるので、水中で皮膜の表面を手で擦る等の作業の必要がない。 It is preferable that the method for manufacturing a film molded product of the present embodiment further includes a demolding step. The demolding step is a step of removing the film molded body from the mold. In the demolding step, the film formed on the surface of the mold is washed with water. As a result, unvulcanized hardened gel remaining on the surface of the film can be washed off, and the flexibility of the CSM film can be exhibited to facilitate demolding. The water washing of the film molded product can be performed, for example, by immersing the film molded product together with the mold in water. The immersion time is preferably 60-120 seconds. During washing with water, air bubbling of water is preferred in order to promote dissolution of the unvulcanized gel in water. Since the unvulcanized gel easily dissolves in water, there is no need to rub the surface of the film by hand in water.
（実施例、比較例）
　表１及び表２に示す、ラテックス組成物と凝固剤の種々の組み合わせを用いて膜成形体である手袋の作製を行い、成膜性、脱型性、膜厚を調べた。手袋の作製は、表中及び下記に断った場合を除いて、次の要領で行った。
　洗浄し乾燥させた型の表面に凝固剤を塗布し、７０℃で１０分間、型を加熱し乾燥させた。次いで型を、室温（２５℃）に維持したラテックス組成物に１０秒間浸漬し、引き上げ、指先の部分を上にして７０℃で６０分間、型を加熱し、皮膜を形成した。
　凝固剤の濃度は、比較例３では１％とし、比較例１、２及び実施例では２５％とした。
　比較例３では、凝固剤中のアルギン酸ナトリウムとラテックス組成物中のカルシウムイオンの反応を促進するため、凝固剤を乾燥させるための型の加熱を行わなかった。 (Example, Comparative Example)
Using various combinations of the latex compositions and coagulants shown in Tables 1 and 2, gloves as film moldings were produced, and the film formability, releasability and film thickness were examined. Gloves were produced in the following manner, except where noted in the table and below.
A coagulant was applied to the surface of the washed and dried mold, and the mold was dried by heating at 70° C. for 10 minutes. The mold was then immersed in the latex composition maintained at room temperature (25° C.) for 10 seconds, withdrawn, fingertips up and heated at 70° C. for 60 minutes to form a film.
The concentration of the coagulant was 1% in Comparative Example 3, and 25% in Comparative Examples 1 and 2 and Example.
In Comparative Example 3, the mold was not heated to dry the coagulant in order to promote the reaction between the sodium alginate in the coagulant and the calcium ions in the latex composition.
　表中、「組成物」はラテックス組成物を意味する。ラテックス組成物は、ＣＳＭのラテックスのほか、表中に示す「組成物中の成分」を０．５％含み、実施例４では、さらに、表中に示す「組成物中の他の成分」を０．２５％含む。
　表中、「凝固剤」は、浸漬工程の前に、型の表面に付着させる溶液を意味する。
　表２中、「浸漬前の冷却」は、凝固剤を付着させた型を乾燥させるための加熱処理を行った後、浸漬工程の前に、室温（２５℃）まで放冷したことを意味する。「浸漬前の冷却」が「無」の実施例では、型の加熱乾燥後、６０秒以内に浸漬工程を行った。 In the table, "composition" means the latex composition. In addition to the CSM latex, the latex composition contains 0.5% of the "components in the composition" shown in the table, and in Example 4, further, "other components in the composition" shown in the table Contains 0.25%.
In the table, "coagulant" means the solution that adheres to the surface of the mold prior to the dipping step.
In Table 2, "cooling before immersion" means that the mold to which the coagulant was adhered was subjected to heat treatment for drying, and then allowed to cool to room temperature (25°C) before the immersion step. . In the examples where "cooling before immersion" was "none", the immersion step was performed within 60 seconds after the mold was dried by heating.
　表中の成分には、下記のものを用いた。
・κ-カラギーナン：富士フィルム和光純薬社製、「κ-カラジーナン」
・ペクチン：富士フィルム和光純薬社製、「ペクチン（リンゴ由来）」
・アルギン酸ナトリウム１：キミカ社製、「Ｂ－３」（数平均分子量１８０万～２００万）
・アルギン酸ナトリウム２：キミカ社製、「ＢＬ－２」（数平均分子量５０万～８０万）
・アルギン酸ナトリウム３：キミカ社製、「Ｂ－８」（数平均分子量２７０万～２９０万）
・硝酸カルシウム：富士フィルム和光純薬社製、「硝酸カルシウム」
・カルボキシメチルセルロース：キミカ社製、「キミカＣＭＣ」
　ＣＳＭのラテックスには、住友精化社製、「セポレックスＣＳＭ」を用いた。 The following were used for the components in the table.
・κ-Carrageenan: FUJIFILM Wako Pure Chemical Co., Ltd., “κ-Carrageenan”
・Pectin: “Pectin (derived from apple)” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
· Sodium alginate 1: Kimika Co., Ltd., "B-3" (number average molecular weight 1,800,000 to 2,000,000)
・ Sodium alginate 2: "BL-2" manufactured by Kimika (number average molecular weight 500,000 to 800,000)
· Sodium alginate 3: "B-8" manufactured by Kimika (number average molecular weight 2.7 million to 2.9 million)
・ Calcium nitrate: “Calcium nitrate” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
・ Carboxymethyl cellulose: Kimika Co., Ltd., "Kimika CMC"
"Seporex CSM" manufactured by Sumitomo Seika Chemicals Co., Ltd. was used as the CSM latex.
　成膜性は、型を引き上げ後に発生した液だれの有無、及び、液だれがなかったものに関しては膜の平滑性を確認し、その結果、液だれがあったものをＣとし、液だれがなかったが、膜の平滑性が悪いものをＢとし、液だれがなく、膜の平滑性が良かったものをＡとし、Ａは成膜性に優れ、Ｂ及びＣは成膜性が悪いと評価した。膜の平滑性の良否は、皮膜に明らかな凹凸や凝集体が表れていないかどうかにより判断した。 For the film formability, the presence or absence of dripping generated after pulling up the mold, and the smoothness of the film for those without dripping were confirmed. B was given when the film had poor smoothness, and A was given when there was no dripping and the film had good smoothness. evaluated. Whether or not the smoothness of the film was good or bad was judged by whether or not the film showed obvious unevenness or aggregates.
　脱型性は、手袋を水洗することなく型から取り外せたものをＡとし、手袋を水洗することで型から取り外せたものをＢとし、手袋を水洗しても型から取り外せず、皮膜が破れたものをＣとし、Ａは脱型性に優れ、Ｂ及びＣは脱型性が悪いと評価した。手袋の水洗は、手袋を型ごと、水に１２０秒間浸漬し、その間、軽く揺り動かすことで行った。 Releasability was rated as A when the glove could be removed from the mold without washing with water, and B when the glove could be removed from the mold by washing with water. A was evaluated as excellent in demoldability, and B and C were evaluated as poor demoldability. The glove was washed with water by immersing the glove together with the mold in water for 120 seconds and gently rocking the glove during that time.
　膜厚は、得られた手袋の５箇所以上でマイクロメータを用いて測定し、測定値の最大値と最小値の範囲で示す。その結果、膜厚の最小値が０．２ｍｍ以上のものを十分な膜厚と評価し、０．２ｍｍ未満のものを不十分な膜厚と評価した。 The film thickness is measured using a micrometer at 5 or more points on the obtained glove, and is shown in the range of the maximum and minimum values of the measured values. As a result, films with a minimum film thickness of 0.2 mm or more were evaluated as having a sufficient film thickness, and films with a minimum film thickness of less than 0.2 mm were evaluated as having an insufficient film thickness.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　実施例１と比較例１，２の対比から、カルシウムイオンを含む溶液を付着させた型を、アルギン酸ナトリウムを含むラテックス組成物に浸漬させることで、成膜性及び脱型性に優れ、十分な膜厚の膜成形体が得られることがわかる。
　比較例１では、組成物中のκ－カラギーナンが固化し、作業性が悪かった。また、固化したκ－カラギーナンの粒が皮膜に付着していた。
　比較例２では、膜厚が不十分で、脱型が困難であった。浸漬時間を長くして同様に膜成形体の作製を行っても、膜厚は変わらなかった。 From the comparison between Example 1 and Comparative Examples 1 and 2, by immersing the mold to which the solution containing calcium ions was adhered in the latex composition containing sodium alginate, excellent film-forming properties and releasability, and sufficient It can be seen that a film molded article having a thickness can be obtained.
In Comparative Example 1, κ-carrageenan in the composition solidified, resulting in poor workability. In addition, solidified κ-carrageenan granules adhered to the film.
In Comparative Example 2, the film thickness was insufficient and demolding was difficult. The film thickness did not change even when the film-formed article was produced in the same manner with a longer immersion time.
　実施例１と比較例３の対比から、ラテックス組成物にアルギン酸ナトリウムを含ませ、凝固剤にカルシウムイオンを含ませることで、成膜性及び脱型性に優れ、十分な膜厚の膜成形体が得られることがわかる。
　比較例３では、凝固剤中のアルギン酸ナトリウムがゲル化したが、液だれが発生し、ラテックス組成物の膜は形成されなかった。そのため、脱型性の評価及び膜厚の測定ができなかった。なお、比較例１，２及び実施例１～５では、浸漬した型の部分のすべてに皮膜が形成されていた。 From the comparison between Example 1 and Comparative Example 3, it was found that by including sodium alginate in the latex composition and calcium ions in the coagulant, a film molded article having excellent film-forming properties and releasability and a sufficient thickness was obtained. is obtained.
In Comparative Example 3, sodium alginate in the coagulant gelled, but dripping occurred and no latex composition film was formed. Therefore, evaluation of releasability and measurement of film thickness could not be performed. Incidentally, in Comparative Examples 1 and 2 and Examples 1 to 5, a film was formed on all the immersed portions of the mold.
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
　実施例１、３と実施例２の対比から、アルギン酸ナトリウムの数平均分子量が１５０万以上であることで、皮膜の膜厚が厚くなることがわかる。
　実施例１と実施例４の対比から、ラテックス組成物が、所定の物質を含むことで、皮膜の膜厚が厚くなることがわかる。
　実施例１と実施例５の対比から、浸漬工程の前に、加熱した型の冷却を行うことで、皮膜の膜厚が厚くなることがわかる。 From the comparison between Examples 1 and 3 and Example 2, it can be seen that the thickness of the film increases when the number average molecular weight of sodium alginate is 1,500,000 or more.
From the comparison between Example 1 and Example 4, it can be seen that the film thickness of the film increases when the latex composition contains a predetermined substance.
From the comparison between Example 1 and Example 5, it can be seen that the thickness of the film increases by cooling the heated mold before the immersion step.
　以上、本発明の膜成形体の製造方法について詳細に説明したが、本発明は上記実施形態及び上記実施例に限定されず、本発明の主旨を逸脱しない範囲において、種々の改良や変更をしてもよいのはもちろんである。 Although the method for producing a film molded article according to the present invention has been described in detail above, the present invention is not limited to the above-described embodiments and examples, and various improvements and modifications can be made without departing from the scope of the present invention. Of course you can.

Claims (7)

  1. 　膜成形体の製造方法であって、
    　膜成形用型の表面に、カルシウムイオンを含む溶液を付着させる付着工程と、
    　前記付着工程の後、前記膜成形用型を、クロロスルホン化ポリエチレンのラテックスと、アルギン酸ナトリウムとを含むラテックス組成物に浸す浸漬工程と、
    　前記膜成形用型を前記ラテックス組成物から引き上げ、前記膜成形用型の表面に前記膜成形体を成形する成形工程と、を備えることを特徴とする膜成形体の製造方法。     A method for producing a film molded body,
    an attaching step of attaching a solution containing calcium ions to the surface of the film-forming mold;
    After the attaching step, a dipping step of dipping the membrane mold in a latex composition comprising a latex of chlorosulfonated polyethylene and sodium alginate;
    and a molding step of pulling up the film-forming mold from the latex composition and molding the film-forming product on the surface of the film-forming mold.
  2. 　前記浸漬工程の前に、前記溶液を付着させた前記膜成形用型を加熱し、乾燥させる加熱工程をさらに備える、請求項１に記載の膜成形体の製造方法。 The method for producing a film molded article according to claim 1, further comprising a heating step of heating and drying the film forming mold to which the solution is attached before the dipping step.
  3. 　前記浸漬工程の前に、前記加熱工程において加熱した前記膜成形用型を冷却する冷却工程をさらに備える、請求項２に記載の膜成形体の製造方法。 The method for manufacturing a film molded product according to claim 2, further comprising a cooling step of cooling the film forming mold heated in the heating step before the immersion step.
  4. 　前記アルギン酸ナトリウムの数平均分子量は４０万～３００万である、請求項１から３のいずれか１項に記載の膜成形体の製造方法。 The method for producing a film compact according to any one of claims 1 to 3, wherein the sodium alginate has a number average molecular weight of 400,000 to 3,000,000.
  5. 　前記ラテックス組成物は、カルボキシメチルセルロース、ポリビニルアルコール、及びポリアクリル酸ナトリウムの少なくとも１つをさらに含む、請求項１から４のいずれか１項に記載の膜成形体の製造方法。 The method for producing a film molded article according to any one of claims 1 to 4, wherein the latex composition further contains at least one of carboxymethylcellulose, polyvinyl alcohol, and sodium polyacrylate.
  6. 　前記浸漬工程における前記膜成形用型の浸漬時間は６０～１２０秒である、請求項１から５のいずれか１項に記載の膜成形体の製造方法。 The method for producing a film molded article according to any one of claims 1 to 5, wherein the film forming mold is immersed in the mold for 60 to 120 seconds in the immersion step.
  7. 　前記膜成形体を前記膜成形用型から取り外す脱型工程をさらに備え、
    　前記脱型工程では、前記膜成形用型の表面に成形された前記膜成形体の水洗を行う、請求項１から６のいずれか１項に記載の膜成形体の製造方法。     Further comprising a demolding step of removing the film molded body from the film forming mold,
    7. The method for producing a film molded article according to claim 1, wherein said film molded article formed on the surface of said film forming mold is washed with water in said demolding step.
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JP2002241412A (en) * 2000-12-12 2002-08-28 Takeda Chem Ind Ltd Latex for dip forming and dip formed material
JP2005200559A (en) * 2004-01-16 2005-07-28 Nippon A & L Kk Latex for dip molding, composition for dip molding and dip molding product
CN109093910A (en) * 2018-06-29 2018-12-28 南通嘉得利安全用品有限公司 The manufacturing method of latex Labor protection gloves

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002241412A (en) * 2000-12-12 2002-08-28 Takeda Chem Ind Ltd Latex for dip forming and dip formed material
JP2005200559A (en) * 2004-01-16 2005-07-28 Nippon A & L Kk Latex for dip molding, composition for dip molding and dip molding product
CN109093910A (en) * 2018-06-29 2018-12-28 南通嘉得利安全用品有限公司 The manufacturing method of latex Labor protection gloves

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