JPH07108552A - Manufacture of surface water-repellent resin molding - Google Patents
Manufacture of surface water-repellent resin moldingInfo
- Publication number
- JPH07108552A JPH07108552A JP25601093A JP25601093A JPH07108552A JP H07108552 A JPH07108552 A JP H07108552A JP 25601093 A JP25601093 A JP 25601093A JP 25601093 A JP25601093 A JP 25601093A JP H07108552 A JPH07108552 A JP H07108552A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- molding
- solid fine
- water
- fine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 38
- 239000011347 resin Substances 0.000 title claims abstract description 38
- 238000000465 moulding Methods 0.000 title claims abstract description 29
- 239000005871 repellent Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000007787 solid Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000010419 fine particle Substances 0.000 abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 abstract 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract 1
- -1 polytetrafluoroethylene Polymers 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は顕著な撥水性を示す表面
層を有する表面撥水性樹脂成形体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a surface water-repellent resin molding having a surface layer exhibiting remarkable water repellency.
【０００２】[0002]
【従来の技術】従来、撥水性を要求される部位にはポリ
テトラフルオロエチレンに代表される含フッ素高分子の
成形体が好適に用いられ、産業上の広い分野で利用され
ている。ところで、半導体産業の分野においては、フロ
ンによる洗浄が一般的であったが、環境問題の点からフ
ロンに代えて超純水による洗浄が行われるようになって
きており、そのため、半導体製造工程でウェハーキャリ
ヤー等の治具やその他の部品、装置類に使用する撥水性
の良好な材料の需要が高まってきた。しかしながら、こ
れまでこうした目的に使用されてきた含フッ素高分子成
形体は、概して高価なものであり、また機械的強度が低
いことから半導体ウェハーの大型化に伴うキャリヤーの
剛性要求に応えられないという問題があった。2. Description of the Related Art Conventionally, a molded product of a fluorine-containing polymer typified by polytetrafluoroethylene has been suitably used for a site where water repellency is required and has been used in a wide range of industrial fields. By the way, in the field of the semiconductor industry, cleaning with chlorofluorocarbon has been common, but due to environmental issues, cleaning with ultrapure water has been performed in place of chlorofluorocarbon, and therefore, in the semiconductor manufacturing process. There has been an increasing demand for materials having good water repellency for use in jigs such as wafer carriers and other parts and devices. However, the fluorine-containing polymer moldings that have been used for such purposes are generally expensive and have low mechanical strength, so that they cannot meet the rigidity requirements of carriers due to the increase in size of semiconductor wafers. There was a problem.
【０００３】一方、これまで低表面張力固体微粒子を用
いて樹脂成形体の表面の撥水性を向上させる試みとして
は、例えばフッ化黒鉛の表面エネルギーに関する研究報
告の中で触れられているフッ化黒鉛とポリエチレンの混
合物を圧縮成形する方法〔渡辺信淳氏ら、Ｂｕｌｌ．Ｃ
ｈｅｍ．Ｓｏｃ．Ｊｐｎ．，５５，２０２９−２０３３
（１９８２）〕等がある。On the other hand, as an attempt to improve the water repellency of the surface of a resin molded body by using low surface tension solid fine particles, for example, a fluorinated graphite mentioned in a research report on the surface energy of fluorinated graphite has been mentioned. Of a mixture of polyethylene and polyethylene by compression molding [Nobuatsu Watanabe et al., Bull. C
hem. Soc. Jpn. , 55, 2029-2033
(1982)].
【０００４】しかしながら、上記の方法の様に低表面張
力固体微粒子を直接基材樹脂と複合化させる場合、原料
段階で配合・混練し、これを成形することになる。しか
し、成形物の表面のみに機能を付与することが目的の場
合、内部に取り込まれる分が無駄になってしまうのであ
まり賢明な方法とは言えないと共に、全体に高充填する
と樹脂強度が低下するという問題があった。However, when the low surface tension solid fine particles are directly compounded with the base resin as in the above method, they are compounded and kneaded at the raw material stage and then molded. However, when the purpose is to give the function only to the surface of the molded product, it is not a wise method because the amount taken in inside is wasted and it is not a wise method. There was a problem.
【０００５】[0005]
【発明が解決しようとする課題】従って、本発明は、上
記の問題点を解決することを目的とするもので、剛性の
高い樹脂あるいは安価な汎用樹脂を用いてその表面の耐
久性があり顕著な撥水性を示す層を形成させ、これによ
って表面撥水性樹脂成形体を提供せんとするものであ
る。SUMMARY OF THE INVENTION Therefore, the present invention is intended to solve the above-mentioned problems, and a resin having a high rigidity or an inexpensive general-purpose resin is used, and its surface durability is remarkable. A layer having excellent water repellency is formed to provide a surface water-repellent resin molding.
【０００６】[0006]
【課題を解決するための手段】そこで、本発明者らは、
上記目的を達成せんと、鋭意検討を行った結果、成形用
金型内面にあらかじめ低表面張力固体微粒子を塗着させ
ておき、この金型を用いて樹脂を成形することで該固体
微粒子が成形体の表面層に転移して埋め込まれ、撥水性
が向上することを知見した。Therefore, the present inventors have
As a result of earnest studies to achieve the above object, as a result of applying a low surface tension solid fine particle to the inner surface of the molding die in advance, and molding the resin using this die, the solid fine particle is molded. It was found that the water repellency is improved by transferring to the surface layer of the body and being embedded.
【０００７】また、内面に細かな凹凸をつけた金型を使
用して前記と同様の成形法で樹脂を成形すると、該固体
微粒子を転移させると同時に成形体の表面にこの凹凸形
状を転写して表面積を増大させることができ、撥水性能
の耐久性を向上できることを知見した。Further, when a resin is molded by the same molding method as described above using a mold having fine irregularities on the inner surface, the solid fine particles are transferred and at the same time the irregularities are transferred to the surface of the molded article. It has been found that the surface area can be increased by increasing the water resistance and the durability of the water repellent performance can be improved.
【０００８】すなわち、本発明は、樹脂成形用金型の内
面に低表面張力固体微粒子を塗着せしめた成形用金型を
用いて樹脂を成形することを特徴とする表面撥水性樹脂
成形体の製造方法を提供するものである。That is, according to the present invention, there is provided a surface water-repellent resin molded product characterized in that a resin is molded by using a molding mold in which low surface tension solid fine particles are coated on the inner surface of the resin molding mold. A manufacturing method is provided.
【０００９】本発明で使用する低表面張力固体微粒子と
しては、臨界表面張力が２５dyne／cm以下、特に１５dy
ne／cm以下のものが好ましい。このような固体微粒子と
しては、例えば（ＣＦ）n ，（Ｃ2Ｆ）n なる組成式で
示されるフッ化黒鉛、低分子量のポリテトラフルオロエ
チレンオリゴマー粒子、あるいはシリカ、アルミナ等の
高表面張力固体の表面をパーフルオロアルキル基含有化
合物で表面処理した固体微粒子が挙げられるが、その中
でも極めて低い表面張力特性を示すフッ化黒鉛（ｒｃ＝
６dyne／cm）が特に好ましい。またこれらはそれぞれの
特性を生かすために二種以上を混ぜて使用することもで
きる。The low surface tension solid fine particles used in the present invention have a critical surface tension of 25 dyne / cm or less, especially 15 dy.
It is preferably ne / cm or less. Examples of such solid fine particles include fluorinated graphite represented by the composition formula (CF) n , (C 2 F) n , low molecular weight polytetrafluoroethylene oligomer particles, or high surface tension solids such as silica and alumina. There are solid fine particles whose surface is treated with a compound containing a perfluoroalkyl group. Among them, fluorinated graphite (rc =
6 dyne / cm) is particularly preferred. In addition, two or more of these may be mixed and used in order to make the best use of their respective characteristics.
【００１０】また本発明に用いられる低表面張力固体微
粒子の粒径分布は、１〜２０μm 、特に５〜１０μm の
ものが好ましい。この範囲外の微粒子では目的とする撥
水性が得られなかったり、撥水性の実用耐久性が乏しく
なる。更に、これらの固体微粒子は成形によって加えら
れる熱処理によっても、表面で粒子形状を保っている方
が効果が大きく、耐久性があることから、使用する基材
樹脂の成形温度において粒子間の融着が起こらない固体
微粒子を選ぶのが好ましい。The low surface tension solid fine particles used in the present invention preferably have a particle size distribution of 1 to 20 μm, particularly 5 to 10 μm. If the fine particles are out of this range, the desired water repellency may not be obtained, or the practical durability of water repellency may be poor. Furthermore, since these solid fine particles are more effective and durable when the particle shape is maintained on the surface even by the heat treatment applied by molding, fusion between particles at the molding temperature of the base resin used It is preferable to select solid fine particles that do not occur.
【００１１】本発明において、低表面張力固体微粒子を
金型内面に塗着させる方法としては、低表面張力固体微
粒子を一度揮発性有機溶剤に攪拌分散してから塗布し、
乾燥させる湿式法及び粉体塗装の要領で静電的に吸着さ
せる乾式法の何れの方法も使用できる。塗着にはハケ塗
り、吹き付けの他、浸漬等各種の方法が適用できるが、
成形体に撥水性を付与したい部分に対応する面に固体微
粒子が一様に付着して覆うようにすることが必要であ
り、そのためには金型の形状を考慮して均一的に供給で
きる方法を選択することが重要である。In the present invention, the method for applying the low surface tension solid fine particles to the inner surface of the mold is as follows. The low surface tension solid fine particles are once stirred and dispersed in a volatile organic solvent and then applied.
Either a wet method of drying or a dry method of electrostatically adhering in the same manner as powder coating can be used. In addition to brush coating, spraying, various methods such as immersion can be applied,
It is necessary to make solid particles uniformly adhere to and cover the surface of the molded body corresponding to the portion to which water repellency is to be imparted. For that purpose, it is possible to supply the particles uniformly considering the shape of the mold. It is important to choose.
【００１２】金型内面に塗着させる低表面張力固体微粒
子の量は、例えばフッ化黒鉛の場合１〜１０mg／cm2の
範囲が適当である。１mg／cm2未満では十分な撥水性の
向上は見られず、また１０mg／cm2を超えると樹脂に取
り込まれずに金型に残る分がでて無駄が多くなり、成形
体表面からの脱離も起こり易い。The amount of low surface tension solid fine particles to be coated on the inner surface of the mold is appropriately in the range of 1 to 10 mg / cm 2 in the case of fluorinated graphite. If it is less than 1 mg / cm 2 , the water repellency is not sufficiently improved, and if it exceeds 10 mg / cm 2 , it is not taken up by the resin and remains in the mold, resulting in a large amount of waste and detachment from the surface of the molded product. Is also likely to occur.
【００１３】湿式法で行う場合に用いる揮発性有機溶剤
としては、例えば低級アルコール、アセトン、メチルエ
チルケトン、トリクロロエチレン、テトラクロロメタン
等の一般的な溶剤の中から作業環境への影響や回収方法
等を考慮して選択することができる。これらは固体微粒
子を均一性のある形で金型内面に吸着させるための助剤
であり、揮発し易く成形後の樹脂表面に影響を及ぼす恐
れの無いものであれば良い。ただし使用する固体微粒子
を良く分散させる必要から、該固体微粒子となじみ易い
液体であるのが望ましい。As the volatile organic solvent used when the wet method is used, for example, the influence on the work environment and the recovery method are considered from among general solvents such as lower alcohol, acetone, methyl ethyl ketone, trichloroethylene and tetrachloromethane. Can be selected. These are auxiliaries for adsorbing the solid fine particles to the inner surface of the mold in a uniform form, and may be any as long as they are easily volatilized and do not affect the resin surface after molding. However, since it is necessary to disperse the solid fine particles to be used well, it is desirable that the liquid be a liquid that is easily compatible with the solid fine particles.
【００１４】本発明の成形体の基材としての樹脂として
は、例えばフェノール樹脂、エポキシ樹脂、メラミン樹
脂等に代表される各種熱硬化性樹脂、及び例えばポリエ
チレン、ポリプロピレン、ポリ塩化ビニル、アクリロニ
トリル−ブタジエン−スチレン共重合樹脂（ＡＢＳ樹
脂）等に代表される各種熱可塑性樹脂の中から使用目的
にあった材料を選択し、幅広く適用することができる。
これに加え、例えばスチレン−ブタジエンラバー（ＳＢ
Ｒ）、アクリロニトリル−ブタジエンラバー（ＮＢ
Ｒ）、クロロプレンラバー（ＣＲ）に代表される合成ゴ
ムの成形にも応用できる。また、これら成形用原料に各
種配合剤、添加剤、加工助剤等を配合して使うことは何
ら差し支えない。Examples of the resin as the base material of the molded article of the present invention include various thermosetting resins represented by, for example, phenol resin, epoxy resin, melamine resin, and polyethylene, polypropylene, polyvinyl chloride, acrylonitrile-butadiene. -A wide variety of thermoplastic resins represented by styrene copolymer resins (ABS resins) can be selected from materials suitable for the intended use.
In addition to this, for example, styrene-butadiene rubber (SB
R), acrylonitrile-butadiene rubber (NB
R) and chloroprene rubber (CR). In addition, it is safe to mix various compounding agents, additives, processing aids, etc. with these molding raw materials.
【００１５】本発明の成形方法に使用する金型として、
金型内面に細かな凹凸をつけたものを用いて成形物の表
面にこの形状と固体微粒子を一度に転写することが採用
でき、これにより更に撥水性を向上し撥水性能の実用耐
久性を改良できる。この場合の細かな凹凸の大きさとい
うのは一概に規定できないが、ＪＩＳ Ｂ ０６０１
「表面粗さの定義と表示」の方法により示せば、Ｒａ
（中心線平均粗さ）０．５〜２０μm 、好ましくは１〜
１０μm である。０．５μm 未満では更なる撥水性向上
の効果は見られず、２０μm を超えると小さな水滴が凹
部に入り込むため撥水性向上の効果は少なくなる。As the mold used in the molding method of the present invention,
It is possible to transfer this shape and solid fine particles to the surface of the molded product at one time by using a mold with fine irregularities on the inner surface, which further improves water repellency and practical durability of water repellency. Can be improved. The size of the fine irregularities in this case cannot be specified unconditionally, but JIS B 0601
If it is shown by the method of “Definition and display of surface roughness”, Ra
(Centerline average roughness) 0.5 to 20 μm, preferably 1 to
It is 10 μm. If it is less than 0.5 μm, the effect of further improving the water repellency is not seen, and if it exceeds 20 μm, small water droplets enter the recesses, and the effect of improving the water repellency is reduced.
【００１６】[0016]
【作用】本発明によると、成形の際樹脂表面に直接低表
面張力固体微粒子を分散させて埋め込むことで、従来の
被膜等に比べ、安定した形で低表面張力固体微粒子と基
材樹脂の複合表面を作り出すことができ、これにより撥
水性が向上するものと考えられる。また、表面に細かな
凹凸をつけたものは、成形時に作られる複合層の表面積
を増大し、低表面張力固体微粒子を取り込む量を増やし
て見かけの複合層の厚さを増せるので、実用耐久性が向
上するものと考えられる。According to the present invention, by dispersing and embedding low surface tension solid fine particles directly on the resin surface during molding, a composite of low surface tension solid fine particles and a base resin can be formed in a more stable form than conventional coatings and the like. It is believed that a surface can be created which improves water repellency. Also, those with fine irregularities on the surface increase the surface area of the composite layer produced during molding, increase the amount of low surface tension solid fine particles to be taken in, and increase the apparent thickness of the composite layer, so that practical durability It is thought that the property will be improved.
【００１７】[0017]
【発明の効果】本発明の方法によれば、樹脂の成形とい
う通常の作業によって容易に樹脂成形体表面の撥水性を
向上させて、剛性の高い、あるいは安価な撥水性樹脂成
形体を製造することができる。かくして得られた撥水性
表面を持つ樹脂成形体は、優れた撥水性と基材樹脂の特
徴を合わせ持つため、かかる特性を必要とする種々の用
途に好適に使用できる。According to the method of the present invention, the water repellency of the surface of the resin molded product can be easily improved by the ordinary work of molding the resin to produce a water repellent resin molded product having high rigidity or low cost. be able to. The resin molded body having a water-repellent surface thus obtained has excellent water repellency and the characteristics of the base resin, and thus can be suitably used for various applications requiring such characteristics.
【００１８】[0018]
【実施例】以下、実施例、比較例及び試験例を示し、本
発明を具体的に説明するが、本発明はこれらに何ら制限
されるものではない。EXAMPLES The present invention will be specifically described below by showing Examples, Comparative Examples and Test Examples, but the present invention is not limited thereto.
【００１９】実施例１ アセトン５ｇにフッ化黒鉛（セントラル硝子（株）「セ
フボンＣＭＡ」）１ｇを分散させた液を作り、これを１
cm2当たり固形分が約１mgとなるようにアルミ板（φ１
５０mm×１mmt）の片面にハケ塗りし、乾燥させた。こ
のアルミ板を、あらかじめ熱プレス内で２５０℃に加熱
しておいた樹脂成形用プレス金型（内径φ１５０mm）の
底に塗着面を上にして敷き、その上から成形用ポリプロ
ピレンペレット（三菱油化（株）「三菱ポリプロＢＣ３
Ｂ」）２０ｇを充填し、熱プレスにセットした。樹脂が
熔融するように５分間待ってから加圧していき、面圧が
１００kg／cm2に達したところで１分間保持し、その後
金型を冷却用プレスに移して加圧状態で冷却した。金型
が十分に冷めてから成形物を取り出したところ、厚さ約
１mmの半透明のシートとなっていた。アルミ板と接して
いた面は、艶はあるものの灰白色に濁っていた。Example 1 A solution was prepared by dispersing 1 g of fluorinated graphite (Central Glass Co., Ltd. “Cefbon CMA”) in 5 g of acetone,
Aluminum plate (φ1 so that the solid content is about 1 mg per cm 2
50 mm × 1 mm t ) was brush coated on one side and dried. This aluminum plate is laid on the bottom of a resin molding press die (inner diameter φ150 mm) that has been preheated to 250 ° C. in a hot press with the coated surface facing upward, and polypropylene pellets for molding (Mitsubishi Oil Chemical Co., Ltd. "Mitsubishi Polypro BC3
B ") 20 g was charged and set in a hot press. After waiting for 5 minutes to melt the resin, pressure was applied, and when the surface pressure reached 100 kg / cm 2 , the resin was held for 1 minute, after which the mold was transferred to a cooling press and cooled under pressure. When the mold was cooled sufficiently and the molded product was taken out, it was a translucent sheet having a thickness of about 1 mm. The surface that was in contact with the aluminum plate was glossy but cloudy in grayish white.
【００２０】実施例２ アルミ板（φ１５０mm×１mmt）を、ショットプラスト
機（（株）ニッチュー「エアープラストマシーンＡＭ−
８」）を用いて、ショット材：モランダム＃６０、ショ
ット時間：２０秒、噴射圧５kg／cm2の条件で粗化し
た。この面の粗さを測定したところ、（測定機：（株）
東京精密「サーフコム１１０Ｂ〜１１３Ｂ」）Ｒａ＝５
μm であった。このアルミ板の粗面を使って実施例１と
同様にポリプロピレンシートを成形した。できあがった
シートは、アルミ板と接していた面が灰白色に濁り、艶
もなく曇っていた。Example 2 An aluminum plate (φ150 mm × 1 mm t ) was attached to a shotplast machine (Nichu Co., Ltd. “Airplast Machine AM-”).
8 ”) was used for roughening under the conditions of shot material: Morundum # 60, shot time: 20 seconds, and injection pressure 5 kg / cm 2 . When the roughness of this surface was measured, (Measuring machine: Co., Ltd.
Tokyo Seimitsu "Surfcom 110B-113B") Ra = 5
It was μm. Using the rough surface of this aluminum plate, a polypropylene sheet was molded in the same manner as in Example 1. The surface of the finished sheet, which was in contact with the aluminum plate, was cloudy grayish white, and was dull and dull.
【００２１】実施例３ 実施例２と同様にショットプラストで粗化したアルミ板
を用い、フッ化黒鉛の代わりに低分子ポリテトラフルオ
ロエチレン（セントラル硝子（株）「セフラルルーブ
Ｉ」）を、ポリプロピレンの代わりにアクリロニトリル
−ブタジエン−スチレン共重合体（日本合成ゴム（株）
「ＪＳＲ−ＡＢＳ ３８ＮＰ」）を使って実施例１と同
様の方法で金型温度２００℃でシートを成形した。Example 3 An aluminum plate roughened by shotplast was used in the same manner as in Example 2 except that low molecular weight polytetrafluoroethylene (Central Glass Co., Ltd. “Sefralulube I”) was used instead of fluorinated graphite. Instead, acrylonitrile-butadiene-styrene copolymer (Nippon Synthetic Rubber Co., Ltd.)
"JSR-ABS 38NP") was used to mold a sheet at a mold temperature of 200 ° C in the same manner as in Example 1.
【００２２】比較例１ アルミ板（φ１５０mm×１mmt）を、あらかじめ熱プレ
ス内で２５０℃に加熱しておいた樹脂成形用プレス金型
（内径φ１５０mm）の底に敷いて通常のシリコーン系離
型剤（信越化学（株）「ＫＦ９６ＳＰ」）をスプレー
し、その上から成形用ポリプロピレンペレット（三菱油
化（株）「三菱ポリプロＢＣ３Ｂ」）２０ｇを充填し、
熱プレスにセットした。樹脂が熔融するように５分間待
ってから加圧していき、面圧が１００kg／cm2に達した
ところで１分間保持し、その後金型を冷却用プレスに移
して加圧状態で冷却した。金型が十分に冷めてから成形
物を取り出したところ、厚さ約１mmの半透明のシートと
なっていた。COMPARATIVE EXAMPLE 1 An aluminum plate (φ150 mm × 1 mm t ) was laid on the bottom of a resin molding press die (inner diameter φ150 mm) which had been heated to 250 ° C. in a hot press in advance, and a usual silicone-based mold release was performed. Spray the agent (Shin-Etsu Chemical Co., Ltd. “KF96SP”), and then fill 20 g of polypropylene pellets for molding (Mitsubishi Yuka Co., Ltd. “Mitsubishi Polypro BC3B”),
It was set in a heat press. After waiting for 5 minutes to melt the resin, pressure was applied, and when the surface pressure reached 100 kg / cm 2 , the resin was held for 1 minute, after which the mold was transferred to a cooling press and cooled under pressure. When the mold was cooled sufficiently and the molded product was taken out, it was a translucent sheet having a thickness of about 1 mm.
【００２３】比較例２ 実施例２と同様にショットプラストで粗化したアルミ板
を用い、ポリプロピレンの代わりに実施例３で用いたア
クリロニトリル−ブタジエン−スチレン共重合体（日本
合成ゴム（株）「ＪＳＲ−ＡＢＳ ３８ＮＰ」）を使っ
て比較例１と同様の方法で金型温度２００℃でシートを
成形した。Comparative Example 2 An acrylonitrile-butadiene-styrene copolymer (Japan Synthetic Rubber Co., Ltd. “JSR”, used in Example 3 instead of polypropylene, using an aluminum plate roughened with shotplast as in Example 2 was used. -ABS 38NP ") was used to mold a sheet at a mold temperature of 200 ° C in the same manner as in Comparative Example 1.
【００２４】試験例 実施例１〜３及び比較例１〜２により得られたシート
を、１５mm×４５mmの大きさにカットし、液滴法により
水との接触角を測定して撥水性を評価した（測定器：協
和界面科学（株）「ＣＡ−ＤＴ型」）。その結果を表１
に示した。Test Example The sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were cut into a size of 15 mm × 45 mm, and the contact angle with water was measured by the droplet method to evaluate the water repellency. (Measuring instrument: Kyowa Interface Science Co., Ltd. "CA-DT type"). The results are shown in Table 1.
It was shown to.
【００２５】[0025]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 斉木 幸則 千葉県千葉市美浜区真砂５−16−３−105 (72)発明者 市川 美奈 千葉県八千代市八千代台北10−15−16 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yukinori Saiki 5-16-3-105 Masago, Mihama-ku, Chiba, Chiba Prefecture (72) Mina Ichikawa 10-15-16 Yachiyo Taipei, Yachiyo City, Chiba Prefecture
Claims (2)
微粒子を塗着せしめた成形用金型を用いて樹脂を成形す
ることを特徴とする表面撥水性樹脂成形体の製造方法。1. A method for producing a surface water-repellent resin molded article, which comprises molding a resin using a molding die in which solid particles of low surface tension are applied to the inner surface of the resin molding die.
型を用いる請求項１記載の樹脂成形体の製造方法。2. The method for producing a resin molded article according to claim 1, wherein a resin molding die having an inner surface formed with fine irregularities is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25601093A JPH07108552A (en) | 1993-10-13 | 1993-10-13 | Manufacture of surface water-repellent resin molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25601093A JPH07108552A (en) | 1993-10-13 | 1993-10-13 | Manufacture of surface water-repellent resin molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07108552A true JPH07108552A (en) | 1995-04-25 |
Family
ID=17286661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25601093A Pending JPH07108552A (en) | 1993-10-13 | 1993-10-13 | Manufacture of surface water-repellent resin molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07108552A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0773093A1 (en) * | 1995-11-08 | 1997-05-14 | Hüls Aktiengesellschaft | Coated mould for molding latex foamed articles |
| JP2014113721A (en) * | 2012-12-07 | 2014-06-26 | Denki Kagaku Kogyo Kk | Laminate sheet having water repellency and film for laminate |
-
1993
- 1993-10-13 JP JP25601093A patent/JPH07108552A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0773093A1 (en) * | 1995-11-08 | 1997-05-14 | Hüls Aktiengesellschaft | Coated mould for molding latex foamed articles |
| JP2014113721A (en) * | 2012-12-07 | 2014-06-26 | Denki Kagaku Kogyo Kk | Laminate sheet having water repellency and film for laminate |
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