JP4943355B2 - Method for spinning sol-like liquid - Google Patents
Method for spinning sol-like liquid Download PDFInfo
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- JP4943355B2 JP4943355B2 JP2008034245A JP2008034245A JP4943355B2 JP 4943355 B2 JP4943355 B2 JP 4943355B2 JP 2008034245 A JP2008034245 A JP 2008034245A JP 2008034245 A JP2008034245 A JP 2008034245A JP 4943355 B2 JP4943355 B2 JP 4943355B2
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- nonwoven fabric
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- 238000009987 spinning Methods 0.000 title claims description 67
- 238000000034 method Methods 0.000 title claims description 41
- 239000007788 liquid Substances 0.000 title description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 114
- 239000000835 fiber Substances 0.000 claims description 85
- 239000000377 silicon dioxide Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 32
- 239000004745 nonwoven fabric Substances 0.000 claims description 31
- -1 Silane compound Chemical class 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000007590 electrostatic spraying Methods 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 10
- 230000005684 electric field Effects 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 239000011780 sodium chloride Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002759 woven fabric Substances 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 201000001880 Sexual dysfunction Diseases 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Description
本発明は、シリカ繊維の製造方法に関する。更に詳細には、本発明は、テトラアルコキシシラン及び／又はその縮合物とアミノ基を含むシラン化合物とホウ酸とを含む混合液を、粘性ゾル化させ、得られるゾル状紡糸液を、電荷付与電極と対向電極との間の電位差によって形成された電界中で静電噴霧法により紡糸する、シリカ含有繊維の紡糸方法に関する。 The present invention relates to a method for producing silica fibers. More specifically, in the present invention, a mixed solution containing tetraalkoxysilane and / or its condensate, an amino group-containing silane compound and boric acid is made into a viscous sol, and the resulting sol-like spinning solution is charged. The present invention relates to a method for spinning a silica-containing fiber, in which spinning is performed by an electrostatic spraying method in an electric field formed by a potential difference between an electrode and a counter electrode.
従来、シリカ繊維の製造方法として、特許文献１に記載のように、テトラエトキシシランと水とエタノール混合液をゾル状にして、静電噴霧法により紡糸し、不織布を得る技術が知られている。 Conventionally, as a method for producing a silica fiber, as described in Patent Document 1, a technique is known in which a mixed solution of tetraethoxysilane, water, and ethanol is made into a sol and spun by electrostatic spraying to obtain a nonwoven fabric. .
しかし、特許文献１は、静電紡糸法の記載はあるが、極細の繊維を得ることが困難であり、繊維径のばらつきが大きいと考えられる。
本発明は、細繊維化ができ、繊維径のばらつき低減が可能なシリカ含有繊維を得ることができる紡糸方法を提供する。 The present invention provides a spinning method capable of obtaining silica-containing fibers that can be made into fine fibers and that can reduce variations in fiber diameter.
本発明は、以下の成分（ａ）、（ｂ）及び（ｃ）を含む混合液を、粘性ゾル化させ、得られるゾル状紡糸液を、電荷付与電極と対向電極との間の電位差によって形成された電界中で静電噴霧法により紡糸する、シリカ含有繊維の紡糸方法に関する：
（ａ）テトラアルコキシシラン及び／又はその縮合物；
（ｂ）以下の式で表わされるアミノ基を含むシラン化合物
Ｒ４−ｎ−Ｓｉ−（ＯＲ’）ｎ
（式中、Ｒはアミノ基含有の有機基を表わし、Ｒ’はメチル基、エチル基またはプロピル基を表わし、ｎは１〜３から選択される整数を表わす）；及び
（ｃ）ホウ酸。
In the present invention, a mixed solution containing the following components (a), (b) and (c) is made into a viscous sol, and the resulting sol-like spinning solution is formed by a potential difference between the charge-providing electrode and the counter electrode. A method for spinning silica-containing fibers, which is spun by electrostatic spraying in a generated electric field:
(A) tetraalkoxysilane and / or a condensate thereof;
(B) Silane compound containing an amino group represented by the following formula: R 4-n —Si— (OR ′) n
(Wherein R represents an amino group-containing organic group, R ′ represents a methyl group, an ethyl group or a propyl group, and n represents an integer selected from 1 to 3); and (c) boric acid.
更に本発明は、前記混合液には、さらに、（ｄ）有機酸を含む、前記のシリカ含有繊維の紡糸方法に関する。
更に本発明は、前記混合液には、さらに、（ｅ）電解質を含む、前記のシリカ含有繊維の紡糸方法に関する。
更に本発明は、前記の紡糸方法によりシリカ含有繊維を紡糸し、前記対向電極面上で前記シリカ含有繊維を堆積させる、シリカ含有繊維からなる不織布の製造方法に関する。
更に本発明は、前記対向電極面に多孔質シート材を張り合わせ、前記の紡糸方法によりシリカ含有繊維を紡糸し、前記シート材に前記シリカ含有繊維を堆積させる、シート材とシリカ含有繊維不織布からなる複合シート材の製造方法に関する。
更に本発明は、前記の製造方法により得られた不織布または複合シート材を含むフィルターに関する。
更に本発明は、前記の方法により不織布を得て、さらに該不織布に樹脂を含浸する積層体の製造方法に関する。
更に本発明は、前記の方法により複合シート材を得て、さらに該複合シート材に樹脂を含浸する積層体の製造方法に関する。
The present invention further relates to the method for spinning silica-containing fibers, wherein the mixed solution further contains (d) an organic acid.
Furthermore, the present invention relates to the method for spinning silica-containing fibers, wherein the mixed solution further contains (e) an electrolyte.
Furthermore, this invention relates to the manufacturing method of the nonwoven fabric which consists of a silica containing fiber which spins a silica containing fiber with the said spinning method, and deposits the said silica containing fiber on the said counter electrode surface.
Furthermore, the present invention comprises a sheet material and a silica-containing fiber nonwoven fabric, in which a porous sheet material is bonded to the surface of the counter electrode, silica-containing fibers are spun by the spinning method, and the silica-containing fibers are deposited on the sheet material. The present invention relates to a method for producing a composite sheet material.
Furthermore, this invention relates to the filter containing the nonwoven fabric or composite sheet material obtained by the said manufacturing method.
Furthermore, this invention relates to the manufacturing method of the laminated body which obtains a nonwoven fabric by the said method and further impregnates this nonwoven fabric with resin.
Furthermore, this invention relates to the manufacturing method of the laminated body which obtains a composite sheet material by the said method, and also impregnates this composite sheet material with resin.
本発明のシリカ含有繊維の紡糸方法によれば、上記成分（ａ）、（ｂ）及び（ｃ）を含む混合液は、安定したゾル状紡糸液を得ることができ、それにより、細繊維化ができ、繊維径のばらつきが低減されたシリカ含有繊維を得ることができる。
更に本発明は、前記のシリカ含有繊維からなる不織布、シート材と前記のシリカ含有繊維不織布からなる複合シート材、前記の不織布または複合シート材を含むフィルター、前記の不織布または複合シート材に樹脂を含浸する積層体、を得ることができる。
According to the spinning method of the silica-containing fiber of the present invention, the mixed solution containing the components (a), (b) and (c) can obtain a stable sol-like spinning solution, thereby reducing the fine fiber. And silica-containing fibers with reduced variation in fiber diameter can be obtained.
Further, the present invention provides a nonwoven fabric comprising the silica-containing fiber, a sheet material and a composite sheet material comprising the silica-containing fiber nonwoven fabric, a filter including the nonwoven fabric or the composite sheet material, and a resin for the nonwoven fabric or the composite sheet material. A laminate to be impregnated can be obtained.
以下に、本発明の実施の形態について、適宜図面を参照しながら説明する。なお、本発明は、これらに限定されるものではない。 Embodiments of the present invention will be described below with reference to the drawings as appropriate. Note that the present invention is not limited to these.
（ａ）成分のテトラアルコキシシラン及び／又はその縮合物は、液体であることが好ましい。アルコキシ基としては、メトキシ、エトキシ、プロポキシ、ブトキシ、及びそれ以上の炭素数を有するアルコキシ基を挙げることができる。メトキシ、エトキシ、プロポキシ、及びブトキシが好ましく、メトキシ及びエトキシがより好ましい。 The tetraalkoxysilane and / or condensate thereof as component (a) is preferably a liquid. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and alkoxy groups having more carbon atoms. Methoxy, ethoxy, propoxy, and butoxy are preferred, and methoxy and ethoxy are more preferred.
（ａ）成分のテトラアルコキシシランの具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシランなどを挙げることができる。その中でも、より好ましいものとしては、テトラエトキシシラン及びテトラメトキシシランを挙げることができる。 Specific examples of the component (a) tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Among these, tetraethoxysilane and tetramethoxysilane are more preferable.
（ａ）成分のテトラアルコキシシラン及び／又はその縮合物の使用量は、成分（ａ）、（ｂ）及び（ｃ）を含む混合液中で、３０〜８０重量％含有するのが好ましい。より好ましくは、４０〜７０重量％である。（ａ）成分の添加量が多すぎる場合には、硬度が低下する傾向があり、逆に、少なすぎる場合には、Ｓｉ含有量が少なくなるので用途によっては硬度が低下したり、化学的耐久性の問題が発生することがある。また、（ａ）成分の添加量が多すぎる場合には、混合液のゾル化時間が長くなることがある。逆に、少なすぎる場合には，混合液が固化することがある。 The amount of the (a) component tetraalkoxysilane and / or its condensate is preferably 30 to 80% by weight in the mixed solution containing the components (a), (b) and (c). More preferably, it is 40 to 70% by weight. When the amount of component (a) is too large, the hardness tends to decrease. Conversely, when the amount is too small, the Si content decreases, so that the hardness may decrease or chemical durability may increase depending on the application. Sexual problems may occur. Moreover, when there is too much addition amount of (a) component, the sol-formation time of a liquid mixture may become long. On the other hand, when the amount is too small, the mixed solution may solidify.
（ａ）成分のテトラアルコキシシランの縮合物としては、上記テトラアルコキシシランの２量体〜２０量体を挙げることができる。その中でも、５量体が特に好ましい。 Examples of the tetraalkoxysilane condensate of component (a) include dimers to 20mers of the above tetraalkoxysilane. Among these, a pentamer is particularly preferable.
（ｂ）成分は、以下の式で表わされるアミノ基を含むシラン化合物である。
Ｒ４−ｎ−Ｓｉ−（ＯＲ’）ｎ
（式中、Ｒはアミノ基含有の有機基を表わし、Ｒ’はメチル基、エチル基またはプロピル基を表わし、ｎは１〜３から選択される整数を表わす。）
The component (b) is a silane compound containing an amino group represented by the following formula.
R4 -n- Si- (OR ') n
(In the formula, R represents an amino group-containing organic group, R ′ represents a methyl group, an ethyl group or a propyl group, and n represents an integer selected from 1 to 3).
ここで、Ｒはアミノ基含有の有機基を表わすが、たとえば、モノアミノメチル、ジアミノメチル、トリアミノメチル、モノアミノエチル、ジアミノエチル、トリアミノエチル、テトラアミノエチル、モノアミノプロピル、ジアミノプロピル、トリアミノプロピル、テトラアミノプロピル、モノアミノブチル、ジアミノブチル、トリアミノブチル、テトラアミノブチル、及び、これらよりも炭素数の多いアルキル基またはアリール基を有する有機基を挙げることができるが、それらに限定されない。γ−アミノプロピルや、アミノエチルアミノプロピルが特に好ましく、γ−アミノプロピルが最も好ましい。 Here, R represents an amino group-containing organic group. For example, monoaminomethyl, diaminomethyl, triaminomethyl, monoaminoethyl, diaminoethyl, triaminoethyl, tetraaminoethyl, monoaminopropyl, diaminopropyl, Examples include triaminopropyl, tetraaminopropyl, monoaminobutyl, diaminobutyl, triaminobutyl, tetraaminobutyl, and organic groups having an alkyl group or aryl group having more carbon atoms than these. It is not limited. γ-aminopropyl and aminoethylaminopropyl are particularly preferred, and γ-aminopropyl is most preferred.
（ｂ）成分中のＲ’はメチル基、エチル基またはプロピル基を表わす。その中でも、メチル基及びエチル基が好ましい。 R 'in the component (b) represents a methyl group, an ethyl group or a propyl group. Among these, a methyl group and an ethyl group are preferable.
（ｂ）成分中のｎは１〜３から選択される整数を表わす。その中でも、ｎは２〜３であるのが好ましく、ｎは３であるのが特に好ましい。
すなわち、（ｂ）成分としては、モノアミノシランが好ましく、γ−アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシランが特に好ましい。
In the component (b), n represents an integer selected from 1 to 3. Among them, n is preferably 2 to 3, and n is particularly preferably 3.
That is, as the component (b), monoaminosilane is preferable, and γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane are particularly preferable.
（ｂ）成分の使用量は、成分（ａ）、（ｂ）及び（ｃ）を含む混合液中で、１０〜４０重量％含有するのが好ましい。より好ましくは、２０〜３５重量％である。 Component (b) is preferably used in an amount of 10 to 40% by weight in the mixed solution containing components (a), (b) and (c). More preferably, it is 20 to 35% by weight.
本発明において、（ｃ）成分のホウ酸の使用量は、成分（ａ）、（ｂ）及び（ｃ）を含む混合液中で、０．１〜１０重量％含有するのが好ましい。より好ましくは、５〜１２重量％である。 In this invention, it is preferable to contain 0.1-10 weight% of usage-amounts of the boric acid of (c) component in the liquid mixture containing component (a), (b) and (c). More preferably, it is 5 to 12% by weight.
本発明において混合液を得るための方法は、特に限定されない。例えば、（ａ）成分、（ｂ）成分及び（ｃ）成分の混合条件（温度、混合時間、混合方法など）は、適宜選択することができる。 The method for obtaining the mixed liquid in the present invention is not particularly limited. For example, the mixing conditions (temperature, mixing time, mixing method, etc.) of the component (a), the component (b) and the component (c) can be appropriately selected.
テトラアルコキシシラン及び／又はその縮合物は、エタノールなどの有機溶剤や水に溶解させると、通常、加水分解と縮合反応によりゾル化して、増粘する。しかし、本発明において、混合液は安定したゾル液とすることができる。これは、（ｂ）成分のアミノ基を含むシラン化合物が活性剤として機能していると考えられ、（ａ）成分のテトラアルコキシシラン及び／又はその縮合物分子量増加のばらつきを低減すること、及び、加水分解が平衡反応として進行するために、安定したゾル液とすることができると考えられる。また、（ｃ）成分のホウ酸は、４配位のホウ素として（ｂ）成分の安定した架橋剤として機能する。 When tetraalkoxysilane and / or a condensate thereof are dissolved in an organic solvent such as ethanol or water, the tetraalkoxysilane is usually made into a sol by hydrolysis and condensation reaction to increase the viscosity. However, in the present invention, the mixed solution can be a stable sol solution. This is considered that the silane compound containing the amino group of the component (b) functions as an activator, and reduces the variation in the molecular weight increase of the tetraalkoxysilane and / or its condensate of the component (a), and It is considered that a stable sol solution can be obtained because hydrolysis proceeds as an equilibrium reaction. Moreover, the boric acid of (c) component functions as a stable crosslinking agent of (b) component as tetracoordinate boron.
本発明において、前記混合液の粘性ゾル化により、１００ｃＰ〜５００ｃＰ（１００ｍＰａ・ｓ〜５００ｍＰａ・ｓ）の粘度を有するゾル状紡糸液とするのが好ましい。
本発明におけるゾル状紡糸液は、純粋なシリカからなるシリカ繊維を製造するために有効である。しかし、用途に応じ、紡糸液に含まれる添加物として従来知られているもの、例えば、ポリエチレングリコール等の粘度調整剤、アルキルアルコキシシラン、粒状シリカ等を含んでもかまわない。
In the present invention, a sol-like spinning solution having a viscosity of 100 cP to 500 cP (100 mPa · s to 500 mPa · s) is preferably obtained by forming the mixed solution into a viscous sol.
The sol spinning solution in the present invention is effective for producing silica fibers composed of pure silica. However, depending on the application, a conventionally known additive contained in the spinning solution, for example, a viscosity modifier such as polyethylene glycol, alkylalkoxysilane, and granular silica may be included.
本発明において、前記混合液を粘性ゾル化させてゾル状紡糸液を得る方法は、特に限定されない。例えば、同ゾル状紡糸液を得るために用いる装置としては、例えば、図１に示すような装置を用いることができる。図１において、エアポンプ１からバイアル２へ空気を送り込み、バイアル２からフラスコ５内へ加湿した空気を導入し、フラスコ５内で、粘性ゾル化反応が行われる。 In the present invention, a method for obtaining a sol-like spinning solution by forming the mixed solution into a viscous sol is not particularly limited. For example, as an apparatus used for obtaining the sol-like spinning solution, for example, an apparatus as shown in FIG. 1 can be used. In FIG. 1, air is fed from the air pump 1 to the vial 2, humid air is introduced from the vial 2 into the flask 5, and a viscous solification reaction is performed in the flask 5.
本発明においては、得られたゾル状紡糸液を紡糸するには、電荷付与電極と対向電極との間の電位差によって形成された電界中で静電噴霧法により紡糸する。このような静電噴霧法による紡糸手段は、特に限定されない。
このような静電噴霧法による紡糸手段として、例えば、ゾル状紡糸液を回転式の電荷付与電極の表面に供給し、回転している電荷付与電極上の表面であって対向電極に近付いた表面上に紡糸表面が発生し、その紡糸表面から対向電極に向かってゾル状紡糸液が紡糸される紡糸方法によって紡糸化させる手段とすることができる。
このような紡糸方法としては、例えば、図２に示すような装置を用いた方法が好ましいものとして挙げられる。図２においては、容器８中にゾル状紡糸液９を入れ、そのゾル紡糸液９に回転式の電荷付与電極１０を部分的に浸漬させる。この電極１０に電圧を印加し、この回転式の電荷付与電極１０が回転することにより、その電極表面に付着したゾル状紡糸液１１が電界中に導入され、回転式の電荷付与電極表面に付着したゾル状紡糸液が対向電極１２に近づいて紡糸表面１３が発生し、その紡糸表面から対向電極に向かってゾル状紡糸液１４が吹き流されて紡糸される。このように、回転式の電荷付与電極を用いることにより、この電極の円周表面に付着したゾル状紡糸液が、電極の回転により対向電極に近づき、円周表面では電界集中の効果により強力な電界が発生し、ゾル状紡糸液表面に荷電を持つイオンが集まり、対向電極に引き寄せられて、紡糸化される。このように、回転式の電荷付与電極を用いることにより、高い紡糸能力が達成される。
また、ローラーからの紡糸の開始点を選択的または、積極的に作るためにローラーに凹凸をつけることがさらに望ましい。
また、ローラー側をマイナス、対向側をプラスに印加することも可能である。
In the present invention, the obtained sol-like spinning solution is spun by electrostatic spraying in an electric field formed by a potential difference between the charge-providing electrode and the counter electrode. The spinning means by such an electrostatic spray method is not particularly limited.
As a spinning means by such an electrostatic spray method, for example, a sol-like spinning solution is supplied to the surface of a rotating charge applying electrode, and the surface on the rotating charge applying electrode is close to the counter electrode. A spinning surface is generated on the spinning surface, and a sol-like spinning solution is spun from the spinning surface toward the counter electrode.
As such a spinning method, for example, a method using an apparatus as shown in FIG. 2 is preferable. In FIG. 2, a sol-like spinning solution 9 is put in a container 8, and a rotary charge applying electrode 10 is partially immersed in the sol spinning solution 9. When a voltage is applied to the electrode 10 and the rotary charge applying electrode 10 rotates, the sol-like spinning solution 11 adhering to the electrode surface is introduced into the electric field and attached to the rotary charge applying electrode surface. The sol-like spinning solution approaches the counter electrode 12 to generate a spinning surface 13, and the sol-like spinning solution 14 is blown and spun from the spinning surface toward the counter electrode. In this way, by using the rotary charge-providing electrode, the sol-like spinning solution adhering to the circumferential surface of this electrode approaches the counter electrode due to the rotation of the electrode, and the circumferential surface has a stronger electric field concentration effect. An electric field is generated, and charged ions are collected on the surface of the sol-like spinning solution, attracted to the counter electrode, and spun. Thus, a high spinning capacity is achieved by using a rotary type charge application electrode.
Further, it is more desirable to make the roller uneven in order to selectively or actively make the starting point of spinning from the roller.
It is also possible to apply the roller side to minus and the opposite side to plus.
本発明では、図３に示したように、対向電極の表面上にシート１５をあらかじめおき、そのシート１５をベルトコンベア１６でゆっくり動かし、回転式の電荷付与電極から対向電極に向かって噴射されるシリカ繊維をそのシートに付着させて膜、シートまたは不織布が形成されるように製造させることもできる。そのようなシートとしては、キャリアーフィルムが挙げられる。
また、回転式の電荷付与電極から対向電極に向かって空気が流れるようにして、回転式の電荷付与電極表面から対向電極に向かってゾル状紡糸液が紡糸されるのを促進し、紡糸されたシリカ繊維を乾燥させることもできる。
このような静電噴霧法による紡糸方法では、回転式の電荷付与電極と対向電極の距離は、通常、１ｃｍから１００ｃｍ、好ましくは、１．２ｃｍから５０ｃｍ、さらに好ましくは１．５ｃｍから４０ｃｍであり、印加する電界強度は、通常、０．１ｋＶ／ｃｍから２５ｋＶ／ｃｍ、好ましくは０．５ｋＶ／ｃｍから２０ｋＶ／ｃｍである。
以上に説明した静電噴霧法による紡糸方法は、ＷＯ ２００５／０２４１０１Ａ１が参照される。
In the present invention, as shown in FIG. 3, a sheet 15 is placed on the surface of the counter electrode in advance, and the sheet 15 is slowly moved by the belt conveyor 16 and sprayed from the rotary charge applying electrode toward the counter electrode. Silica fibers can be attached to the sheet so that a film, sheet or nonwoven fabric is formed. An example of such a sheet is a carrier film.
In addition, air was allowed to flow from the rotary charge applying electrode toward the counter electrode, and the sol-like spinning solution was spun from the surface of the rotary charge applying electrode toward the counter electrode. Silica fibers can also be dried.
In the spinning method based on the electrostatic spraying method, the distance between the rotary charge applying electrode and the counter electrode is usually 1 cm to 100 cm, preferably 1.2 cm to 50 cm, more preferably 1.5 cm to 40 cm. The applied electric field strength is usually from 0.1 kV / cm to 25 kV / cm, preferably from 0.5 kV / cm to 20 kV / cm.
WO 2005/024101 A1 is referred to for the spinning method based on the electrostatic spray method described above.
このようにして得られたゲル状のシリカ繊維を、例えば、６００から１０００℃で加熱焼成することによりガラス状のシリカ繊維を製造することができる。 A glassy silica fiber can be produced by heating and baking the gel-like silica fiber thus obtained at 600 to 1000 ° C., for example.
本発明における混合液は、粘性ゾル化のために増粘するには、数十時間もの長い時間かかることがある。そこで、同混合液は、上記の（ａ）成分、（ｂ）成分及び（ｃ）成分以外に、有機酸（（ｄ）成分）を含むことができ、これにより、約５〜３０分で増粘することができる。（ｄ）成分の有機酸としては特に限定されないが、例えば、クエン酸、フタル酸、マレイン酸、及び酢酸を挙げることができ、好ましくは、クエン酸を挙げることができる。（ｄ）成分の使用量は、特に限定されないが、同混合液中で、０〜１０重量％含有するのが好ましい。より好ましくは０．１〜１０重量％、更に好ましくは、０．５〜８重量％である。（ｄ）成分の添加により、径がより細い繊維（フィラメント）を容易に得ることができ、得られる繊維のばらつきも小さくなる傾向となる。これは、（ｄ）成分の有機酸を添加することにより、（ｂ）成分のアミノ基を含むシラン化合物の加水分解が進むことで、増粘時間が短縮できるとともに、（ａ）成分の加水分解も（ｂ）成分の触媒的な働きにより促進させるからだと考えられる。これにより、分子量のばらつきが小さくなるため、紡糸条件による細いフィラメント径を得ることが容易になり、ばらつきも小さくなると考えられる。 The liquid mixture in the present invention may take as long as several tens of hours to thicken due to viscous sol formation. Therefore, the liquid mixture can contain an organic acid (component (d)) in addition to the components (a), (b) and (c) described above, thereby increasing in about 5 to 30 minutes. Can be sticky. Although it does not specifically limit as an organic acid of (d) component, For example, a citric acid, a phthalic acid, a maleic acid, and an acetic acid can be mentioned, Preferably a citric acid can be mentioned. Although the usage-amount of (d) component is not specifically limited, It is preferable to contain 0 to 10weight% in the same liquid mixture. More preferably, it is 0.1-10 weight%, More preferably, it is 0.5-8 weight%. By adding the component (d), fibers (filaments) having a smaller diameter can be easily obtained, and variations in the obtained fibers tend to be reduced. This is because the addition of the organic acid of component (d) advances the hydrolysis of the silane compound containing the amino group of component (b), thereby shortening the thickening time and the hydrolysis of component (a). This is also because it is promoted by the catalytic action of component (b). Thereby, since the variation in molecular weight is reduced, it is easy to obtain a thin filament diameter depending on the spinning conditions, and the variation is considered to be reduced.
本発明における混合液は、更に、電解質（（ｅ）成分）を含むことができる。（ｅ）成分の添加により、電気伝導度が上昇し、フィラメント径をより細くする（例えば、１μｍ以下にする）ことができる。（ｅ）成分の電解質は特に限定されないが、例えば、ナトリウムエチラート及びＮａＣｌなどのＮａ化合物を挙げることができ、好ましくは、ＮａＣｌメタノール溶液を挙げることができる。（ｅ）成分の使用量は、特に限定されないが、同混合液中で、０〜２重量％含有するのが好ましい。より好ましくは、０．００００１〜０．５重量％である。 The mixed liquid in the present invention can further contain an electrolyte (component (e)). By adding the component (e), the electrical conductivity is increased, and the filament diameter can be further reduced (for example, 1 μm or less). Although the electrolyte of (e) component is not specifically limited, For example, Na compounds, such as sodium ethylate and NaCl, can be mentioned, Preferably, a NaCl methanol solution can be mentioned. Although the usage-amount of (e) component is not specifically limited, It is preferable to contain 0 to 2weight% in the same liquid mixture. More preferably, it is 0.00001 to 0.5 weight%.
静電紡糸法は、電場によってノズル先端の気液界面上（半球状の液体表面）に誘起された帯電荷間の静電反発力に基づく紡糸法である。絶縁性の液体に比べると、ある程度電気伝導性のある液体の方が、電気抵抗が小さいため気液界面にかかる実効的な電場が大きくなり、その結果静電反発力が強くなるために、細径化が起こると考えられる。ただし、液体の電気伝導度が大きくなりすぎると、帯電した電荷が液体内で循環電流を形成し、静電反発力は反対に強くなる。 The electrostatic spinning method is a spinning method based on an electrostatic repulsion force between band charges induced on the gas-liquid interface at the nozzle tip (hemispherical liquid surface) by an electric field. Compared to insulating liquids, liquids that have a certain degree of electrical conductivity have a lower electrical resistance, so the effective electric field applied to the gas-liquid interface is larger, and as a result, the electrostatic repulsion is stronger. It is thought that diameter reduction occurs. However, if the electrical conductivity of the liquid becomes too high, the charged charges form a circulating current in the liquid, and the electrostatic repulsion force becomes stronger on the contrary.
このように、（ａ）成分及び（ｂ）成分及び（ｃ）成分を含む混合液を用いると、フィラメント径が１．０〜１０μｍのシリカ含有繊維フィラメントを得ることができるのに対し、（ａ）成分〜（ｅ）成分を含む混合液を用いると、フィラメント径が１μｍ以下の非常に細く、フィラメント径のばらつきがより小さいフィラメントを得ることができる。本発明においては、前記混合液は、上記（ａ）成分〜（ｅ）成分以外に、残余の水を含むことができる。 As described above, when a mixed solution containing the component (a), the component (b), and the component (c) is used, a silica-containing fiber filament having a filament diameter of 1.0 to 10 μm can be obtained. When a mixed solution containing the components (a) to (e) is used, a filament with a very small filament diameter of 1 μm or less and a smaller variation in filament diameter can be obtained. In the present invention, the mixed liquid may contain residual water in addition to the components (a) to (e).
本発明においては、上記の本発明の紡糸方法によりシリカ含有繊維を紡糸し、前記対向電極面上で前記シリカ含有繊維を堆積させることにより、シリカ含有繊維からなる不織布を製造することができる。当該堆積方法は特に限定されない。得られる不織布の単位重量は特に限定されず、どのようにでも制御可能であるが、実用上、１〜１００ｇ／ｍ２程度が好ましい。 In this invention, the nonwoven fabric which consists of a silica containing fiber can be manufactured by spinning a silica containing fiber with the said spinning method of this invention, and depositing the said silica containing fiber on the said counter electrode surface. The deposition method is not particularly limited. The unit weight of the resulting nonwoven fabric is not particularly limited and can be controlled in any way, but is preferably about 1 to 100 g / m 2 for practical use.
本発明においては、前記対向電極面に多孔質シート材を張り合わせ、上記の本発明の紡糸方法によりシリカ含有繊維を紡糸し、前記シート材に前記シリカ含有繊維を堆積させることにより、シート材とシリカ含有繊維不織布からなる複合シート材を製造することができる。当該多孔質シート材としては特に限定されないが、金属箔、樹脂シート、織布、不織布などを挙げることができ、好ましくは、ガラスクロスなどのガラス繊維織布及びガラス繊維不織布を挙げることができる。 In the present invention, a porous sheet material is bonded to the surface of the counter electrode, the silica-containing fiber is spun by the spinning method of the present invention, and the silica-containing fiber is deposited on the sheet material, whereby the sheet material and the silica are deposited. The composite sheet material which consists of a containing fiber nonwoven fabric can be manufactured. Although it does not specifically limit as the said porous sheet material, Metal foil, a resin sheet, a woven fabric, a nonwoven fabric etc. can be mentioned, Preferably, glass fiber woven fabrics and glass fiber nonwoven fabrics, such as a glass cloth, can be mentioned.
本発明より得られる前記シリカ含有繊維からなる不織布及び複合シート材は、従来公知の結合剤で補強してもよい。国際公開公報ＷＯ２００６／１２９６９５Ａ１の特許請求の範囲に記載の有機シラン化合物とホウ素化合物からなる高分子物質を結合剤として使用すると、屈折率をあわせることができるため、透明なシートを作製できるために、好ましい。 The nonwoven fabric and composite sheet material made of the silica-containing fibers obtained from the present invention may be reinforced with a conventionally known binder. In order to produce a transparent sheet because a refractive index can be adjusted by using a polymer material composed of an organosilane compound and a boron compound as described in the claims of International Publication WO2006 / 129695A1, preferable.
本発明より得られる前記シリカ含有繊維は抗菌性を有し、また本発明における上記混合液または前記の結合剤に、銀イオン（硝酸銀など）を含有する抗菌剤を追加すれば、より抗菌性の効果が高い不織布や複合シート材を得ることができる。 The silica-containing fiber obtained from the present invention has antibacterial properties, and if an antibacterial agent containing silver ions (such as silver nitrate) is added to the mixed solution or the binder in the present invention, the antibacterial properties are further improved. A highly effective nonwoven fabric or composite sheet material can be obtained.
本発明においては、上記の本発明により得られた不織布または複合シート材を含むフィルターを得ることができる。このようなフィルターとしては、例えば、当該不織布を有機質繊維または無機質繊維の織布で挟み込んだフィルターや、当該複合シート材と有機質繊維または無機質繊維の織布を積層したフィルターなどを挙げることができる。 In this invention, the filter containing the nonwoven fabric or composite sheet material obtained by said this invention can be obtained. Examples of such a filter include a filter in which the nonwoven fabric is sandwiched between woven fabrics of organic fibers or inorganic fibers, and a filter in which the composite sheet material is laminated with a woven fabric of organic fibers or inorganic fibers.
本発明においては、上記の本発明により得られた不織布あるいは複合シート材に樹脂を含浸することにより、積層体を製造することができる。 In this invention, a laminated body can be manufactured by impregnating resin in the nonwoven fabric or composite sheet material obtained by said this invention.
以下に、本発明を実施例および比較例により更に詳細に説明するが、本発明はこれらの例に何ら限定されるものではない。 The present invention will be described in more detail with reference to examples and comparative examples below, but the present invention is not limited to these examples.
実施例
表１に示す各成分の添加量を配合し、それぞれのフィラメントを作製した。
Example The addition amount of each component shown in Table 1 was mix | blended, and each filament was produced.
実施例１
（ａ）成分としてテトラエトキシシラン（ＴＥＯＳ）、（ｂ）成分としてγ−アミノプロピルトリエトキシシラン、（ｃ）成分としてホウ酸を用い、表１に示す添加量を配合して混合液を得、混合して粘性ゾル化させ、１００ｃＰまで増粘する時間を測定した。１００ｃＰまで増粘した後に、得られたゾル状紡糸液を、図２に示す装置を用いて静電噴霧法により紡糸し、シリカ含有繊維を得た。静電噴霧は、電圧２０ｋＶ、電極基板間距離１２ｃｍで実施した。得られた繊維のフィラメント直径を測定した。このようにして得られた結果を、表１に示す。
Example 1
Using tetraethoxysilane (TEOS) as component (a), γ-aminopropyltriethoxysilane as component (b), boric acid as component (c), and adding the amounts shown in Table 1 to obtain a mixture, The mixture was mixed to form a viscous sol, and the time for increasing the viscosity to 100 cP was measured. After thickening to 100 cP, the obtained sol-like spinning solution was spun by electrostatic spraying using the apparatus shown in FIG. 2 to obtain silica-containing fibers. The electrostatic spraying was performed at a voltage of 20 kV and a distance between electrode substrates of 12 cm. The filament diameter of the obtained fiber was measured. The results thus obtained are shown in Table 1.
実施例２
（ｄ）成分の有機酸としてクエン酸を用い、表１に示す添加量を配合した以外は、実施例１と同様にして実施した。得られた結果を、表１に示す。
Example 2
(D) It carried out like Example 1 except using citric acid as an organic acid of an ingredient, and blending the addition amount shown in Table 1. The obtained results are shown in Table 1.
実施例３
（ｅ）成分の電解質としてＮａＣｌを用い、表１に示す添加量を配合した以外は、実施例１と同様にして実施した。得られた結果を、表１に示す。
Example 3
(E) It carried out like Example 1 except using NaCl as an electrolyte of an ingredient and having blended the addition amount shown in Table 1. The obtained results are shown in Table 1.
実施例４
（ｄ）成分の有機酸としてクエン酸を用い、（ｅ）成分の電解質としてＮａＣｌを用い、表１に示す添加量を配合した以外は、実施例１と同様にして実施した。得られた結果を、表１に示す。
Example 4
It was carried out in the same manner as in Example 1 except that citric acid was used as the organic acid of component (d), NaCl was used as the electrolyte of component (e), and the addition amounts shown in Table 1 were blended. The obtained results are shown in Table 1.
比較例１
粘性ゾル化を１０時間で中止し、７０ｃＰまで増粘した後に、得られたゾル状紡糸液を紡糸した以外は、実施例１と同様にして実施した。得られた結果を、表１に示す。
Comparative Example 1
It was carried out in the same manner as in Example 1 except that the viscous solation was stopped in 10 hours, the viscosity was increased to 70 cP, and then the obtained sol-like spinning solution was spun. The obtained results are shown in Table 1.
実施例５（粘度の検討）
（ａ）成分としてＴＥＯＳの代わりにテトラエトキシシランの縮合物（５量体）を用い、以下の粘度（７０ｃＰ、１１０ｃＰ、あるいは、３００ｃＰ）まで増粘した後に、得られたゾル状紡糸液を紡糸した以外は、実施例１と同様にして実施した。
１−Ａ： ７０ｃＰ（比較例）
１−Ｂ：１１０ｃＰ
１−Ｃ：３００ｃＰ
得られたシリカ含有繊維の写真を、図４に示す。低い粘度（７０ｃＰ）では、繊維が作製できずに粒子形状しか得られなかったのに対し、粘度が上昇するにつれ（１１０ｃＰあるいは３００ｃＰ）、繊維形状を示した。
Example 5 (Examination of viscosity)
(A) A tetraethoxysilane condensate (pentamer) is used in place of TEOS as the component, and after thickening to the following viscosity (70 cP, 110 cP, or 300 cP), the resulting sol spinning solution is spun. Except that, it was carried out in the same manner as in Example 1.
1-A: 70 cP (comparative example)
1-B: 110 cP
1-C: 300 cP
A photograph of the resulting silica-containing fiber is shown in FIG. At low viscosity (70 cP), fibers could not be produced and only a particle shape was obtained, whereas as the viscosity increased (110 cP or 300 cP), the fiber shape was shown.
実施例６（（ｄ）成分の添加量の検討）
実施例１で使用した混合液に、（ｄ）成分としてクエン酸を以下の濃度添加して、紡糸した以外は、実施例１と同様にして実施した。なお、静電噴霧法により紡糸できるようになるまでのゾル状紡糸液の粘度（１１０ｃＰ〜２００ｃＰ）となるまでの時間は、実施例１の３０時間から、５〜３０分に短縮できた。
２−Ａ： １．５ ｗｔ％
２−Ｂ： ２．０ ｗｔ％
２−Ｃ： ２．５ ｗｔ％
２−Ｄ： ３．０ ｗｔ％
得られたシリカ含有繊維の写真を、図５に示す。（ｄ）成分を添加しない１−Ｂに比べてフィラメント径の細い繊維が得られた。また、より高い濃度（２−Ｃ及び２−Ｄ）では、より細く（平均繊維径は、２−Ｃでは１．２μｍ、２−Ｄでは、２．１μｍ）、より均一なファイバーが得られた。
Example 6 (Examination of addition amount of component (d))
The same procedure as in Example 1 was performed except that citric acid was added to the mixed solution used in Example 1 as a component (d) in the following concentration and spun. In addition, the time until it became the viscosity (110 cP to 200 cP) of the sol-like spinning solution until spinning by the electrostatic spraying method was shortened from 30 hours in Example 1 to 5 to 30 minutes.
2-A: 1.5 wt%
2-B: 2.0 wt%
2-C: 2.5 wt%
2-D: 3.0 wt%
The photograph of the obtained silica containing fiber is shown in FIG. (D) A fiber having a smaller filament diameter was obtained compared to 1-B to which no component was added. Further, at higher concentrations (2-C and 2-D), the fibers were thinner (average fiber diameter was 1.2 μm for 2-C and 2.1 μm for 2-D), and a more uniform fiber was obtained. .
実施例７（（ｅ）成分の添加量の検討）
実施例６で使用した混合液（２−Ｃ）に、（ｅ）成分としてＮａＣｌメタノール溶液をＮａＣｌ濃度として以下の濃度添加して、紡糸した以外は、実施例６と同様にして実施した。なお、１１０ｃＰ〜２００ｃＰの粘度を有するゾル状紡糸液を紡糸した。ここでは、ゾル状紡糸液に電解質を添加することによる細径化を試みた。
３−Ａ： １６ ｍｇ／Ｌ
３−Ｂ： ３．４ ｇ／Ｌ
得られたシリカ含有繊維の写真を、図６に示す。（ｅ）成分を添加しない２−Ｃに比べてフィラメント径が細く（平均繊維径は、３−Ａでは０．８２μｍ、３−Ｂでは、０．４２μｍ）、より均一な繊維（ファイバー）が得られた。
Example 7 (Examination of addition amount of component (e))
The same procedure as in Example 6 was carried out except that the mixture (2-C) used in Example 6 was spun by adding a NaCl methanol solution as the (e) component at the following concentration as the NaCl concentration and spinning. A sol spinning solution having a viscosity of 110 cP to 200 cP was spun. Here, an attempt was made to reduce the diameter by adding an electrolyte to the sol spinning solution.
3-A: 16 mg / L
3-B: 3.4 g / L
The photograph of the obtained silica containing fiber is shown in FIG. (E) The filament diameter is smaller than that of 2-C to which no component is added (average fiber diameter is 0.82 μm for 3-A and 0.42 μm for 3-B), and a more uniform fiber (fiber) is obtained. It was.
実施例８（（ｅ）成分の添加量の検討）
添加した（ｅ）成分のＮａＣｌの濃度を様々に変えた以外は、実施例７と同様にして実施した。得られたシリカ含有繊維の平均繊維径と、添加した（ｅ）成分のＮａＣｌの濃度との関係を表わすグラフを、図７に示す。図７のグラフ（「ＮａＣｌ添加による平均繊維径の変化」）において、横軸は、添加した（ｅ）成分のＮａＣｌの濃度Ｃ（対数目盛）を表わし、縦軸は、得られたシリカ含有繊維の平均繊維径を表わす。ＮａＣｌ濃度の増加と共に、得られたシリカ含有繊維の平均繊維径は、約０．４μｍ程度に接近した。
Example 8 (Examination of addition amount of component (e))
The same procedure as in Example 7 was performed, except that the concentration of the added component (e) NaCl was variously changed. FIG. 7 shows a graph representing the relationship between the average fiber diameter of the obtained silica-containing fibers and the concentration of the added component (e) NaCl. In the graph of FIG. 7 (“change in average fiber diameter due to addition of NaCl”), the horizontal axis represents the concentration C (logarithmic scale) of NaCl of the added component (e), and the vertical axis represents the obtained silica-containing fiber. Represents the average fiber diameter. As the NaCl concentration increased, the average fiber diameter of the obtained silica-containing fibers approached about 0.4 μm.
実施例９（（a）〜（ｃ）成分の検討）
実施例１に対して（ａ）ＴＥＯＳ４４．５重量％、（ｂ）γ−アミノプロピルトリエトキシシラン４４．５重量％、（ｃ）ホウ酸１１．1重量％の組成でゾル化を検討した。ゾル状紡糸液（１１０ｃＰ〜２００ｃＰ）の粘度となるまでの時間に変化はなく、直径５μｍの均一なファイバーが得られた。
Example 9 (Examination of (a) to (c) components)
With respect to Example 1, sol-formation was studied with a composition of (a) 44.5% by weight of TEOS, (b) 44.5% by weight of γ-aminopropyltriethoxysilane, and (c) 11.1% by weight of boric acid. There was no change in the time until the viscosity of the sol spinning solution (110 cP to 200 cP) was reached, and a uniform fiber having a diameter of 5 μm was obtained.
（試料の抗菌性についての効果）
実施例２及び４で得られた繊維を不織布にし、ＪＩＳ Ｌ１９０２「繊維製品の抗菌性試験方法・抗菌効果」に準じ、黄色ブドウ球菌に対する抗菌性を確認したところ抗菌性が認められた。得られた結果を、表２に示す。
(Effects on antibacterial properties of samples)
The fibers obtained in Examples 2 and 4 were made into non-woven fabrics, and antibacterial properties against Staphylococcus aureus were confirmed according to JIS L1902 “Method for testing antibacterial properties of fiber products / antibacterial effect”. The results obtained are shown in Table 2.
本発明のシリカ含有繊維の紡糸方法によれば、安定したゾル状紡糸液を得ることができ、それにより、細繊維化ができ、繊維径のばらつきが低減されたシリカ含有繊維を得ることができる。
更に本発明によれば、前記のシリカ含有繊維からなる不織布、シート材と前記のシリカ含有繊維不織布からなる複合シート材、前記の不織布または複合シート材を含むフィルター、前記の不織布または複合シート材に樹脂を含浸する積層体、を得ることができる。
According to the spinning method of the silica-containing fiber of the present invention, a stable sol-like spinning solution can be obtained, whereby a silica-containing fiber that can be made into a fine fiber and that has a reduced fiber diameter variation can be obtained. .
Further, according to the present invention, the nonwoven fabric composed of the silica-containing fiber, the composite sheet material composed of the sheet material and the silica-containing fiber nonwoven fabric, the filter including the nonwoven fabric or the composite sheet material, the nonwoven fabric or the composite sheet material A laminate that is impregnated with a resin can be obtained.
１ エアポンプ
２ バイアル
３ 油浴
４ スターラ
５ フラスコ
６ 冷却管
７ テトラエトキシシランの縮重合体を溶解させた混合溶媒
８ 容器
９ ゾル状紡糸液
１０ 回転式の電荷付与電極
１１ ゾル状紡糸液
１２ 対向電極
１３ 紡糸表面
１４ ゾル状紡糸液
１５ シート
１６ ベルトコンベア
DESCRIPTION OF SYMBOLS 1 Air pump 2 Vial 3 Oil bath 4 Stirrer 5 Flask 6 Cooling tube 7 Mixed solvent which melt | dissolved polycondensation polymer of tetraethoxysilane 8 Container 9 Sol-type spinning solution 10 Rotating-type charge-providing electrode 11 Sol-type spinning solution 12 Counter electrode 13 Spinning surface 14 Sol-like spinning solution 15 Sheet 16 Belt conveyor
Claims (8)
（ａ）テトラアルコキシシラン及び／又はその縮合物；
（ｂ）以下の式で表わされるアミノ基を含むシラン化合物
Ｒ４−ｎ−Ｓｉ−（ＯＲ’）ｎ
（式中、Ｒはアミノ基含有の有機基を表わし、Ｒ’はメチル基、エチル基またはプロピル基を表わし、ｎは１〜３から選択される整数を表わす）；及び
（ｃ）ホウ酸。 In a mixed solution containing the following components (a), (b) and (c ), 30 to 80% by weight of component (a), 10 to 40% by weight of component (b) and 0. A sol-like spinning solution having a viscosity of 100 cP to 500 cP (100 mPa · s to 500 mPa · s) obtained by making a mixed solution containing 1 to 10% by weight into a viscous sol is formed between the charge applying electrode and the counter electrode. A method for spinning a silica-containing fiber, which is spun by an electrostatic spraying method in an electric field formed by a potential difference of:
(A) tetraalkoxysilane and / or a condensate thereof;
(B) Silane compound containing an amino group represented by the following formula: R 4-n —Si— (OR ′) n
(Wherein R represents an amino group-containing organic group, R ′ represents a methyl group, an ethyl group or a propyl group, and n represents an integer selected from 1 to 3); and (c) boric acid.
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