JP2000185936A - Lead-free low-melting point glass composition for cement product - Google Patents
Lead-free low-melting point glass composition for cement productInfo
- Publication number
- JP2000185936A JP2000185936A JP10363315A JP36331598A JP2000185936A JP 2000185936 A JP2000185936 A JP 2000185936A JP 10363315 A JP10363315 A JP 10363315A JP 36331598 A JP36331598 A JP 36331598A JP 2000185936 A JP2000185936 A JP 2000185936A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- glass composition
- lead
- glaze
- free low
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 239000004568 cement Substances 0.000 title claims abstract description 27
- 238000002844 melting Methods 0.000 title claims abstract description 16
- 239000011521 glass Substances 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010304 firing Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims 1
- 230000006866 deterioration Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract 3
- 150000001875 compounds Chemical class 0.000 abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000006253 efflorescence Methods 0.000 description 6
- 206010037844 rash Diseases 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- -1 O or SrO Chemical class 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 102100031083 Uteroglobin Human genes 0.000 description 1
- 108090000203 Uteroglobin Proteins 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Landscapes
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、低温焼成したセメ
ント製品の表面状態を改質するための釉薬に使用する鉛
を含まない低融点ガラス組成物、いわゆるフリット組成
物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-melting glass composition containing no lead, which is used as a glaze for modifying the surface condition of a low-temperature calcined cement product, a so-called frit composition.
【０００２】[0002]
【従来の技術】近年、粘土資源の枯渇に伴い、陶磁器の
代替品として焼成セメント製品が出現した。この焼成セ
メント製品は、焼成中、セメント中の結晶水が失われる
ことになり、焼成直後に機械的強度が失われハンドリン
グ性を失うばかりではなく、欠けを生じやすく、また、
養生期間中に白華を生じやすく、表面状態が荒れてしま
う。このため、焼成前のセメント製品に釉薬を施して、
焼成によるこのような問題を解消する手当が行われてき
た。2. Description of the Related Art In recent years, with the depletion of clay resources, calcined cement products have emerged as substitutes for ceramics. This calcined cement product loses crystal water in the cement during calcining, not only loses mechanical strength immediately after calcining and loses handling properties, but also tends to chip,
During the curing period, efflorescence easily occurs, and the surface condition becomes rough. For this reason, glaze is applied to the cement product before firing,
Attempts have been made to eliminate such problems due to firing.
【０００３】従来から、このための釉薬組成物として、
鉛系あるいはリン酸系の釉薬が用いられてきたが、これ
らは、元来が比較的低温焼成物のためのものであるた
め、セメント製品のように６５０℃以上の温度での焼成
では、耐候性、耐薬品性に劣り、また、野外で使用され
る製品に適用した場合には、光沢が失われてしまうとい
う欠点があった。[0003] Conventionally, as a glaze composition for this purpose,
Lead-based or phosphoric acid-based glazes have been used, but since these are originally intended for relatively low-temperature fired products, when fired at a temperature of 650 ° C. or more, such as cement products, they are resistant to weathering. Inferior in properties and chemical resistance, and when applied to products used outdoors, there is a drawback that gloss is lost.
【０００４】このような従来の釉薬組成物の欠点を解消
して、セメント製品の釉薬に適した組成物として、より
高温の焼成温度に耐えられるように、ＳｉＯ2を主体と
し、Ａｌ2Ｏ3その他を加え、ＳｉＯ2とＡｌ2Ｏ3との量
調整を行った組成物が特公平６−４８４６４号公報、特
公平４−３２０２２号公報等に開示されている。[0004] As a composition suitable for glazes of cement products, it is mainly composed of SiO 2 and Al 2 O 3 so as to be able to withstand higher firing temperatures as a composition suitable for glazes of cement products. In addition to the above, compositions in which the amounts of SiO 2 and Al 2 O 3 are adjusted are disclosed in JP-B-6-48464, JP-B-4-32022 and the like.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これら
の高温の焼成用の釉薬組成物は、専ら、焼成後、表面に
形成された釉薬の耐候性を重視したものであるため、実
際には、釉薬としての表面状態を形成させるためには、
焼成温度を８５０℃以上の高温にせざるを得ないもので
ある。そのため、その基材であるセメントの焼成後の劣
化は著しく、そのため、焼成直後の強度の低下によるハ
ンドリングの悪さ、白華の発生による見苦しさ等は避け
られなかった。However, these glaze compositions for firing at a high temperature mainly focus on the weather resistance of the glaze formed on the surface after firing, so that the glaze composition is actually In order to form the surface state as
The sintering temperature must be 850 ° C. or higher. Therefore, the deterioration of the cement, which is the base material, after firing is remarkable. Therefore, poor handling due to a decrease in strength immediately after firing, unsightlyness due to occurrence of efflorescence, and the like cannot be avoided.
【０００６】本発明が解決すべき課題は、釉薬としての
機能が発揮でき、セメント製品の焼成温度で、しかも、
その焼成温度範囲内の低温での焼成温度に適用しても、
焼成後の釉薬の表面状態、耐候性を劣化させることがな
く、焼成セメント基材の劣化を最小に抑えることができ
る釉薬を提供することにある。[0006] The problem to be solved by the present invention is that the function as a glaze can be exhibited, and at the firing temperature of the cement product,
Even if applied to the firing temperature at a low temperature within the firing temperature range,
An object of the present invention is to provide a glaze capable of minimizing deterioration of a calcined cement substrate without deteriorating the surface condition and weather resistance of the glaze after firing.
【０００７】[0007]
【課題を解決するための手段】本発明は、焼成セメント
製品における焼成温度の下限は、７００℃であり、ま
た、その上限は、燃費は勿論、養生時間の短縮によるコ
ストダウン、白華防止、単位時間当たりの生産性等から
考えて８５０℃とする着想の下で完成した。According to the present invention, the lower limit of the calcination temperature in the calcination cement product is 700 ° C., and the upper limit thereof is not only the fuel consumption but also the cost reduction by shortening the curing time, the prevention of bleaching, It was completed under the idea of 850 ° C. in view of productivity per unit time and the like.
【０００８】すなわち、本発明の無鉛低融点ガラス組成
物は、７００〜８５０℃の温度範囲で、釉薬としての機
能が発揮できる無鉛低融点ガラス組成物（フリット組成
物）であって、Ｒ2ＯをＮａ2Ｏ，Ｋ2Ｏの中の何れか１
種とし、ＲＯをＭｇＯ，ＣａＯ，ＺｎＯ，ＢａＯ，Ｓｒ
Ｏの中の少なくとも１種としたとき、全量中、 ＳｉＯ2 ３５〜６０ モル％ Ｂ2Ｏ3 １６〜２６ モル％ Ｌｉ2Ｏ ６〜８ モル％ Ｒ2Ｏ ４〜１７ モル％ ＲＯ ５〜１５ モル％ を含有することを特徴とする。That is, the lead-free low-melting glass composition of the present invention
The material is used as a glaze in a temperature range of 700 to 850 ° C.
Lead-free low-melting glass composition (frit composition)
Object) and RTwoO to NaTwoO, KTwoAny one of O
RO as MgO, CaO, ZnO, BaO, Sr
When at least one of O is used, SiOTwo 35-60 mol% BTwoOThree16-26 mol% LiTwoO 6-8 mol% RTwoIt is characterized by containing 4 to 17 mol% of O and 5 to 15 mol% of RO.
【０００９】上記組成において、ＳｉＯ2 は、その骨格
をなすもので、釉薬として融点を規定するものである。
また、釉薬の耐酸性を向上させるもので、そのために
は、３５モル％以上必要であり、６０モル％を超えると
耐火性が増し、釉薬として機能しなくなる。In the above composition, SiO 2 forms its skeleton and defines a melting point as a glaze.
Further, it improves the acid resistance of the glaze, and for that purpose, it needs to be 35 mol% or more. If it exceeds 60 mol%, the fire resistance increases and the glaze does not function.
【００１０】Ｂ2Ｏ3 は、ＳｉＯ2を基材とする組成物を
ガラス形成のための融剤として機能するもので、釉薬の
低融化に寄与し、ＳｉＯ2とのモル％比で、ＳｉＯ2：Ｂ
2Ｏ3が３５〜６０：１６〜２６の間にあることが、失透
を起こさないと同時に他成分の結晶化を防げる点から最
も好都合である。[0010] B 2 O 3 is a composition SiO 2 as a base material which functions as a fluxing agent for glass formation, contribute to the glaze low-melting, by mol% ratio of SiO 2, SiO 2 : B
It is most advantageous that the 2 O 3 is between 35 and 60:16 and 26 in order not to cause devitrification and at the same time to prevent crystallization of other components.
【００１１】 Ｌｉ2Ｏは、６．０モル％以上の添加によ
り、８００℃以下のでのフリットの溶融温度の低下に寄
与し、７５０℃〜８００℃の焼成を可能とする釉薬が得
られる。しかしながら、８モル％を超えると耐酸性が悪
くなる。[0011] LiTwoO is added by adding 6.0 mol% or more.
Lowering the melting temperature of the frit below 800 ° C
To obtain a glaze that can be fired at 750 ° C to 800 ° C.
Can be However, when it exceeds 8 mol%, acid resistance is poor.
It becomes.
【００１２】Ｒ2Ｏとして表わされるＮａ2ＯあるいはＫ
2Ｏは、釉薬としての機能を維持させながら、その融点
の調整剤としての機能を持たせたもので、その目的とす
る７００℃以上、８５０℃以下の温度範囲で釉薬として
の機能を維持させるためには、４〜１７モル％の含有量
が必要である。Na 2 O or K, represented as R 2 O
2 O is while maintaining the function as a glaze, but have a function of an adjusting agent of its melting point, 700 ° C. or higher and an object thereof to maintain the function of the glaze in the temperature range of 850 ° C. or less For this purpose, a content of 4 to 17 mol% is necessary.
【００１３】ＲＯは、ＭｇＯ，ＣａＯ，ＺｎＯ，Ｂａ
Ｏ，ＳｒＯ等のアルカリ土類金属の酸化物を意味し、そ
の中の少なくとも１種以上が用いられる。これは、耐摩
耗性、耐候性、熱膨張係数低下材として機能し、５〜１
５モル％含有する必要がある。また、本発明の組成物に
は、全量中、耐薬品性の向上、分相抑制に寄与するＡｌ
2Ｏ3を耐候性向上のために含有させることができる。し
かしながら、その配合量が増えると、融点が急激に上昇
するので、その融点が８５０℃以下での釉薬として機能
させるためには、その上限は１０モル％に抑える必要が
ある。RO is composed of MgO, CaO, ZnO, Ba.
It means an oxide of an alkaline earth metal such as O or SrO, and at least one of them is used. It functions as a material having a low abrasion resistance, weather resistance, and thermal expansion coefficient.
It is necessary to contain 5 mol%. Further, the composition of the present invention contains, in the total amount, Al which contributes to improvement of chemical resistance and suppression of phase separation.
2 O 3 can be included for improving weather resistance. However, as the blending amount increases, the melting point sharply increases. Therefore, in order to function as a glaze at a melting point of 850 ° C. or lower, the upper limit must be suppressed to 10 mol%.
【００１４】さらに、本発明の組成物には、その光沢、
乳白性、さらには、膨脹の程度を調整するために、一般
式がＲＯ2で表されるＺｒＯ2、ＴｉＯ2を全量中、１０
モル％以下配合することができる。Further, the composition of the present invention has a gloss,
In order to adjust the milkiness and the degree of expansion, 10% of the total amount of ZrO 2 and TiO 2 represented by the general formula of RO 2 is used.
Molar% or less can be added.
【００１５】また、さらに、Ｒ2Ｏ5で表されるＴａ
2Ｏ5、Ｎｂ2Ｏ5、Ｖ2Ｏ5の中の少なくとも１種を、同じ
く、その光沢、濁り、さらには、膨脹の程度を微調整す
るために、４モル％以下配合することができる。Further, Ta represented by R 2 O 5
At least one of 2 O 5 , Nb 2 O 5 , and V 2 O 5 can also be blended in an amount of 4 mol% or less in order to finely adjust the gloss, turbidity, and degree of expansion. .
【００１６】この無鉛低融点ガラス組成物を釉薬として
使用するには、通常のように、顔料、粘土と混合し、こ
れをＣＭＣと水によってスリップとし、ハケ塗り、スプ
レーによって、セメント製品の表面に塗布して焼成に供
する。In order to use this lead-free low-melting glass composition as a glaze, as usual, it is mixed with a pigment and clay, slipped with CMC and water, brushed and sprayed onto a cement product surface. Apply and serve for baking.
【００１７】[0017]
【発明の実施の形態】本発明の実施の形態を以下に示す
実施例によって説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described with reference to the following examples.
【００１８】配合物の組成 表１に示す組成を有する配合物を調製した。Composition of Formulation A formulation having the composition shown in Table 1 was prepared.
【００１９】[0019]
【表１】 [Table 1]
【表２】 同表において、テストＮｏ.ｈ〜ｌは本発明の実施例を
示し、他は比較例を示す。[Table 2] In the same table, Test Nos. H to l show examples of the present invention, and others show comparative examples.
【００２０】釉薬の調合 釉薬調合は、表１に示す組成物１００ｇに対して、表２
に示すｇ単位の顔料、粘土、ＣＭＣを配合し、２ｋｇポ
ットミルを使用し、粉砕粒度を１〜３ｇ／１００メッシ
ュ／５０ｃｃにそろえスリップを作成した。Preparation of glaze The preparation of the glaze was based on 100 g of the composition shown in Table 1 and Table 2
The pigments, clay and CMC in the units of g shown in Table 1 were blended, and a 2 kg pot mill was used to prepare a slip having a crushed particle size of 1 to 3 g / 100 mesh / 50 cc.
【００２１】施釉 作成したスリップを８０ｇ（ｗｅｔ）をスプレーガンに
よって強制乾燥済のセメント製品に３０ｃｍ×３０ｃｍ
の面に施釉した。Glaze Apply 80 g (wet) of the prepared slip to a cement product which has been forcibly dried by a spray gun at a size of 30 cm × 30 cm.
Glazed on the surface.
【００２２】焼成 施釉したセメント製品を乾燥後、ガス炉で７５０℃で焼
成（昇温時間は４時間、保持時間１時間）し、焼成後、
２００℃まで自然冷却をして炉から取り出した。Firing After the glazed cement product is dried, it is fired in a gas furnace at 750 ° C. (heating time is 4 hours, holding time is 1 hour).
It was cooled naturally to 200 ° C. and taken out of the furnace.
【００２３】その表面状態は、本発明の実施例の場合、
７５０℃で焼成すると光沢良好、なめらかであるのに対
して、比較例の場合は、釉薬としての機能が不十分で、
表面が凸凹し、光沢不良で明らかに釉薬のとけ不足を示
した。The surface condition is as follows in the case of the embodiment of the present invention.
When baked at 750 ° C., gloss is good and smooth, whereas in the case of Comparative Example, the function as a glaze is insufficient.
The surface was uneven, and the gloss was poor and the glaze was clearly insufficient.
【００２４】水分補給 取り出した焼成物を直ちに水中に１０分間浸し、水を吸
収させ結晶水の補給を行い、６０℃で蒸気養生を行っ
た。養生時間は今まで７日間であったものが、本発明の
実施例の場合、３日間で十分な強度が得られた。Water replenishment The fired product taken out was immediately immersed in water for 10 minutes, water was absorbed to replenish crystal water, and steam curing was performed at 60 ° C. The curing time was seven days, but in the case of the present invention, sufficient strength was obtained in three days.
【００２５】また、耐候テスト、耐酸テスト、耐アルカ
リテスト、白華（エフロ）発生の確認テスト、強度テス
トの結果は、比較例とほぼ同等であった。The results of the weather resistance test, the acid resistance test, the alkali resistance test, the test for confirming the occurrence of efflorescence and the strength test were almost the same as those of the comparative example.
【００２６】耐候テスト 紫外線による変化を見るためにウエザーメーターを使用
し２０００時間の変化を観察した。Weather resistance test A change of 2000 hours was observed using a weather meter in order to check a change due to ultraviolet rays.
【００２７】評価は色差と光の反射率をみた。For evaluation, the color difference and the reflectance of light were examined.
【００２８】光沢評価は反射率をみた。The gloss was evaluated by looking at the reflectance.
【００２９】 反射率 ８０％以上 Ａ ６０％以上 ７９％以下 Ｂ ４０％以上 ５９％以下 Ｃ ３９％以下 Ｄ 色差の評価はウエザーメーターテスト前後のΔＥ*を見た ΔＥ*＝０．５以下 Ａ ΔＥ*＝０．５以上 １以下 Ｂ ΔＥ*＝ １以上 ２以下 Ｃ ΔＥ*＝ ２以上 Ｄ 本発明の実施例と比較例との対比：本発明の反射率は、
８０％以上を示し、比較例は６３％であった。又、色差
は本発明でΔＥ*＝０．４７であり、比較例はΔＥ*＝
０．７８を示した。Reflectance 80% or more A 60% or more and 79% or less B 40% or more and 59% or less C 39% or less D Evaluation of color difference is ΔE * before and after the weather meter test ΔE * = 0.5 or less A ΔE * = 0.5 or more and 1 or less B ΔE * = 1 or more and 2 or less C ΔE * = 2 or more D Comparison between Examples of the Present Invention and Comparative Examples: The reflectance of the present invention is:
80% or more, and the comparative example was 63%. In the present invention, the color difference is ΔE * = 0.47, and the comparative example is ΔE * = 0.47.
0.78 was shown.
【００３０】耐酸テスト ＪＩＳＡ５２０９陶磁器タイルの釉薬品試験に準じ、３
％塩酸液を作成し、それに切り出した瓦を浸して２４時
間後の変化を目視で観察評価した。Acid resistance test According to JIS A5209 ceramic tile glaze chemical test, 3
% Hydrochloric acid solution was prepared, the cut roof tile was immersed in the solution, and the change after 24 hours was visually observed and evaluated.
【００３１】評価は 全くマークがつかない −Ａ かすかにマークがつく −Ｂ マークがつくが変色なし −Ｃ マークが変色している −Ｄ とした。The evaluation was as follows: no mark was attached; -A mark was slightly attached; -B mark was attached but no discoloration was made; -C mark was discolored -D.
【００３２】耐アルカリテスト 同様に焼成したセメント製品を切り取って３％水酸化ナ
トリウム溶液に浸けて変化を見た。Alkali Resistance Test A cement product similarly baked was cut out and immersed in a 3% sodium hydroxide solution to observe changes.
【００３３】白華（エフロ）発生の確認 養生期間を経て屋外に１週間放置後の白華の発生を観察
した。Confirmation of Efflorescence Occurrence of efflorescence after one week of standing outdoors after a curing period was observed.
【００３４】評価は 白華の確認が出来ない −Ａ わずかに白華 −Ｂ 貫入部分の白華著しい −Ｃ 本発明の実施例の場合と比較例との対比：本発明では白
華の確認が出来なかったが、比較例はわずかに白華を生
じた。In the evaluation, no white flower could be confirmed. -A Slight white flower -B White flower in the penetrated portion was significant -C Comparison between the example of the present invention and the comparative example: In the present invention, the white flower was confirmed. Although not possible, the comparative example produced slight efflorescence.
【００３５】強度テスト 曲げ破壊試験器を使用してＪＩＳ５４０２に基づく強度
を比較した。Strength Test The strength based on JIS5402 was compared using a bending fracture tester.
【００３６】本発明の実施例の場合と比較例との比較：
ともに差は認められなかった。Comparison between the embodiment of the present invention and the comparative example:
No difference was observed in both cases.
【００３７】[0037]
【発明の効果】本発明の組成物によって以下の効果を奏
する。The composition of the present invention has the following effects.
【００３８】１） 比較的低温での釉焼が可能なのでセ
メント製品の焼成による劣化の程度が少ない。1) Since the glaze can be fired at a relatively low temperature, the degree of deterioration due to firing of the cement product is small.
【００３９】２） セメント基材への施釉、焼成では養
生期間が短くてすみ、経済性が高い。 ３） 耐凍害性に優れた基材が得られる。2) Glazing and sintering of a cement base material requires only a short curing period and is economically efficient. 3) A substrate excellent in frost damage resistance can be obtained.
【００４０】４） 高温焼成の釉薬と同等の耐候性、耐
酸性が得られる。4) Weather resistance and acid resistance equivalent to glazes fired at high temperatures can be obtained.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１１年１月２８日（１９９９．１．２
８）[Submission date] January 28, 1999 (1999.1.2
8)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１１】Ｌｉ2Ｏは、フリットの溶融温度の低下に
寄与し、６．０モル％以上の添加により、７００℃〜８
５０℃の焼成を可能とする釉薬が得られる。しかしなが
ら、８モル％を超えると耐酸性が悪くなる。[0011] Li 2 O reduces the melting temperature of the frit.
The contribution to the addition of more than 6.0 mol%, 700 ° C. to 8
A glaze that can be fired at 50 ° C. is obtained. However, when it exceeds 8 mol%, the acid resistance becomes poor.
フロントページの続き Ｆターム(参考） 4G028 DA01 DB02 DC01 4G062 AA08 AA09 BB05 CC10 DA05 DA06 DB01 DB02 DB03 DC04 DD01 DE00 DE01 DE02 DE03 DE04 DF01 EA03 EB01 EB02 EB03 EB04 EC01 EC02 EC03 EC04 ED00 ED01 ED02 ED03 ED04 EE00 EE01 EE02 EE03 EE04 EF00 EF01 EF02 EF03 EF04 EG00 EG01 EG02 EG03 EG04 FA01 FA10 FB01 FB02 FB03 FC01 FC02 FC03 FD01 FE01 FF01 FF02 FF03 FG01 FG02 FG03 FH01 FH02 FH03 FJ01 FK01 FK02 FK03 FL01 GA01 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ04 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM07 NN32 NN34Continued on the front page F-term (reference) 4G028 DA01 DB02 DC01 4G062 AA08 AA09 BB05 CC10 DA05 DA06 DB01 DB02 DB03 DC04 DD01 DE00 DE01 DE02 DE03 DE04 DF01 EA03 EB01 EB02 EB03 EB04 EC01 EC02 EC03 EC04 ED00 ED03 ED03 ED03 ED03 EF00 EF01 EF02 EF03 EF04 EG00 EG01 EG02 EG03 EG04 FA01 FA10 FB01 FB02 FB03 FC01 FC02 FC03 FD01 FE01 FF01 FF02 FF03 FG01 FG02 FG03 FH01 FH02 FH03 HJ01 FK01 H01 H01 H01 H01 GA01 JJ01 JJ03 JJ04 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM07 NN32 NN34
Claims (5)
て使用するセメント製品用無鉛低融点ガラス組成物であ
って、 全量中、Ｒ2ＯをＮａ2Ｏ，Ｋ2Ｏの中の何れか１種と
し、ＲＯをＭｇＯ，ＣａＯ，ＺｎＯ，ＢａＯ，ＳｒＯの
中の少なくとも１種としたとき、 ＳｉＯ2 ３５〜６０ モル％ Ｂ2Ｏ3 １６〜２６ モル％ Ｌｉ2Ｏ ６〜８ モル％ Ｒ2Ｏ ４〜１７ モル％ ＲＯ ５〜１５ モル％ を含有するセメント製品用無鉛低融点ガラス組成物。1. A glaze in a firing range of 700 to 850 ° C.
Lead-free low melting glass composition for cement products
I mean, RTwoO to NaTwoO, KTwoAny one of O
And RO is made of MgO, CaO, ZnO, BaO, SrO.
When at least one of them is used, SiOTwo 35-60 mol% BTwoOThree16-26 mol% LiTwoO 6-8 mol% RTwoA lead-free low-melting glass composition for cement products containing 4 to 17 mol% of O and 5 to 15 mol% of RO.
する請求項１に記載のセメント製品用無鉛低融点ガラス
組成物。2. The lead-free low-melting glass composition for a cement product according to claim 1, which contains 10 mol% or less of Al 2 O 3 in the total amount.
Ｏ2を１０モル％以下含有する請求項１あるいは請求項
２に記載のセメント製品用無鉛低融点ガラス組成物。3. ZrO 2 , Ti represented by RO 2 in the total amount
O 2 to claim 1 or cement products for lead-free low-melting-point glass composition as claimed in claim 2 containing less than 10 mol%.
ｂ2Ｏ5、Ｖ2Ｏ5の中の少なくとも１種を４モル％以下含
有する請求項１から請求項３の何れかに記載のセメント
製品用無鉛低融点ガラス組成物。4. Ta 2 O 5 , N represented by R 2 O 5 in the total amount
b 2 O 5, V 2 O cement products for lead-free low-melting-point glass composition according to any one of claims 1 to 3, which contains at least one 4 mol% or less in 5.
ｂ2Ｏ3中の少なくとも１種を４モル％以下含有する請求
項１から請求項４の何れかに記載のセメント製品用無鉛
低融点ガラス組成物。5. La 2 O 3 , S represented by R 2 O 3 in the total amount
b 2 O 3 cement products for lead-free low-melting-point glass composition according to claim 1 which contains at least one 4 mol% or less to claim 4 in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36331598A JP2990194B1 (en) | 1998-12-21 | 1998-12-21 | Lead-free low melting point glass composition for cement products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36331598A JP2990194B1 (en) | 1998-12-21 | 1998-12-21 | Lead-free low melting point glass composition for cement products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2990194B1 JP2990194B1 (en) | 1999-12-13 |
| JP2000185936A true JP2000185936A (en) | 2000-07-04 |
Family
ID=18479029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36331598A Expired - Fee Related JP2990194B1 (en) | 1998-12-21 | 1998-12-21 | Lead-free low melting point glass composition for cement products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2990194B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7605104B2 (en) | 2005-07-29 | 2009-10-20 | Samsung Electro-Mechanics Co., Ltd. | Glass composition for low temperature sintering, dielectric composition and multilayer ceramic capacitor using the same |
| CN102659314A (en) * | 2012-04-27 | 2012-09-12 | 中南大学 | Barium oxide based crystal lead-free glass and preparation method thereof |
| KR101195002B1 (en) | 2011-02-28 | 2012-10-29 | 이화다이아몬드공업 주식회사 | Vitrified bonder for micro blade, micro blade using the vitrified bonder and manufacturing method of the micro blade |
-
1998
- 1998-12-21 JP JP36331598A patent/JP2990194B1/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7605104B2 (en) | 2005-07-29 | 2009-10-20 | Samsung Electro-Mechanics Co., Ltd. | Glass composition for low temperature sintering, dielectric composition and multilayer ceramic capacitor using the same |
| US7691762B2 (en) | 2005-07-29 | 2010-04-06 | Samsung Electro-Mechanics Co., | Glass composition for low temperature sintering, glass frit, dielectric composition and multilayer ceramic capacitor using the same |
| US7851393B2 (en) | 2005-07-29 | 2010-12-14 | Samsung Electro-Mechanics Co., Ltd. | Glass composition for low temperature sintering, glass frit, dielectric composition and multilayer ceramic capacitor using the same |
| KR101195002B1 (en) | 2011-02-28 | 2012-10-29 | 이화다이아몬드공업 주식회사 | Vitrified bonder for micro blade, micro blade using the vitrified bonder and manufacturing method of the micro blade |
| CN102659314A (en) * | 2012-04-27 | 2012-09-12 | 中南大学 | Barium oxide based crystal lead-free glass and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2990194B1 (en) | 1999-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR950006202B1 (en) | Lead-free glass frit compositions | |
| KR100215256B1 (en) | Glass composition | |
| US4970178A (en) | Lead-free glass frit compositions | |
| NO123379B (en) | ||
| US5650364A (en) | Self-opacifying enamel frits for the enamelling of aluminum or aluminum alloys | |
| JPH05270860A (en) | Lead-and cadmium-free glass composition for glazing, enameling and decorating and its use | |
| JPH05270859A (en) | Glaze composition and glazing method | |
| JP5033339B2 (en) | Glass composition | |
| JP2002241143A (en) | Sealing composition | |
| GB2068933A (en) | Lead free glazes for alumina bodies | |
| JPH1143351A (en) | Glass composition for glaze | |
| EP1966099B1 (en) | Composition, frit, enamel and ceramic components and process to make the same | |
| JP4874492B2 (en) | Glass composition and glass-forming material containing the composition | |
| JP3098307B2 (en) | Non-toxic glass frit and glaze and decoration method for glass, glass ceramic and ceramic products | |
| US2972543A (en) | Ceramic glaze composition | |
| JP2990194B1 (en) | Lead-free low melting point glass composition for cement products | |
| CN1021112C (en) | Low-temp. ceramic glazing dyestuff and its preparation method | |
| JP2001322832A (en) | Sealing composition | |
| KR20090063408A (en) | Lead-free glass frit and display panel sealing composition containing same | |
| US2918384A (en) | Preparation of ceramic frit compositions | |
| KR101130555B1 (en) | Fabrication of Pb-free white dielectric layer adding mixing filler for soda-lime silecate glasses | |
| JPS6219372B2 (en) | ||
| JP2658723B2 (en) | Raster glaze | |
| JP2546123B2 (en) | Lead-free frit glaze | |
| JP3056978B2 (en) | Lead-free glaze for silver tiles with good color stability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |