JPH04238807A - Fine particulate semi-spherical silica and production thereof and resin film using the same - Google Patents
Fine particulate semi-spherical silica and production thereof and resin film using the sameInfo
- Publication number
- JPH04238807A JPH04238807A JP41801590A JP41801590A JPH04238807A JP H04238807 A JPH04238807 A JP H04238807A JP 41801590 A JP41801590 A JP 41801590A JP 41801590 A JP41801590 A JP 41801590A JP H04238807 A JPH04238807 A JP H04238807A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- fine
- subspherical
- silica particles
- particles
- 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.)
- Withdrawn
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000011347 resin Substances 0.000 title claims description 18
- 229920005989 resin Polymers 0.000 title claims description 18
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000010419 fine particle Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- -1 silicon alkoxide Chemical class 0.000 claims abstract description 12
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 210000003739 neck Anatomy 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000314 lubricant Substances 0.000 abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229920000728 polyester Polymers 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 7
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、微粒子亜球状シリカ及
びその製造方法並びにこれを用いた樹脂フィルムに係り
、詳しくは磁気テープ用、光学写真用、蒸着用、コンデ
ンサー用、包装用等に利用されるポリエステル等の樹脂
フィルムの表面に凹凸を均一に形成して滑り性及び平坦
性を改良し、かつ、フィルムからの脱落を生じない、フ
ィルム用滑剤として有効な微粒子亜球状シリカ及びその
製造方法並びにこれを用いた樹脂フィルムに関する。[Industrial Application Field] The present invention relates to fine-particle subspherical silica, a method for producing the same, and a resin film using the same, and more specifically, its use in magnetic tapes, optical photography, vapor deposition, condensers, packaging, etc. Particulate subspherical silica which is effective as a lubricant for films, which improves slipperiness and flatness by uniformly forming irregularities on the surface of resin films such as polyester, and which does not fall off from the film, and a method for producing the same. The present invention also relates to a resin film using the same.
【０００２】0002
【従来の技術】従来より、ポリエステル等の樹脂フィル
ムの滑剤及びその製造方法として、以下の方法が知られ
ている。BACKGROUND OF THE INVENTION Conventionally, the following methods have been known as lubricants for resin films such as polyester and methods for producing the same.
【０００３】例えば、シリカ、シリカ−アルミナ化合物
、炭酸カルシウム、クレイ等の無機微粒子で平均粒径が
０．００１〜１０μｍのものがフィルムの用途に応じて
使い分けられている（特公昭５９−８２１６号、特開昭
５２−３６４５号公報等）。しかしながら、これらの無
機微粒子は、ケイ酸ナトリウム湿式法による凝集塊の粉
砕シリカであったり、天然品の粉砕体を原料としたもの
であり、粒径分布が非常に広く、ほとんどの粒子形状が
不定形であるために、フィルム表面の凹凸の均一性に欠
け、従って表面の平坦化には限界があった。そして、最
近になって、磁気記録の高密度化、高性能化が一段と促
進されるにつれて、フィルム表面の平坦化の要求が益々
強くなってきており、これらの無機微粒子ではその要求
に応えきれなくなってきた。For example, inorganic fine particles such as silica, silica-alumina compounds, calcium carbonate, and clay with an average particle size of 0.001 to 10 μm are used depending on the purpose of the film (Japanese Patent Publication No. 59-8216). , Japanese Unexamined Patent Publication No. 52-3645, etc.). However, these inorganic fine particles are made from pulverized silica aggregates produced using a sodium silicate wet method, or are made from pulverized natural products, and have a very wide particle size distribution, with most particles having irregular shapes. Due to the regular shape, the film surface lacks uniformity in unevenness, and therefore there is a limit to flattening the surface. Recently, as the density and performance of magnetic recording has been further promoted, the demand for flattening the film surface has become stronger, and these inorganic fine particles are no longer able to meet these demands. It's here.
【０００４】また、シリコンアルコキシドをアルコール
性溶液中で加水分解して微粒子球状シリカを製造する方
法が一般によく知られている。このような方法で得られ
た微粒子球状シリカをポリエステルフィルムの滑剤とし
て用いた例としては、平均粒子径が０．０５〜２μｍの
範囲でかつ粒子径の標準偏差値が１〜１．５の範囲にあ
る球状シリカを、ポリエステルに対して０．０１〜５重
量％添加する方法が知られている（特開昭６２−２０７
３５６号公報）。しかしながら、これらの微粒子球状シ
リカは、その形状がほぼ真球であるため、微粒子とポリ
エステルとの境界に剥離が生じ易く、微粒子の廻りにボ
イドが形成され易い。このボイドは、大きくなればなる
程その摩擦係数が高くなり、繰り返し使用時に生じたポ
リエステルフィルムのボイド上の小さな傷（スクラッチ
）によっても粒子の脱落が起こり、耐久性を低下させる
と共に削れ粉発生の原因にもなっている。[0004] Furthermore, a method of producing fine spherical silica particles by hydrolyzing silicon alkoxide in an alcoholic solution is generally well known. As an example of using fine particle spherical silica obtained by such a method as a lubricant for a polyester film, the average particle diameter is in the range of 0.05 to 2 μm and the standard deviation value of the particle diameter is in the range of 1 to 1.5. A method is known in which 0.01 to 5% by weight of spherical silica is added to polyester (Japanese Unexamined Patent Publication No. 62-207).
Publication No. 356). However, since these particulate spherical silica particles are almost perfectly spherical in shape, peeling is likely to occur at the boundary between the particulate and polyester, and voids are likely to be formed around the particulate. The larger these voids are, the higher their coefficient of friction becomes. Even small scratches on the voids of the polyester film that occur during repeated use can cause particles to fall off, reducing durability and increasing the possibility of abrasions. It is also the cause.
【０００５】[0005]
【発明が解決しようとする課題】そこで、本発明者らは
、これら従来技術が有する問題を解決すべく鋭意研究を
重ねた結果、微粒子球状シリカの５０重量％以上が少な
くとも２個以上強いネックで結合し平均粒子径が０．１
〜２μｍの微粒子亜球状シリカをフィルム滑剤用として
樹脂中に配合することにより、滑り性や平坦性更にはシ
リカ粒子のフィルムからの脱落がなくて耐久性に優れた
樹脂フィルム得ることが出来ることを見出し、本発明を
完成した。[Problems to be Solved by the Invention] The inventors of the present invention have conducted extensive research to solve these problems of the prior art, and have found that 50% by weight or more of fine spherical silica has at least two or more strong bottlenecks. Combined with an average particle size of 0.1
By blending subspherical silica particles of ~2 μm into a resin as a film lubricant, it is possible to obtain a resin film with excellent slipperiness, flatness, and durability without the silica particles falling off the film. The present invention has been completed.
【０００６】従って、本発明の目的は、樹脂フィルム中
に配合し、フィルムの滑り性や平坦性更にはシリカ粒子
のフィルムからの脱落がなくて耐久性等の表面特性を改
善できる微粒子亜球状シリカを提供することにある。Therefore, an object of the present invention is to use fine-particle subspherical silica which can be incorporated into a resin film to improve surface characteristics such as slipperiness and flatness of the film, as well as durability without the silica particles falling off the film. Our goal is to provide the following.
【０００７】また、本発明の他の目的は、このようなフ
ィルム滑剤用の微粒子亜球状シリカを効率よく安定的に
製造することが出来る方法を提供することにある。Another object of the present invention is to provide a method for efficiently and stably producing fine-particle subspherical silica for film lubricants.
【０００８】更に、本発明の他の目的は、このような微
粒子亜球状シリカをフィルム滑剤として使用して得られ
、フィルムの滑り性や平坦性更にはシリカ粒子のフィル
ムからの脱落がなくて耐久性等において優れた表面特性
を有する樹脂フィルムを提供することにある。Furthermore, another object of the present invention is to improve the slipperiness and flatness of the film by using such fine-grained subspherical silica as a film lubricant, as well as to improve durability since the silica particles do not fall off from the film. The object of the present invention is to provide a resin film having excellent surface properties such as surface properties.
【０００９】[0009]
【課題を解決するための手段】すなわち、本発明は、微
粒子球状シリカの５０重量％以上が少なくとも２個以上
強いネックで結合し平均粒子径が０．１〜２μｍである
微粒子亜球状シリカである。また、本発明は、シリコン
アルコキシドを溶媒中に滴下して加水分解することによ
りシリカ粒子を製造する方法において、添加剤として水
酸化テトラアルキルアンモニウムを用いる微粒子亜球状
シリカの製造方法である。更に、本発明は、上記微粒子
亜球状シリカを、樹脂に対して０．０１〜２重量％添加
した樹脂フィルムである。[Means for Solving the Problems] That is, the present invention provides fine subspherical silica particles in which 50% by weight or more of the fine spherical silica particles are bonded by at least two strong necks and have an average particle diameter of 0.1 to 2 μm. . Further, the present invention is a method for producing fine subspherical silica particles using tetraalkylammonium hydroxide as an additive in a method for producing silica particles by dropping silicon alkoxide into a solvent and hydrolyzing it. Furthermore, the present invention is a resin film in which 0.01 to 2% by weight of the above-mentioned fine particle subspherical silica is added to the resin.
【００１０】本発明における微粒子亜球状シリカは、２
個以上の球状シリカが結合したと思われる繭型形状をし
ており、おそらくはその生成過程において、ある程度成
長した球状粒子同士が結合し、更に成長することによっ
て結合部に強いネックを有する繭型の粒子が生成するも
のと思われる。この結合部は実質的に一体化しているの
で再び離れることはない。[0010] The fine particle subspherical silica in the present invention has 2
It has a cocoon-shaped shape, which is thought to be made up of more than 1,000 spherical silica particles bonded together.Probably, during the production process, the spherical particles that have grown to a certain extent bond with each other, and as they grow further, a cocoon-shaped shape with a strong neck at the bonding part is formed. It is thought that particles are generated. This bond is substantially integral and will not separate again.
【００１１】以下、本発明のフィルム滑剤用の微粒子亜
球状シリカの製造方法について具体的に説明する。本発
明において使用できるシリコンアルコキシドとしては、
テトラメチルオルソシリケート、テトラエチルオルソシ
リケート、テトライソプロピルオルソシリケート等を用
いることが出来るが、工業的に入手し易いテトラメチル
オルソシリケート、テトラエチルオルソシリケートが好
ましい。[0011] Hereinafter, the method for producing the fine particulate subspherical silica for film lubricant of the present invention will be explained in detail. Silicon alkoxides that can be used in the present invention include:
Tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropylorthosilicate, etc. can be used, but tetramethylorthosilicate and tetraethyl orthosilicate are preferred because they are industrially easily available.
【００１２】また、本発明において使用できる溶媒とし
ては、メタノール、エタノール、イソプロパノール等水
と相溶性があるアルコール等があげられる。[0012] Also, examples of solvents that can be used in the present invention include alcohols that are compatible with water, such as methanol, ethanol, and isopropanol.
【００１３】本発明において加水分解に使用する水は、
シリコンアルコキシド１モルに対して２〜３０モルの範
囲、より好ましくは４〜１５モルの範囲である。水の使
用量が２モルに満たない場合は、シリカ粒子が生成せず
反応溶液全体がゲル状となり、３０モルより多いと反応
の制御が困難になり不規則に凝集した粒子が生成する。[0013] The water used for hydrolysis in the present invention is
The amount is in the range of 2 to 30 mol, more preferably 4 to 15 mol, per 1 mol of silicon alkoxide. When the amount of water used is less than 2 moles, silica particles are not produced and the entire reaction solution becomes gel-like, and when it is more than 30 moles, it becomes difficult to control the reaction and irregularly aggregated particles are produced.
【００１４】また、本発明において、アルコール溶媒の
使用量は、特に制限される物ではないが、例えばメタノ
ールの場合は３〜１００モルの範囲、より好ましくは５
〜２０モルの範囲である。溶媒の使用量が３モルに満た
ない場合は反応の制御が困難になり不規則に凝集した粒
子が生成し、１００モルより多いと生成するシリカ粒子
の濃度が薄く生産効率上好ましくない。Further, in the present invention, the amount of alcohol solvent used is not particularly limited, but for example, in the case of methanol, it is in the range of 3 to 100 moles, more preferably 5 to 100 moles.
~20 moles. If the amount of the solvent used is less than 3 moles, it will be difficult to control the reaction and irregularly agglomerated particles will be produced, while if it is more than 100 moles, the concentration of the silica particles produced will be too low, which is unfavorable in terms of production efficiency.
【００１５】本発明においては、必要に応じて、反応触
媒としてアンモニアを添加する。アンモニアの量は、シ
リコンアルコキシド１モルに対して０．０５〜飽和溶解
量、好ましくは０．１〜飽和溶解量の範囲である。アン
モニアの添加量が０．０５モルに満たない場合はシリカ
粒子が充分に成長せずゲル状となるので好ましくない。
なお、アンモニアは、アンモニアガスであっても、水溶
液として用いてもよいが、水溶液として用いた場合には
この水溶液中に含まれる水は上記加水分解用の水として
扱われる。In the present invention, ammonia is added as a reaction catalyst if necessary. The amount of ammonia is in the range of 0.05 to saturated solubility, preferably 0.1 to saturated solubility per mole of silicon alkoxide. If the amount of ammonia added is less than 0.05 mol, the silica particles will not grow sufficiently and will become gel-like, which is not preferable. Note that ammonia may be used as ammonia gas or as an aqueous solution, but when used as an aqueous solution, the water contained in this aqueous solution is treated as the water for the above-mentioned hydrolysis.
【００１６】また、本発明において使用される水酸化テ
トラアルキルアンモニウムとしては、水酸化テトラメチ
ルアンモニウム、水酸化テトラエチルアンモニウム等が
挙げられ、その添加量はシリコンアルコキシド１モルに
対して５×１０−３〜０．１モルの範囲、より好ましく
は０．０１〜０．０５モルの範囲である。水酸化テトラ
アルキルアンモニウムの添加量が５×１０−３モルに満
たない場合は、無添加の時と同様に球状シリカしか生成
せず、０．１モルより多いとシリカ粒子同士の結合が激
しくなって不規則な塊になる。[0016] Tetraalkylammonium hydroxide used in the present invention includes tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., and the amount added is 5 x 10-3 per mole of silicon alkoxide. -0.1 mol, more preferably 0.01-0.05 mol. If the amount of tetraalkylammonium hydroxide added is less than 5 x 10-3 mol, only spherical silica will be produced as in the case without the addition, and if it is more than 0.1 mol, the bonds between silica particles will become strong. It becomes an irregular lump.
【００１７】本発明の加水分解反応は、水、アルコール
、アンモニア及び水酸化テトラアルキルアンモニウムの
混合溶液中に攪拌下にシリコンアルコキシドを滴下する
ことによって行うことが出来る。なお、シリコンアルコ
キシドは必要に応じてアルコールで希釈しておいても構
わない。反応が完結した後、エバポレーター等で乾燥し
微粒子亜球状シリカを得ることが出来る。粒子径の大き
なものについてはデカンテーションでこの微粒子亜球状
シリカを分離することもできる。また、微粒子亜球状シ
リカをポリエステル等の樹脂フィルム成形時に添加する
ことを考えると、加水分解反応が完結した後に乾燥又は
デカンテーションすることなく、直接溶媒をグリコール
に置換して微粒子亜球状シリカのグリコール分散品とし
て得ることが望ましい。ここで言うグリコールとはエチ
レングリコール、プロピレングリコール、１，４−ブタ
ンジオール等のグリコール類である。The hydrolysis reaction of the present invention can be carried out by dropping silicon alkoxide into a mixed solution of water, alcohol, ammonia and tetraalkylammonium hydroxide while stirring. Note that silicon alkoxide may be diluted with alcohol if necessary. After the reaction is completed, it can be dried using an evaporator or the like to obtain fine subspherical silica particles. If the particle size is large, the fine subspherical silica particles can be separated by decantation. In addition, considering that fine-grained subspherical silica is added during molding of a resin film such as polyester, it is possible to directly replace the solvent with glycol without drying or decantation after the hydrolysis reaction is completed. It is desirable to obtain it as a dispersed product. The glycol mentioned here refers to glycols such as ethylene glycol, propylene glycol, and 1,4-butanediol.
【００１８】微粒子亜球状シリカの粒径は加水分解反応
の条件を適宜選択することにより制御することが出来る
。例えば、アンモニアの濃度あるいは水酸化テトラアル
キルアンモニウムの濃度を高くするか、水の濃度を低く
すると粒径を大きくすることが出来る。また、シリコン
アルコキシドの滴下速度を変えることにより粒径を制御
でき、滴下速度を大きくしていくと粒径が大きくなる。
極端な例としてシリコンアルコキシドを一括添加しても
かまわない。また、反応温度を変えることでも粒径を制
御でき、温度を低くすると粒径は大きくなる。この時の
反応温度は凝固点温度〜沸点温度、好ましくは０〜５０
℃の範囲である。微粒子亜球状シリカの形状は水酸化テ
トラアルキルアンモニウムの濃度を調整することにより
制御することが出来る。水酸化テトラアルキルアンモニ
ウムの濃度を低くするとシリカ粒子の結合数が減り球状
粒子や２個程度結合した粒子の割合が大きくなり、濃度
を高くするとシリカ粒子の結合数が増え複数個結合した
粒子の割合が大きくなり球状粒子は殆ど存在しなくなる
。The particle size of the fine subspherical silica particles can be controlled by appropriately selecting the conditions for the hydrolysis reaction. For example, the particle size can be increased by increasing the concentration of ammonia or tetraalkylammonium hydroxide, or by decreasing the concentration of water. Furthermore, the particle size can be controlled by changing the dropping rate of silicon alkoxide, and as the dropping rate increases, the particle size increases. As an extreme example, silicon alkoxide may be added all at once. The particle size can also be controlled by changing the reaction temperature; lowering the temperature increases the particle size. The reaction temperature at this time is from freezing point temperature to boiling point temperature, preferably from 0 to 50
℃ range. The shape of the fine subspherical silica particles can be controlled by adjusting the concentration of tetraalkylammonium hydroxide. When the concentration of tetraalkylammonium hydroxide is lowered, the number of bonds between silica particles decreases and the proportion of spherical particles and particles with about two bonds increases.When the concentration is increased, the number of bonds between silica particles increases and the proportion of particles with multiple bonds is increased. becomes larger and almost no spherical particles exist.
【００１９】また、樹脂としては、フィルムに成形でき
るものであれば特に制限はないが、好ましくはポリエス
テルであり、このポリエステルは、テレフタル酸または
そのエステル形成性誘導体を主たるジカルボン酸成分と
し、エチレングリコール、プロピレングリコール等のグ
リコールまたはそのエステル形成性誘導体を主たるグリ
コール成分とするポリエステル類がよい。[0019] The resin is not particularly limited as long as it can be molded into a film, but polyester is preferred. , polyesters whose main glycol component is a glycol such as propylene glycol or an ester-forming derivative thereof are preferable.
【００２０】微粒子亜球状シリカをポリエステル系に添
加する時期は、ポリエステル重縮合反応の初期に行うな
ど一般に知られている方法で行うことが出来る。また、
ポリエステル等の樹脂フィルムと微粒子亜球状シリカと
の親和性を向上させるために生成した微粒子亜球状シリ
カの表面に公知の方法でシランカップリング処理を施し
てもよい。[0020] The timing of adding the particulate subspherical silica to the polyester system can be carried out by a generally known method, such as at the beginning of the polyester polycondensation reaction. Also,
In order to improve the affinity between a resin film such as polyester and the fine subspherical silica particles, the surface of the fine subspherical silica particles produced may be subjected to a silane coupling treatment by a known method.
【００２１】[0021]
【実施例】以下、実施例及び比較例に基づいて、本発明
を詳細に説明する。
実施例１〜７
テトラメチルオルソシリケート１モルに対して、メタノ
ール１７モルと、水、アンモニア水及び水酸化テトラア
ルキルアンモニウムを第１表に示す割合で反応容器に仕
込み、そこに攪拌下にテトラメチルオルソシリケートを
滴下し、シリカ粒子を製造した。[Examples] The present invention will be explained in detail below based on Examples and Comparative Examples. Examples 1 to 7 17 moles of methanol, water, aqueous ammonia, and tetraalkylammonium hydroxide were charged into a reaction vessel in the proportions shown in Table 1 per mole of tetramethyl orthosilicate, and tetramethyl was added thereto under stirring. Orthosilicate was added dropwise to produce silica particles.
【００２２】得られたシリカ粒子を走査型電子顕微鏡で
観察したところ、球状粒子が数個強いネックで結合した
微粒子亜球状シリカが多数存在した。更に粒度分布を測
定したところ粒度分布図にメインピークの他にショルダ
ーがみられた。平均粒子径をメインピークの粒子径およ
び、ＳＥＭと粒度分布図から求めた微粒子球状シリカの
重量％を第１表に示す。When the obtained silica particles were observed with a scanning electron microscope, it was found that there were many fine subspherical silica particles in which several spherical particles were bonded together with strong necks. Furthermore, when the particle size distribution was measured, a shoulder was observed in addition to the main peak in the particle size distribution diagram. Table 1 shows the average particle diameter, the particle diameter at the main peak, and the weight percent of the fine particle spherical silica determined from the SEM and the particle size distribution diagram.
【００２３】次に、得られた微粒子亜球状シリカをポリ
エステル中に０．５重量％添加し、フィルムを成形し、
得られたフィルムの走行面の削れ性を評価した。結果を
第１表に示す。更に、このフィルムの表面を顕微鏡で観
察したところ、フィルムの傷つき及び微粒子亜球状シリ
カの脱落は殆ど認められなかった。Next, 0.5% by weight of the obtained fine particle subspherical silica was added to polyester, and a film was formed.
The abrasion resistance of the running surface of the obtained film was evaluated. The results are shown in Table 1. Furthermore, when the surface of this film was observed under a microscope, almost no scratches on the film or falling off of the fine subspherical silica particles were observed.
【００２４】[0024]
【表１】[Table 1]
【００２５】実施例８
テトラメチルオルソシリケート１モルに対し、水２０モ
ル、メタノール８０モル、水酸化テトラメチルアンモニ
ウム０．０７モルをそれぞれ反応容器に仕込み、そこに
攪拌下にテトラメチルオルソシリケートを滴下し、シリ
カ粒子を製造した。Example 8 To 1 mole of tetramethylorthosilicate, 20 moles of water, 80 moles of methanol, and 0.07 moles of tetramethylammonium hydroxide were charged into a reaction vessel, and tetramethylorthosilicate was added dropwise thereto with stirring. Then, silica particles were produced.
【００２６】得られたシリカ粒子を走査型電子顕微鏡で
観察したところ、各粒子は球状粒子同士の結合がかなり
進行した微粒子亜球状シリカであった。平均粒子径は０
．５０μｍ、微粒子球状シリカは２１．９重量％、メイ
ンピークの粒子径は０．４０μｍであった。ポリエステ
ル中に０．５重量％添加して得られたフィルムについて
その表面特性を評価した。結果は、上記実施例１〜７と
同様に良好であり、削れ粉の発生もほとんど認められな
かった。When the obtained silica particles were observed with a scanning electron microscope, each particle was found to be fine subspherical silica particles in which the bonding between spherical particles had progressed considerably. Average particle size is 0
．． 50 μm, fine particle spherical silica was 21.9% by weight, and the main peak particle size was 0.40 μm. The surface properties of a film obtained by adding 0.5% by weight of polyester to polyester were evaluated. The results were as good as in Examples 1 to 7 above, and almost no scraping powder was observed.
【００２７】比較例１〜３
テトラメチルオルソシリケート１モルに対し、水、メタ
ノール及びアンモニアを第２表に示す割合で反応容器に
仕込み、そこに攪拌下にテトラメチルオルソシリケート
を滴下し、シリカ粒子を製造した。Comparative Examples 1 to 3 Water, methanol and ammonia were charged into a reaction vessel in the proportions shown in Table 2 per mole of tetramethylorthosilicate, and tetramethylorthosilicate was added dropwise thereto with stirring to form silica particles. was manufactured.
【００２８】得られたシリカ粒子を走査型電子顕微鏡で
観察したところ、各粒子はほぼ真球の微粒子球状シリカ
であった。また、なかには球状シリカ同士が結合したも
のもほんの僅か認められたが、再現性良く得ることはで
きなかった。これらの粒度分布を測定したところ、単分
散性には優れるが、球状シリカ同士が数個結合したもの
は殆ど存在しないことが確認された。When the obtained silica particles were observed with a scanning electron microscope, each particle was found to be a fine spherical silica particle having a substantially perfect sphere. In addition, a few cases in which spherical silica particles were bonded to each other were observed, but they could not be obtained with good reproducibility. When the particle size distribution of these particles was measured, it was confirmed that although they were excellent in monodispersity, there were almost no particles in which several spherical silica particles were bonded together.
【００２９】得られた球状シリカをポリエステル中に０
．５重量％添加して得られたフィルムについてその表面
特性を実施例と同様に評価した。結果を第２表に示す。
また、フィルムの傷及び球状シリカの脱落がかなり認め
られた。[0029] The obtained spherical silica was dissolved in polyester.
．． The surface properties of the film obtained by adding 5% by weight were evaluated in the same manner as in the examples. The results are shown in Table 2. Further, scratches on the film and considerable falling off of spherical silica were observed.
【００３０】[0030]
【表２】[Table 2]
【００３１】[0031]
【発明の効果】本発明方法によれば、微粒子球状シリカ
の５０重量％以上が少なくとも２個以上強いネックで結
合し平均粒子径が０．１〜２μｍである微粒子亜球状シ
リカを効率よく安定的に製造することが出来る。この様
な微粒子亜球状シリカは磁気テープ用、光学写真用、蒸
着用、コンデンサー用、包装用等のポリエステルフィル
ム等の表面に凹凸を均一に形成して滑り性及び平坦性を
改良し、かつ、フィルムからの脱落を生じない樹脂フィ
ルム用滑剤として特に有用である。従って、このような
微粒子亜球状シリカをフィルム用滑剤として使用するこ
とにより、優れた表面特性の樹脂フィルムが得られる。[Effects of the Invention] According to the method of the present invention, 50% by weight or more of fine spherical silica particles are bonded by at least two strong necks, and fine subspherical silica particles having an average particle diameter of 0.1 to 2 μm can be efficiently and stably produced. It can be manufactured in Such particulate subspherical silica uniformly forms irregularities on the surface of polyester films for magnetic tapes, optical photography, vapor deposition, condensers, packaging, etc. to improve slipperiness and flatness, and It is particularly useful as a lubricant for resin films that does not fall off from the film. Therefore, by using such fine-grained subspherical silica as a film lubricant, a resin film with excellent surface properties can be obtained.
Claims (3)
少なくとも２個以上強いネックで結合し平均粒子径が０
．１〜２μｍであることを特徴とする微粒子亜球状シリ
カ。Claim 1: At least 50% by weight of the fine spherical silica particles are bonded by at least two strong necks and have an average particle diameter of 0.
．． Fine particle subspherical silica characterized by having a particle size of 1 to 2 μm.
して加水分解することによりシリカ粒子を製造する方法
において、添加剤として水酸化テトラアルキルアンモニ
ウムを用いることを特徴とする微粒子亜球状シリカの製
造方法。2. A method for producing particulate subspherical silica, the method comprising using tetraalkylammonium hydroxide as an additive in a method for producing silica particles by dropping silicon alkoxide into a solvent and hydrolyzing the mixture.
、樹脂に対して０．０１〜２重量％添加したことを特徴
とする樹脂フィルム。3. A resin film, characterized in that 0.01 to 2% by weight of the particulate subspherical silica according to claim 1 is added to the resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41801590A JPH04238807A (en) | 1990-12-28 | 1990-12-28 | Fine particulate semi-spherical silica and production thereof and resin film using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41801590A JPH04238807A (en) | 1990-12-28 | 1990-12-28 | Fine particulate semi-spherical silica and production thereof and resin film using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04238807A true JPH04238807A (en) | 1992-08-26 |
Family
ID=18525987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP41801590A Withdrawn JPH04238807A (en) | 1990-12-28 | 1990-12-28 | Fine particulate semi-spherical silica and production thereof and resin film using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04238807A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012006789A (en) * | 2010-06-24 | 2012-01-12 | Fuji Xerox Co Ltd | Silica particles, and method for producing the same |
| JP2012006796A (en) * | 2010-06-25 | 2012-01-12 | Fuji Xerox Co Ltd | Silica particle and method of producing the same |
| JP2013040081A (en) * | 2011-08-18 | 2013-02-28 | Fuji Xerox Co Ltd | Silica particle and method of producing the same |
| US8962139B2 (en) | 2011-01-20 | 2015-02-24 | Fuji Xerox Co., Ltd. | Resin particle and method for producing the same |
| US9243145B2 (en) | 2013-01-28 | 2016-01-26 | Fuji Xerox Co., Ltd. | Silica composite particles and method of preparing the same |
| US9394413B2 (en) | 2011-01-19 | 2016-07-19 | Fuji Xerox Co., Ltd. | Resin particle and method for producing the same |
| US9708191B2 (en) | 2011-12-01 | 2017-07-18 | Fuji Xerox Co., Ltd. | Silica composite particles and method of preparing the same |
-
1990
- 1990-12-28 JP JP41801590A patent/JPH04238807A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012006789A (en) * | 2010-06-24 | 2012-01-12 | Fuji Xerox Co Ltd | Silica particles, and method for producing the same |
| US9187502B2 (en) | 2010-06-24 | 2015-11-17 | Fuji Xerox Co., Ltd. | Silica particles and method for producing the same |
| JP2012006796A (en) * | 2010-06-25 | 2012-01-12 | Fuji Xerox Co Ltd | Silica particle and method of producing the same |
| US8871344B2 (en) | 2010-06-25 | 2014-10-28 | Fuji Xerox Co., Ltd. | Hydrophobization treatment of silica particles |
| US9394413B2 (en) | 2011-01-19 | 2016-07-19 | Fuji Xerox Co., Ltd. | Resin particle and method for producing the same |
| US8962139B2 (en) | 2011-01-20 | 2015-02-24 | Fuji Xerox Co., Ltd. | Resin particle and method for producing the same |
| JP2013040081A (en) * | 2011-08-18 | 2013-02-28 | Fuji Xerox Co Ltd | Silica particle and method of producing the same |
| US9708191B2 (en) | 2011-12-01 | 2017-07-18 | Fuji Xerox Co., Ltd. | Silica composite particles and method of preparing the same |
| US9243145B2 (en) | 2013-01-28 | 2016-01-26 | Fuji Xerox Co., Ltd. | Silica composite particles and method of preparing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR910008721B1 (en) | Monodispersed glycol sospension of fine inorganic oxide particles having excellent dispersion stability and method of improving the slipperiness of polyester film using the monodispersed suspension | |
| JP5602358B2 (en) | Non-spherical silica sol, method for producing the same, and polishing composition | |
| JP4907317B2 (en) | Kinpe sugar-like inorganic oxide sol, method for producing the same, and abrasive containing the sol | |
| WO2010052945A1 (en) | Aspherical silica sol, process for producing the same, and composition for polishing | |
| JP6284443B2 (en) | Method for producing colloidal silica containing core-shell type silica particles | |
| JP2000345044A (en) | Spherical silicone resin minute particle | |
| JPWO2004074180A1 (en) | Alkali-resistant cocoon-type colloidal silica particles and method for producing the same | |
| US5139980A (en) | Method for production of inorganic oxide particles | |
| KR101101207B1 (en) | CMP Composition for Polishing Metal | |
| WO2019189610A1 (en) | Silica particle dispersion, polishing composition, and method for manufacturing silica particle dispersion | |
| JPH054812A (en) | Finely particulate semi-spherical silica, production thereof and resin film using same | |
| JP6207345B2 (en) | Method for producing silica particles | |
| JPH04238807A (en) | Fine particulate semi-spherical silica and production thereof and resin film using the same | |
| JP2021059490A (en) | Silica-based particle dispersion and method for producing the same | |
| JP2004203638A (en) | Peanut-like twin colloidal silica particle, and production method therefor | |
| JP2018108924A (en) | Silica particle dispersion and production method thereof | |
| CN112299425B (en) | Silica sol with convex colloid surface and preparation method and application thereof | |
| JP2021054684A (en) | Silica particle dispersion and its production method | |
| JP2001342335A (en) | Polyester resin composition for film production | |
| JP3568234B2 (en) | Silica-modified alumina sol and method for producing the same | |
| JPH04249541A (en) | Resin film | |
| JP2007153672A (en) | Method for manufacturing anisotropic-shape silica sol | |
| JP5346167B2 (en) | Particle-linked alumina-silica composite sol and method for producing the same | |
| WO2016106766A1 (en) | Chemical mechanical polishing liquid and application thereof | |
| WO2018135585A1 (en) | Silica particle liquid dispersion and production method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980312 |