JPH09263422A - Antimold glass fiber - Google Patents
Antimold glass fiberInfo
- Publication number
- JPH09263422A JPH09263422A JP8097314A JP9731496A JPH09263422A JP H09263422 A JPH09263422 A JP H09263422A JP 8097314 A JP8097314 A JP 8097314A JP 9731496 A JP9731496 A JP 9731496A JP H09263422 A JPH09263422 A JP H09263422A
- Authority
- JP
- Japan
- Prior art keywords
- glass fiber
- glass
- cao
- cuo
- antimold
- 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
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
- C03C13/00—Fibre or filament compositions
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はガラス繊維強化プラ
スチック、フィルタ−、建築用内装材などに用いられる
防かび性ガラスよりなるガラス繊維及びその製品に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass fiber made of antifungal glass used for glass fiber reinforced plastics, filters, interior materials for construction and the like, and a product thereof.
【０００２】[0002]
【従来の技術】近年、ビル、住宅などの建築にアルミサ
ッシュ、プラスチック系の化粧板、ビニル壁紙の等を使
用することで気密性が上がり、結露が生じやすく壁紙な
どにかびが発生したり、空調機のフィルタ−、ドレンパ
ンなどについたごみに、かびなどが発生しやすくなって
いる。これらの、かびやその胞子が室内に飛散し人体に
悪影響をおよぼしたり、悪臭を発生して住人を不愉快に
させるなどの問題がおきている。ガラス繊維は無機質で
あり、かびが発生し難く、腐らず、不燃であり、補強効
果をもつため、上記用途に使用されている。2. Description of the Related Art In recent years, the use of aluminum sash, plastic-based decorative boards, vinyl wallpaper, etc., for building, housing, etc. has increased the airtightness, and it is easy for dew condensation to occur, causing mold on the wallpaper, etc. It is easy for mold to form on the dust on the air conditioner filter and drain pan. These molds and their spores are scattered in the room and have an adverse effect on the human body, and there are problems such as generation of a foul odor and making the resident unpleasant. Since glass fiber is an inorganic substance, it is less likely to cause mold, does not rot, is nonflammable, and has a reinforcing effect, it is used for the above-mentioned applications.
【０００３】このガラス繊維をガラス繊維強化プラスチ
ック、フィルタ−や、タイルカ−ペット、壁紙の裏打ち
材などかびの発生しやすいものに使用する試みがなさ
れ、たとえば特開平７−２２９０５７号公報に開示され
ているように防かび剤を担持させたゼオライト粒子をガ
ラス繊維表面に付着させるもの、あるいは特開平７−２
５２７２０号公報にあるように亜鉛イオンを含有する溶
解性ガラスを粉末として防かび剤、あるいは防かび剤の
入ったの入ったアクリル樹脂エマルジョンを塗布したガ
ラス繊維、あるいは銀化合物を含む原料を繊維化し、ガ
ラス繊維自体を防かび性にしようとする特開平７−８９
７４６号公報に開示された技術もある。Attempts have been made to use the glass fibers in glass fiber reinforced plastics, filters, tile carpets, wallpaper linings and other mold-prone materials, which are disclosed in, for example, JP-A-7-229057. A method of adhering zeolite particles carrying an antifungal agent to the surface of glass fiber, or JP-A-7-2
As disclosed in Japanese Patent No. 52720, glass fibers coated with a soluble glass containing zinc ions as a powder and coated with an antifungal agent or an acrylic resin emulsion containing an antifungal agent, or a raw material containing a silver compound is fibrillated. Japanese Patent Application Laid-Open No. 7-89 which attempts to make the glass fiber itself antifungal
There is also a technique disclosed in Japanese Patent Publication No. 746.
【０００４】[0004]
【発明が解決しようとする課題】上記のようにガラス繊
維の表面に粉末状の防かび剤を付着させる方法は、バイ
ンダ−が粉末表面を覆い防かび性が低下するし、付着量
をむやみに多くすることができず効果を長時間持続させ
ることが難しい。また、高温多湿の条件下では接着剤の
劣化が起き、防かび剤が剥落することもある。一方銀を
含むガラス繊維は、紡糸に高度の技術必要で、原料価格
も製造費用も高く、したがって製品も高価になってい
る。As described above, the method of adhering the powdery mildewproofing agent to the surface of the glass fiber is such that the binder covers the surface of the powdery agent and the antifungal property is lowered, and the amount of adhering is excessive. It is difficult to maintain the effect for a long time because it cannot be increased. In addition, under high temperature and high humidity conditions, the adhesive may deteriorate, and the fungicide may peel off. On the other hand, the glass fiber containing silver requires high technology for spinning, the raw material price and the manufacturing cost are high, and therefore the product is expensive.
【０００５】[0005]
【課題を解決するための手段】本発明者はガラス組成中
に防かび効果が大きい銅イオンを発生することのできる
成分を配合することを検討することにより、紡糸が容易
で、原料価格も、製造費用も安く製造出来るガラス繊維
自体に防かび性を持たせることに成功した。Means for Solving the Problems The present inventor has studied the incorporation of a component capable of generating a copper ion having a large antifungal effect into a glass composition, thereby facilitating spinning and reducing the raw material cost. We have succeeded in imparting mold resistance to the glass fiber itself, which can be manufactured at low cost.
【０００６】[0006]
【発明の実施の形態】（本明細書においては単位の％
は、以下特に断らない限り重量％を意味するものとす
る。）本発明は、以下のガラス繊維が得られるように原
料配合する。ＳｉＯ2 ５０−６０％、Ａｌ2 Ｏ3 １
０−２０％、Ｂ2 Ｏ3 ５−１３％、ＣａＯ ２−２３
％、ＭｇＯ ０−６％、Ｎａ2 Ｏ＋Ｋ2 Ｏ ０−１％、
の組成に必須成分として組成中のＣａＯを置換する形で
ＣｕＯを２−２０％、配合する、ただしＣａＯ＋ＣｕＯ
が ４−２５％になるよう調整される。その他の成分と
してＦｅ2 Ｏ3 ０−１％、Ｆ ０−１％を含有しても良
い。この配合の更に好ましい組成の範囲は、ＳｉＯ2
５２−５６％、Ａｌ2 Ｏ3１２−１６％、Ｂ2 Ｏ3 ８−
１３％、ＣａＯ ５−２３％、ＭｇＯ ０−６％、Ｎａ
2 Ｏ＋Ｋ2 Ｏ ０−１％、の組成に必須成分として組成
中のＣａＯを置換する形でＣｕＯを２−２０％、配合す
る、ただしＣａＯ＋ＣｕＯが ５−２３％になるよう調
整したものであり、その他の成分としてＦｅ2 Ｏ3 ０−
１％、Ｆ０−１％を含有しても良い。このように、ガラ
ス組成を限定した理由は以下の通りである。ＳｉＯ2 は
基本構成成分で、ガラスの骨格を形成し、ＳｉＯ2 が５
０％より少ないと耐薬品性が悪化し、６０％を越えると
溶融しにくくなると共に失透しやすくなる。Ａｌ2 Ｏ3
は基本構成成分で、ガラスの骨格を形成し、含有量が１
０％より少ないと液相温度が上昇し、ガラスが失透しや
すくなり、２０％をこえるとガラスの粘度が上昇し、溶
融及び紡糸が困難になる。BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, “%” means “% by weight” unless otherwise specified. ) In the present invention, raw materials are blended so that the following glass fibers are obtained. SiO 2 50-60%, Al 2 O 3 1
0-20%, B 2 O 3 5-13 %, CaO 2-23
%, MgO 0-6%, Na 2 O + K 2 O 0-1%,
2-20% of CuO is added to the composition as an essential component to replace CaO in the composition, provided that CaO + CuO
Is adjusted to 4-25%. As other components, Fe 2 O 3 0-1% and F 0-1% may be contained. A more preferable composition range of this composition is SiO 2
52-56%, Al 2 O 3 12-16%, B 2 O 3 8-
13%, CaO 5-23%, MgO 0-6%, Na
2 O + K 2 O 0-1% , of the CuO in the form of substitution of CaO in the composition as an essential component in the composition 2-20%, formulated, but is obtained by adjusting so that CaO + CuO is 5-23%, Fe 2 O 3 0-as other components
You may contain 1% and F0-1%. The reason for limiting the glass composition in this way is as follows. SiO 2 is a basic component, to form a skeleton of glass, SiO 2 is 5
If it is less than 0%, the chemical resistance deteriorates, and if it exceeds 60%, it becomes difficult to melt and devitrification easily occurs. Al 2 O 3
Is a basic constituent and forms the skeleton of glass, and the content is 1
If it is less than 0%, the liquidus temperature rises and the glass tends to devitrify, and if it exceeds 20%, the viscosity of the glass rises, making melting and spinning difficult.
【０００７】ＣａＯは基本構成成分であるとともに、融
剤として作用しＣａＯの含有量が２％以下ではガラスの
粘度が上昇し、溶融及び紡糸が困難になり２３％を越え
ると失透しやすくなると共に耐薬品性が悪くなる。Ｃｕ
ＯはＣａＯと置換することにより防かび性を持たせるも
のであり、２−２１％、としたのは２％以下では防かび
効果が少なく、２１％以上ではガラスの粘度が上昇し、
溶融及び紡糸が困難になる。またＣａＯ＋ＣｕＯの合計
を重量で４−２５％にした理由は、４％以下、あるいは
２５％以上ではガラス繊維として紡糸が困難なためであ
る。ＭｇＯは失透を制御するとともに融剤として作用す
る。Ｂ2 Ｏ3 は融剤として作用し、ガラスの粘度を下
げ、溶融及び紡糸を容易にする。Ｎａ2 Ｏ＋Ｋ2 Ｏは原
料からの不純物として１％以下は含有しても良い。CaO is a basic constituent and also acts as a fluxing agent, and when the content of CaO is 2% or less, the viscosity of the glass rises, making melting and spinning difficult, and when it exceeds 23%, devitrification tends to occur. At the same time, the chemical resistance becomes worse. Cu
O is antifungal by substituting with CaO, and it is 2-21%, because the antifungal effect is less than 2%, and the viscosity of the glass rises above 21%.
Difficult to melt and spin. Further, the reason why the total of CaO + CuO is set to 4-25% by weight is that it is difficult to spin as glass fiber at 4% or less, or 25% or more. MgO controls devitrification and acts as a flux. B 2 O 3 acts as a flux, lowers the viscosity of the glass and facilitates melting and spinning. Na 2 O + K 2 O may be contained as an impurity from the raw material in an amount of 1% or less.
【０００８】本発明のガラス繊維は通常のガラス繊維か
らなる製品一般と同様の加工品を製造することができ、
その形態は、例えばロ−ビング、チョップドストラン
ド、ヤ−ン、クロス、チョップドストランドマット、ガ
ラスペ−パ−、ガラス繊維粉末などがある。その使用方
法もガラス繊維加工品単体で使用するほか、普通のガラ
ス繊維同様、熱可塑性樹脂あるいは熱硬化性樹脂に配合
して、ＦＲＴＰあるいはＦＲＰの製品とする。本発明の
ガラス繊維は水分に接するとＣｕ2+のイオンが溶解し、
防かび効果を発揮するものであるから、ガラス繊維の平
均直径は小さい方が良く、２−１９μｍのものが主とし
て製造される。The glass fiber of the present invention can produce a processed product similar to general products made of ordinary glass fiber,
Its form is, for example, roving, chopped strand, yarn, cloth, chopped strand mat, glass paper, glass fiber powder and the like. In addition to using the glass fiber processed product as a single body, it is also compounded with a thermoplastic resin or a thermosetting resin in the same manner as ordinary glass fiber to obtain a FRTP or FRP product. When the glass fiber of the present invention comes into contact with water, Cu 2+ ions are dissolved,
Since it exhibits a fungicidal effect, it is preferable that the average diameter of the glass fibers is small, and those having a glass fiber diameter of 2-19 μm are mainly produced.
【０００７】[0007]
【実施例】以下に実施例及び比較例を挙げて本発明を具
体的に説明する。。 Ａ、繊維の作成 ＜実施例１＞ＳｉＯ2 ５４．８％、Ａｌ2 Ｏ3 １
４．２％、ＣａＯ ２１．５％、ＭｇＯ １．２％、Ｎ
ａ2 Ｏ＋Ｋ2 Ｏ ０．２％、Ｂ2 Ｏ3 ６．１％、Ｃｕ
Ｏ ２．０％、Ｆｅ２Ｏ３ ０．２％、Ｆ ０．５％の
成分になるよう配合したガラス繊維原料を白金ルツボを
使用して１、５００℃の電気炉中で溶融し、ガラスカレ
ットを作成し、これを小型ポット炉により紡糸しガラス
繊維を得た。この繊維をボ−ルミルにより平均繊維長１
００μｍのガラス繊維パウダ−に粉砕した。The present invention will be specifically described below with reference to examples and comparative examples. . A, Fabrication of fiber <Example 1> SiO 2 54.8%, Al 2 O 3 1
4.2%, CaO 21.5%, MgO 1.2%, N
a 2 O + K 2 O 0.2%, B 2 O 3 6.1%, Cu
A glass cullet is prepared by melting glass fiber raw materials blended to have O 2.0%, Fe 2 O 3 0.2% and F 0.5% components in an electric furnace at 1,500 ° C. using a platinum crucible. Then, this was spun in a small pot furnace to obtain glass fiber. The average fiber length of this fiber is 1 by a ball mill.
It was crushed into a glass fiber powder having a diameter of 00 μm.
【０００８】＜実施例２＞ＣｕＯの量を１０％に増量
し、ＣａＯを１３．５％に減量した他は実施例１と同様
にしてガラス繊維パウダ−を得た。<Example 2> A glass fiber powder was obtained in the same manner as in Example 1 except that the amount of CuO was increased to 10% and the amount of CaO was decreased to 13.5%.
【０００９】＜実施例３＞ＣｕＯの量を２０％に増量
し、ＣａＯを ３．５％に減量した他は実施例１と同様
にしてガラス繊維パウダ−を得た。Example 3 A glass fiber powder was obtained in the same manner as in Example 1 except that the amount of CuO was increased to 20% and the amount of CaO was decreased to 3.5%.
【００１０】＜比較例１＞ＣｕＯの量を０％とし、Ｃａ
Ｏの含有量を２３．５％としたほかは実施例１と同様に
してガラス繊維パウダ−を得た。<Comparative Example 1> When the amount of CuO is set to 0%, Ca
A glass fiber powder was obtained in the same manner as in Example 1 except that the O content was 23.5%.
【００１１】Ｂ、試験方法 かび抵抗性試験方法（ＪＩＳ Ｚ ２９１１）に規定さ
れている寒天培地に、ガラス繊維パウダ−を撹拌分散さ
せたものの表面に、混合胞子懸液を散布し、かびの発生
状況を観察した。 １、寒天培地組成 精製水 １０００ｍｌ、 硝酸アンモニュウム ３ｇ、 リン酸一カリウム １．０ｇ、 硫酸マグネシュウム ０．５ｇ、 塩化カリウム ０．２５ｇ、 硫酸第一鉄 ０．００２５ｇ、 寒天 ２５ｇ， ガラス繊維パウダ− ５ｇ、 ガラス繊維パウダ−には実施例１−３、比較例１で得た
ものを使用した。寒天培地を溶解後、９０ｍｍのシャ−
レに流し、固化させたのち、混合胞子懸濁液１ｍｌを培
地の表面に均等にまきかけ、シャ−レの蓋をして２８±
２℃の試験機内で７日間培養した。B. Test method The mixed spore suspension was sprayed on the surface of an agar medium defined by the fungal resistance test method (JIS Z 2911) to which glass fiber powder was agitated and dispersed, and mold was generated. I observed the situation. 1. Composition of agar medium Purified water 1000 ml, ammonium nitrate 3 g, monopotassium phosphate 1.0 g, magnesium sulfate 0.5 g, potassium chloride 0.25 g, ferrous sulfate 0.0025 g, agar 25 g, glass fiber powder 5 g, The glass fiber powders used in Examples 1-3 and Comparative Example 1 were used. After thawing the agar medium, 90 mm shear
After allowing the mixture to solidify, 1 ml of the mixed spore suspension is sprinkled evenly on the surface of the medium, and the dish is covered with a lid of 28 ±.
The cells were cultured in a tester at 2 ° C for 7 days.
【００１２】２、混合胞子懸濁液中の試験菌の種類 アスペルギルス ニゲル、ペニシリウムフニクロサム、
クラドスポリウムクラドスポリオイデス、オ−レオパシ
デュウムプルランス、グリオクラディウムビレンス。2. Kind of test bacteria in mixed spore suspension Aspergillus niger, Penicillium funiculosum,
Cladsporium Cladsporioides, Oleopacidium pullulans, Gliocladium vilens.
【００１３】３、試験結果3, test results
【表１】 [Table 1]
【００１４】[0014]
【発明の効果】本発明のガラス繊維は組成中に水と接触
したとき銅イオンを遊離する成分を含有するので、防か
び性がある。その防かび性には、従来の防かび剤をガラ
ス繊維表面に接着剤で付与するものにくらべ、接着剤に
よる効果の低下がない、接着剤の劣化による剥落がな
い、ガラス繊維に耐薬品性があるので銅イオンの放出は
徐々に行われ、効果が長期間持続するなどの特徴があ
る。また、ガラス繊維としてＦＲＰ、ＰＲＴＰに使用で
きるので、補強効果と防かび性を同時に要求される分野
に使用可能である。またＣｕＯは無機物でガラスの一成
分になっているので、耐熱性があり有機の防かび剤の使
用出来ない高温で射出成型される樹脂製品の防かび対策
などに特に好適である。The glass fiber of the present invention has antifungal properties because it contains a component that liberates copper ions when it comes into contact with water in the composition. Its mildew-proof property is that, compared to the conventional fungicides applied to the glass fiber surface with an adhesive, the effect of the adhesive does not decrease, there is no peeling due to the deterioration of the adhesive, and the glass fiber has chemical resistance. Therefore, the release of copper ions is carried out gradually, and the effect is long-lasting. Further, since it can be used as FRP and PRTP as glass fiber, it can be used in a field in which a reinforcing effect and mold resistance are required at the same time. Further, since CuO is an inorganic substance and is a component of glass, it is particularly suitable for antifungal measures of resin products injection-molded at high temperature, which has heat resistance and cannot use organic antifungal agents.
Claims (1)
3 １０−２０％、Ｂ2 Ｏ3 ８−１３％、ＣａＯ ２−
２３％、ＣｕＯ ２−２１％、ただしＣａＯ＋ＣｕＯ
４−２５％、ＭｇＯ ０−６％、Ｎａ2 Ｏ＋Ｋ2 Ｏ ０
−１％、の組成を有する防かび性ガラス繊維。1. SiO 2 50-60% by weight, Al 2 O
3 10-20%, B 2 O 3 8-13%, CaO 2-
23%, CuO 2-21%, but CaO + CuO
4-25%, MgO 0-6%, Na 2 O + K 2 O 0
Antifungal glass fiber having a composition of -1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8097314A JPH09263422A (en) | 1996-03-28 | 1996-03-28 | Antimold glass fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8097314A JPH09263422A (en) | 1996-03-28 | 1996-03-28 | Antimold glass fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09263422A true JPH09263422A (en) | 1997-10-07 |
Family
ID=14189034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8097314A Pending JPH09263422A (en) | 1996-03-28 | 1996-03-28 | Antimold glass fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09263422A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016027999A (en) * | 2014-07-10 | 2016-02-25 | 石塚硝子株式会社 | Deodorant |
| WO2016129255A1 (en) * | 2015-02-13 | 2016-08-18 | 日本板硝子株式会社 | Glass for laser processing, and method for producing glass with hole using said glass for laser processing |
| WO2017217496A1 (en) * | 2016-06-17 | 2017-12-21 | 日本板硝子株式会社 | Glass plate for laser processing |
| WO2017221637A1 (en) * | 2016-06-23 | 2017-12-28 | 日本電気硝子株式会社 | Method for manufacturing glass fiber |
-
1996
- 1996-03-28 JP JP8097314A patent/JPH09263422A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016027999A (en) * | 2014-07-10 | 2016-02-25 | 石塚硝子株式会社 | Deodorant |
| WO2016129255A1 (en) * | 2015-02-13 | 2016-08-18 | 日本板硝子株式会社 | Glass for laser processing, and method for producing glass with hole using said glass for laser processing |
| CN107250073A (en) * | 2015-02-13 | 2017-10-13 | 日本板硝子株式会社 | Laser Processing glass and the manufacture method for having used its glass with hole |
| KR20170118115A (en) * | 2015-02-13 | 2017-10-24 | 닛본 이따 가라스 가부시끼가이샤 | Glass for laser processing and method for manufacturing glass with hole using the same |
| JPWO2016129255A1 (en) * | 2015-02-13 | 2017-11-24 | 日本板硝子株式会社 | Glass for laser processing and method for producing glass with holes using the same |
| TWI658024B (en) * | 2015-02-13 | 2019-05-01 | 日商日本板硝子股份有限公司 | Laser processing glass and manufacturing method of holed glass using the same |
| US10329185B2 (en) | 2015-02-13 | 2019-06-25 | Nippon Sheet Glass Company, Limited | Glass for laser processing and method for producing perforated glass using same |
| WO2017217496A1 (en) * | 2016-06-17 | 2017-12-21 | 日本板硝子株式会社 | Glass plate for laser processing |
| WO2017221637A1 (en) * | 2016-06-23 | 2017-12-28 | 日本電気硝子株式会社 | Method for manufacturing glass fiber |
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