JP2515041B2 - Crystal glass tableware with low lead elution - Google Patents
Crystal glass tableware with low lead elutionInfo
- Publication number
- JP2515041B2 JP2515041B2 JP2157339A JP15733990A JP2515041B2 JP 2515041 B2 JP2515041 B2 JP 2515041B2 JP 2157339 A JP2157339 A JP 2157339A JP 15733990 A JP15733990 A JP 15733990A JP 2515041 B2 JP2515041 B2 JP 2515041B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- lead
- lead elution
- crystal glass
- amount
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0028—Compositions for glass with special properties for crystal glass, e.g. lead-free crystal glass
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、鉛溶出の少ないクリスタルガラス食器に関
するものである。TECHNICAL FIELD The present invention relates to crystal glass tableware in which lead elution is small.
（従来の技術） 例えば、高級ガラス食器などに使われる鉛クリスタル
ガラスは、例えば、英国規格において24重量％以上のPb
Oを含有することを規定されているが、通常、鉛クリス
タルガラスは、PbOの含有量が増えるほど鉛の溶出量が
多くなることが知られている。(Prior Art) For example, lead crystal glass used in high-grade glass tableware, for example, has a Pb content of 24% by weight or more according to the British standard.
Although it is specified to contain O, it is generally known that in lead crystal glass, the lead elution amount increases as the PbO content increases.
（発明が解決しようとする課題） しかし、食器用鉛クリスタルガラスでは、鉛の溶出量
の少ないことが一般的に望ましいということができるの
で、本発明者は、従来の鉛クリスタルガラスとしての特
質を保持しつつ、鉛溶出量の少ないガラス食器を提供で
きる鉛クリスタルガラス組成物、及びかかる組成物から
なるガラス器を提供することを目的として本発明をなす
に至ったものである。(Problems to be Solved by the Invention) However, in lead crystal glass for tableware, it can be said that it is generally desirable that the elution amount of lead is small. Therefore, the present inventor has identified the characteristics as conventional lead crystal glass. The present invention has been made for the purpose of providing a lead crystal glass composition capable of providing glass tableware with a small amount of lead elution while maintaining the same, and a glass container made of such a composition.
（課題を解決する手段） 上記目的を実現するための本発明の特徴は、重量％で
SiO244〜57％、Al2O30〜３％、B2O30〜２％、ZrO20〜３
％、CaO0〜3.5％、MgO0〜５％、BaO0.〜3.5％、SrO0〜
3.5％、ZnO0〜3.5％、Li2O0〜１％、Na2O0〜12.5％、K2
O0〜12.5％、PbO23〜33％、SnO20〜３％、La2O30〜３％
でかつ SnO2＋La2O3＝１〜６％ Li2O＋Na2O＋K2O＝20−｛（PbO＋CaO＋MgO＋BaO＋SrO＋
ZnO）×Ｒ｝の関係式で示されたＲの値が0.22〜0.29の
範囲である組成物を溶融して成形してなる鉛溶出の少な
いクリスタルガラス食器にある。(Means for Solving the Problems) The feature of the present invention for achieving the above-mentioned object is that the weight% is
SiO 2 44 to 57%, Al 2 O 3 to 3%, B 2 O 3 0 to 2%, ZrO 2 0 to 3
%, CaO0-3.5%, MgO0-5%, BaO0-3.5%, SrO0-
3.5%, ZnO0~3.5%, Li 2 O0~1%, Na 2 O0~12.5%, K 2
O0~12.5%, PbO23~33%, SnO 2 0~3%, La 2 O 3 0~3%
And SnO 2 + La 2 O 3 = 1-6% Li 2 O + Na 2 O + K 2 O = 20-{(PbO + CaO + MgO + BaO + SrO +
ZnO) × R}, which is a crystal glass tableware with little lead elution formed by melting and molding a composition having an R value in the range of 0.22 to 0.29.
本発明においてガラスの組成範囲の上記の範囲に限定
して理由は、次のとおりである。In the present invention, the reason for limiting the glass composition range to the above range is as follows.
まず基礎ガラス組成中SiO2は、44％未満では、化学的
耐久性が下がり、鉛溶出量が増加する。57％を越えると
溶融ガラスの粘性が増加すると共に失透の発生傾向も高
くなる。First, if the SiO 2 content in the basic glass composition is less than 44%, the chemical durability will decrease and the lead elution amount will increase. If it exceeds 57%, the viscosity of the molten glass increases and the tendency of devitrification to occur also increases.
Al2O3とZrO2は、ガラスの耐失透性と化学的耐久性を
向上させるが、いずれも３％を越えると溶融ガラスの粘
性を増大させて好ましくない。Al 2 O 3 and ZrO 2 improve the devitrification resistance and chemical durability of the glass, but if both exceed 3%, the viscosity of the molten glass increases, which is not preferable.
B2O3はガラスの高温粘性を下げ有効であるが、２％を
越えるとB2O3の揮発により脈理ができやすくなる。B 2 O 3 is effective in lowering the high temperature viscosity of the glass, but if it exceeds 2%, striations are likely to occur due to volatilization of B 2 O 3 .
Li2O,Na2O,K2Oはガラス溶融の融剤として効果があ
り、このうちのLi2Oは、少量でその効果が表われるので
０〜１％とすることが適当である。Li 2 O, Na 2 O, and K 2 O are effective as a flux for melting glass, and Li 2 O among them exhibits its effect even in a small amount, so it is suitable to be 0 to 1%.
CaO,MgO,BaO,SrO,ZnOは、いずれも基礎ガラスの特性
を調整用として添加されるもので、このうちCaOは溶融
温度を低下させるのに有効であるが、含有量が多くなる
と熱膨張率を高めると共にガラスの乳白化現象を促進す
る。MgOは作業温度範囲の粘性曲線をゆるやかにし、そ
の添加により作業性のよいガラスが得られるが、含有量
が多くなると溶融温度を上昇させる傾向が大きくなる。
BaOは高温でのガラスの粘性を下げるが、含有量が多く
なると転移温度、軟化温度を上昇させるため、作業温度
範囲のせまい、作業性の劣るガラスとなる。SrOはフラ
ックスとして働きガラスの溶融性を高め有効であるが、
含有量が多くなると、鉛溶出量が増加する。ZnOは粘性
温度曲線をゆるやかにし成形性を向上させ有効である
が、含有量が多くなると鉛溶出量が増加する。CaO, MgO, BaO, SrO, ZnO are all added for adjusting the characteristics of the basic glass. Of these, CaO is effective in lowering the melting temperature, but when the content increases, thermal expansion It increases the rate and promotes the opalification phenomenon of glass. MgO makes the viscosity curve in the working temperature range gentle, and the addition of MgO makes it possible to obtain glass with good workability. However, as the content increases, the tendency to raise the melting temperature increases.
BaO lowers the viscosity of glass at high temperatures, but when its content increases, it raises the transition temperature and the softening temperature, so the working temperature range is narrow and the glass becomes inferior in workability. SrO acts as a flux and is effective in increasing the meltability of glass,
As the content increases, the lead elution amount increases. ZnO is effective in making the viscosity temperature curve gentle and improving the formability, but the lead elution amount increases as the content increases.
これらの理由から、CaO,MgO,BaO,SrO,ZnOは、共に基
礎ガラスの特性の調整用として使用されるのでCaO,BaO,
SrO,ZnOは3.5％、MgOは５％以下とされることがよい。For these reasons, CaO, MgO, BaO, SrO, ZnO are both used for adjusting the properties of the basic glass, so CaO, BaO,
It is preferable that SrO and ZnO be 3.5% and MgO be 5% or less.
PbOは、23％未満ではガラスの屈折率があまり高くな
らず、輝きが不足し、反対に33％を越えると溶融時の揮
発により、脈理、石及び失透の発生が多くなる問題を招
くので上記範囲とされる。When the content of PbO is less than 23%, the refractive index of the glass is not so high that the brightness is insufficient, and when it exceeds 33%, volatilization during melting causes striae, stones and devitrification. Therefore, the above range is set.
SnO2＋La2O3は、１％未満では鉛溶出量を減少させる
能力が小さく、また６％を越えると鉛溶出量を減少させ
る能力が低下するが、SnO2は、単独で３％を越えた場
合、ガラス中への溶解性が悪いため鉛溶出減少の効果が
得られない。またLa2O3は、単独で３％を越えると鉛溶
出量を減少させる能力が低下する。If SnO 2 + La 2 O 3 is less than 1%, the ability to reduce the amount of lead elution is small, and if it exceeds 6%, the ability to reduce the amount of lead elution decreases, but SnO 2 alone exceeds 3%. In such a case, the effect of reducing the elution of lead cannot be obtained because the solubility in glass is poor. Further, when La 2 O 3 alone exceeds 3%, the ability to reduce the amount of lead eluted decreases.
本発明のガラス組成物は、上記各成分の限定に加え、
更にLi2O＋Na2O＋K2O＝20−｛（PbO＋CaO＋MgO＋BaO＋S
rO＋ZnO）×Ｒ｝の式におけるＲを、0.22〜0.29とする
ことによって初めて本発明の目的を達成することができ
る。The glass composition of the present invention, in addition to the limitations of the above components,
Furthermore, Li 2 O + Na 2 O + K 2 O = 20-{(PbO + CaO + MgO + BaO + S
The object of the present invention can be achieved only by setting R in the formula of rO + ZnO) × R} to 0.22 to 0.29.
PbO及びアルカリ土類金属及びZnOの総量に対するアル
カリ金属の添加量が上記の如く限定されるのは、Ｒ＝0.
29を越えるとLi2O＋Na2O＋K2Oの合計量が少なく、失透
が発生しやすく、0.22に満たないとLi2O＋Na2O＋K2Oの
合計量が多くなり、鉛溶出量が増加するからである。こ
れらのことはガラス食器から溶出する鉛量を減少させる
という問題に着目し本発明者の種々の研究の結果に基づ
くものであり、特に、酸化錫および／又は酸化ランタン
を添加することにより、ガラスからの鉛溶出量が減少す
るという知見に関連して見いだされたものである。The amount of alkali metal added to the total amount of PbO and alkaline earth metals and ZnO is limited as described above, R = 0.
If it exceeds 29, the total amount of Li 2 O + Na 2 O + K 2 O is small and devitrification is likely to occur. If it is less than 0.22, the total amount of Li 2 O + Na 2 O + K 2 O increases and the lead elution amount increases. Is. These are based on the results of various studies conducted by the present inventor, focusing on the problem of reducing the amount of lead eluted from glass tableware. In particular, the addition of tin oxide and / or lanthanum oxide makes glass It was found in connection with the finding that the amount of lead leached from aluminum decreases.
なお本発明の組成物において、SiO2＋Al2O3＋B2O3＋Z
rO2の合計は、48％〜58％とすることが好ましい。48％
未満では鉛溶出量が増加し、58％を越えると溶融が困難
となるからである。In the composition of the present invention, SiO 2 + Al 2 O 3 + B 2 O 3 + Z
The total amount of rO 2 is preferably 48% to 58%. 48%
If it is less than 50%, the amount of lead elution increases, and if it exceeds 58%, melting becomes difficult.
また本発明の組成物は、上記以外に清澄剤としてSO3,
As2O3,Sb2O3、着色剤としてCoO,NiO,Er2O3等の金属酸化
物を含んでもよい。Further, the composition of the present invention, in addition to the above, SO 3 as a fining agent,
As 2 O 3 , Sb 2 O 3 and a colorant may include a metal oxide such as CoO, NiO, Er 2 O 3 .
本発明のガラス組成物は、常法に従ってガラス原料を
溶融し、ガラスゴブを切り出して機械成形又は手吹き等
の成形加工を行うことによってガラス器を製造すること
ができる。The glass composition of the present invention can be manufactured into a glass container by melting a glass raw material according to a conventional method, cutting out a glass gob, and performing a molding process such as mechanical molding or hand blowing.
（発明の効果） 本発明により得られるクリスタルガラス食器の製品
は、色調は一般鉛クリスタルガラス食器と同程度の透明
度を有している。特に、本発明よりなるガラス器は、当
社の従来の鉛クリスタルガラス器と比較して鉛溶出量の
少ない性質を示すものでその有用性は大である。(Effect of the Invention) The product of the crystal glass tableware obtained by the present invention has the same degree of transparency as the color tone of general lead crystal glass tableware. In particular, the glassware according to the present invention has a property of less lead elution than the conventional lead crystal glassware of the present invention, and its utility is great.
（発明の実施例） 以下実施例について説明する。(Examples of the Invention) Examples will be described below.
実施例１ 珪砂、水酸化アルミニウム、硼砂、酸化ジルコニウ
ム、炭酸カルシウム、水酸化マグネシウム、炭酸ストロ
ンチウム、炭酸カリウム、酸化鉛、酸化ランタン、酸化
スズ、酸化アンチモンを原料として表１の資料番号Ｉ〜
XIXの組成を満足するバッチを夫々調合した後、各々の
バッチを連帯式坩堝炉に入れ、1450℃の温度で８時間溶
融した。得られた溶融ガラスを吹き竿で巻き取って通常
用いられている金型で吹き込み成形し、成形後、直ちに
成形品を徐冷炉により最高温度450〜500℃で徐冷した。
製造工程における歩留まりも良好であった。Example 1 Quartz sand, aluminum hydroxide, borax, zirconium oxide, calcium carbonate, magnesium hydroxide, strontium carbonate, potassium carbonate, lead oxide, lanthanum oxide, tin oxide, and antimony oxide are used as raw materials, and the material number I to Table 1 is used.
After preparing each batch satisfying the composition of XIX, each batch was put into a solid-state crucible furnace and melted at a temperature of 1450 ° C. for 8 hours. The obtained molten glass was wound up with a blowing rod and blow-molded by a commonly used mold. Immediately after molding, the molded product was annealed at a maximum temperature of 450 to 500 ° C. in an annealing furnace.
The yield in the manufacturing process was also good.
実施例２ 表１のＩ〜XIX組成から得られたガラスすべてについ
て、鉛溶出量を測定し、その結果を表１中に示した。Example 2 The lead elution amount was measured for all the glasses obtained from the compositions I to XIX in Table 1, and the results are shown in Table 1.
鉛溶出量の測定は以下によった。 The lead elution amount was measured as follows.
JIS R3502−1958に規定されているアルカリ溶出試験
に準じた方法により、ガラスを粉砕し、JIS Z8801の標
準網フルイ420μを通過し、250μにとどまる大きさのガ
ラス粉末の比重と同じｇ数を４％酢酸50ml中で１時間煮
沸した。鉛溶出量の定量は原子吸光分析装置（島津製作
所製AA−640−12）を使用し、結果は溶出液全体に含ま
れるPbmg数に換算して表わした。By the method according to the alkali elution test stipulated in JIS R3502-1958, the glass is crushed, passed through the JIS Z8801 standard mesh sieve 420μ, and the same g number as the specific gravity of the glass powder of 250μ is 4 Boiled in 50 ml% acetic acid for 1 hour. The lead elution amount was quantified using an atomic absorption spectrometer (AA-640-12 manufactured by Shimadzu Corporation), and the result was expressed in terms of the Pbmg number contained in the entire eluate.
これによれば、Ｒ値はすべて0.22〜0.29の範囲にあ
り、鉛溶出量は、当社の代表的な鉛クリスタルガラスの
鉛溶出量と比較して約1/2以下であった。According to this, the R values were all in the range of 0.22 to 0.29, and the lead elution amount was about 1/2 or less compared to the lead elution amount of our typical lead crystal glass.
比較例１ 表２に示す酸化錫および／または酸化ランタンを含有
しない組成の鉛クリスタルガラスのガラス器を常法によ
り製造し、その鉛溶出量を上記実施例と同様にして測定
し、その結果を表２中に示した。 Comparative Example 1 A glass container of lead crystal glass having a composition not containing tin oxide and / or lanthanum oxide shown in Table 2 was manufactured by a conventional method, and the lead elution amount thereof was measured in the same manner as in the above-mentioned example, and the result was obtained. The results are shown in Table 2.
Claims (1)
％、CaO0〜3.5％、MgO0〜５％、BaO0〜3.5、SrO0〜3.5
％、ZnO0〜3.5％、Li2O0〜１％、Na2O0〜12.5％、K2O0
〜12.5％、PbO23〜33％、SnO20〜３％、La2O30〜３％で かつ SnO2＋La2O3＝１〜６％ Li2O＋Na2O＋K2O＝20−｛（PbO＋CaO＋MgO＋BaO ＋SrO＋ZnO）×Ｒ｝ の関係式で示されたＲの値が0.22〜0.29の範囲である組
成物を溶融して成形してなることを特徴とする鉛溶出の
少ないクリスタルガラス食器。1. By weight%, SiO 2 44-57%, Al 2 O 3 0-3%, B 2 O 3 0-2%, ZrO 2 0-3.
%, CaO0-3.5%, MgO0-5%, BaO0-3.5, SrO0-3.5
%, ZnO0~3.5%, Li 2 O0~1 %, Na 2 O0~12.5%, K 2 O0
~12.5%, PbO23~33%, SnO 2 0~3%, La 2 O 3 0~3% a and SnO 2 + La 2 O 3 = 1~6% Li 2 O + Na 2 O + K 2 O = 20 - {(PbO + CaO + MgO + BaO + SrO + ZnO) × R} A crystal glass tableware with less lead elution characterized by being formed by melting a composition having an R value in the range of 0.22 to 0.29 shown by the relational expression.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2157339A JP2515041B2 (en) | 1990-06-15 | 1990-06-15 | Crystal glass tableware with low lead elution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2157339A JP2515041B2 (en) | 1990-06-15 | 1990-06-15 | Crystal glass tableware with low lead elution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0450133A JPH0450133A (en) | 1992-02-19 |
| JP2515041B2 true JP2515041B2 (en) | 1996-07-10 |
Family
ID=15647530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2157339A Expired - Lifetime JP2515041B2 (en) | 1990-06-15 | 1990-06-15 | Crystal glass tableware with low lead elution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2515041B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2906104B2 (en) * | 1992-10-20 | 1999-06-14 | 東洋ガラス 株式会社 | Lead-free crystal glass composition |
| ATE199082T1 (en) * | 1997-06-09 | 2001-02-15 | Swarovski & Co | GLASS COMPOSITION |
| KR101133480B1 (en) * | 2007-04-17 | 2012-04-10 | 아사히 가라스 가부시키가이샤 | Method for producing alkali?free glass |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4582760A (en) * | 1985-05-20 | 1986-04-15 | Corning Glass Works | Glazes for glass-ceramic articles |
-
1990
- 1990-06-15 JP JP2157339A patent/JP2515041B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0450133A (en) | 1992-02-19 |
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