JPH10330122A - Mold for glass molding - Google Patents

Mold for glass molding

Info

Publication number
JPH10330122A
JPH10330122A JP13717297A JP13717297A JPH10330122A JP H10330122 A JPH10330122 A JP H10330122A JP 13717297 A JP13717297 A JP 13717297A JP 13717297 A JP13717297 A JP 13717297A JP H10330122 A JPH10330122 A JP H10330122A
Authority
JP
Japan
Prior art keywords
mold
group
glass
metal
molding die
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
Application number
JP13717297A
Other languages
Japanese (ja)
Inventor
Masaru Yoshitake
優 吉武
Eiji Yanagisawa
栄治 柳沢
Naoki Yoshida
直樹 吉田
Hiromi Katsuta
宏美 勝田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP13717297A priority Critical patent/JPH10330122A/en
Publication of JPH10330122A publication Critical patent/JPH10330122A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C03B11/06Construction of plunger or mould
    • C03B11/08Construction of plunger or mould for making solid articles, e.g. lenses
    • C03B11/084Construction of plunger or mould for making solid articles, e.g. lenses material composition or material properties of press dies therefor
    • C03B11/086Construction of plunger or mould for making solid articles, e.g. lenses material composition or material properties of press dies therefor of coated dies
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C03B11/06Construction of plunger or mould
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00Press-moulding glass
    • C03B2215/02Press-mould materials
    • C03B2215/08Coated press-mould dies
    • C03B2215/10Die base materials
    • C03B2215/11Metals
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00Press-moulding glass
    • C03B2215/02Press-mould materials
    • C03B2215/08Coated press-mould dies
    • C03B2215/14Die top coat materials, e.g. materials for the glass-contacting layers
    • C03B2215/16Metals or alloys, e.g. Ni-P, Ni-B, amorphous metals
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00Press-moulding glass
    • C03B2215/02Press-mould materials
    • C03B2215/08Coated press-mould dies
    • C03B2215/30Intermediate layers, e.g. graded zone of base/top material
    • C03B2215/32Intermediate layers, e.g. graded zone of base/top material of metallic or silicon material

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a mold for glass molding that scarcely causes flaw on-the molded glass surface by the press-molding in no need of application of a mold- releasing agent by forming, on the outermost surface of the mold base made of stainless alloy, a coated layer which is constituted with a combination of the areas of a metal-coated layer of an element in group 6 of the periodic table with the other areas of a metal-coated layer in which mold-releasing fine particles are dispersed in the matrix of an element in the iron group. SOLUTION: The coated layer is formed by combining the areas the layer A of a metal in group 6 of the periodic table (for example, Cr plated layer) with the other areas of the layer B in which fine particles manifesting mold- releasing properties, selected from (fluorinated) graphite, BN, carbon black, MoS2 , WS2 and CF2 are dispersed in the matrix of a metal in the iron group or an alloy mainly containing an iron-group element with an element selected from group 6 and Re (such as Ni matrix). In a preferred embodiment, the metal- coated layer A is formed on the areas in which the friction between the mold and the glass is reduced among the outermost surface.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、ガラス成形用とり
わけTVブラウン管成形用の金型に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mold for molding glass, especially for molding a CRT.

【0002】[0002]

【従来の技術】TVブラウン管は前面のパネルとじょう
ご型のファンネルおよびネックを別々に作り、パネル内
面への蛍光体塗布等を行い、電極を取り付けた後、これ
らを結合して製造される。そのため、パネル内面の性状
についてはきわめて厳しい品質管理が要求される。近年
ブラウン管表面の画像表示部分の反射防止処理などによ
り内面の欠陥が顕在化し一層要求品質が高度になる傾向
にある。
2. Description of the Related Art A TV cathode ray tube is manufactured by separately forming a front panel, a funnel type funnel and a neck, applying a phosphor to the inner surface of the panel, attaching electrodes, and then combining them. Therefore, extremely strict quality control is required for the properties of the inner surface of the panel. In recent years, defects on the inner surface become apparent due to anti-reflection processing of the image display portion on the surface of the cathode ray tube, and the required quality tends to be higher.

【0003】上記パネルの成形は、溶融した1,000
℃程度の高温にあるガラスに金属製金型(プランジャ)
を押しつけることによってなされる。この金型は機械的
強度、耐熱性、高温のガラスに対して化学的に安定であ
ること、成形ガラス面に微少亀裂などの欠陥を発生させ
ないなどの特性が求められる。
[0003] The above-mentioned panel is formed by melting 1,000 pieces.
Metal mold (plunger) for glass at a high temperature of about ℃
This is done by pressing This mold is required to have properties such as mechanical strength, heat resistance, being chemically stable to high-temperature glass, and not generating defects such as minute cracks on the formed glass surface.

【0004】このような目的に適う金型として、従来よ
りステンレス合金上にクロムめっきやニッケル−タング
ステン合金めっきを施したものが多用されている。金型
用に適したクロムめっきは、サージェント浴、混合触媒
浴、高効率浴などがあるが、成形時に金型側面で成形さ
れるガラス表面に傷が生じやすく、これを低減させるた
め当該部分に頻繁に離型剤を塗布せねばならない欠点が
ある。
[0004] As a mold suitable for such a purpose, a mold in which chromium plating or nickel-tungsten alloy plating is applied on a stainless steel alloy has been frequently used. The chromium plating suitable for molds includes Sargent baths, mixed catalyst baths, and high-efficiency baths, but the surface of the glass formed on the side of the mold tends to be damaged during molding. There is a disadvantage that a release agent must be frequently applied.

【0005】一方、近年開発されたニッケル−タングス
テンめっき被膜はパネル成形用金型の表面被膜として用
いた場合、金型側面での傷発生が抑えられ離型剤の塗布
頻度がクロムに比べて少なくて済むが、被膜に含まれる
タングステンが酸化されやすく、また高温下での機械的
強度が必ずしも十分ではないため、高温での長時間の使
用に際してはクロムに比べて短時間でプレス成形面の不
均一性を生じやすい欠点がある。
On the other hand, when a nickel-tungsten plating film developed in recent years is used as a surface coating of a panel forming die, the occurrence of scratches on the side of the die is suppressed, and the frequency of application of a release agent is smaller than that of chromium. However, since the tungsten contained in the coating is easily oxidized and the mechanical strength at high temperatures is not always sufficient, the press-formed surface cannot be repaired in a shorter time than chromium when used at high temperatures for a long time. There is a disadvantage that uniformity tends to occur.

【0006】本出願人は、先に特開平8−188424
において金型の最表面としてニッケル系のマトリックス
被膜中に離型性を発現する微粒子を分散させた被膜を提
案した。また、製瓶用としてはニッケル系のマトリック
ス被膜中に、それ自身の層状の結晶構造から潤滑性を有
する黒鉛粒子を分散したものが知られている(例えば、
特公平7−35259)。この種の被膜は離型性に優れ
金型側面における前記欠点は改善されるが、金型の側面
以外の領域ではより高温に曝されることもあり、上記ニ
ッケル−タングステンめっき被膜と同様に、金型の寿命
がクロムめっきに比べるとどうしても短くなる。
[0006] The present applicant has previously disclosed in Japanese Patent Application Laid-Open No. 8-188424.
Proposed a coating in which fine particles exhibiting releasability were dispersed in a nickel-based matrix coating as the outermost surface of a mold. In addition, for bottles, it is known to disperse graphite particles having lubricity from its own layered crystal structure in a nickel-based matrix coating (for example,
Japanese Patent Publication No. 7-35259). This type of coating has excellent mold release properties and improves the above-mentioned disadvantages on the side of the mold, but may be exposed to higher temperatures in regions other than the side of the mold. The life of the mold is inevitably shorter than that of chrome plating.

【0007】[0007]

【発明が解決しようとする課題】離型剤の塗布について
は、この作業が高度の熟練が必要であるほか、離型剤が
金型から剥離しパネル内に落下した場合には、パネル面
に欠点を生ずるおそれがある等の問題があり、高温での
耐久性がありかつ離型剤塗布の必要のない、または離型
剤塗布が少なくて済む金型の開発が要望されている。
In applying a release agent, this operation requires a high degree of skill. In addition, when the release agent separates from the mold and falls into the panel, it is applied to the panel surface. There is a problem that a defect may be caused, and there is a demand for the development of a mold that is durable at high temperatures and does not require the application of a release agent, or requires less application of the release agent.

【0008】[0008]

【課題を解決するための手段】本発明者らは、金型の部
分または位置によって被膜に要求される特性が異なるこ
とに着目し、離型剤の使用頻度が少なくてもガラス表面
に傷が生じにくいガラス成形用金型につき鋭意検討し
た。
Means for Solving the Problems The present inventors have focused on the fact that the required properties of the coating differ depending on the part or position of the mold, and have found that even if the release agent is used less frequently, the glass surface is not damaged. We studied diligently for a glass molding die that is unlikely to occur.

【0009】その結果、ステンレス合金を基体とし、そ
の相対的に高温に曝され酸化されやすいまたは高温での
機械的強度が強く求められる領域、例えば前記パネルの
光を透過または画像を投影、結像させるフェース部を成
形する領域に、6族元素からなる金属被膜を、それ以外
の金型側面のようにガラスとの擦れが多い領域に、潤滑
性を有するフッ化黒鉛、黒鉛、窒化ホウ素、カーボンブ
ラック、二硫化モリブデン、二硫化タングステン、フッ
化カルシウム等の微粒子を内部に分散させた、鉄族元素
からなる分散めっき被膜または鉄族元素を主成分としこ
れと6族元素およびレニウムから選ばれる1種以上の元
素との合金からなる分散めっき被膜とを組み合わせて形
成することにより、従来の全面がクロム被膜、ニッケル
−タングステン被膜または潤滑粒子分散めっき被膜であ
る金型より、プレス成形時にガラス表面に傷が付きにく
く、成形歩留りが向上し、さらに成形作業中に離型剤塗
布をほとんど行わずに高温で長時間使用しても、金型成
形面の表面粗度の維持が良好で、総合的に金型寿命がク
ロム被膜に比べても長くなることを見い出し、本発明を
提供するに至った。
As a result, a stainless steel base material is exposed to a relatively high temperature and easily oxidized, or a region where high mechanical strength at a high temperature is required, for example, light is transmitted from the panel or an image is projected and formed. In the region where the face part to be formed is formed, a metal film made of a Group 6 element is applied, and in the other region where the friction with glass is large, such as the side surface of the mold, fluorinated graphite, graphite, boron nitride, carbon, etc. Black, molybdenum disulfide, tungsten disulphide, calcium fluoride, or other fine particles dispersed inside, a dispersed plating film made of an iron group element, or an iron group element as a main component and selected from a group 6 element and rhenium By forming a combination with a dispersed plating film made of an alloy with more than one element, the conventional entire surface can be coated with chromium and nickel-tungsten. Or, compared to the mold that is a lubricated particle dispersed plating film, the glass surface is less likely to be scratched during press molding, the molding yield is improved, and it is used for a long time at high temperature with almost no release agent application during the molding operation In addition, the present inventors have found that the surface roughness of the molding surface of the mold is well maintained, and that the overall life of the mold is longer than that of the chromium film, and the present invention has been provided.

【0010】すなわち本発明は、6族元素(すなわちC
r、Mo、Wから選ばれる1種または2種以上)からな
る金属被膜Aの領域と、鉄族元素(すなわちFe、C
o、Niから選ばれる1種または2種以上)からなるま
たは鉄族元素を主成分とし6族元素およびレニウムから
選ばれる1種以上の元素との合金からなるマトリックス
中に離型性を発現する微粒子を分散させた金属被膜Bの
領域とを組み合わせてなる被膜層が、ステンレス合金か
らなる基体の最表面に形成されていることを特徴とする
ガラス成形用金型を提供する。
That is, the present invention relates to a group 6 element (ie, C
a region of the metal coating A made of one or more selected from r, Mo, and W) and an iron group element (that is, Fe, C
o, Ni or one or more selected from the group consisting of iron and a group 6 element and an alloy of one or more elements selected from rhenium. Provided is a glass molding die, wherein a coating layer formed by combining a region of a metal coating B in which fine particles are dispersed is formed on the outermost surface of a substrate made of a stainless alloy.

【0011】[0011]

【発明の実施の形態】以下、本発明の詳細について実施
例とともに説明する。本発明における金型は、ステンレ
ス合金を基体とし、その成形面に被膜またはめっきを施
して得られる。そして、ガラス成形用金型であれば、上
型および下型のいずれに対しても適用できるが、実質的
にメリットがあるのは上型(プランジャ)である。一般
に、下型では使用条件が緩く前記したような金型の成形
面の劣化に起因する欠点の発生が少ないからである。本
発明の金型は各種ガラス製品成形用金型のうちでも、特
にブラウン管パネルのように高い品質および厳しい光学
特性が求められるガラス製品を歩留り良く生産する金型
に好適である。
DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below along with embodiments. The mold in the present invention is obtained by applying a coating or plating to a molding surface of a stainless steel alloy as a substrate. The glass mold can be applied to both the upper mold and the lower mold, but the upper mold (plunger) has a substantial advantage. This is because, in general, the use conditions of the lower mold are loose and the occurrence of defects due to the deterioration of the molding surface of the mold as described above is small. The mold of the present invention is suitable for a mold for producing glass products requiring high quality and strict optical characteristics, such as a cathode ray tube panel, with high yield among various molds for molding glass products.

【0012】本発明が対象とする金型の最表面被膜(金
属被膜)は、金属または合金からなり、その形成法は、
電気めっき法、化学めっき法、CVD法、PVD法およ
び溶射法が適用できる。電気めっき法は比較的低コスト
であり特に好適である。
The outermost surface coating (metal coating) of the mold to which the present invention is applied is made of a metal or an alloy.
Electroplating, chemical plating, CVD, PVD and thermal spraying can be applied. Electroplating is relatively low cost and is particularly suitable.

【0013】成形中にガラスとの擦れが少ない、または
高温で被膜が酸化されやすい金型の領域、例えばブラウ
ン管パネルの光を透過または画像を投影、結像させるフ
ェース部に対応する金型領域には、6族元素からなる金
属被膜が好適であり、とりわけクロムを主成分とする金
属被膜が耐酸化性の点で好ましい。
[0013] In a mold region where friction with glass is small during molding or a film is easily oxidized at a high temperature, for example, a mold region corresponding to a face portion of a cathode ray tube panel which transmits light or projects and forms an image. Is preferably a metal film made of a Group 6 element, and particularly preferably a metal film containing chromium as a main component from the viewpoint of oxidation resistance.

【0014】これ以外の主に金型側面の領域には、マト
リックス中に離型性を発現する微粒子を分散させた金属
被膜を形成する。このマトリックスとしては、鉄族元素
または鉄族元素を主成分としこれと6族元素およびレニ
ウムから選ばれる1種以上の元素との合金が好適であ
り、とりわけニッケルを主成分とするものが、分散めっ
きの制御の容易さとコストの点で好ましい。
In the other region mainly on the side surface of the mold, a metal film in which fine particles exhibiting releasability are dispersed in a matrix is formed. As the matrix, an iron-group element or an alloy of the iron-group element as a main component and one or more elements selected from a group 6 element and rhenium is preferable. This is preferable in terms of ease of plating control and cost.

【0015】被膜中に分散させる前記微粒子としては、
フッ化黒鉛、黒鉛、窒化ホウ素、カーボンブラック、二
硫化モリブデン、二硫化タングステン、フッ化カルシウ
ムなどの粒子が用いられる。これらの微粒子が存在する
ことで、被膜の高温下における潤滑性を付与するととも
に機械強度を増大させる効果が得られる。特に黒鉛、窒
化ホウ素、カーボンブラックは、ガラス成形温度近傍ま
で良好な潤滑性を示すため好ましい。
The fine particles dispersed in the coating include:
Particles such as graphite fluoride, graphite, boron nitride, carbon black, molybdenum disulfide, tungsten disulfide, and calcium fluoride are used. The presence of these fine particles has the effect of imparting lubricity at high temperatures of the coating and increasing the mechanical strength. In particular, graphite, boron nitride, and carbon black are preferable because they exhibit good lubricity up to around the glass forming temperature.

【0016】被膜中でのこれら分散粒子の濃度は、前記
の良好な潤滑性が得られるようにする点で、0.1〜5
0体積%が好ましく、5〜30体積%がより好ましい。
また,分散粒子の平均粒径は、平滑な成形面を得るため
のめっき被膜とするうえで、最表面被膜の膜厚以下でか
つ0.001〜5μmであるのが好適である。ブラウン
管用パネルなどに適した高精度に平坦な成形面とするた
めには、0.005〜3μmがガラス成形に適するめっ
き表面を得るうえでより好適である。
The concentration of these dispersed particles in the coating is 0.1 to 5 in order to obtain the above-described good lubricity.
0 vol% is preferable, and 5 to 30 vol% is more preferable.
The average particle diameter of the dispersed particles is preferably not more than the thickness of the outermost surface coating and 0.001 to 5 μm in order to form a plated film for obtaining a smooth molded surface. In order to form a flat molding surface with high precision suitable for a cathode ray tube panel or the like, 0.005 to 3 μm is more suitable for obtaining a plating surface suitable for glass molding.

【0017】また、カーボンブラックは、それ自体層状
の結晶構造から離型性に優れることが知られている黒鉛
等に比べて微粉化が容易であるため、めっき法によりマ
トリックス中に、より微細かつ均一に分散させうること
から、表面性状の品質管理基準の厳しいガラス成形金型
に対しては、金型表面の精密な粗度制御を可能にする観
点から特に好適となる。カーボンブラックは、天然ガス
や石油などの炭化水素を気相中で不完全燃焼または熱分
解して得られる微粒子の炭素材料であり、製法によって
チャンネルブラック、ファーネスブラック、サーマルブ
ラック、ランプブラック、ローラーおよびディスクブラ
ックなどに大別される。また、原料にアセチレンを用い
たものはアセチレンブラックと呼ばれるが、本発明にお
いてはいずれのカーボンブラックも使用できる。
Further, since carbon black is easier to pulverize than graphite or the like, which is known to have excellent releasability due to its layered crystal structure, carbon black is finer and finer in a matrix by a plating method. Since it can be uniformly dispersed, it is particularly suitable for a glass molding die having strict quality control standards for surface properties, from the viewpoint of enabling precise roughness control of the die surface. Carbon black is a particulate carbon material obtained by incompletely burning or thermally decomposing hydrocarbons such as natural gas and petroleum in the gas phase.Depending on the manufacturing method, carbon black, furnace black, thermal black, lamp black, rollers and rollers are used. It is roughly divided into disk black and the like. Further, those using acetylene as a raw material are called acetylene black, and any carbon black can be used in the present invention.

【0018】金型最表面の被膜の厚さは、1μmより薄
いと高温による酸化、機械的変形を受けやすくなり、5
00μmより厚いと、効果面でそれほど差異がないう
え、被膜形成に長時間を要し、技術的、コスト的に有効
な範囲を超えるので、1〜500μmが好ましい。
If the thickness of the coating on the outermost surface of the mold is less than 1 μm, it is susceptible to oxidation and mechanical deformation due to high temperature.
When the thickness is more than 00 μm, there is not much difference in the effect, and it takes a long time to form a film, which exceeds the technically and cost-effective range.

【0019】金型基体と最表面被膜との間に、8族、9
族、10族および11族から選ばれる1種以上の金属を
含む薄膜を、中間膜または下地膜として形成させること
により、基体と被膜との結合が強固になるとともに、最
表面被膜の作製が容易になる。8族〜11族から選ばれ
る1種以上の元素としては、鉄、ルテニウム、コバル
ト、ロジウム、ニッケル、パラジウム、白金、銅、銀、
金などが好ましい。通常は、例えばニッケル、コバル
ト、鉄、クロム、パラジウム等を、めっき、CVD、P
VD、溶射等の薄膜形成法で作製する。特にめっき法
は、被膜形成速度、被膜の平滑性およびコスト等の点で
好適である。また、これらの元素は、主成分として40
〜100%であることが、それら元素の特性を活かすう
えで好適である。この副成分としては、通常Ni−Pま
たはNi−B等であり、被膜特性を損なわない範囲であ
れば不純物も許容される。
[0019] Between the mold substrate and the outermost surface coating, a group VIII, 9
By forming a thin film containing at least one metal selected from Group 10, Group 10 and Group 11 as an intermediate film or a base film, the bond between the substrate and the film is strengthened, and the outermost surface film is easily formed. become. One or more elements selected from Group 8 to Group 11 include iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver,
Gold is preferred. Usually, for example, nickel, cobalt, iron, chromium, palladium, etc. are plated,
It is manufactured by a thin film forming method such as VD or thermal spraying. In particular, the plating method is preferable in terms of the film formation speed, the film smoothness, the cost, and the like. In addition, these elements contain 40% as a main component.
It is preferable that the content be 100% or less in order to utilize the characteristics of these elements. This subcomponent is usually Ni-P or Ni-B, and impurities are also allowed as long as the film characteristics are not impaired.

【0020】この場合、上記薄膜の厚さは、0.1μm
より薄いと全面を実効的に被覆することが困難であり、
50μmより厚いと残留ひずみが増大して中間層として
の意味がなくなるので、0.1〜50μmが好適であ
る。金型の基体としては、機械的強度、耐食性、熱伝導
性、熱膨張特性等の点からマルテンサイト系ステンレス
合金が好適である。
In this case, the thickness of the thin film is 0.1 μm
If it is thinner, it is difficult to effectively cover the entire surface,
If the thickness is more than 50 μm, the residual strain increases and the meaning as an intermediate layer is lost, so that 0.1 to 50 μm is preferable. As a mold base, a martensitic stainless steel alloy is preferable in terms of mechanical strength, corrosion resistance, thermal conductivity, thermal expansion characteristics, and the like.

【0021】なお、金型の成形面の異なる領域にこれら
領域に適った被膜を選択的に組み合わせて形成する場
合、この形成作業の便宜を図るため、前記成形面の全体
に一方の被膜を形成した後に、この被膜の所定の領域に
他方の被膜を重ねて形成するようにしてもよい。
In the case where films suitable for these regions are selectively combined in different regions on the molding surface of the mold, one film is formed on the entire molding surface in order to facilitate the forming operation. After that, the other film may be formed so as to overlap a predetermined region of the film.

【0022】[0022]

【作用】本発明のガラス成形用金型の被膜は、高温の溶
融ガラスと直接接触し、かつ最も厳しい面精度品質が要
求されるガラス製品の部分、例えばTVブラウン管用パ
ネルの光を透過または画像を投影、結像させるフェース
部に対応する領域には、耐酸化性に優れる金属被膜を設
けることにより長時間安定した面精度を維持し、また冷
却された成形ガラスとの相互の接触により傷の発生しや
すい金型側面のような領域には、潤滑性を有する微粒子
を分散させた金属被膜すなわち分散被膜を設けることに
より、離型剤塗布頻度をほとんど不要になるほどに顕著
に低減せしめ、金型の耐久性を高めるとともに成形歩留
りを向上せしめる。
The coating of the glass molding die of the present invention is in direct contact with the high-temperature molten glass and transmits or transmits light of a glass product part requiring the strictest surface precision quality, for example, a panel of a TV cathode-ray tube. By providing a metal coating with excellent oxidation resistance in the area corresponding to the face part where the image is projected and focused, stable surface accuracy is maintained for a long time, and scratches due to mutual contact with cooled molded glass By providing a metal film in which fine particles having lubricity are dispersed, that is, a dispersed film, in a region such as a mold side surface that is likely to occur, the frequency of release agent application is significantly reduced so that it becomes almost unnecessary, and the mold is formed. And improve the molding yield.

【0023】この分散被膜の効果が得られる理由は必ず
しも明確ではないが、上記の分散粒子が金属中に分散固
定されることにより、溶融ガラスとの接触が被膜中に分
散された粒子でなされるため、マトリックス金属または
合金の酸化表面に比べて界面エネルギーが大きく異なり
濡れにくいこと、およびマトリックスに比べて脆いた
め、成形時に分散粒子からガラス面との界面にその一部
が極微量ずつ供給されることにより潤滑剤として作用す
るためと考えられる。
Although the reason why the effect of the dispersed film is obtained is not clear, the contact between the dispersed particles and the molten glass is made by the particles dispersed in the film by dispersing and fixing the dispersed particles in a metal. Therefore, the interfacial energy is significantly different from the oxidized surface of the matrix metal or alloy, making it difficult to wet, and because it is brittle compared to the matrix, a small amount of it is supplied from the dispersed particles to the interface with the glass surface at the time of molding. It is considered that this acts as a lubricant.

【0024】また、本発明の分散被膜は、高温下での機
械的強度がこれまでの被膜より向上する。その理由は必
ずしも明確ではないが、上記の分散粒子が金属中に分散
固定されることにより、高温下でのマトリックスの変形
が抑制されること、および分散粒子による微細な凹凸の
作用や分散粒子のマトリックスと比較した熱伝導率の低
さにより、溶融ガラスとの熱接触、熱伝導が軽減され、
金型の温度上昇が実質的に抑制されるためと考えられ
る。
Further, the dispersion coating of the present invention has improved mechanical strength at high temperatures as compared with conventional coatings. Although the reason is not necessarily clear, the above-mentioned dispersed particles are dispersed and fixed in the metal, whereby the deformation of the matrix at high temperatures is suppressed, and the action of fine irregularities due to the dispersed particles and the dispersion particles are prevented. Due to the lower thermal conductivity compared to the matrix, thermal contact with the molten glass, heat conduction is reduced,
It is considered that the temperature rise of the mold is substantially suppressed.

【0025】[0025]

【実施例】以下に本発明の実施例(例1、例2)および
比較例(例3、例4)を示すが、本発明はこれらに限定
されない。これらの例は、図1に示すブラウン管パネル
成形用の金型(プランジャ)を用いて行った。図の1は
基体、2は金型側面、3はパネルのフェース部成形面
で、これら2および3が成形面である。
Examples Examples of the present invention (Examples 1 and 2) and comparative examples (Examples 3 and 4) are shown below, but the present invention is not limited to these. These examples were performed using a mold (plunger) for forming a CRT panel shown in FIG. In the figure, 1 is a substrate, 2 is a mold side surface, 3 is a face forming surface of a panel, and these 2 and 3 are forming surfaces.

【0026】(例1)SUS420J2(JIS−G4
303)基体の全表面に、硫酸クロムをその主要成分と
して含む水溶液を用いて膜厚10μmのクロムめっき被
膜を形成した後に、ニッケルワット浴中に分散剤として
平均粒径0.3μmの窒化ホウ素を分散添加した浴を用
いて、金型側面のみにニッケルをマトリックスとし、窒
化ホウ素を20体積%を含む平均膜厚10μmの最表面
被膜を形成させた。この金型を用いてガラス成形を行
い、金型側面との接触によりガラス成形体に生じるマイ
クロクラック・微小擦り傷発生率、離型剤塗布頻度、金
型連続使用可能時間を調べた。結果を表1に示す。
(Example 1) SUS420J2 (JIS-G4
303) After forming a chromium plating film having a thickness of 10 μm on the entire surface of the substrate using an aqueous solution containing chromium sulfate as a main component, boron nitride having an average particle diameter of 0.3 μm is used as a dispersant in a nickel watt bath. Using the bath to which the dispersion was added, an outermost surface coating having an average film thickness of 10 μm and containing 20% by volume of boron nitride was formed using nickel as a matrix only on the side surfaces of the mold. Glass molding was performed using this mold, and the incidence of microcracks and micro-abrasions generated in the glass molded body due to contact with the side surface of the mold, the frequency of release agent application, and the continuous usable time of the mold were examined. Table 1 shows the results.

【0027】(例2)SUS420J2(JIS−G4
303)基体の表面に、塩化ニッケル浴を用いて1.5
μm厚のニッケル層を析出させ、その後、金型側面のみ
に分散剤として長軸の平均粒径3μmの黒鉛を添加分散
させた硫酸ニッケル、タングステン酸ナトリウム、クエ
ン酸を主成分とするめっき液から、ニッケル−タングス
テン合金(68重量%:32重量%)をマトリックスと
し黒鉛を35体積%を含む膜厚9μmの最表面被膜を形
成し、それ以外の表面に酸化クロム、酸化モリブデン、
クエン酸アンモニウム、硫酸クロムをその主要成分とし
て含む水溶液を用いて、クロム−モリブデン合金(88
重量%:12重量%)を含む膜厚9μmの最表面被膜を
形成させた。この金型を用いてガラス成形を行い、金型
側面との接触によりガラス成形体に生じるマイクロクラ
ック・微小擦り傷発生率、離型剤塗布頻度、金型連続使
用可能時間を調べた。結果を表1に示す。
(Example 2) SUS420J2 (JIS-G4
303) The surface of the substrate is 1.5
A nickel layer having a thickness of 3 μm is deposited as a dispersing agent only on the side of the mold, and then dispersed in a plating solution containing nickel sulfate, sodium tungstate, and citric acid as main components. A nickel-tungsten alloy (68% by weight: 32% by weight) is used as a matrix to form a 9 μm thick outermost film containing 35% by volume of graphite, and chromium oxide, molybdenum oxide,
Using an aqueous solution containing ammonium citrate and chromium sulfate as its main components, a chromium-molybdenum alloy (88
(% By weight: 12% by weight). Glass molding was performed using this mold, and the incidence of microcracks and micro-abrasions generated in the glass molded body due to contact with the side surface of the mold, the frequency of release agent application, and the continuous usable time of the mold were examined. Table 1 shows the results.

【0028】(例3)SUS420J2(JIS−G4
303)基体の表面に、硫酸クロムをその主要成分とし
てクロムからなる膜厚10μmの最表面被膜を形成させ
た。この金型を用いてガラス成形を行い、金型側面との
接触によりガラス成形体に生じるマイクロクラック・微
小擦り傷発生率、離型剤塗布頻度、金型連続使用可能時
間を調べた。結果を表1に示す。
(Example 3) SUS420J2 (JIS-G4
303) On the surface of the substrate, a 10 μm-thick outermost film made of chromium with chromium sulfate as its main component was formed. Glass molding was performed using this mold, and the incidence of microcracks and micro-abrasions generated in the glass molded body due to contact with the side surface of the mold, the frequency of release agent application, and the continuous usable time of the mold were examined. Table 1 shows the results.

【0029】(例4)SUS420J2(JIS−G4
303)基体の表面に、塩化ニッケル浴を用いて4μm
厚のニッケル層を析出させ、その後、硫酸ニッケル、タ
ングステン酸ナトリウム、クエン酸ナトリウムを主要成
分とする液を用いて、粉砕により長辺の平均サイズが8
μmの黒鉛粒子を10体積%分散させた膜厚11μmの
黒鉛分散ニッケル−タングステン合金(70重量%:3
0重量%)からなる最表面被膜を形成させた。この金型
を用いてガラス成形を行い、金型側面との接触によりガ
ラス成形体に生じるマイクロクラック・微小擦り傷発生
率、離型剤塗布頻度、金型連続使用可能時間を調べた。
結果を表1に示す。
(Example 4) SUS420J2 (JIS-G4
303) 4 μm on the surface of the substrate using a nickel chloride bath
A thick nickel layer is deposited, and then, a liquid having nickel sulfate, sodium tungstate, and sodium citrate as main components is crushed to reduce the average size of the long side to 8%.
11 μm-thick graphite-dispersed nickel-tungsten alloy (70 wt%: 3)
0% by weight). Glass molding was performed using this mold, and the incidence of microcracks and micro-abrasions generated in the glass molded body due to contact with the side surface of the mold, the frequency of release agent application, and the continuous usable time of the mold were examined.
Table 1 shows the results.

【0030】例1〜4において、ブラウン管パネルガラ
スとしては、重量で酸化ケイ素62.0%、酸化ナトリ
ウム7.5%、酸化カリウム8.1%、酸化ストロンチ
ウム11.6%、酸化バリウム2.2%、その他酸化ジ
ルコニウム等8.6%を含むブラウン管用ガラスを用い
た。
In Examples 1 to 4, the CRT panel glass was 62.0% by weight of silicon oxide, 7.5% by weight of sodium oxide, 8.1% by weight of potassium oxide, 11.6% by weight of strontium oxide, and 2.2% by weight of barium oxide. % And other 8.6% glass such as zirconium oxide.

【0031】表1において、金型側面でのマイクロクラ
ック、微小擦り傷発生確率、離型剤塗布頻度、金型連続
使用可能時間の各種評価については、例3を10とした
場合の相対値で示している。
In Table 1, various evaluations of the probability of occurrence of microcracks, minute scratches on the mold side surface, the frequency of release agent application, and the continuous usable time of the mold are shown by relative values when Example 3 is set to 10. ing.

【0032】[0032]

【表1】 [Table 1]

【0033】[0033]

【発明の効果】実施例からもわかるように、ステンレス
合金を基体とする金型の最表面に、6族元素からなる金
属被膜と、鉄族元素からなる、または鉄族元素を主成分
としこれと6族元素およびレニウムから選ばれる1種以
上の元素との合金からなるマトリックス中に、離型性を
発現する微粒子を分散させた金属被膜とを、金型の位置
に合わせて選択的に組み合わせ形成することにより、従
来のクロム被膜より離型性に優れ、離型剤の塗布がほと
んど不要となり、ガラス表面に傷が発生しなくなる。ま
たニッケル−タングステン被膜より高温下での機械的強
度が優れ、平滑な表面性状を長く持続させる効果が得ら
れる。これにより金型全体の耐久性を向上させ、高品質
のガラス製品を歩留りよく生産できる。
As can be seen from the examples, the outermost surface of a die made of a stainless steel alloy is coated with a metal film made of a Group 6 element and a metal film made of an iron group element or containing an iron group element as a main component. And a metal coating in which fine particles exhibiting releasability are dispersed in a matrix made of an alloy of one or more elements selected from Group 6 elements and rhenium, and selectively combined with the position of the mold. By forming the film, the release property is superior to that of the conventional chromium film, the application of the release agent is almost unnecessary, and the glass surface is not damaged. Further, the mechanical strength at high temperatures is superior to that of the nickel-tungsten coating, and the effect of maintaining a smooth surface property for a long time can be obtained. Thereby, the durability of the whole mold is improved, and high quality glass products can be produced with good yield.

【図面の簡単な説明】[Brief description of the drawings]

【図1】本発明の実施例に用いる金型の側面図。FIG. 1 is a side view of a mold used in an embodiment of the present invention.

【符号の説明】[Explanation of symbols]

1:基体 2:金型側面 3:フェース部成形面 1: Base 2: Mold side surface 3: Face molding surface

───────────────────────────────────────────────────── フロントページの続き (72)発明者 勝田 宏美 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hiromi Katsuta 1150 Hazawacho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture, Central Research Laboratory of Asahi Glass Co., Ltd.

Claims (9)

【特許請求の範囲】[Claims] 【請求項1】6族元素からなる金属被膜Aの領域と、鉄
族元素からなるまたは鉄族元素を主成分とし6族元素お
よびレニウムから選ばれる1種以上の元素との合金から
なるマトリックス中に離型性を発現する微粒子を分散さ
せた金属被膜Bの領域とを組み合わせてなる被膜層が、
ステンレス合金からなる基体の最表面に形成されている
ことを特徴とするガラス成形用金型。
1. A matrix comprising a region of a metal coating A comprising a Group 6 element and an alloy comprising an iron group element or one or more elements selected from a Group 6 element and rhenium, which contains an iron group element as a main component. A coating layer formed by combining a region of the metal coating B in which fine particles exhibiting releasability are dispersed,
A glass forming mold formed on the outermost surface of a substrate made of a stainless alloy.
【請求項2】前記金属被膜Aが、最表面のうちで金型と
ガラスとの擦れが少ない領域に形成されている請求項1
記載のガラス成形用金型。
2. The metal coating A is formed in a region of the outermost surface where friction between the mold and the glass is small.
The glass molding die according to the above.
【請求項3】前記被膜層の厚さが1〜500μmである
請求項1記載のガラス成形用金型。
3. The glass molding die according to claim 1, wherein said coating layer has a thickness of 1 to 500 μm.
【請求項4】前記微粒子がフッ化黒鉛、黒鉛、窒化ホウ
素、カーボンブラック、二硫化モリブデン、二硫化タン
グステンおよびフッ化カルシウムから選ばれる1種以上
からなる請求項1記載のガラス成形用金型。
4. The glass molding die according to claim 1, wherein said fine particles are at least one selected from graphite fluoride, graphite, boron nitride, carbon black, molybdenum disulfide, tungsten disulfide and calcium fluoride.
【請求項5】前記微粒子の平均粒径が金属被膜Bの厚さ
以下でありかつ0.001〜5μmである請求項1記載
のガラス成形用金型。
5. The glass molding die according to claim 1, wherein the average particle diameter of the fine particles is not more than the thickness of the metal coating B and is 0.001 to 5 μm.
【請求項6】前記金属被膜B中の微粒子の濃度が0.1
〜50体積%である請求項1記載のガラス成形用金型。
6. The method according to claim 1, wherein the concentration of the fine particles in the metal film B is 0.1.
The glass molding die according to claim 1, wherein the amount is from 50 to 50% by volume.
【請求項7】前記基体と前記被膜層との間に8族、9
族、10族および11族から選ばれる1種以上の元素を
主成分とする薄膜を有する請求項1記載のガラス成形用
金型。
7. Group 8 or 9 between said substrate and said coating layer.
The glass molding die according to claim 1, comprising a thin film containing one or more elements selected from Group 10, Group 11, and Group 11 as main components.
【請求項8】前記薄膜の厚さが0.1〜50μmである
請求項7記載のガラス成形用金型。
8. The glass molding die according to claim 7, wherein said thin film has a thickness of 0.1 to 50 μm.
【請求項9】前記基体がマルテンサイト系ステンレス合
金である請求項1記載のガラス成形用金型。
9. The glass forming mold according to claim 1, wherein said base is a martensitic stainless steel alloy.
JP13717297A 1997-05-27 1997-05-27 Mold for glass molding Pending JPH10330122A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP13717297A JPH10330122A (en) 1997-05-27 1997-05-27 Mold for glass molding

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP13717297A JPH10330122A (en) 1997-05-27 1997-05-27 Mold for glass molding

Publications (1)

Publication Number Publication Date
JPH10330122A true JPH10330122A (en) 1998-12-15

Family

ID=15192506

Family Applications (1)

Application Number Title Priority Date Filing Date
JP13717297A Pending JPH10330122A (en) 1997-05-27 1997-05-27 Mold for glass molding

Country Status (1)

Country Link
JP (1) JPH10330122A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006101956A1 (en) * 2005-03-16 2006-09-28 Diamond Innovations, Inc. Wear and texture coatings for components used in manufacturing glass light bulbs
US7562858B2 (en) * 2005-03-16 2009-07-21 Diamond Innovations, Inc. Wear and texture coatings for components used in manufacturing glass light bulbs
WO2015082851A1 (en) 2013-12-06 2015-06-11 Sofiplast Process for manufacturing a container made of glass

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006101956A1 (en) * 2005-03-16 2006-09-28 Diamond Innovations, Inc. Wear and texture coatings for components used in manufacturing glass light bulbs
US7562858B2 (en) * 2005-03-16 2009-07-21 Diamond Innovations, Inc. Wear and texture coatings for components used in manufacturing glass light bulbs
WO2015082851A1 (en) 2013-12-06 2015-06-11 Sofiplast Process for manufacturing a container made of glass

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