JP2019189773A - Liquid repellent article and manufacturing method thereof - Google Patents
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- 239000005871 repellent Substances 0.000 title claims abstract description 111
- 239000007788 liquid Substances 0.000 title claims abstract description 110
- 230000002940 repellent Effects 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims description 33
- 239000002245 particle Substances 0.000 claims abstract description 148
- 229920005989 resin Polymers 0.000 claims abstract description 145
- 239000011347 resin Substances 0.000 claims abstract description 145
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 136
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 136
- 239000011737 fluorine Substances 0.000 claims abstract description 136
- 239000002344 surface layer Substances 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 235000013305 food Nutrition 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000002776 aggregation Effects 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 238000004220 aggregation Methods 0.000 claims description 3
- 235000015067 sauces Nutrition 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 235000012907 honey Nutrition 0.000 description 6
- 235000014347 soups Nutrition 0.000 description 5
- 235000013555 soy sauce Nutrition 0.000 description 5
- YBHQCJILTOVLHD-YVMONPNESA-N Mirin Chemical compound S1C(N)=NC(=O)\C1=C\C1=CC=C(O)C=C1 YBHQCJILTOVLHD-YVMONPNESA-N 0.000 description 4
- 235000012149 noodles Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 1
- QQODLKZGRKWIFG-UHFFFAOYSA-N cyfluthrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=C(F)C(OC=2C=CC=CC=2)=C1 QQODLKZGRKWIFG-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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Abstract
Description
本発明は、撥液性物品及びその製造方法に関する。 The present invention relates to a liquid repellent article and a method for producing the same.
撥液性表面層を有する種々の撥液性物品が知られている。例えば、特許文献１に記載される撥液性物品は、基材表面に形成された撥液性表面層を有し、撥液性表面層は、第１フッ素系樹脂粒子と、第２フッ素系樹脂粒子と、基材表面及び第１フッ素系樹脂粒子を覆うとともに第１フッ素系樹脂粒子を基材表面に固着する第１フッ素系樹脂被膜と、第１フッ素系樹脂被膜及び第２フッ素系樹脂粒子を覆うとともに第２フッ素系樹脂粒子を第１フッ素系樹脂被膜に固着する第２フッ素系樹脂被膜と、で構成されている。特許文献１によれば、この撥液性表面層は、第１フッ素系樹脂溶液に第１フッ素系樹脂粒子を分散させた第１懸濁液で基材表面を被覆し、第１懸濁液を乾燥させる第１工程と、第１工程によって形成された表面を、第２フッ素系樹脂溶液に第２フッ素系樹脂粒子を分散させた第２懸濁液で被覆し、第２懸濁液を乾燥させる第２工程と、を経ることによって形成される。 Various liquid repellent articles having a liquid repellent surface layer are known. For example, the liquid-repellent article described in Patent Document 1 has a liquid-repellent surface layer formed on the surface of a substrate, and the liquid-repellent surface layer includes first fluorine-based resin particles and second fluorine-based layers. Resin particles, a first fluorine-based resin coating that covers the substrate surface and the first fluorine-based resin particles and that fixes the first fluorine-based resin particles to the substrate surface, a first fluorine-based resin coating, and a second fluorine-based resin And a second fluorine-based resin film that covers the particles and fixes the second fluorine-based resin particles to the first fluorine-based resin film. According to Patent Document 1, the liquid repellent surface layer covers the substrate surface with a first suspension in which first fluorine resin particles are dispersed in a first fluorine resin solution. The first step of drying the coating, and the surface formed by the first step is coated with a second suspension in which the second fluorine resin particles are dispersed in the second fluorine resin solution, And a second step of drying.
しかし、懸濁液を乾燥させる工程を１度経るだけで撥液性表面層を形成することができれば、製造コストの観点等から有利である。また、水に対する撥液性を得ることよりも、ソース、醤油、はちみつ、麺つゆ、みりん等の食品に対する撥液性を得ることの方が困難である。しかし、このような食品に対する撥液性を発揮できる樹脂表面を得ることができれば、例えば、その樹脂表面を、食品を吐出可能に収容する容器に適用することにより、そのような容器の吐出部における内容物の付着の汚れや容器内の内容物の残量が多いという課題を有利に解決することが可能となる。特に比較的粘度の高いソース、はちみつについては、吐出部における内容物の付着の汚れや容器内の内容物の残量が多いということは一般的に知られており、できるだけ有利な解決が望まれている課題である。 However, if the liquid-repellent surface layer can be formed by only one step of drying the suspension, it is advantageous from the viewpoint of manufacturing cost. In addition, it is more difficult to obtain liquid repellency for foods such as sauce, soy sauce, honey, noodle soup and mirin rather than to obtain liquid repellency for water. However, if a resin surface capable of exhibiting liquid repellency with respect to such food can be obtained, for example, by applying the resin surface to a container that can discharge food, the discharge portion of such a container It is possible to advantageously solve the problem that the contents adhere to dirt and the contents remaining in the container are large. In particular, it is generally known that a relatively high viscosity source and honey have a large amount of dirt on the discharge part and a large amount of content remaining in the container, and an advantageous solution is desired. It is a problem.
本発明は、このような点に鑑みてなされたもので、水及び／又は食品に対する撥液性を有利に実現した撥液性物品及びその製造方法を提供することを目的とする。 This invention is made | formed in view of such a point, and it aims at providing the liquid repellent article which advantageously implement | achieved the liquid repellency with respect to water and / or a foodstuff, and its manufacturing method.
本発明の一態様に係る撥液性物品は、
基材表面に形成された撥液性表面層を有し、
前記撥液性表面層は、
３〜３３μｍの平均粒径を有する１以上の第１フッ素系樹脂粒子と、
１μｍ以下の平均粒径を有する第２フッ素系樹脂粒子と、
前記基材表面、前記１以上の第１フッ素系樹脂粒子及び前記第２フッ素系樹脂粒子を少なくとも部分的に覆うとともに、前記１以上の第１フッ素系樹脂粒子及び前記第２フッ素系樹脂粒子を前記基材表面に固着するフッ素系樹脂被膜と、で構成されている。
The liquid repellent article according to one aspect of the present invention is:
Having a liquid repellent surface layer formed on the substrate surface;
The liquid repellent surface layer is
One or more first fluororesin particles having an average particle size of 3 to 33 μm;
Second fluororesin particles having an average particle size of 1 μm or less;
The substrate surface, the one or more first fluorine-based resin particles and the second fluorine-based resin particles are at least partially covered, and the one or more first fluorine-based resin particles and the second fluorine-based resin particles are And a fluorine-based resin film that adheres to the surface of the substrate.
本発明に係る撥液性物品は、全ての前記１以上の第１フッ素系樹脂粒子と前記第２フッ素系樹脂粒子との重量比が、３：２０〜２５：５であってもよい。 In the liquid-repellent article according to the present invention, a weight ratio of all the one or more first fluorine-based resin particles to the second fluorine-based resin particles may be 3:20 to 25: 5.
本発明に係る撥液性物品は、
前記撥液性表面層が、
前記１以上の第１フッ素系樹脂粒子のそれぞれと前記第２フッ素系樹脂粒子との重畳によって凹凸状に形成された１以上の第１表面と、
前記第２フッ素系樹脂粒子の凝集によって凹凸状に形成された第２表面と、を有してもよい。
The liquid repellent article according to the present invention is:
The liquid repellent surface layer is
One or more first surfaces formed in an uneven shape by superposition of each of the one or more first fluorine-based resin particles and the second fluorine-based resin particles;
And a second surface formed in an uneven shape by agglomeration of the second fluorine-based resin particles.
本発明に係る撥液性物品は、前記１以上の第１フッ素系樹脂粒子が、それぞれ、ポリテトラフルオロエチレン（ＰＴＦＥ）によって形成されていてもよい。 In the liquid-repellent article according to the present invention, the one or more first fluorine-based resin particles may be formed of polytetrafluoroethylene (PTFE).
本発明に係る撥液性物品は、前記第２フッ素系樹脂粒子が、ポリテトラフルオロエチレン（ＰＴＦＥ）によって形成されていてもよい。 In the liquid repellent article according to the present invention, the second fluorine resin particles may be formed of polytetrafluoroethylene (PTFE).
本発明に係る撥液性物品は、前記フッ素系樹脂被膜が、パーフルオロアルキル基を有するポリマーによって形成されていてもよい。 In the liquid-repellent article according to the present invention, the fluorine resin film may be formed of a polymer having a perfluoroalkyl group.
本発明に係る撥液性物品は、前記撥液性物品が、水及び／又は食品用の、容器又は容器構成部材であってもよい。 In the liquid repellent article according to the present invention, the liquid repellent article may be a container or a container component for water and / or food.
本発明の一態様に係る撥液性物品の製造方法は、
基材表面に形成された撥液性表面層を有する撥液性物品の製造方法であって、
３〜３３μｍの平均粒径を有する１以上の第１フッ素系樹脂粒子と１μｍ以下の平均粒径を有する第２フッ素系樹脂粒子とをフッ素系樹脂溶液に分散させた懸濁液を準備する準備工程と、
前記基材表面の少なくとも一部を前記懸濁液で被覆する被覆工程と、
前記懸濁液を乾燥させることにより、前記１以上の第１フッ素系樹脂粒子と前記第２フッ素系樹脂粒子と前記フッ素系樹脂溶液の乾燥によって形成されたフッ素系樹脂被膜とによって前記撥液性表面層を形成する乾燥工程と、を有するものである。
A method for producing a liquid-repellent article according to an aspect of the present invention includes:
A method for producing a liquid repellent article having a liquid repellent surface layer formed on a substrate surface,
Preparation for preparing a suspension in which one or more first fluorine resin particles having an average particle diameter of 3 to 33 μm and second fluorine resin particles having an average particle diameter of 1 μm or less are dispersed in a fluorine resin solution Process,
A coating step of coating at least a part of the substrate surface with the suspension;
By drying the suspension, the one or more first fluorine resin particles, the second fluorine resin particles, and the fluorine resin film formed by drying the fluorine resin solution, the liquid repellency. And a drying step of forming a surface layer.
本発明に係る撥液性物品の製造方法は、全ての前記１以上の第１フッ素系樹脂粒子と前記第２フッ素系樹脂粒子との重量比が、３：２０〜２５：５であってもよい。 In the method for producing a liquid-repellent article according to the present invention, the weight ratio of all the one or more first fluorine-based resin particles to the second fluorine-based resin particles is 3:20 to 25: 5. Good.
本発明に係る撥液性物品の製造方法は、
前記撥液性表面層が、
前記１以上の第１フッ素系樹脂粒子のそれぞれと前記第２フッ素系樹脂粒子との重畳によって凹凸状に形成された１以上の第１表面と、
前記第２フッ素系樹脂粒子の凝集によって凹凸状に形成された第２表面と、を有してもよい。
The method for producing a liquid-repellent article according to the present invention includes:
The liquid repellent surface layer is
One or more first surfaces formed in an uneven shape by superposition of each of the one or more first fluorine-based resin particles and the second fluorine-based resin particles;
And a second surface formed in an uneven shape by agglomeration of the second fluorine-based resin particles.
本発明に係る撥液性物品の製造方法は、前記１以上の第１フッ素系樹脂粒子が、それぞれ、ポリテトラフルオロエチレン（ＰＴＦＥ）によって形成されていてもよい。 In the method for producing a liquid-repellent article according to the present invention, each of the one or more first fluorine-based resin particles may be formed of polytetrafluoroethylene (PTFE).
本発明に係る撥液性物品の製造方法は、前記第２フッ素系樹脂粒子が、ポリテトラフルオロエチレン（ＰＴＦＥ）によって形成されていてもよい。 In the method for producing a liquid repellent article according to the present invention, the second fluorine resin particles may be formed of polytetrafluoroethylene (PTFE).
本発明に係る撥液性物品の製造方法は、前記フッ素系樹脂溶液が、パーフルオロアルキル基を有するポリマーによって形成されていてもよい。 In the method for producing a liquid repellent article according to the present invention, the fluororesin solution may be formed of a polymer having a perfluoroalkyl group.
本発明に係る撥液性物品の製造方法は、前記撥液性物品が、水及び／又は食品用の、容器又は容器構成部材であってもよい。 In the method for producing a liquid-repellent article according to the present invention, the liquid-repellent article may be a container for water and / or food or a container constituent member.
本発明によれば、水及び／又は食品に対する撥液性を有利に実現した撥液性物品及びその製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the liquid repellent article which implement | achieved the liquid repellency advantageously with respect to water and / or foodstuffs, and its manufacturing method can be provided.
以下、図面を参照して、本発明の一実施形態に係る撥液性物品について詳細に例示説明する。 Hereinafter, with reference to drawings, the liquid repellent article concerning one embodiment of the present invention is illustrated and explained in detail.
図１に示すように、本実施形態に係る撥液性物品１は、基材２の表面（基材表面）２ａに形成された撥液性表面層３を有している。基材２は、例えばポリプロピレン（ＰＰ）又はポリエチレン（ＰＥ）等の合成樹脂によって形成されていることが好ましい。しかし、基材２は、合成樹脂以外の材料によって形成されてもよい。撥液性表面層３は、３〜３３μｍの平均粒径を有する１以上の第１フッ素系樹脂粒子４と、１μｍ以下の平均粒径を有する第２フッ素系樹脂粒子５と、フッ素系樹脂被膜６と、で構成されている。 As shown in FIG. 1, a liquid repellent article 1 according to this embodiment has a liquid repellent surface layer 3 formed on a surface (base material surface) 2a of a base material 2. The substrate 2 is preferably formed of a synthetic resin such as polypropylene (PP) or polyethylene (PE). However, the base material 2 may be formed of a material other than the synthetic resin. The liquid repellent surface layer 3 includes one or more first fluorine resin particles 4 having an average particle diameter of 3 to 33 μm, second fluorine resin particles 5 having an average particle diameter of 1 μm or less, and a fluorine resin film. 6.
図１には１の第１フッ素系樹脂粒子４のみが示されているが、撥液性表面層３は、２以上の第１フッ素系樹脂粒子４で構成されている。例えば、撥液性表面層３は、後述するサンプル２５のように、３３μｍの平均粒径を有する第１フッ素系樹脂粒子４と、１０μｍの平均粒径を有する第１フッ素系樹脂粒子４と、６．２μｍの平均粒径を有する第１フッ素系樹脂粒子４と、３μｍの平均粒径を有する第１フッ素系樹脂粒子４と、からなる４の第１フッ素系樹脂粒子４で構成されてもよい。また、撥液性表面層３は、１の第１フッ素系樹脂粒子４で構成されてもよい。本明細書において、平均粒径とは、レーザー回折散乱法によって測定される５０％粒径ｄ５０を意味する。 Although only one first fluorine-based resin particle 4 is shown in FIG. 1, the liquid repellent surface layer 3 is composed of two or more first fluorine-based resin particles 4. For example, the liquid-repellent surface layer 3 includes a first fluorine-based resin particle 4 having an average particle diameter of 33 μm and a first fluorine-based resin particle 4 having an average particle diameter of 10 μm, as in Sample 25 described later. Even if it is composed of four first fluorine-based resin particles 4 including the first fluorine-based resin particles 4 having an average particle diameter of 6.2 μm and the first fluorine-based resin particles 4 having an average particle diameter of 3 μm. Good. The liquid repellent surface layer 3 may be composed of one first fluorine resin particle 4. In this specification, the average particle diameter means a 50% particle diameter d50 measured by a laser diffraction scattering method.
１以上の第１フッ素系樹脂粒子４は、それぞれ、ポリテトラフルオロエチレン（ＰＴＦＥ）によって形成されていることが、優れた撥液性を得る上で好ましい。しかし、１以上のフッ素系樹脂は、それぞれ、ＰＴＦＥ以外のフッ素系樹脂によって形成されてもよい。 The one or more first fluorine-based resin particles 4 are each preferably formed of polytetrafluoroethylene (PTFE) in order to obtain excellent liquid repellency. However, each of the one or more fluororesins may be formed of a fluororesin other than PTFE.
第２フッ素系樹脂粒子５は、１μｍ以下の最大粒径を有することが、優れた撥液性を得る上で好ましい。撥液性表面層３は、１の第２フッ素系樹脂粒子５を有していることが、優れた撥液性を得る上で好ましい。しかし、撥液性表面層３は、１以上の第２フッ素系樹脂粒子５を有していてもよい。 The second fluorine-based resin particles 5 preferably have a maximum particle size of 1 μm or less in order to obtain excellent liquid repellency. The liquid repellent surface layer 3 preferably has one second fluorine resin particle 5 in order to obtain excellent liquid repellency. However, the liquid repellent surface layer 3 may have one or more second fluorine resin particles 5.
第２フッ素系樹脂粒子５は、ＰＴＦＥによって形成されていることが、優れた撥液性を得る上で好ましい。しかし、第２フッ素系樹脂粒子５は、ＰＴＦＥ以外のフッ素系樹脂によって形成されてもよい。 The second fluorine resin particles 5 are preferably formed of PTFE in order to obtain excellent liquid repellency. However, the second fluorine resin particles 5 may be formed of a fluorine resin other than PTFE.
フッ素系樹脂被膜６は、基材表面２ａ、１以上の第１フッ素系樹脂粒子４及び第２フッ素系樹脂粒子５を少なくとも部分的に覆っている。また、フッ素系樹脂被膜６は、１以上の第１フッ素系樹脂粒子４及び第２フッ素系樹脂粒子５を基材表面２ａに固着している。その結果、本実施形態では、撥液性表面層３は、１以上の第１フッ素系樹脂粒子４のそれぞれと第２フッ素系樹脂粒子５との重畳によって凹凸状に形成された１以上の第１表面７と、第２フッ素系樹脂粒子５の凝集によって凹凸状に形成された第２表面８と、を有している。このような撥液性表面層３の一例を示す走査型電子顕微鏡（ＳＥＭ）画像を図４に示す。この画像から、第１表面７と第２表面８とによる多数のエアポケットが形成されていることが視認できる。 The fluorine resin coating 6 at least partially covers the substrate surface 2a, the one or more first fluorine resin particles 4 and the second fluorine resin particles 5. The fluorine-based resin coating 6 has one or more first fluorine-based resin particles 4 and second fluorine-based resin particles 5 fixed to the substrate surface 2a. As a result, in the present embodiment, the liquid repellent surface layer 3 has one or more first fluorinated resin particles 4 and one or more first fluorinated resin particles 5 formed in an uneven shape by overlapping the second fluorinated resin particles 5. 1 surface 7 and the 2nd surface 8 formed in the uneven | corrugated shape by aggregation of the 2nd fluorine-type resin particle 5. A scanning electron microscope (SEM) image showing an example of such a liquid repellent surface layer 3 is shown in FIG. From this image, it can be visually recognized that a large number of air pockets are formed by the first surface 7 and the second surface 8.
フッ素系樹脂被膜６は、パーフルオロアルキル基を有するポリマーによって形成されていることが、優れた撥液性を得る上で好ましい。しかし、フッ素系樹脂被膜６は、このようなパーフルオロアルキル基を有するポリマー以外のフッ素系樹脂によって形成されてもよい。 The fluororesin film 6 is preferably formed of a polymer having a perfluoroalkyl group in order to obtain excellent liquid repellency. However, the fluorine resin film 6 may be formed of a fluorine resin other than the polymer having such a perfluoroalkyl group.
全ての１以上の第１フッ素系樹脂粒子４と第２フッ素系樹脂粒子５との重量比は、３：２０〜２５：５であることが、優れた撥液性を得る上で好ましい。しかし、この重量比は、この範囲外であってもよい。 The weight ratio of all the one or more first fluorine-based resin particles 4 and second fluorine-based resin particles 5 is preferably 3:20 to 25: 5 in order to obtain excellent liquid repellency. However, this weight ratio may be outside this range.
撥液性物品１は、水及び／又は食品用の、容器又は容器構成部材（例えばキャップ）であってもよい。しかし、撥液性物品１は、容器及び容器構成部材以外の物品であってもよい。撥液性表面層３を容器の内側に設けた場合には、容器の内面への付着によって使い切れない内容物の残量（内容物の使い残し）を低減することができる。また、撥液性表面層３を容器の外側に設けた場合には、容器の外面への内容物の付着による汚れの発生を抑制することができる。容器は、筒状の口部と口部の下方に連なる胴部と胴部の下端を閉塞する底部とを有する容器本体と、容器本体の口部に装着されるとともに内容物を吐出可能な、例えば筒状の、吐出部を有するキャップとを備えてもよい。撥液性物品１は、このようなキャップであってもよく、撥液性表面層３は、このようなキャップの吐出部に設けられてもよい。撥液性表面層３をこのようなキャップの吐出部に設けた場合には、容器本体の胴部をスクイズ（押圧）して内容物としてのソース、醤油、はちみつ、麺つゆ、みりん等の食品をキャップの吐出部を通じて外部に吐出する際に、吐出部における内容物の液切れを良くするとともに吐出部への液の付着を抑制することができ、もって、吐出部での汚れの発生を抑制することができる。 The liquid repellent article 1 may be a container or a container component (for example, a cap) for water and / or food. However, the liquid repellent article 1 may be an article other than the container and the container constituent member. When the liquid repellent surface layer 3 is provided on the inner side of the container, the remaining amount of the content that cannot be used due to adhesion to the inner surface of the container (remaining content) can be reduced. In addition, when the liquid repellent surface layer 3 is provided outside the container, it is possible to suppress the occurrence of contamination due to the adhesion of the contents to the outer surface of the container. The container is a container body having a cylindrical mouth part and a trunk part connected to the lower part of the mouth part and a bottom part closing the lower end of the trunk part, and is mounted on the mouth part of the container body and can discharge the contents. For example, a cylindrical cap having a discharge portion may be provided. The liquid repellent article 1 may be such a cap, and the liquid repellent surface layer 3 may be provided in the discharge portion of such a cap. When the liquid-repellent surface layer 3 is provided in the discharge part of such a cap, food such as sauce, soy sauce, honey, noodle soup, mirin, etc. as the contents by squeezing the body part of the container body When the liquid is discharged to the outside through the discharge part of the cap, it is possible to improve the drainage of the contents in the discharge part and to suppress the adhesion of the liquid to the discharge part, thereby suppressing the occurrence of dirt in the discharge part can do.
撥液性物品１は、後述する本発明の一実施形態に係る撥液性物品の製造方法によって得ることができる。しかし、撥液性物品１は、他の製造方法によって得てもよい。 The liquid repellent article 1 can be obtained by a method for producing a liquid repellent article according to an embodiment of the present invention described later. However, the liquid repellent article 1 may be obtained by other manufacturing methods.
本実施形態では、撥液性表面層３は、１以上の第１フッ素系樹脂粒子４と、第２フッ素系樹脂粒子５と、基材表面２ａ、１以上の第１フッ素系樹脂粒子４及び第２フッ素系樹脂粒子５を少なくとも部分的に覆うとともに１以上の第１フッ素系樹脂粒子４及び第２フッ素系樹脂粒子５を基材表面２ａに固着するフッ素系樹脂被膜６と、で構成されている。したがって、本実施形態に係る撥液性物品１によれば、１以上の第１フッ素系樹脂粒子４と第２フッ素系樹脂粒子５とをフッ素系樹脂溶液９（図２参照）に分散させた懸濁液１０を乾燥させる工程を１度経るだけで撥液性表面層３を形成することができるため、製造コストの低減を図ることができる。 In the present embodiment, the liquid repellent surface layer 3 includes one or more first fluorine-based resin particles 4, second fluorine-based resin particles 5, a substrate surface 2 a, one or more first fluorine-based resin particles 4, and And at least partially covering the second fluorine-based resin particles 5 and one or more first fluorine-based resin particles 4 and a fluorine-based resin coating 6 for fixing the second fluorine-based resin particles 5 to the substrate surface 2a. ing. Therefore, according to the liquid-repellent article 1 according to the present embodiment, one or more first fluorine-based resin particles 4 and second fluorine-based resin particles 5 are dispersed in the fluorine-based resin solution 9 (see FIG. 2). Since the liquid-repellent surface layer 3 can be formed only by passing the step of drying the suspension 10 once, the manufacturing cost can be reduced.
また、本実施形態では、撥液性表面層３は、１以上の第１表面７と、第２表面８と、を有している。したがって、本実施形態に係る撥液性物品１によれば、水は勿論、食品に対しても優れた撥液性を発揮することができる。 In the present embodiment, the liquid repellent surface layer 3 has one or more first surfaces 7 and a second surface 8. Therefore, according to the liquid repellent article 1 according to the present embodiment, excellent liquid repellency can be exhibited not only for water but also for food.
次に、図面を参照して、本発明の一実施形態に係る撥液性物品の製造方法について詳細に例示説明する。以下では、前述した本発明の一実施形態に係る撥液性物品１を製造する場合を例として説明するが、本発明の一実施形態に係る撥液性物品の製造方法は、その他の構成の撥液性物品を製造するために適宜応用することができる。 Next, with reference to drawings, the manufacturing method of the liquid repellent article which concerns on one Embodiment of this invention is illustrated and demonstrated in detail. Hereinafter, the case where the liquid repellent article 1 according to the embodiment of the present invention is manufactured will be described as an example. However, the method for manufacturing the liquid repellent article according to the embodiment of the present invention has other configurations. It can be applied as appropriate to produce a liquid repellent article.
図３に示すように、本実施形態に係る撥液性物品の製造方法では、準備工程ｐ１、被覆工程ｐ２及び乾燥工程ｐ３をこの順に経ることにより、前述した本発明の一実施形態に係る撥液性物品１を製造する。 As shown in FIG. 3, in the method for manufacturing a liquid repellent article according to this embodiment, the preparation step p1, the covering step p2, and the drying step p3 are performed in this order, thereby the repellent property according to the embodiment of the present invention described above. The liquid article 1 is manufactured.
準備工程ｐ１は、１以上の第１フッ素系樹脂粒子４と第２フッ素系樹脂粒子５とをフッ素系樹脂溶液９に分散させた懸濁液１０を準備する工程である。フッ素系樹脂溶液９のフッ素系樹脂溶質は、パーフルオロアルキル基を有するポリマーによって形成されていることが、優れた撥液性を得る上で好ましい。しかし、フッ素系樹脂溶液９のフッ素系樹脂溶質は、このようなパーフルオロアルキル基を有するポリマー以外のフッ素系樹脂によって形成されてもよい。準備工程ｐ１においては、例えば、１以上の第１フッ素系樹脂粒子４と第２フッ素系樹脂粒子５とを含むフッ素系樹脂溶液９に超音波を５〜１０分適用することにより、１以上の第１フッ素系樹脂粒子４と第２フッ素系樹脂粒子５とが良好に分散した懸濁液１０を得ることができる。 The preparation step p1 is a step of preparing a suspension 10 in which one or more first fluorine-based resin particles 4 and second fluorine-based resin particles 5 are dispersed in a fluorine-based resin solution 9. The fluororesin solute of the fluororesin solution 9 is preferably formed of a polymer having a perfluoroalkyl group in order to obtain excellent liquid repellency. However, the fluororesin solute of the fluororesin solution 9 may be formed of a fluororesin other than the polymer having such a perfluoroalkyl group. In the preparation step p1, for example, by applying an ultrasonic wave to the fluorine-based resin solution 9 including one or more first fluorine-based resin particles 4 and second fluorine-based resin particles 5 for 5 to 10 minutes, A suspension 10 in which the first fluorine resin particles 4 and the second fluorine resin particles 5 are well dispersed can be obtained.
被覆工程ｐ２は、図２に示すように、基材表面２ａの少なくとも一部を懸濁液１０で被覆する工程である。懸濁液１０による基材表面２ａの少なくとも部分的な被覆は、例えば、塗布又は浸漬等によって行うことができる。その際、基材表面２ａにプライマーの適用又は表面処理を行う必要はない。 The coating step p2 is a step of coating at least a part of the substrate surface 2a with the suspension 10 as shown in FIG. The at least partial coating of the substrate surface 2a with the suspension 10 can be performed, for example, by coating or dipping. At that time, it is not necessary to apply a primer or perform a surface treatment on the substrate surface 2a.
乾燥工程ｐ３は、懸濁液１０を乾燥させることにより、１以上の第１フッ素系樹脂粒子４と第２フッ素系樹脂粒子５とフッ素系樹脂溶液９の乾燥によって形成されたフッ素系樹脂被膜６とによって撥液性表面層３（図１参照）を形成する工程である。乾燥工程ｐ３において、懸濁液１０の乾燥は、例えば８０℃で５〜１０分放置することによって行うことができるが、常温での放置によって行ってもよい。 In the drying step p3, the suspension 10 is dried to dry one or more of the first fluorine resin particles 4, the second fluorine resin particles 5, and the fluorine resin solution 9, and the fluorine resin film 6 formed. To form the liquid repellent surface layer 3 (see FIG. 1). In the drying step p3, the suspension 10 can be dried, for example, by leaving it at 80 ° C. for 5 to 10 minutes.
本実施形態では、準備工程ｐ１において、懸濁液１０に含まれる全ての１以上の第１フッ素系樹脂粒子４と第２フッ素系樹脂粒子５とを合わせたフッ素系樹脂粒子の濃度は、１３〜３０重量％であり、懸濁液１０に含まれる第２フッ素系樹脂粒子の濃度は、５重量％以上である。懸濁液１０に含まれる各成分の濃度をこのような範囲に設定することにより、前述したような１以上の第１表面７と第２表面８とを有する撥液性表面層３を安定して得ることができる。なお、懸濁液１０に含まれるフッ素系樹脂溶液９のフッ素系樹脂溶質の濃度は、５重量％程度とすることが好ましい。 In the present embodiment, in the preparation step p1, the concentration of the fluororesin particles including all of the one or more first fluororesin particles 4 and the second fluororesin particles 5 included in the suspension 10 is 13 The concentration of the second fluorine resin particles contained in the suspension 10 is 5% by weight or more. By setting the concentration of each component contained in the suspension 10 in such a range, the liquid repellent surface layer 3 having one or more first surfaces 7 and second surfaces 8 as described above is stabilized. Can be obtained. The concentration of the fluororesin solute in the fluororesin solution 9 contained in the suspension 10 is preferably about 5% by weight.
本実施形態に係る撥液性物品の製造方法によれば、１度の乾燥工程によって撥液性表面層３を形成することができるので、製造コストの低減を図ることができる。 According to the method for manufacturing a liquid-repellent article according to the present embodiment, the liquid-repellent surface layer 3 can be formed by a single drying step, so that the manufacturing cost can be reduced.
前述した本実施形態は、本発明の実施形態の一例にすぎず、発明の要旨を逸脱しない範囲で種々変更可能であることはいうまでもない。 The above-described embodiment is merely an example of the embodiment of the present invention, and it is needless to say that various modifications can be made without departing from the gist of the invention.
発明者は、種々の平均粒径を有するフッ素系樹脂粒子を用いて樹脂板上に撥液性表面層を形成し、撥液性の評価を行った。その結果を表１に示す。比較例としてサンプル１は、樹脂板単体とした。また、比較例としてサンプル２は、樹脂板上にパーフルオロアルキル基を有するポリマーによるフッ素系樹脂被膜のみによって撥液性表面層を形成した。サンプル３〜２７、３４、３５、３８〜４１、及び４６〜６４は、前述した実施形態に係る撥液性物品の製造方法に従って製作した実施例である。サンプル２８〜３３、３６、３７、４２〜４５は、第２フッ素系樹脂粒子を含まない点を除いては、前述した実施形態に係る撥液性物品の製造方法に従って製作した比較例である。 The inventor formed a liquid repellent surface layer on a resin plate using fluorine-based resin particles having various average particle diameters, and evaluated the liquid repellency. The results are shown in Table 1. As a comparative example, Sample 1 was a resin plate alone. As a comparative example, in sample 2, a liquid repellent surface layer was formed only on a resin plate with a fluororesin film made of a polymer having a perfluoroalkyl group. Samples 3 to 27, 34, 35, 38 to 41, and 46 to 64 are examples manufactured according to the method for manufacturing a liquid repellent article according to the above-described embodiment. Samples 28 to 33, 36, 37, and 42 to 45 are comparative examples manufactured according to the method for manufacturing a liquid repellent article according to the above-described embodiment, except that the second fluorine resin particles are not included.
撥液性の評価は、水のみならず、ソース（ブルドックソース社「中農ソース」および「ウスターソース」）、醤油（キッコーマン社「特選丸大豆しょうゆ」）、はちみつ（加藤美蜂園「サクラ印 純粋はちみつ」）、麺つゆ（ヤマサ醤油「昆布つゆ」）、みりん（ミツカン社「本みりん」）についても行った。すなわち、水、ソース、醤油、はちみつ、麺つゆ、みりんのそれぞれに対する滑落角を測定し、これら全ての滑落角が３０°以内だったものを○、いずれか一つでも３０°を越えたものを×で表１に示している。滑落角の測定は、各サンプルに各液を一滴付着させて、サンプルを傾け、各液が滑り落ち始める角度を測定することによって行った。 Evaluation of liquid repellency is not only water, but also sauces (Bulldock Sauce “Nakano Sauce” and “Worcester Sauce”), soy sauce (Kikkoman Corporation “Selected Maru Soy Soy Sauce”), honey (Kato Bishouen “Sakura Ink Pure” Honey "), noodle soup (Yamasa soy sauce" Konbu soup "), and mirin (Mitskan" Hon Mirin "). That is, the sliding angle for each of water, sauce, soy sauce, honey, noodle soup and mirin was measured, and all these sliding angles were within 30 °, and any one exceeded 30 °. It shows in Table 1 with x. The sliding angle was measured by attaching a drop of each liquid to each sample, tilting the sample, and measuring the angle at which each liquid started to slide down.
第１フッ素系樹脂粒子としては、株式会社喜多村製のＫＴＬ−４００Ｍ（平均粒径３３μｍ）、ＫＴＬ−４５０Ａ（平均粒径１７．５μｍ）、ＫＴＬ−６２０（平均粒径１１．５μｍ）、ＫＴＬ−１０Ｓ（平均粒径１０μｍ）、ＫＴＬ−９Ｓ（平均粒径６．２μｍ）、及びＫＴＬ−４Ｎ（平均粒径３μｍ）を用いた。第２フッ素系樹脂粒子としては、株式会社喜多村社製ＫＴＬ−５００Ｆ（平均粒径１μｍ以下）を用いた。サンプル３〜４７において用いた粒子の濃度を表１に示す。準備工程において、懸濁液に含まれるフッ素系樹脂溶液は、ＡＧＣセイミケミカル株式会社製の「エスエフコート」を用いた。このフッ素系樹脂溶液中のフッ素系樹脂溶質の濃度は、５重量％程度であった。
表１に示す結果においては、実施例の中でも、食品に対する良好な撥液性が得られるのは、全ての１以上の第１フッ素系樹脂粒子と第２フッ素系樹脂粒子との重量比が３：２０〜２５：５であるサンプル３〜２７及び４８〜６４に限られた。また、濃度に着目すると、このサンプル３〜２７及び４８〜６４では、懸濁液に含まれる全ての１以上の第１フッ素系樹脂粒子と第２フッ素系樹脂粒子とを合わせたフッ素系樹脂粒子の濃度が１３〜３０重量％であり、懸濁液に含まれる第２フッ素系樹脂粒子の濃度が５重量％以上となっていることが分かる。 In the results shown in Table 1, among the examples, good liquid repellency with respect to food is obtained when the weight ratio of all the one or more first fluororesin particles and second fluororesin particles is 3 : Samples 3 to 27 and 48 to 64 which are 20 to 25: 5. Further, focusing on the concentration, in Samples 3 to 27 and 48 to 64, fluorine resin particles in which all of one or more first fluorine resin particles and second fluorine resin particles included in the suspension are combined. It can be seen that the concentration of is 13 to 30% by weight, and the concentration of the second fluorine resin particles contained in the suspension is 5% by weight or more.
また、発明者は、サンプル１３と同様の要領でボトル状容器用のキャップの内側面に撥液性表面層を形成し、ソースに対する撥液性の確認テストを実施した。図５に示すように、キャップ１１は、円板状の天壁１１ａと、天壁１１ａの外周から垂下する円筒状の周壁１１ｂと、を有するものとした。そして、天壁１１ａの底面全体の半分の領域のみに、撥液性表面層を形成した。図５において、撥液性表面層を形成した領域Ｒを網掛けによって示している。このキャップ１１を、ソースを収容したボトル状の容器本体１２の口部１２ａに装着し、容器全体を反転させて、ソースをキャップ１１の天壁１１ａの底面全体に接触させた後に、キャップ１１を容器本体１２から取り外して撥液性を目視で確認した。 Further, the inventor formed a liquid repellent surface layer on the inner surface of the cap for the bottle-shaped container in the same manner as for the sample 13, and conducted a liquid repellency confirmation test on the source. As shown in FIG. 5, the cap 11 has a disk-shaped top wall 11a and a cylindrical peripheral wall 11b that hangs down from the outer periphery of the top wall 11a. And the liquid repellent surface layer was formed only in the half area | region of the whole bottom face of the top wall 11a. In FIG. 5, the region R where the liquid repellent surface layer is formed is shown by shading. The cap 11 is attached to the mouth portion 12a of the bottle-shaped container main body 12 containing the sauce, the whole container is inverted, and the sauce is brought into contact with the entire bottom surface of the top wall 11a of the cap 11. The container was removed from the container body 12 and the liquid repellency was visually confirmed.
容器本体１２に装着する前後に撮影したキャップ１１の写真を図６に示す。図６の写真は、キャップ１１の天壁１１ａを底面側から撮影している。図６において、天壁１１ａの底面における右半分の領域（図５に網掛けで示した領域Ｒ）が撥液性表面層となっているが、この領域がソースに対して明らかに撥液していることが分かる。 FIG. 6 shows photographs of the cap 11 taken before and after mounting on the container body 12. In the photograph of FIG. 6, the top wall 11a of the cap 11 is taken from the bottom side. In FIG. 6, the right half region (region R shown by shading in FIG. 5) on the bottom surface of the top wall 11a is a liquid repellent surface layer. I understand that
１ 撥液性物品
２ 基材
２ａ 基材表面
３ 撥液性表面層
４ 第１フッ素系樹脂粒子
５ 第２フッ素系樹脂粒子
６ フッ素系樹脂被膜
７ 第１表面
８ 第２表面
９ フッ素系樹脂溶液
１０ 懸濁液
１１ キャップ
１１ａ 天壁
１１ｂ 周壁
１２ 容器本体
１２ａ 口部
Ｒ 領域
DESCRIPTION OF SYMBOLS 1 Liquid repellent article 2 Base material 2a Base material surface 3 Liquid repellent surface layer 4 1st fluorine resin particle 5 2nd fluorine resin particle 6 Fluorine resin film 7 1st surface 8 2nd surface 9 Fluorine resin solution DESCRIPTION OF SYMBOLS 10 Suspension 11 Cap 11a Top wall 11b Perimeter wall 12 Container body 12a Mouth R area
Claims (14)
前記撥液性表面層は、
３〜３３μｍの平均粒径を有する１以上の第１フッ素系樹脂粒子と、
１μｍ以下の平均粒径を有する第２フッ素系樹脂粒子と、
前記基材表面、前記１以上の第１フッ素系樹脂粒子及び前記第２フッ素系樹脂粒子を少なくとも部分的に覆うとともに、前記１以上の第１フッ素系樹脂粒子及び前記第２フッ素系樹脂粒子を前記基材表面に固着するフッ素系樹脂被膜と、で構成されている、
撥液性物品。 Having a liquid repellent surface layer formed on the substrate surface;
The liquid repellent surface layer is
One or more first fluororesin particles having an average particle size of 3 to 33 μm;
Second fluororesin particles having an average particle size of 1 μm or less;
The substrate surface, the one or more first fluorine-based resin particles and the second fluorine-based resin particles are at least partially covered, and the one or more first fluorine-based resin particles and the second fluorine-based resin particles are A fluorine-based resin film that is fixed to the substrate surface;
Liquid repellent article.
前記１以上の第１フッ素系樹脂粒子のそれぞれと前記第２フッ素系樹脂粒子との重畳によって凹凸状に形成された１以上の第１表面と、
前記第２フッ素系樹脂粒子の凝集によって凹凸状に形成された第２表面と、を有する、
請求項１又は２に記載の撥液性物品。 The liquid repellent surface layer is
One or more first surfaces formed in an uneven shape by superposition of each of the one or more first fluorine-based resin particles and the second fluorine-based resin particles;
A second surface formed in an uneven shape by aggregation of the second fluorine-based resin particles,
The liquid repellent article according to claim 1 or 2.
３〜３３μｍの平均粒径を有する１以上の第１フッ素系樹脂粒子と１μｍ以下の平均粒径を有する第２フッ素系樹脂粒子とをフッ素系樹脂溶液に分散させた懸濁液を準備する準備工程と、
前記基材表面の少なくとも一部を前記懸濁液で被覆する被覆工程と、
前記懸濁液を乾燥させることにより、前記１以上の第１フッ素系樹脂粒子と前記第２フッ素系樹脂粒子と前記フッ素系樹脂溶液の乾燥によって形成されたフッ素系樹脂被膜とによって前記撥液性表面層を形成する乾燥工程と、を有する、
撥液性物品の製造方法。 A method for producing a liquid repellent article having a liquid repellent surface layer formed on a substrate surface,
Preparation for preparing a suspension in which one or more first fluorine resin particles having an average particle diameter of 3 to 33 μm and second fluorine resin particles having an average particle diameter of 1 μm or less are dispersed in a fluorine resin solution Process,
A coating step of coating at least a part of the substrate surface with the suspension;
By drying the suspension, the one or more first fluorine resin particles, the second fluorine resin particles, and the fluorine resin film formed by drying the fluorine resin solution, the liquid repellency. A drying step of forming a surface layer,
A method for producing a liquid repellent article.
前記１以上の第１フッ素系樹脂粒子のそれぞれと前記第２フッ素系樹脂粒子との重畳によって凹凸状に形成された１以上の第１表面と、
前記第２フッ素系樹脂粒子の凝集によって凹凸状に形成された第２表面と、を有する、
請求項８又は９に記載の撥液性物品の製造方法。 The liquid repellent surface layer is
One or more first surfaces formed in an uneven shape by superposition of each of the one or more first fluorine-based resin particles and the second fluorine-based resin particles;
A second surface formed in an uneven shape by aggregation of the second fluorine-based resin particles,
The method for producing a liquid-repellent article according to claim 8 or 9.
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| JP2021037650A (en) * | 2019-08-30 | 2021-03-11 | 株式会社吉野工業所 | Liquid-repellent article |
| JP2021187481A (en) * | 2020-05-28 | 2021-12-13 | 株式会社吉野工業所 | Container cap and manufacturing method therefor |
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| JP7427340B2 (en) | 2020-05-28 | 2024-02-05 | 株式会社吉野工業所 | Container cap and its manufacturing method |
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