JPH05169459A - Mold for resin or rubber, part of resin or rubber molding apparatus and method for molding resin or rubber - Google Patents
Mold for resin or rubber, part of resin or rubber molding apparatus and method for molding resin or rubberInfo
- Publication number
- JPH05169459A JPH05169459A JP3356260A JP35626091A JPH05169459A JP H05169459 A JPH05169459 A JP H05169459A JP 3356260 A JP3356260 A JP 3356260A JP 35626091 A JP35626091 A JP 35626091A JP H05169459 A JPH05169459 A JP H05169459A
- Authority
- JP
- Japan
- Prior art keywords
- carbon film
- resin
- diamond
- fluorine
- intermediate layer
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 74
- 239000011347 resin Substances 0.000 title claims abstract description 74
- 229920001971 elastomer Polymers 0.000 title claims abstract description 38
- 239000005060 rubber Substances 0.000 title claims abstract description 38
- 238000000465 moulding Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 27
- 238000010068 moulding (rubber) Methods 0.000 title claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 76
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 62
- 239000011737 fluorine Substances 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 49
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 15
- 239000010410 layer Substances 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 29
- 239000002344 surface layer Substances 0.000 claims description 15
- 229910000838 Al alloy Inorganic materials 0.000 claims description 14
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 14
- 239000010959 steel Substances 0.000 claims description 14
- 238000007747 plating Methods 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 11
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 6
- 238000005121 nitriding Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005885 boration reaction Methods 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000007733 ion plating Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims 4
- 150000004767 nitrides Chemical class 0.000 claims 4
- 229910052710 silicon Inorganic materials 0.000 claims 4
- 229910052719 titanium Inorganic materials 0.000 claims 4
- 229910052721 tungsten Inorganic materials 0.000 claims 4
- 229910052720 vanadium Inorganic materials 0.000 claims 4
- 229910052726 zirconium Inorganic materials 0.000 claims 4
- 238000002203 pretreatment Methods 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 24
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 24
- 238000005299 abrasion Methods 0.000 abstract description 10
- 239000000919 ceramic Substances 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 120
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 47
- 238000012360 testing method Methods 0.000 description 26
- 239000007789 gas Substances 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 238000005240 physical vapour deposition Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000006082 mold release agent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000003578 releasing effect Effects 0.000 description 5
- 102200082816 rs34868397 Human genes 0.000 description 5
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 5
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical group C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Moulds For Moulding Plastics Or The Like (AREA)
- Physical Vapour Deposition (AREA)
Abstract
(57)【要約】
【目的】 樹脂またはゴムを成形する金型及び部品は、
離型性と耐摩耗性が要求される。ＰＴＦＥを被覆したも
のは離型性が良いが耐摩耗性がない。硬質の金属、セラ
ミックを被覆したものは耐摩耗性が優れているが離型性
は悪い。両方において優れた金型及び部品を提供するこ
とが目的である。
【構成】 金型及び部品の基材の上に弗素を１〜２０原
子％添加した硬質カ−ボン膜またはダイヤモンド状炭素
膜を被覆する。弗素のために離型性が良い。硬質カ−ボ
ン膜またはダイヤモンド状炭素膜であるので耐摩耗性が
良い。中間層として硬度の高い硬質金属、硬質セラミッ
ク層を設けるとさらによい。
(57) [Summary] [Purpose] Molds and parts for molding resin or rubber are
Releasability and wear resistance are required. The product coated with PTFE has good mold releasability but does not have abrasion resistance. Those coated with a hard metal or ceramic have excellent wear resistance, but poor releasability. It is an object to provide excellent molds and parts in both. [Structure] A hard carbon film or a diamond-like carbon film to which fluorine is added in an amount of 1 to 20 atomic% is coated on the base material of a mold and parts. Good releasability due to fluorine. Since it is a hard carbon film or a diamond-like carbon film, it has good wear resistance. It is more preferable to provide a hard metal or hard ceramic layer having high hardness as the intermediate layer.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、離型性に優れた硬質皮
膜を表面に形成した、樹脂やゴム等の粘着性の高い材料
をモ−ルド成形あるいはブロ−成型する際に用いられる
金型と、成型装置部品に関する。金型というのは良く知
られているように、２つまたはそれ以上の部材からなり
これらは閉じられた空間を形成し内部に流動性のある材
料を導入して加圧加熱または冷却して材料を内部空間の
形状通りに成型するものである。成型装置部品というの
はより広く、押出成形機における樹脂やゴムの流路、ブ
レ−カ−プレ−ト、ダイ、リップなどの樹脂あるいはゴ
ムと接触する部品全てに関するものである。本発明は金
型と成型装置部品に関するものであるが簡単のため、以
下「金型及び部品」と略記することにする。また図面も
金型と部品を含んでいるものとして描かれている。従っ
てこれら図面は基材と表層部の構成を略示するのに重点
が置かれている。実際の金型や部品の形状に正確に対応
する訳ではない。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal used for molding or blow-molding a highly adhesive material such as resin or rubber having a hard film excellent in releasability formed on the surface thereof. Molds and molding equipment parts. As is well known, a mold is made up of two or more members that form a closed space and introduce a fluid material into the interior to heat or cool the material under pressure. Is molded according to the shape of the internal space. Molding equipment parts are broader and relate to all parts that come into contact with resin or rubber such as resin and rubber passages, breaker plates, dies and lips in extruders. Although the present invention relates to a mold and parts of a molding apparatus, it will be abbreviated as “mold and parts” below for simplicity. The drawings are also drawn as including molds and parts. Therefore, these drawings are focused on schematically showing the constitution of the substrate and the surface layer portion. It does not correspond exactly to the actual shapes of molds and parts.
【０００２】[0002]
【従来の技術】樹脂やゴム等の粘着性の高い材料を金型
に閉じ込めて成形する、いわゆるモ−ルド成形等におい
ては、金型及び部品の材料として、従来から鋼が主に用
いられている。最近では、加工性のよいアルミ合金製金
型や銅合金製金型も用いられている。樹脂やゴム等の成
形金型及び部品は離型性がよいことと、耐摩耗性が高い
ことの両方が要求される。従来の金属表面が露呈した金
型及び部品は耐摩耗性、離型性の両方の点で不十分であ
る。とくに硬度を増すためにフィラ−等硬質粒子を含む
樹脂ゴムなどの場合は高い耐摩耗性が必要である。樹脂
やゴムに充填する硬質粒子に対する金型及び部品の耐摩
耗性向上を目的として、上記金型及び部品の材料の表面
に硬質皮膜を形成したものが製作されている。例えば、 湿式法（電解メッキあるいは無電解メッキ等）による
硬質クロムメッキやニッケルメッキ等の硬質金属膜や
（図５）、 乾式法（ＣＶＤ法やＰＶＤ法等）による窒化チタン、
炭化チタンあるいは窒化クロム等の硬質セラミック膜
（図６）、 を前記金属基材の上に被覆したものである。ここで図面
は基材と皮膜を示すための概略図で、実際の金型及び部
品に形状寸法等が対応しているものではない。上記の硬
質皮膜を表面に形成した金型及び部品は硬度が高く耐摩
耗性に優れる。しかしながら、これらの材料はいずれも
上記樹脂やゴムとの離型性がきわめて悪い。離型性を補
う為にシリコンスプレ−等の離型剤を塗布してから用い
ることが一般的となっている。離型性なしでは殆ど利用
できない。2. Description of the Related Art Steel is conventionally mainly used as a material for molds and parts in so-called mold molding in which a highly adhesive material such as resin or rubber is enclosed in a mold for molding. There is. Recently, molds made of aluminum alloys and copper alloys having good workability are also used. Molding dies and parts made of resin, rubber and the like are required to have both good releasability and high wear resistance. Conventional molds and parts with exposed metal surfaces are insufficient in terms of both wear resistance and releasability. In particular, in the case of resin rubber containing hard particles such as filler to increase hardness, high abrasion resistance is required. For the purpose of improving the wear resistance of molds and parts against hard particles filled in resin or rubber, those in which a hard coating is formed on the surface of the material of the molds and parts have been manufactured. For example, a hard metal film such as hard chrome plating or nickel plating by a wet method (electrolytic plating or electroless plating) (FIG. 5), titanium nitride by a dry method (CVD method, PVD method, etc.),
A hard ceramic film of titanium carbide or chromium nitride (FIG. 6) is coated on the metal base material. Here, the drawings are schematic views for showing the base material and the coating, and the shape dimensions and the like do not correspond to actual molds and parts. Molds and parts having the above hard coating formed on the surface thereof have high hardness and excellent wear resistance. However, all of these materials have extremely poor releasability from the resin or rubber. In order to supplement the mold releasability, it is general to apply a mold release agent such as a silicone spray before using it. It can hardly be used without releasability.
【０００３】ところが、例えばモ−ルド成形の作業能率
改善や、製品の品質安定化に対しては、離型剤塗布作業
は決して好ましいものではない。これは、成形の度に金
型に離型剤を塗布する必要があるため、その度に成形作
業を中断しなければならないこと、及び、離型剤の塗布
ムラにより、被成形品の表面状態にムラが生じる等の理
由による。また、離型剤を使っていても、長期間使用す
るうちに、金型の隅等の樹脂やゴムの流れの悪い場所
に、樹脂やゴムのみならず、変質した離型剤までもが残
留し、しばしば成形作業を中断して金型の掃除を行う必
要がある。このような理由から、作業現場からは、離型
剤の要らない金型材料を望む声が絶えない。一方、金型
以外の成形機部品においては、金型のように離型剤を塗
布することが困難か、あるいは不可能であるために、離
型性向上のニ−ズはさらに大きくなっている。さて、金
型及び部品の離型性を向上させる方法としては、ポリテ
トラフルオロエチレン（以下、ＰＴＦＥと略す）に代表
される弗素含有高分子材料の薄膜をこれらの金型及び部
品の表面に形成する方法が公知である。これらを被覆し
た金型及び部品（図７）は離型性に優れる。ＰＴＦＥ
は、弗素と炭素のみからなる高分子材料であり、弗素と
炭素との間に分極率の小さい共有結合が存在する。この
ため分子間凝集力が低く、表面自由エネルギ−が著しく
低くなるという特質を持つ。この結果、摩擦係数が低
く、水や油をはじくという特異な性質を発現する。この
性質が優れた離型性を金型及び部品に与えるのである。However, in order to improve the work efficiency of mold forming and to stabilize the quality of products, for example, the work of applying the release agent is not preferable. This is because it is necessary to apply a mold release agent to the mold each time molding is performed, so the molding operation must be interrupted each time, and due to uneven coating of the mold release agent, the surface condition of the molded product This is because of unevenness in the surface. Even if a mold release agent is used, not only the resin or rubber but also the deteriorated mold release agent remains in the corners of the mold where the resin or rubber does not flow well over a long period of use. However, it is often necessary to interrupt the molding operation and clean the mold. For these reasons, there is a constant demand from the work site for mold materials that do not require a release agent. On the other hand, in molding machine parts other than the mold, it is difficult or impossible to apply a mold release agent like the mold, so that the need for improving the mold release property is further increased. .. Now, as a method for improving the releasability of the mold and parts, a thin film of a fluorine-containing polymer material typified by polytetrafluoroethylene (hereinafter abbreviated as PTFE) is formed on the surfaces of these molds and parts. The method of doing is known. The mold and parts (FIG. 7) coated with these have excellent releasability. PTFE
Is a polymer material composed only of fluorine and carbon, and a covalent bond having a small polarizability exists between fluorine and carbon. Therefore, it has the characteristics that the intermolecular cohesive force is low and the surface free energy is significantly low. As a result, it has a low coefficient of friction and exhibits a unique property of repelling water and oil. This property gives the mold and the parts excellent mold releasability.
【０００４】[0004]
【発明が解決しようとする課題】ところが、ＰＴＦＥの
欠点は、それ自身の硬さがきわめて低く、容易に傷がつ
く（耐摩耗性に劣る）という点である。金型及び部品を
被覆する保護膜として用いる時にも、この欠点が露呈
し、長期間安心して使えるものではなかった。そこで登
場したのが、ＰＴＦＥの微粒子を硬質クロムやニッケル
等の金属皮膜中に分散させた、いわゆる複合メッキ（分
散メッキとも呼ぶ）をした金型及び部品（図８）であ
る。この結果ＰＴＦＥの離型性を活かしながら、硬質金
属皮膜で耐摩耗性を確保することが可能になった。しか
しながら、これらのＰＴＦＥを含む硬質メッキ皮膜のビ
ッカ−ス硬度はたかだか１００ｋｇ／ｍｍ2 程度であ
る。金型あるいは部品に被覆した場合、離型性の点では
十分であるが、耐摩耗性では未だ不十分である。特に硬
質粒子を含む樹脂やゴムを成形するのに用いられる場合
は充填材である硬質粒子との摩擦に耐えなければならな
いので、金型成形面などの樹脂、ゴムと接触する面のビ
ッカ−ス硬度として２０００ｋｇ／ｍｍ2 以上が必要で
ある。ＰＴＦＥを分散した硬質メッキ膜も耐摩耗性の点
では、決して満足できるものではなかった。However, the drawback of PTFE is that it has extremely low hardness and is easily scratched (inferior in abrasion resistance). Even when it is used as a protective film for covering molds and parts, this defect is exposed and it cannot be used with a sense of security for a long time. What appeared there was a so-called composite plating (also called dispersion plating) mold and parts (FIG. 8) in which fine particles of PTFE were dispersed in a metal film such as hard chromium or nickel. As a result, it has become possible to secure wear resistance with a hard metal film while utilizing the releasability of PTFE. However, the Vickers hardness of these hard plating films containing PTFE is about 100 kg / mm 2 . When the metal mold or the component is coated, the mold releasability is sufficient, but the wear resistance is still insufficient. Especially when it is used to mold resin or rubber containing hard particles, it must withstand friction with hard particles as a filler, so Vickers of a surface such as a mold molding surface that comes into contact with resin or rubber. A hardness of 2000 kg / mm 2 or more is required. A hard plating film in which PTFE is dispersed has never been satisfactory in terms of wear resistance.
【０００５】樹脂あるいはゴム成形用金型及び部品以外
の分野で、弗素と炭素を含む被覆を設け表面の性質を改
善するようにした工夫は幾つもある。特公平２−２９７
４９はプラスチックや金属の表面にダイヤモンド膜を形
成しさらにダイヤモンド膜の最表面を弗化処理したもの
を提案している。弗化処理したダイヤモンド膜は、耐薬
品性、疎水性、耐摩耗性、潤滑性に優れている。この被
覆をしたものは、プラスチックの場合は磁気テ−プ、フ
ィルム、セラミックの場合は人工骨、瓦、金属の場合は
液中で使用する機械材料、摺動材に使えるとしている。
これは最表面において全ての炭素原子について弗素との
結合Ｃ−Ｆを形成するものでありＰＴＦＥよりも疎水性
に優れているとある。最表面での弗素の含有量は１００
％に近い。これは液中で使用する機械部品を作るための
もので、疎水性の向上に力点が置かれた発明である。樹
脂あるいはゴム成形用金型及び部品に関する工夫ではな
い。In fields other than resin or rubber molding dies and parts, there have been various ideas for improving the surface properties by providing a coating containing fluorine and carbon. Japanese Patent Fair 2-297
No. 49 proposes that a diamond film is formed on the surface of plastic or metal, and the outermost surface of the diamond film is fluorinated. The fluorinated diamond film has excellent chemical resistance, hydrophobicity, abrasion resistance and lubricity. It is said that this coating can be used as a magnetic tape, a film in the case of plastic, an artificial bone in the case of ceramics, a roof tile, a mechanical material used in a liquid in the case of metal, and a sliding material.
It is said that this forms a bond C-F with fluorine for all carbon atoms on the outermost surface and is more hydrophobic than PTFE. Fluorine content on the outermost surface is 100
Close to%. This is for making mechanical parts to be used in liquid, and is an invention that emphasizes the improvement of hydrophobicity. It is not a device or mold for resin or rubber molding.
【０００６】特開昭６１−３０６７１は工具や機構部品
の表面に水素と弗素を含む硬質カ−ボン膜を提案してい
る。硬質カ−ボン膜に水素を含ませると摩擦係数が低下
し、弗素を含ませると耐湿性が向上すると述べている。
これは軸受、歯車、シ−ル、螺子等への応用を考えてい
る。摩擦係数の低いことが重要である。主に水素を不純
物として含有し水素の作用により摩擦係数は真空中でも
０．０１という優れた値を示したとある。水素の含有量
は３％以上である。弗素は耐湿性が必要な場合に添加す
るものであって水素に比べ副次的なものである。これも
樹脂あるいはゴム成形用金型及び部品に関するものでは
ない。Japanese Unexamined Patent Publication No. 61-30671 proposes a hard carbon film containing hydrogen and fluorine on the surface of tools and mechanical parts. It is stated that when the hard carbon film contains hydrogen, the friction coefficient is lowered, and when fluorine is contained, the moisture resistance is improved.
This is considered to be applied to bearings, gears, seals, screws, etc. It is important that the coefficient of friction is low. It is said that it mainly contains hydrogen as an impurity, and due to the action of hydrogen, the friction coefficient showed an excellent value of 0.01 even in a vacuum. The hydrogen content is 3% or more. Fluorine is added when moisture resistance is required and is a secondary substance compared to hydrogen. This is also not related to a resin or rubber molding die and parts.
【０００７】特開平２−２５０９６８は弗素化硬質カ−
ボン膜を被覆した機械部材を提案している。ビデオヘッ
ド、ビデオポ−ル、モ−タ回転軸、ベアリングなど機械
部材の上に１５０℃以下の低温で硬質カ−ボン膜を形成
する。これは炭素の他に水素を含む。そこでこれを、弗
素化合物のプラズマで処理しＣ−Ｈ結合の一部をＣ−Ｆ
結合に置き換えたものである。これも水素の方が有力で
あり、最外表面でのＣ−Ｈ／Ｃ−Ｆの比は２〜１０であ
る。硬質カ−ボン膜の不純物としては第１に水素であ
り、弗素はその１／１０〜１／３である。機構部品であ
るので耐摩耗性の減少が目的である。離型性等は問題に
ならず樹脂あるいはゴム成形用金型及び部品への応用は
考えていない。このように硬質カ−ボン膜に水素と弗素
を含ませた被覆材は既に機械部品の表面被覆に用いられ
ている。耐摩耗性や疎水性を高揚するためである。何れ
も水素がより大量に含まれる不純物である。樹脂あるい
はゴム成形用金型及び部品への応用を考えたものはなく
離型性は問題にならない。Japanese Unexamined Patent Publication No. 2-250968 discloses a fluorinated hard cover.
A mechanical member coated with a Bonn film is proposed. A hard carbon film is formed on a mechanical member such as a video head, a video pole, a motor rotating shaft, and a bearing at a low temperature of 150 ° C. or lower. This includes hydrogen in addition to carbon. Therefore, this is treated with plasma of a fluorine compound so that a part of C—H bond is C—F.
It is replaced by a bond. Also in this case, hydrogen is more effective, and the C-H / CF ratio on the outermost surface is 2 to 10. Hydrogen is the first impurity in the hard carbon film, and fluorine is 1/10 to 1/3 of the hydrogen. Since it is a mechanical part, its purpose is to reduce wear resistance. Releasability is not a problem and we do not consider application to molds and parts for resin or rubber molding. The coating material containing hydrogen and fluorine in the hard carbon film has already been used for coating the surface of machine parts. This is to improve wear resistance and hydrophobicity. Both are impurities that contain a larger amount of hydrogen. There is nothing considering application to resin or rubber molding dies and parts, and releasability is not a problem.
【０００８】[0008]
［本発明の基本形］ 本発明は、ＰＴＦＥの持つ離型性
と、セラミック皮膜の持つ耐摩耗性を合わせ持つ、高離
型性硬質皮膜を形成された、樹脂及びゴム用金型及び部
品を提供しようとするものである。高離型性硬質皮膜と
しては、その少なくとも最表面がダイヤモンド状炭素膜
あるいは硬質カ−ボン膜であり、該ダイヤモンド状炭素
膜あるいは硬質カ−ボン膜中に、添加成分として弗素を
１〜２０原子％含むことを特徴とする。図１に本発明の
金型の構成を示す。ここで、弗素は皮膜の中に一様に含
まれていても良いし、最外表面だけに含ませても良い。
図１の上方に皮膜での弗素の分布例を示す。アは一様な
分布で、イは最外表面のみで高い分布を示す。ここで硬
質カ−ボン膜という言葉とダイヤモンド状炭素膜という
言葉は同義語として使っている。同じものを両方の呼び
名で呼んでいるからである。[Basic Form of the Present Invention] The present invention provides molds and parts for resins and rubbers, which have a high mold-releasing hard film having both the mold-releasing property of PTFE and the wear resistance of a ceramic film. Is what you are trying to do. At least the outermost surface of the highly releasable hard film is a diamond-like carbon film or a hard carbon film, and 1 to 20 atoms of fluorine is added as an additive component in the diamond-like carbon film or the hard carbon film. % Is included. FIG. 1 shows the structure of the mold of the present invention. Here, fluorine may be uniformly contained in the film, or may be contained only in the outermost surface.
An example of fluorine distribution in the film is shown in the upper part of FIG. A has a uniform distribution, and A has a high distribution only on the outermost surface. Here, the terms hard carbon film and diamond-like carbon film are used as synonyms. This is because the same thing is called by both names.
【０００９】［中間層の形成］ また一般に金型及び部
品の材料（鋼などの金属）の硬度は該ダイヤモンド状炭
素膜あるいは硬質カ−ボン膜の硬度に比べてはるかに低
い。このため金型及び部品の樹脂あるいはゴムに触れる
面（以下、成形面と略す）に直接硬質カ−ボン膜または
ダイヤモンド状炭素膜をコーティングしても、十分な密
着性及び耐久性が得られない場合が多い。このようなと
きは、母材表面に窒化、炭化、ほう化等の拡散硬化処理
を施したり、上記湿式法による硬質金属皮膜を形成した
り、あるいは上記乾式法による硬質セラミック皮膜を形
成したりして、中間層を形成する。この中間層の上に、
ダイヤモンド状炭素膜あるいは硬質カ−ボン膜を形成
し、該ダイヤモンド状炭素膜あるいは硬質カ−ボン膜の
全体、あるいは直接樹脂あるいはゴムに接する最表面層
のみに弗素を添加する。図２に中間層を設けたものの構
成を示す。こうすることにより耐摩耗性を改善しながら
優れた離型性を付与することができる。[Formation of Intermediate Layer] Generally, the hardness of the material (metal such as steel) of the mold and parts is much lower than the hardness of the diamond-like carbon film or the hard carbon film. For this reason, even if the hard carbon film or diamond-like carbon film is directly coated on the surface of the mold and parts that comes into contact with the resin or rubber (hereinafter abbreviated as the molding surface), sufficient adhesion and durability cannot be obtained. In many cases. In such a case, the surface of the base material may be subjected to a diffusion hardening treatment such as nitriding, carbonization or boration, a hard metal film may be formed by the wet method, or a hard ceramic film may be formed by the dry method. To form an intermediate layer. On top of this middle layer,
A diamond-like carbon film or a hard carbon film is formed, and fluorine is added to the entire diamond-like carbon film or the hard carbon film, or only the outermost surface layer that is in direct contact with the resin or rubber. FIG. 2 shows the structure of the structure provided with the intermediate layer. By doing so, excellent releasability can be imparted while improving wear resistance.
【００１０】[0010]
［離型性の生ずる原因］ ＰＴＦＥの持つ優れた離型性
は、既に述べたように、ＰＴＦＥを構成する元素が炭素
及び弗素のみであることに起因する。また、テトラフル
オロエチレンと他の弗素系ポリマ−との共重合体の代表
であるＰＦＡ（テトラフルオロエチレン−パ−フルオロ
アルキルビニルエ−テル（モノマ−の化学式：ＣＦ2 ＝
ＣＦＯＣ3 Ｆ7 ）共重合体）やＦＥＰ（テトラフルオロ
エチレン−ヘキサフルオロプロピレン（同：ＣＦ2 ＝Ｃ
ＦＣＦ3 ）共重合体）も、炭素と弗素（前者のみ酸素を
含有する）からなり、ＰＴＦＥと同様に、優れた離型性
を示す。また、ポリテトラフルオロエチレン（モノマ−
の化学式：ＣＦ2 ＝ＣＦ2 ）とポリエチレン（同：ＣＨ
2 ＝ＣＨ2 ）との共重合体であるＥＴＦＥ（エチレンテ
トラフルオロエチレン）はＰＴＦＥよりも離型性がやや
劣る。これは、化合物中あるいは共重合体中での弗素の
含有率によって離型性の制御が可能であるためと考えら
れる。すなわち、炭素と水素と弗素の存在比率を制御す
ることによって、離型性を自由に制御することが可能で
ある。以上述べた弗素系ポリマ−の特徴を検討する中か
ら、本発明者らは、炭素と弗素、水素のみからなる化合
物を合成すれば、上記弗素系ポリマ−と同様の特性を得
ることができると考えた。また、ＰＦＡの例からわかる
ように、若干の酸素の混入は、離型性に大きく影響しな
いと考えた。[Cause of Releasability] The excellent releasability of PTFE is due to the fact that the elements constituting PTFE are only carbon and fluorine, as described above. Further, PFA (tetrafluoroethylene-perfluoroalkylvinylether (monomer chemical formula: CF 2 =, which is a representative of a copolymer of tetrafluoroethylene and another fluorine-based polymer,
CFOC 3 F 7 ) copolymer) and FEP (tetrafluoroethylene-hexafluoropropylene (the same: CF 2 ═C)
The FCF 3 ) copolymer) is also composed of carbon and fluorine (only the former contains oxygen), and exhibits excellent releasability like PTFE. In addition, polytetrafluoroethylene (monomer
Chemical formula: CF 2 = CF 2 ) and polyethylene (the same: CH
ETFE (ethylene tetrafluoroethylene) which is a copolymer with 2 = CH 2 ) is slightly inferior in releasability to PTFE. It is considered that this is because the releasability can be controlled by the content of fluorine in the compound or the copolymer. That is, the releasability can be freely controlled by controlling the abundance ratios of carbon, hydrogen and fluorine. In consideration of the characteristics of the fluorine-based polymer described above, the inventors of the present invention can obtain the same characteristics as the above-mentioned fluorine-based polymer by synthesizing a compound containing only carbon, fluorine and hydrogen. Thought. Further, as can be seen from the example of PFA, it was considered that a slight mixing of oxygen did not significantly affect the releasability.
【００１１】［発明思想］ そこで、炭素と水素を主成
分とするダイヤモンド状炭素膜あるいは硬質カ−ボン膜
に弗素を添加し、樹脂あるいはゴム成形金型及び部品に
適用することで、離型性と耐摩耗性に優れた金型及び部
品を実現するに至った。また、本発明者らは、該ダイヤ
モンド状炭素膜あるいは硬質カ−ボン膜に離型性を付与
するためには、皮膜中の弗素の組成比を、１〜２０原子
％とする必要があることを見いだした。組成比が１％以
下であると、弗素添加の効果がほとんど現れず優れた離
型性が得られない。逆に組成比が２０％を越えると、皮
膜の硬度が著しく低下し、耐摩耗性が損なわれる。この
ために弗素の比率が１〜２０原子％に限定される。[Invention idea] Therefore, by adding fluorine to a diamond-like carbon film or a hard carbon film containing carbon and hydrogen as main components and applying it to a resin or rubber molding die and parts, the mold releasability is improved. And we have come to realize molds and parts with excellent wear resistance. Further, the present inventors need to set the composition ratio of fluorine in the film to 1 to 20 atomic% in order to impart releasability to the diamond-like carbon film or the hard carbon film. I found it. If the composition ratio is 1% or less, the effect of adding fluorine hardly appears, and excellent releasability cannot be obtained. On the other hand, if the composition ratio exceeds 20%, the hardness of the coating is remarkably reduced and the wear resistance is impaired. For this reason, the proportion of fluorine is limited to 1 to 20 atomic%.
【００１２】［中間層の形成と役割］ しかし現実に
は、金型及び部品の成形面に直接該ダイヤモンド状炭素
膜あるいは硬質カ−ボン膜を被覆しても、不慮の当て傷
や、樹脂、ゴム中にしばしば見られる硬質の異物による
引っかき傷に対しては、充分な耐久性が得られない。そ
こで、実際に金型及び部品に適用するに当たって、すで
に述べたような中間層を形成し、下地の硬度を充分に上
げた上に該ダイヤモンド状炭素膜あるいは硬質カ−ボン
膜を被覆すれば、該ダイヤモンド状炭素膜あるいは硬質
カ−ボン膜の優れた離型性を長期間にわたって引き出す
ことが可能であることを見いだした。これは、金型及び
部品の成形面の硬度（通常ビッカ−ス硬度で４００〜８
００ｋｇ／ｍｍ2 ）が該ダイヤモンド状炭素膜あるいは
硬質カ−ボン膜の硬度（ビッカ−ス硬度で２０００ｋｇ
／ｍｍ2 以上）に比べて極端に低いことに起因し、局部
的な応力がかかった時に、金型及び部品の成形面の金属
が変形し、被覆された膜がこのような変形に追従できず
に破壊し剥離するために起こる現象である。[Formation and Role of Intermediate Layer] However, in reality, even if the diamond-like carbon film or the hard carbon film is directly coated on the molding surfaces of the mold and parts, accidental scratches, resin, Sufficient durability cannot be obtained with respect to scratches caused by hard foreign substances often found in rubber. Therefore, when actually applied to a mold and parts, if the intermediate layer as described above is formed, and the diamond-like carbon film or the hard carbon film is coated after sufficiently increasing the hardness of the base, It has been found that the excellent releasability of the diamond-like carbon film or the hard carbon film can be brought out for a long period of time. This is the hardness of the molding surface of the mold and parts (usually 400 to 8 in Vickers hardness).
00 kg / mm 2 ) is the hardness of the diamond-like carbon film or the hard carbon film (2000 kg in Vickers hardness).
/ Mm 2 or more), the metal on the molding surface of the mold and parts is deformed when a local stress is applied, and the coated film can follow such deformation. It is a phenomenon that occurs because it is destroyed and peeled off.
【００１３】硬質の中間層を設けることによりこのよう
な膜の剥離破壊を防ぐことができる。中間層として、 （ａ）窒化、炭化、ほう化等の拡散硬化処理（硬度９
００〜１５００ｋｇ／ｍｍ2 ）（図２（ａ））、 （ｂ）湿式メッキ法によるクロムＣｒやニッケルＮｉ等
の硬質金属皮膜（硬度５００〜１２００ｋｇ／ｍｍ2 ）
（図２（ｂ））、 （ｃ）乾式法（ＰＶＤ法やＣＶＤ法）による窒化チタン
ＴｉＮや炭化チタンＴｉＣ、窒化クロムＣｒＮ等の硬質
セラミック皮膜（硬度１５００〜３０００ｋｇ／ｍｍ
2 ）（図２（ｃ）） 等の硬質皮膜を、いずれか単独であるいは複合させて形
成し、局部的な応力に耐えられる下地を形成しこの上に
本発明の硬質カ−ボン膜を形成すれば、この現象は防止
できる。局部的な応力が加えられたとしても、中間層が
硬くて変形を許さないので、最表面の硬質カ−ボン膜が
変形せず剥離しないのである。By providing a hard intermediate layer, it is possible to prevent such peeling damage of the film. As an intermediate layer, (a) diffusion hardening treatment (hardness 9
(0 to 1500 kg / mm 2 ) (FIG. 2 (a)), (b) Hard metal coating of chromium Cr, nickel Ni, etc. by the wet plating method (hardness 500 to 1200 kg / mm 2 ).
(FIG. 2 (b)), (c) Hard ceramic coating (hardness 1500-3000 kg / mm) of titanium nitride TiN, titanium carbide TiC, chromium nitride CrN, etc. by a dry method (PVD method or CVD method).
2 ) A hard coating such as that shown in FIG. 2C is formed alone or in combination to form a base that can withstand local stress, and the hard carbon film of the present invention is formed thereon. If this is done, this phenomenon can be prevented. Even if local stress is applied, since the intermediate layer is hard and does not allow deformation, the outermost hard carbon film does not deform and does not peel off.
【００１４】［ダイヤモンド状炭素膜、硬質カ−ボン膜
の形成］ ダイヤモンド状炭素膜あるいは硬質カ−ボン
膜の形成方法としては、 高周波あるいは直流電力によるグロ−放電プラズマを
用いたプラズマＣＶＤ（化学的気相析出）法 炭化水素ガスのイオンビ−ムを用いたイオンビ−ム蒸
着法、 固体炭素の昇華・析出を利用したイオンプレ−ティン
グ等のＰＶＤ（物理的気相析出）法、 がすでに知られている。いずれの方法も、本発明による
樹脂及びゴム金型及び部品へのダイヤモンド状炭素膜あ
るいは硬質カ−ボン膜の形成に利用できる。但し、該ダ
イヤモンド状炭素膜あるいは硬質カ−ボン膜に弗素を添
加するために、いずれの方法においても、合成の雰囲気
に四フッ化炭素（ＣＦ4 ）や三フッ化窒素（ＮＦ3 ）等
の弗素を含有した気体原料を導入することが必要であ
る。[Formation of diamond-like carbon film or hard carbon film] As a method of forming a diamond-like carbon film or a hard carbon film, plasma CVD using glow discharge plasma with high frequency or DC power (chemical Vapor Deposition Method Ion beam evaporation method using ion beam of hydrocarbon gas, PVD (physical vapor deposition) method such as ion plating using sublimation / precipitation of solid carbon are already known. There is. Either method can be used to form a diamond-like carbon film or a hard carbon film on the resin and rubber molds and parts according to the present invention. However, in order to add fluorine to the diamond-like carbon film or the hard carbon film, in any method, carbon tetrafluoride (CF 4 ) or nitrogen trifluoride (NF 3 ) is added to the synthesis atmosphere. It is necessary to introduce a gaseous raw material containing fluorine.
【００１５】［中間層とダイヤモンド状炭素膜の連続的
形成］ 一方、中間層を効果的に利用するためには、中
間層の形成と該ダイヤモンド状炭素膜あるいは硬質カ−
ボン膜の形成を、途中で真空を破ることなく、連続的に
行うことが好ましい。即ち、前記の（ｃ）の場合（図２
（ｃ））、公知のプラズマＣＶＤ法により中間層となる
窒化チタン等の硬質セラミック皮膜を形成したあと、直
ちに原料ガスを入れ替え、引き続いてプラズマＣＶＤ法
によりダイヤモンド状炭素膜を形成する。こうすれば、
中間層と該ダイヤモンド状炭素膜との界面に不純物等の
吸着が起こらず、優れた密着性が得られる。同様に前記
の（ｃ）の場合で公知のＰＶＤ法により中間層の形成を
行う場合も同様に、中間層形成後に原料ガスを入れ替
え、プラズマＣＶＤ法等により該ダイヤモンド状炭素膜
の形成を行えばよい。また、前記の（ａ）に示すように
拡散硬化処理によって金型母材の表面硬度を上げれば、
不慮の当て傷等に対する耐久性が向上する。この場合に
おいても、拡散硬化処理であるイオン窒化と中間層とな
る硬質セラミック皮膜形成、該ダイヤモンド状炭素膜あ
るいは硬質カ−ボン膜形成の３つの表面処理工程を、途
中で真空を破ることなく連続的に行う。こうすれば各層
の境界面に不純物等が吸着せず、優れた密着性が得られ
るため好ましい。[Continuous formation of intermediate layer and diamond-like carbon film] On the other hand, in order to effectively utilize the intermediate layer, formation of the intermediate layer and the diamond-like carbon film or the hard carbon film are performed.
It is preferable to continuously form the Bonn film without breaking the vacuum. That is, in the case of the above (c) (see FIG.
(C)) After forming a hard ceramic film such as titanium nitride as an intermediate layer by a known plasma CVD method, the raw material gas is immediately replaced, and subsequently a diamond-like carbon film is formed by a plasma CVD method. This way
Impurities are not adsorbed on the interface between the intermediate layer and the diamond-like carbon film, and excellent adhesion is obtained. Similarly, when the intermediate layer is formed by the known PVD method in the case of the above (c), the raw material gas is replaced after the intermediate layer is formed, and the diamond-like carbon film is formed by the plasma CVD method or the like. Good. If the surface hardness of the die base material is increased by the diffusion hardening treatment as shown in (a) above,
Durability against accidental scratches is improved. Also in this case, three surface treatment steps of ion nitriding which is a diffusion hardening treatment, formation of a hard ceramic film as an intermediate layer, and formation of the diamond-like carbon film or hard carbon film are continuously performed without breaking the vacuum during the process. To do it. This is preferable because impurities and the like are not adsorbed on the boundary surface of each layer and excellent adhesion is obtained.
【００１６】[0016]
［実施例１（ゴムに対する離型性の評価）］本発明によ
る高離型性硬質皮膜について、ゴムに対する離型性を評
価した。試験片としては、ゴム成形金型の代表的な材料
であるＳ４５Ｃを用い、ＪＩＳ Ｋ６３０１に従って接
着性（離型性）評価試験を行った。なお、試験にはエチ
レンプロピレンゴムを用い、加硫により試験片に接着さ
れたゴムを試験面に対して９０度の方向に引き剥がした
ときの、試験片表面に残留したゴムの面積比（残留面積
／接着面積）を比較した。[Example 1 (Evaluation of releasability from rubber)] With respect to the high releasability hard film according to the present invention, releasability from rubber was evaluated. As a test piece, S45C, which is a typical material of a rubber molding die, was used, and an adhesiveness (release property) evaluation test was performed according to JIS K6301. In the test, ethylene propylene rubber was used, and the area ratio of the rubber remaining on the surface of the test piece when the rubber adhered to the test piece by vulcanization was peeled off in the direction of 90 degrees to the test surface (residual Area / adhesion area) was compared.
【００１７】さて、本発明による弗素添加ダイヤモンド
状炭素膜の作成方法は、次の通りである。まず、基材で
あるＳ４５Ｃ材（以下、被処理材と略す）の被覆する面
を所定の面粗度まで研磨仕上げする。０．５μｍ以下の
平均粗さが好ましい。この被処理材を有機溶剤や、洗
剤、水等を用いて洗浄し、表面に無機あるいは有機のい
かなる汚れも残留しないようにする。洗浄された被処理
物を、図３に示されるダイヤモンド状炭素膜の形成装置
の中の、電極２に取り付ける。真空容器１の中を真空排
気装置３によって１０-5Ｔｏｒｒまで排気し、その後、
ガス供給系４から、真空容器１内にアルゴンガス（Ａ
ｒ）を０．１Ｔｏｒｒの真空度になるまで導入する。次
に電極２に接続された直流電源５を用い、電極２にマイ
ナス１０００Ｖの直流電圧を印加して放電を発生させ、
被処理材６の表面をイオンクリ−ニングする。イオンク
リ−ニングを３０分間行った後、ガス供給系４から真空
容器１内にメタンガス（ＣＨ4 ）を導入する。メタンガ
ス導入に際しては、アルゴンガス流量を徐々に減らしな
がらメタンガス流量を徐々に増やし、真空容器内部の放
電を止めずに行う。メタンガス導入と同時にダイヤモン
ド状炭素膜の形成が始まる。約１分間かけて、アルゴン
ガスからメタンガスへとガスを完全に切り替えてから、
１５分間ダイヤモンド状炭素膜の形成を行う。所定の時
間が経過したら、ガス供給系４から四フッ化炭素ガス
（ＣＦ4 ）を導入し、すでに導入しているメタンガスと
の混合雰囲気中で、弗素添加ダイヤモンド状炭素膜の形
成をさらに１５分間続ける。メタンガスと四弗化炭素ガ
スとの流量比は、目標とする弗素の添加量に応じて変化
させるが、本実施例においては、同流量比を１０：１
（ＣＨ4 ：ＣＦ4 ＝１０：１）として行った。The method of forming the fluorine-containing diamond-like carbon film according to the present invention is as follows. First, the surface of the S45C material (hereinafter abbreviated as the material to be treated) that is the base material is polished to a predetermined surface roughness. An average roughness of 0.5 μm or less is preferable. The material to be treated is washed with an organic solvent, detergent, water or the like to prevent any inorganic or organic stains from remaining on the surface. The cleaned object is attached to the electrode 2 in the diamond-like carbon film forming apparatus shown in FIG. The inside of the vacuum container 1 is evacuated to 10 −5 Torr by the vacuum exhaust device 3, and then,
From the gas supply system 4, the argon gas (A
r) is introduced until the degree of vacuum reaches 0.1 Torr. Next, using a DC power supply 5 connected to the electrode 2, a negative 1000 V DC voltage is applied to the electrode 2 to generate a discharge,
The surface of the material 6 to be processed is ion-cleaned. After performing ion cleaning for 30 minutes, methane gas (CH 4 ) is introduced into the vacuum container 1 from the gas supply system 4. When introducing methane gas, the flow rate of methane gas is gradually increased while gradually reducing the flow rate of argon gas, and the discharge inside the vacuum vessel is not stopped. Simultaneously with the introduction of methane gas, the formation of a diamond-like carbon film begins. After completely switching the gas from argon gas to methane gas for about 1 minute,
A diamond-like carbon film is formed for 15 minutes. After a lapse of a predetermined time, a carbon tetrafluoride gas (CF 4 ) is introduced from the gas supply system 4, and a fluorine-added diamond-like carbon film is formed for a further 15 minutes in a mixed atmosphere with the already introduced methane gas. to continue. The flow rate ratio between the methane gas and the carbon tetrafluoride gas is changed according to the target amount of fluorine added, but in this embodiment, the flow rate ratio is 10: 1.
(CH 4 : CF 4 = 10: 1).
【００１８】この様にして、直流グロ−放電によるプラ
ズマＣＶＤ法により、全体厚さが約１μｍのダイヤモン
ド状炭素膜を得た（図４ａ）。比較のために、弗素添加
を行わずに３０分間ダイヤモンド状炭素膜のみを形成し
た試験片（図４ｂ）も作成した。なお、本試験において
は、耐久性の評価は行わないため、Ｓ４５Ｃ基材に直接
ダイヤモンド状炭素膜の被覆を行った。また、比較のた
めに、従来から金型及び部品の保護膜として用いられて
いる塗布法によるＰＴＦＥ膜（図４ｆ）、湿式メッキ法
による硬質クロム膜（図４ｃ）、ＰＶＤ法による窒化チ
タン膜（図４ｄ）をそれぞれ形成した試験片、及び表面
処理を全く行わないＳ４５Ｃ材に（図４ｅ）ついても、
同じ評価を行った。結果を表１に示す。なお、表中で、
ダイヤモンド状炭素膜を「ＤＬＣ膜」と略した。In this way, a diamond-like carbon film having a total thickness of about 1 μm was obtained by the plasma CVD method using direct current glow discharge (FIG. 4a). For comparison, a test piece (FIG. 4b) in which only the diamond-like carbon film was formed for 30 minutes without adding fluorine was also prepared. In this test, since the durability was not evaluated, the S45C base material was directly coated with the diamond-like carbon film. Further, for comparison, a PTFE film by a coating method (FIG. 4f), a hard chromium film by a wet plating method (FIG. 4c), and a titanium nitride film by a PVD method, which have been conventionally used as protective films for molds and parts ( 4d) is formed on each of the formed test pieces and the S45C material without any surface treatment (FIG. 4e),
The same evaluation was done. The results are shown in Table 1. In the table,
The diamond-like carbon film is abbreviated as “DLC film”.
【００１９】[0019]
【表１】 [Table 1]
【００２０】表からもわかるように、弗素を含まない皮
膜は、弗素添加を行わなかったダイヤモンド状炭素膜も
含めて、いずれも離型性に乏しく、試験片の表面にゴム
の一部が残留する。これに対して、本発明による弗素添
加したダイヤモンド状炭素膜は試験片にゴムが全く残留
せず、ＰＴＦＥ膜並の優れた離型性を有することが確認
できた。As can be seen from the table, the fluorine-free coating, including the diamond-like carbon coating without the addition of fluorine, has poor releasability, and some rubber remains on the surface of the test piece. To do. On the other hand, the fluorine-containing diamond-like carbon film according to the present invention did not leave any rubber on the test piece, and it was confirmed that the diamond-like carbon film had excellent releasability comparable to that of the PTFE film.
【００２１】［実施例２（樹脂に対する離型性）］本発
明による高離型性硬質皮膜について、樹脂に対する離型
性を評価した。試験片としては、樹脂成形金型の代表的
な材料であるＳＫＤ１１を用い、樹脂としては、接着性
に富むエポキシ樹脂（２液を混合するタイプ）を用い
た。試験方法として、試験片表面に混合された樹脂を塗
布し、１５０℃、３０分間樹脂を硬化させたあと、試験
片から樹脂を引き剥がしたときの、試験片表面への樹脂
の残留率（残留面積／塗布面積）を比較した。試験片の
作成方法は、実施例１に記載の通りとした。本発明の実
施例として全体の膜厚が約１μｍの弗素添加ダイヤモン
ド状炭素膜を形成した（図４ａ）。比較のために、弗素
添加を行わないダイヤモンド状炭素膜試験片（図４ｂ）
も作成した。また、比較のために、従来から金型及び部
品の保護膜として用いられている塗布法によるＰＴＦＥ
膜（図４ｆ）、湿式メッキ法による硬質クロム膜（図４
ｃ）、ＰＶＤ法による窒化チタン膜（図４ｄ）をそれぞ
れ形成した試験片、及び表面処理を全く行わないＳ４５
Ｃ材（図４ｅ）についても、同じ評価を行った。結果を
表２に示す。なお、表中で、ダイヤモンド状炭素膜を、
「ＤＬＣ膜」と略した。[Example 2 (Releasability to resin)] The hard-releasing hard coating according to the present invention was evaluated for releasability to resin. As the test piece, SKD11, which is a typical material of a resin molding die, was used, and as the resin, an epoxy resin having a high adhesiveness (a type in which two liquids were mixed) was used. As a test method, a mixed resin was applied to the surface of the test piece, the resin was cured at 150 ° C. for 30 minutes, and then the resin was peeled off from the test piece. The area / coated area) was compared. The method for preparing the test piece was as described in Example 1. As an example of the present invention, a fluorine-containing diamond-like carbon film having a total film thickness of about 1 μm was formed (FIG. 4a). For comparison, a diamond-like carbon film specimen without fluorine addition (Fig. 4b)
Also created. In addition, for comparison, PTFE by a coating method that is conventionally used as a protective film for molds and parts
Film (Fig. 4f), hard chromium film by wet plating method (Fig. 4f)
c), test pieces each having a titanium nitride film (FIG. 4d) formed by the PVD method, and S45 without any surface treatment.
The same evaluation was performed for material C (FIG. 4e). The results are shown in Table 2. In the table, the diamond-like carbon film is
Abbreviated as "DLC film".
【００２２】[0022]
【表２】 [Table 2]
【００２３】表からもわかるように、弗素を含まない皮
膜は、弗素添加を行わなかったダイヤモンド状炭素膜も
含めて、いずれも離型性に乏しく、試験片に樹脂の一部
が残留する。これに対して本発明による弗素添加したダ
イヤモンド状炭素膜は、試験片に樹脂が全く残留せず、
ＰＴＦＥ膜並の優れた離型性を有することが確認でき
た。As can be seen from the table, the fluorine-free coatings, including the diamond-like carbon coatings without the addition of fluorine, have poor releasability, and some of the resin remains on the test pieces. On the other hand, in the fluorine-containing diamond-like carbon film according to the present invention, no resin remains on the test piece,
It was confirmed that it had excellent releasability comparable to that of the PTFE membrane.
【００２４】［実施例（耐摩耗性の試験）］本発明に
よる高離型性硬質皮膜について、樹脂成形金型における
耐久性試験を実施した。試験片としては、ＳＫＤ１１か
らなる６個取りのモ−ルド金型のキャビティ部を全て入
れ子とし、実施例１及び２と同様の６種類の表面処理
（うち１種類は無処理）をそれぞれの入れ子に施したも
のを用いた。樹脂としては、耐摩耗性と離型性を同時に
評価するために、フィラ−としてシリカ（ＳｉＯ2 ）を
３０重量％含んだエポキシ樹脂を用いた。なお、本実験
では、従来通り離型剤を使用した。以上述べた試験用金
型及び樹脂を用い、１万ショット使用後の金型の摩耗量
（ゲ−ト部の寸法変化量）、キャビティ内部への樹脂の
残留状態等をそれぞれ評価した。結果を表３に示す。Example (Abrasion Resistance Test) With respect to the highly releasable hard coating of the present invention, a durability test in a resin molding die was carried out. As test pieces, all the cavity parts of a mold die of 6 pieces made of SKD11 were used as nests, and the same 6 kinds of surface treatments as in Examples 1 and 2 (one of them was not treated) were used as nests. What was given to was used. As the resin, an epoxy resin containing 30% by weight of silica (SiO 2 ) was used as a filler in order to simultaneously evaluate abrasion resistance and releasability. In this experiment, a release agent was used as usual. Using the test mold and resin described above, the amount of wear of the mold (the amount of dimensional change in the gate portion) after 10,000 shots, the state of resin remaining inside the cavity, etc. were evaluated. The results are shown in Table 3.
【００２５】[0025]
【表３】 [Table 3]
【００２６】表からもわかるように、本発明による弗素
添加されたダイヤモンド状炭素膜（表中Ｆ−ＤＬＣ）は
摩耗量が０．４μｍであり樹脂が残留していない。本発
明の金型が耐摩耗性と離型性を兼ね備えていることが確
認できた。一方、離型性では問題のないＰＴＦＥ膜は、
硬度が低いために早期に皮膜が失われ、著しく摩耗して
しまう。このため樹脂も一部残留する。耐摩耗性では問
題のない弗素添加なしのダイヤモンド状炭素膜（表中Ｄ
ＬＣ）及びＴｉＮ膜については、離型性の点で問題があ
り、樹脂が残留し、頻繁に金型の掃除が必要であること
などが確認できた。As can be seen from the table, the fluorine-containing diamond-like carbon film (F-DLC in the table) according to the present invention has a wear amount of 0.4 μm and no resin remains. It was confirmed that the mold of the present invention has both wear resistance and releasability. On the other hand, the PTFE film, which has no problem in releasability,
Due to its low hardness, the film is lost early and wears significantly. Therefore, a part of the resin also remains. Diamond-like carbon film without fluorine addition, which has no problem in abrasion resistance (D in the table)
It was confirmed that the LC) and the TiN film had a problem in mold releasability, the resin remained, and the mold had to be frequently cleaned.
【００２７】［実施例（樹脂の流路における耐久性と
離型性）］以上に説明したものは金型に本発明を実施し
たものであった。ここでは金型以外の応用について説明
する。例としてリップへの適用を述べる。すなわち本発
明による高離型性硬質被膜について、ポリプロピレン樹
脂の押し出し成型機のリップにおける耐久性と離型性の
評価を行った。リップ部に要求される特性としては、リ
ップ部の隙間寸法の維持及びリップ出口と樹脂との滑り
（離型性）とが挙げられる。リップ出口と樹脂との滑り
（離型性）が悪いと、押し出される樹脂フィルムにしわ
が生じ、製品不良となることがわかっていた。このため
従来は、滑り（離型性）を重視して、テフロン樹脂コ−
ティングが使用されていた。テフロン樹脂コ−ティング
は既に述べたように離型性に極めて優れている。しかし
これは柔らかいので、樹脂中にしばしば混入する硬質の
異物によって、約１週間でリップ部に傷が入る。このた
め押し出される樹脂に縦筋が入り、製品不良となること
が多かった。[Examples (Durability and Releasability of Resin in Flow Path)] What has been described above was the present invention applied to a mold. Here, applications other than the mold will be described. As an example, application to the lip will be described. That is, the high releasability hard coating film according to the present invention was evaluated for durability and releasability in the lip of a polypropylene resin extrusion molding machine. The characteristics required of the lip portion include maintenance of the gap size of the lip portion and slippage (release property) between the lip outlet and the resin. It has been known that if the slip (release property) between the lip outlet and the resin is poor, the extruded resin film is wrinkled, resulting in a defective product. For this reason, in the past, the Teflon resin core was attached with emphasis on slippage (release property).
Was used. Teflon resin coating is extremely excellent in releasability as described above. However, since it is soft, a hard foreign substance often mixed in the resin will scratch the lip portion in about one week. As a result, the extruded resin often has vertical streaks, resulting in defective products.
【００２８】そこで、本発明による硬質高離型性被膜を
適用し、実際に製造ラインに組み込んで、リップ部の寿
命評価を行った。硬質高離型性被膜の形成方法として
は、Ｓ４５Ｃ基材にイオン窒化処理を行い、基材表面を
硬化した後に、連続してプラズマＣＶＤ法により炭化チ
タンコ−ティングを施し、さらにこの上に連続してプラ
ズマＣＶＤ法により弗素を１０原子％添加したダイヤモ
ンド状炭素膜を形成した。イオン窒化深さは約１００μ
ｍとし、炭化チタンの厚さは２μｍ、最上層の弗素添加
ダイヤモンド状炭素膜の厚みは１μｍとなるように調整
した。なお、比較材として、プラズマＣＶＤ法によるＳ
ｉ3 Ｎ4 コ−ティング（厚さ３μｍ）と、同じくプラズ
マＣＶＤ法による弗素添加を行わないダイヤモンド状炭
素膜（下地層としてイオン窒化処理及び炭化チタンコ−
ティングを，本発明品と同様に実施）を取り上げた。Therefore, the hard high-releasing coating according to the present invention was applied and actually incorporated in the production line to evaluate the life of the lip portion. As a method for forming a hard and highly releasable coating, the S45C base material is subjected to ion nitriding treatment to cure the surface of the base material, and then titanium carbide coating is continuously applied by a plasma CVD method. Then, a diamond-like carbon film containing 10 atomic% of fluorine was formed by plasma CVD. Ion nitriding depth is about 100μ
The thickness of titanium carbide was adjusted to 2 μm, and the thickness of the uppermost fluorine-containing diamond-like carbon film was adjusted to 1 μm. As a comparative material, S produced by the plasma CVD method was used.
i 3 N 4 coating (thickness: 3 μm) and a diamond-like carbon film without fluorine addition by the plasma CVD method (ionnitriding treatment and titanium carbide coating as a base layer).
The same as the product of the present invention).
【００２９】この結果、弗素添加を行わなかったダイヤ
モンド状炭素膜及びＳｉ3 Ｎ4 コ−ティングでは、テス
ト開始と同時に、押し出された製品にしわが入り、耐久
試験に移ることができなかった。これは、樹脂とリップ
出口との滑りが悪いため生じたものと思われる。一方、
本発明による弗素添加ダイヤモンド状炭素膜において
は、良好な外観を持った製品を押し出すことができ、さ
らに、１ヵ月以上使用してもリップに傷が入ることもな
く、継続使用可能との評価が得られた。即ち、本発明に
よる弗素添加したダイヤモンド状炭素膜は、樹脂との滑
り（離型性）に優れるだけでなく、優れた耐摩耗性も合
わせ持つことが確認できた。As a result, in the diamond-like carbon film and Si 3 N 4 coating which were not added with fluorine, the extruded product was wrinkled simultaneously with the start of the test, and the durability test could not be started. This is probably due to poor slip between the resin and the lip outlet. on the other hand,
With the fluorine-containing diamond-like carbon film according to the present invention, a product having a good appearance can be extruded, and even if it is used for 1 month or more, the lip is not scratched and it is evaluated that it can be continuously used. Was obtained. That is, it was confirmed that the fluorine-containing diamond-like carbon film according to the present invention has not only excellent sliding property (releasing property) with the resin but also excellent abrasion resistance.
【００３０】[0030]
【発明の効果】以上述べた様に、本発明により見いださ
れた、弗素添加されたダイヤモンド状炭素膜あるいは硬
質カ−ボン膜を形成された樹脂及びゴム用金型及び部品
は、ＰＴＦＥ等の弗素含有高分子材料に匹敵する離型性
と、ダイヤモンドなみの耐摩耗性をあわせ持っている。
長期間にわたって優れた離型性を維持できる金型及び部
品を実現でき、成形品の品質維持・向上の観点から、き
わめて有用である。Industrial Applicability As described above, the resin and rubber molds and parts formed with the fluorine-added diamond-like carbon film or the hard carbon film, which are found by the present invention, are fluorine-containing materials such as PTFE. It has both releasability comparable to the contained polymer material and abrasion resistance similar to diamond.
It is possible to realize molds and parts that can maintain excellent releasability over a long period of time, and it is extremely useful from the viewpoint of maintaining and improving the quality of molded products.
【図１】本発明の樹脂およびゴムのための金型及び部品
の構造を略示する断面図。FIG. 1 is a sectional view schematically showing the structure of a mold and parts for resin and rubber of the present invention.
【図２】基材とダイヤモンド状炭素膜の間に中間層を設
けた本発明の金型及び部品の構造を略示する断面図。FIG. 2 is a cross-sectional view schematically showing the structure of the mold and component of the present invention in which an intermediate layer is provided between the base material and the diamond-like carbon film.
【図３】実施例において用いられたダイヤモンド状炭素
膜の形成装置の概略図である。FIG. 3 is a schematic view of an apparatus for forming a diamond-like carbon film used in the examples.
【図４】ゴムに対する離型性、樹脂に対する離型性、耐
摩耗性を試験するための試験片の概略の構造を示す断面
図。FIG. 4 is a cross-sectional view showing a schematic structure of a test piece for testing releasability for rubber, releasability for resin, and abrasion resistance.
【図５】基材の上に硬質Ｃｒ、Ｎｉメッキをした従来例
に係る金型及び部品の概略断面図。FIG. 5 is a schematic cross-sectional view of a mold and parts according to a conventional example in which hard Cr and Ni plating are applied on a base material.
【図６】基材の上に硬質のセラミックを被覆した従来例
に係る金型及び部品の概略断面図。FIG. 6 is a schematic cross-sectional view of a mold and a component according to a conventional example in which a hard ceramic is coated on a base material.
【図７】基材の上にＰＴＦＥを被覆した従来例に係る金
型及び部品の概略断面図。FIG. 7 is a schematic cross-sectional view of a mold and a component according to a conventional example in which a base material is coated with PTFE.
【図８】基材の上にＰＴＦＥを分散した硬質金属のメッ
キをした金型及び部品の概略断面図。FIG. 8 is a schematic cross-sectional view of a die and a component in which a hard metal in which PTFE is dispersed is plated on a base material.
１ 真空容器 ２ 電極 ３ 真空排気装置 ４ ガス供給系 ５ 直流電源 ６ 被処理材 1 vacuum container 2 electrode 3 vacuum evacuation device 4 gas supply system 5 direct current power supply 6 processed material
Claims (13)
皮膜を形成してなる樹脂あるいはゴム用金型及び樹脂あ
るいはゴム成形装置部品において、硬質皮膜の少なくと
も最表面が弗素を１〜２０原子％含むダイヤモンド状炭
素膜あるいは硬質カ−ボン膜であることを特徴とする樹
脂あるいはゴム用金型。1. In a resin or rubber mold and a resin or rubber molding apparatus component having a hard coating formed on the surface of steel, an aluminum alloy, a copper alloy, etc., at least the outermost surface of the hard coating contains 1 to 20 fluorine. A metal mold for resin or rubber, which is a diamond-like carbon film or a hard carbon film containing atomic%.
の上に硬質皮膜よりなる中間層を設け、さらに中間層の
上に弗素を１〜２０原子％含むダイヤモンド状炭素膜あ
るいは硬質カ−ボン膜よりなる表面層を形成したことを
特徴とする樹脂あるいはゴム用金型。2. A base material made of steel, aluminum alloy or copper alloy, on which an intermediate layer made of a hard film is provided, and further on the intermediate layer a diamond-like carbon film containing 1 to 20 atomic% of fluorine or a hard carbon film. A resin or rubber mold having a surface layer made of a Bon film.
の上に炭化、窒化、ほう化による拡散硬化処理膜を設
け、さらにこの硬化処理膜の上に弗素を１〜２０原子％
含むダイヤモンド状炭素膜あるいは硬質カ−ボン膜より
なる表面層を形成したことを特徴とする樹脂あるいはゴ
ム用金型。3. A base material made of steel, aluminum alloy, or copper alloy, on which a diffusion hardening treatment film by carbonization, nitriding, or boration is provided, and fluorine is added on the hardening treatment film in an amount of 1 to 20 atomic%.
A resin or rubber mold, wherein a surface layer made of a diamond-like carbon film or a hard carbon film containing is formed.
の上にクロムメッキあるいはニッケルメッキの中間層を
設け、さらにこの中間層の上に弗素を１〜２０原子％含
むダイヤモンド状炭素膜あるいは硬質カ−ボン膜よりな
る表面層を形成したことを特徴とする樹脂あるいはゴム
用金型。4. A diamond-like carbon film comprising a base material of steel, aluminum alloy or copper alloy, on which a chromium-plated or nickel-plated intermediate layer is provided, and further comprising 1 to 20 atomic% of fluorine on the intermediate layer. Alternatively, a resin or rubber mold having a surface layer formed of a hard carbon film.
の上にＴｉ、Ｚｒ、Ｖ、Ｃｒ、Ｗ、Ｓｉもしくはそれら
の窒化物又は炭化物から選ばれる一種以上の成分よりな
る中間層を設け、さらに中間層の上に弗素を１〜２０原
子％含むダイヤモンド状炭素膜あるいは硬質カ−ボン膜
よりなる表面層を形成したことを特徴とする樹脂あるい
はゴム用金型。5. A steel, aluminum alloy, or copper alloy as a base material, on which an intermediate layer made of one or more components selected from Ti, Zr, V, Cr, W, Si or their nitrides or carbides is provided. A resin or rubber mold, characterized in that a surface layer comprising a diamond-like carbon film containing 1 to 20 atomic% of fluorine or a hard carbon film is formed on the intermediate layer.
の上にＴｉ、Ｚｒ、Ｖ、Ｃｒ、Ｗ、Ｓｉもしくはそれら
の窒化物又は炭化物から選ばれる一種以上の成分よりな
る中間層を設け、さらに中間層の上に弗素を１〜２０原
子％含むダイヤモンド状炭素膜あるいは硬質カ−ボン膜
よりなる表面層を形成することとし、これらの中間層及
び表面層の形成を、途中で真空を破ることなく連続して
プラズマＣＶＤ法あるいはイオンプレ−ティング法によ
り実施することを特徴とする樹脂あるいはゴム用金型の
製造方法。6. A base material of steel, aluminum alloy or copper alloy, on which an intermediate layer comprising one or more components selected from Ti, Zr, V, Cr, W, Si or their nitrides or carbides. A diamond-like carbon film containing 1 to 20 atomic% of fluorine or a surface layer made of a hard carbon film is formed on the intermediate layer, and the intermediate layer and the surface layer are vacuum-formed during the formation. A method for producing a resin or rubber mold, which is carried out continuously by a plasma CVD method or an ion plating method without breaking.
の上に弗素を１〜２０原子％含むダイヤモンド状炭素膜
あるいは硬質カ−ボン膜よりなる表面層を形成した金型
に、離型剤を塗付することなく、ゴムあるいは樹脂材料
を充填して成形することを特徴とする樹脂あるいはゴム
の成形方法。7. A mold comprising a base material of steel, aluminum alloy, or copper alloy, on which a surface layer comprising a diamond-like carbon film or a hard carbon film containing 1 to 20 atomic% of fluorine is formed. A method for molding a resin or rubber, characterized by filling and molding a rubber or a resin material without applying a molding agent.
皮膜を形成してなる樹脂あるいはゴム成形装置部品にお
いて、硬質皮膜の少なくとも最表面が弗素を１〜２０原
子％含むダイヤモンド状炭素膜あるいは硬質カ−ボン膜
であることを特徴とする樹脂あるいはゴム成形装置部
品。8. A resin or rubber molding apparatus component having a hard coating formed on the surface of steel, aluminum alloy, copper alloy, etc., wherein at least the outermost surface of the hard coating is a diamond-like carbon film containing 1 to 20 atomic% of fluorine. Alternatively, a resin or rubber molding device component characterized by a hard carbon film.
の上に硬質皮膜よりなる中間層を設け、さらに中間層の
上に弗素を１〜２０原子％含むダイヤモンド状炭素膜あ
るいは硬質カ−ボン膜よりなる表面層を形成したことを
特徴とする樹脂あるいはゴム成形装置部品。9. A base material made of steel, aluminum alloy, or copper alloy, on which an intermediate layer made of a hard coating is provided, and further on the intermediate layer, a diamond-like carbon film containing 1 to 20 atomic% of fluorine or a hard coating. -A resin or rubber molding device part having a surface layer formed of a Bon film.
この上に炭化、窒化、ほう化による拡散硬化処理膜を設
け、さらにこの硬化処理膜の上に弗素を１〜２０原子％
含むダイヤモンド状炭素膜あるいは硬質カ−ボン膜より
なる表面層を形成したことを特徴とする樹脂あるいはゴ
ム成形装置部品。10. A base material of steel, aluminum alloy, or copper alloy,
A diffusion hardening treatment film by carbonization, nitriding and boration is provided on this, and fluorine is further added to the hardening treatment film at 1 to 20 atomic%
A resin or rubber molding device component having a surface layer formed of a diamond-like carbon film or a hard carbon film containing the same.
この上にクロムメッキあるいはニッケルメッキの中間層
を設け、さらにこの中間層の上に弗素を１〜２０原子％
含むダイヤモンド状炭素膜あるいは硬質カ−ボン膜より
なる表面層を形成したことを特徴とする樹脂あるはゴム
成形装置部品。11. A steel, an aluminum alloy, or a copper alloy as a base material,
An intermediate layer of chromium plating or nickel plating is provided on top of this, and fluorine is further added to this intermediate layer in an amount of 1 to 20 atomic%.
A resin or rubber molding device part characterized in that a surface layer comprising a diamond-like carbon film or a hard carbon film containing is formed.
この上にＴｉ、Ｚｒ、Ｖ、Ｃｒ、Ｗ、Ｓｉもしくはそれ
らの窒化物又は炭化物から選ばれる一種以上の成分より
なる中間層を設け、さらに中間層の上に弗素を１〜２０
原子％含むダイヤモンド状炭素膜あるいは硬質カ−ボン
膜よりなる表面層を形成したことを特徴とする樹脂ある
いはゴム成形装置部品。12. A steel, an aluminum alloy, or a copper alloy as a base material,
An intermediate layer made of one or more components selected from Ti, Zr, V, Cr, W, Si or their nitrides or carbides is provided on the intermediate layer, and fluorine is added on the intermediate layer in an amount of 1 to 20.
A resin or rubber molding device component having a surface layer formed of a diamond-like carbon film or a hard carbon film containing atomic%.
この上にＴｉ、Ｚｒ、Ｖ、Ｃｒ、Ｗ、Ｓｉもしくはそれ
らの窒化物又は炭化物から選ばれる一種以上の成分より
なる中間層を設け、さらに中間層の上に弗素を１〜２０
原子％含むダイヤモンド状炭素膜あるいは硬質カ−ボン
膜よりなる表面層を形成することとし、これらの中間層
及び表面層の形成を、途中で真空を破ることなく連続し
てプラズマＣＶＤ法あるいはイオンプレ−ティング法に
より実施することを特徴とする樹脂あるいはゴム成型装
置部品。13. A steel, an aluminum alloy, or a copper alloy as a base material,
An intermediate layer made of one or more components selected from Ti, Zr, V, Cr, W, Si or their nitrides or carbides is provided on the intermediate layer, and fluorine is added on the intermediate layer in an amount of 1 to 20.
A surface layer made of a diamond-like carbon film or a hard carbon film containing atomic% is formed, and the intermediate layer and the surface layer are formed continuously by a plasma CVD method or an ion pre-treatment without breaking the vacuum. A resin or rubber molding device part characterized by being applied by the Ting method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35626091A JP3189347B2 (en) | 1991-12-24 | 1991-12-24 | Resin mold, resin mold manufacturing method, and resin molding method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35626091A JP3189347B2 (en) | 1991-12-24 | 1991-12-24 | Resin mold, resin mold manufacturing method, and resin molding method |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001082342A Division JP3292199B2 (en) | 2001-03-22 | 2001-03-22 | Rubber mold, method for manufacturing rubber mold, and method for molding rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05169459A true JPH05169459A (en) | 1993-07-09 |
| JP3189347B2 JP3189347B2 (en) | 2001-07-16 |
Family
ID=18448143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35626091A Expired - Fee Related JP3189347B2 (en) | 1991-12-24 | 1991-12-24 | Resin mold, resin mold manufacturing method, and resin molding method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3189347B2 (en) |
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| US5948166A (en) * | 1996-11-05 | 1999-09-07 | 3M Innovative Properties Company | Process and apparatus for depositing a carbon-rich coating on a moving substrate |
| WO2001020055A1 (en) * | 1999-09-10 | 2001-03-22 | Åmic AB | A method for the manufacturing of a matrix and a matrix manufactured according to the method |
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| JP2001240956A (en) * | 2000-03-01 | 2001-09-04 | Ion Engineering Research Institute Corp | Method of surface treatment for metallic material, and fluoridated metallic mold |
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