JP2009046320A5

JP2009046320A5 -

Info

Publication number: JP2009046320A5
Application number: JP2007210978A
Authority: JP
Filing date: 2007-08-13
Publication date: 2010-05-20
Anticipated expiration: 2027-08-13

Description

本発明の光学ガラス素子成形型は、耐熱性、耐酸化性が高い母材と、前記母材のガラス成形面に形成された中間層であって、Ｚｒ、Ｔｉ、Ｖ、Ｃｒ、Ｍｏ、Ｎｂ、Ｐｄ及びＡｕからなる群より選ばれた少なくとも一種、または、これらの合金からなる中間層と、前記中間層の上に形成された、Ｒｕ、Ｒｈ、Ｐｄ、Ｒｅ及びＡｕからなる群より選ばれた少なくとも一種と、Ｉｒ、Ｐｔからなる群より選ばれた少なくとも一種と、Ｗ、Ｍｏからなる群より選ばれた少なくとも一種との合金からなる保護膜と、からなることを特徴とするものである。 The optical glass element molding die of the present invention is a base material having high heat resistance and oxidation resistance, and an intermediate layer formed on the glass molding surface of the base material, and includes Zr, Ti, V, Cr, Mo, Nb At least one selected from the group consisting of Pd and Au, or an intermediate layer made of these alloys , and selected from the group consisting of Ru, Rh, Pd, Re and Au formed on the intermediate layer And a protective film made of an alloy of at least one selected from the group consisting of Ir and Pt and at least one selected from the group consisting of W and Mo. .

また、本発明の光学ガラス素子成形型の好適例としては、中間層の厚さが０．０５〜２μｍであること、保護膜が、Ｗ、Ｍｏからなる群より選ばれた少なくとも一種を１〜６０重量％含有すること、Ｉｒ、Ｐｔからなる群より選ばれた少なくとも一種を２０〜８０重量％含有していること、Ｒｕ、Ｒｈ、Ｐｄ、Ｒｅ及びＡｕからなる群より選ばれた少なくとも一種を１０〜４０重量％含有していること、保護膜の膜厚が、０．０５〜１０μｍであること、がある。 At least one preferred examples of the optical glass element forming die of the present invention, the thickness of the intermediate layer is 0.05 to 2 [mu] m, coercive Mamorumaku is, the W, selected from M o or Ranaru group in that it contains 1 to 60 wt%, that are at least containing one of 20 to 80 wt% selected from the group consisting of I r, Pt, selected from the group consisting of R u, Rh, Pd, Re and Au 10 to 40% by weight of at least one of the above, and the thickness of the protective film may be 0.05 to 10 μm.

本発明者は、ガラス成形面に保護膜が設けられた光学ガラス素子の成形時における保護膜の組成について鋭意検討をした結果、中間層を設け、さらに中間層がＺｒ、Ｔｉ、Ｖ、Ｃｒ、Ｍｏ、Ｎｂ、Ｐｂ及びＡｕからなる群より選ばれた少なくとも一種、または、これらの合金からなり、Ｒｕ、Ｒｈ、Ｐｄ、ＲｅおよびＡｕからなる群より選ばれた少なくとも一種と、Ｉｒ、Ｐｔからなる群より選ばれた少なくとも一種と、Ｗ、Ｍｏからなる群より選ばれた少なくとも一種との合金からなる保護膜を用いたところ、例えばリン酸塩ガラスからなるガラス素子の成形を行った場合にもリン酸塩ガラスが成形面に付着しにくいのみならず、ガラス素子の成形時において発生するＨ_２Ｏなどの揮発物による保護膜の劣化、及び変色が効果的に抑制できるとの知見を得た。 As a result of intensive studies on the composition of the protective film at the time of molding the optical glass element having a protective film provided on the glass molding surface, the present inventor has provided an intermediate layer, and the intermediate layer is further composed of Zr, Ti, V, Cr, At least one selected from the group consisting of Mo, Nb, Pb and Au, or an alloy thereof, and at least one selected from the group consisting of Ru , Rh, Pd, Re and Au, and Ir and Pt. and at least one selected from the group consisting went W, was used a protective film made of an alloy of at least one selected from M o or Ranaru group, for example the molding of a glass element consisting of phosphate glass Even in this case, phosphate glass is not only difficult to adhere to the molding surface, but also effectively prevents deterioration and discoloration of the protective film due to volatiles such as H ₂ O generated during molding of the glass element. I got the knowledge that I can do it.

保護膜５は、Ｒｕ、Ｒｈ、Ｐｄ、Ｒｅ及びＡｕからなる群より選ばれた少なくとも一種と、Ｉｒ、Ｐｔからなる群より選ばれた少なくとも一種と、Ｗ、Ｍｏからなる群より選ばれた少なくとも一種との合金からなる。 Protective film 5, Ru, Rh, Pd, and at least one selected from the group consisting of Re and Au, Ir, and at least one selected from the group consisting of Pt, W, selected from M o or Ranaru group And at least one kind of alloy.

Ｗ、Ｍｏからなる群から選ばれた少なくとも一種の含有量は、１〜６０重量％、好ましくは２〜４０重量％とする。何れかの含有量が１重量％よりも少なくても、また、６０重量％より多すぎても、成形時のガラス加熱により発生するＨ_２Ｏ等の揮発物による膜劣化や変色の抑制効果が得られない。 W, the content of at least one selected from M o or Ranaru group, 1 to 60 wt%, preferably 2 to 40 wt%. Even if any content is less than 1% by weight or more than 60% by weight, the effect of suppressing film deterioration and discoloration by volatiles such as H ₂ O generated by glass heating at the time of molding can be obtained. I can't get it.

中間層４、保護膜５の形成方法としては、特に制限されず種々の方法が採用できるが、例えば、Ｒｕ、Ｒｈ、Ｐｄ、Ｒｅ及びＡｕからなる群より選ばれた少なくとも一種と、Ｉｒ、Ｐｔからなる群から選ばれた少なくとも一種と、Ｗ、Ｍｏからなる群より選ばれた少なくとも一種との各金属粉末を焼結してターゲットを作成し、スパッタリングする方法、１つの構成成分の金属からなるターゲットの上に他の成分チップを配置し、スパッタリングする方法、イオンプレーティング法などを採用することができる。中間層４、保護膜５の組成は、例えば、スパッタリングする方法による場合にはターゲットを調製する際の原料となる各金属粉末の配合比によって調整し、オンチップの場合はチップ数量を所望の数量に変更することによって調整することができる。 The method for forming the intermediate layer 4 and the protective film 5 is not particularly limited, and various methods can be adopted. For example, at least one selected from the group consisting of Ru, Rh, Pd, Re, and Au, Ir, Pt At least the one selected from the group consisting of, W, M o or each metal powder of at least the one selected from Ranaru group sintered to create a target, a method of sputtering, of one constituent metal It is possible to employ a sputtering method, an ion plating method, or the like by disposing another component chip on a target made of The composition of the intermediate layer 4 and the protective film 5 is adjusted by, for example, the blending ratio of each metal powder used as a raw material when preparing the target in the case of sputtering, and in the case of on-chip, the number of chips is a desired number. It can be adjusted by changing to

＜実施例１〜１０＞
直径１２ｍｍの超硬合金（ＷＣ９９wt％、残りＣｏ及び不可避成分）からなるガラス成形型基材を、それぞれ曲率半径１０ｍｍ（ガラス成形型基材３）および２０ｍｍ（ガラス成形型基材２）の凹面に加工し、０．５μｍ粒度のダイヤモンドペーストにより研磨し、成形面を鏡面とした。これにより上下一対のガラス成形型基材２、３を作製した。
一方、以下の表１に示す実施例１〜１０のコーティング組成でそれぞれ焼結または溶解加工した保護膜形成用のターゲットを作製し、さらに以下の表１の中間層の組成でそれぞれ焼結または溶解加工した中間層形成用の金属ターゲットを準備した。次に、前記のようにして作製した上下一対の光学ガラス素子成形型基材２、３をスパッタ装置にセットし、中間層形成用の金属ターゲットを用いてガラス成形型基材２、３のそれぞれの成形面に０．５μｍ厚みの中間層４を形成し、さらに前記組成で焼結した保護膜形成用のターゲットを用いて中間層４の表面に図１に示す保護膜５を２μｍ厚みで形成することにより、実施例１〜１０の光学ガラス素子成形型を製造した。 <Examples 1 to 10 >
A glass mold base made of a cemented carbide (WC 99 wt%, remaining Co and inevitable components) having a diameter of 12 mm is formed on the concave surfaces having a curvature radius of 10 mm (glass mold base 3) and 20 mm (glass mold base 2), respectively. The processed surface was polished with a diamond paste having a particle size of 0.5 μm, and the molding surface was a mirror surface. Thus, a pair of upper and lower glass mold bases 2 and 3 were produced.
On the other hand, targets for forming a protective film were prepared by sintering or dissolution processing with the coating compositions of Examples 1 to 10 shown in Table 1 below, and further sintered or dissolved with the composition of the intermediate layer in Table 1 below. A processed metal target for forming an intermediate layer was prepared. Next, the pair of upper and lower optical glass element forming mold bases 2 and 3 produced as described above are set in a sputtering apparatus, and each of the glass forming mold bases 2 and 3 is used using a metal target for forming an intermediate layer. An intermediate layer 4 having a thickness of 0.5 μm is formed on the molding surface, and a protective film 5 shown in FIG. 1 is formed to a thickness of 2 μm on the surface of the intermediate layer 4 using a protective film-forming target sintered with the above composition. By doing this, the optical glass element shaping | molding die of Examples 1-10 was manufactured.

前記のようにして製造した実施例１〜１０の光学ガラス素子成形型を用いて、リン酸系高融点ガラスＫ−ＰＳＫＦｎ１｛商品名、住田光学製、屈折率（ｎｄ）：１．９０６８、アッベ数（νｄ）：２１．２、転移点（Ｔｇ）：４９８℃、屈伏点（Ａｔ）：５４３℃｝を直径７ｍｍのボールプリフォームに加工したプリフォームを原料とし、図２に示す成形機を用いて光学ガラスレンズを下記の要領で成形した。
なお、図２において、１０はチャンバーで、内部にヒータ１１が円筒体状にセットされ、該円筒体状ヒータ１１の内側に下軸１２と、チャンバー１０の天部外側に設けられているエアーシリンダー１４に連結された上軸１３とがセットされ、該上下軸１３、１２の各々の成形面に保護膜５が積層された光学ガラス素子成形型基材２、３を夫々固定し、上型、及び下型としている。 Using the optical glass element molds of Examples 1 to 10 manufactured as described above, phosphate-based high melting point glass K-PSKFn1 {trade name, manufactured by Sumita Optical Co., Ltd., refractive index (nd): 1.068, Abbe The molding machine shown in FIG. 2 is made using a preform obtained by processing a number (νd): 21.2, a transition point (Tg): 498 ° C., and a yield point (At): 543 ° C.} into a ball preform having a diameter of 7 mm. The optical glass lens was molded in the following manner.
In FIG. 2, reference numeral 10 denotes a chamber, in which a heater 11 is set in a cylindrical shape, and a lower shaft 12 is provided inside the cylindrical heater 11 and an air cylinder provided outside the top of the chamber 10. The upper glass 13 connected to the upper shaft 13 is set, and the optical glass element forming mold bases 2 and 3 each having the protective film 5 laminated on the molding surfaces of the upper and lower shafts 13 and 12 are fixed, respectively. And the lower mold.

この成形機の上型と下型の間に、前記のボールプリフォームを配置し、チャンバー１０内に窒素を１０Ｌ／分で注入しつつ、該チャンバー１０内を５５５℃に加熱し、３０００Ｎの荷重でプレス成形した。プレス終了後、２５０℃の温度まで冷却し、成形品であるレンズを取り出した。
これを３０００回行ったときの、実施例１〜１０の上型の光学ガラス素子成形型基材２、および下型の光学ガラス素子成形型基材３の各保護膜５面へのガラスの付着と、劣化並びに変色を目視により確認されなかった。
なお、評価において、「劣化」とは離型性や耐熱性等の本来保護膜５に必要とされる性能を有さなくなった場合や、該保護膜５に変色が認められ本来保護膜５に必要とされる性能は未だ保持しているが変色した場合をいう。
結果を以下の表１に示す。 The ball preform is placed between the upper mold and the lower mold of the molding machine, and nitrogen is injected into the chamber 10 at a rate of 10 L / min, while the chamber 10 is heated to 555 ° C. and a load of 3000 N And press-molded. After the press, the product was cooled to a temperature of 250 ° C., and the lens as a molded product was taken out.
When this is performed 3000 times, glass adheres to the protective film 5 surfaces of the upper optical glass element mold base material 2 of Examples 1 to 10 and the lower optical glass element mold base material 3 And deterioration and discoloration were not confirmed visually.
In the evaluation, “deterioration” means that the protective film 5 does not have the performance required for the original protective film 5 such as releasability and heat resistance, or the protective film 5 is discolored and is inherently in the protective film 5. This refers to the case where the required performance is still maintained but the color is changed.
The results are shown in Table 1 below.

＜比較例１〜２＞
表１に示す比較例１〜２の組成比でそれぞれ焼結したターゲットを作成し、実施例１〜１０のようにして作製した上下一対の光学ガラス素子成形型基材２、３をスパッタ装置にセットし、ガラス成形型基材２、３のそれぞれの成形面に前記組成のターゲットを用いて、中間層４を設けずに図１に示す保護膜５を２μｍ厚みで成形することにより、比較例１〜２の光学ガラス素子成形型を製造した。 <Comparative Examples 1 and 2 >
The targets sintered respectively in the composition ratios of Comparative Examples 1 and 2 shown in Table 1 were prepared, and a pair of upper and lower optical glass element mold base materials 2 and 3 prepared as in Examples 1 to 10 were used as a sputtering apparatus. A comparative example is obtained by setting the protective film 5 shown in FIG. 1 to a thickness of 2 μm without providing the intermediate layer 4 using the target having the above composition on each molding surface of the glass mold bases 2 and 3. 1-2 optical glass element molds were produced.

前記実施例１〜１０と同様にプレス成形を行うと、１５００回迄に成形型の成形面へのガラスの付着や成形面保護膜へのガラス付着や保護膜の劣化が認められた。
結果を以下の表１に示す。 When press molding was performed in the same manner as in Examples 1 to 10 , glass adhesion to the molding surface of the molding die, glass adhesion to the molding surface protective film, and deterioration of the protective film were observed up to 1500 times.
The results are shown in Table 1 below.

Claims

A base material having high heat resistance and oxidation resistance and an intermediate layer formed on the glass molding surface of the base material, selected from the group consisting of Zr, Ti, V, Cr, Mo, Nb, Pd and Au. And at least one selected from the group consisting of Ru, Rh, Pd, Re and Au formed on the intermediate layer, and an intermediate layer made of these alloys , and Ir and Pt. An optical glass element molding die comprising: a protective film made of an alloy of at least one selected from the group and at least one selected from the group consisting of W and Mo.

Said protective film, W, optical glass element molding die according to claim 1, characterized in that it contains at least one 1 to 60 wt% selected from M o or Ranaru group.

The optical glass element molding die according to claim 1 or 2 , wherein the protective film contains 20 to 80% by weight of at least one selected from the group consisting of Ir and Pt.

The said protective film contains 10 to 40weight% of at least 1 type chosen from the group which consists of Ru, Rh, Pd, Re, and Au, The any one of Claims 1-3 characterized by the above-mentioned. Optical glass element molding die.