JPH04249541A - Resin film - Google Patents
Resin filmInfo
- Publication number
- JPH04249541A JPH04249541A JP41801490A JP41801490A JPH04249541A JP H04249541 A JPH04249541 A JP H04249541A JP 41801490 A JP41801490 A JP 41801490A JP 41801490 A JP41801490 A JP 41801490A JP H04249541 A JPH04249541 A JP H04249541A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- spherical silica
- film
- resin
- silica
- 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- Withdrawn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
- 239000011347 resin Substances 0.000 title claims abstract description 25
- 229920005989 resin Polymers 0.000 title claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- 239000011164 primary particle Substances 0.000 claims abstract description 9
- 239000011163 secondary particle Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000314 lubricant Substances 0.000 abstract description 6
- 238000004873 anchoring Methods 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- -1 silicon alkoxide Chemical class 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- 229920006267 polyester film Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000003756 stirring Methods 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-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
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 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
- 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
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、滑剤入り樹脂フィルム
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、包装用等のポリエステルフィルム等
の表面に均一に凹凸を形成してその滑り性及び平坦性を
改良し、かつ、フィルムからの滑剤の脱落に対する耐久
性を改良した樹脂フィルムに関する。[Industrial Application Field] The present invention relates to a lubricant-containing resin film, and more specifically, it forms irregularities uniformly on the surface of polyester films for use in magnetic tapes, optical photography, vapor deposition, condensers, packaging, etc. The present invention relates to a resin film having improved slipperiness and flatness, and improved durability against slipping of a lubricant from the film.
【０００２】0002
【従来の技術】従来より、ポリエステルフィルム等の滑
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 polyester films 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。しかるに、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、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
えられなくなってきた。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. Since the film has a regular shape, the unevenness of the film surface lacks uniformity, and therefore there is a limit to flattening the surface. However, in recent years, 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. Ta.
【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
％添加したものが知られている（特開昭６２−２０７３
５６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に、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、また、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. It is known that 0.01 to 5% by weight of spherical silica is added to polyester (Japanese Unexamined Patent Publication No. 62-2073).
Publication No. 56). However, since these fine spherical silica particles are almost perfectly spherical in shape, peeling is likely to occur at the boundary between the fine particles and polyester, and voids are likely to be formed around the fine particles. The larger these voids are, the higher their coefficient of friction becomes.Furthermore, small scratches on the voids of the polyester film that occur during repeated use can cause particles to fall off, reducing durability and causing shavings. It is also the cause of the outbreak.
【０００５】[0005]
【発明が解決しようとする課題】そこで、本発明者は、
上記の様な問題点を解決するため鋭意研究を行った結果
、アルコキシシランをアルコール性溶液中で加水分解し
て製造されたもので、特に表面に１０〜３０ｎｍの１次
粒子による凹凸を有する非真球状タイプの球状シリカ（
以下、これを「表面凹凸球状シリカ」という）をポリエ
ステル等の樹脂に対して０．０１〜２重量％添加する事
により、この球状シリカの凹凸に基づく樹脂へのアンカ
ー効果が発揮され、この樹脂により形成された樹脂フィ
ルムの滑り性とシリカ粒子のフィルムからの脱落を可及
的に防止でき、滑り性と耐久性とが同時に改良される事
を見出し、本発明を完成した。[Problem to be solved by the invention] Therefore, the inventors of the present invention
As a result of extensive research in order to solve the above problems, we found that alkoxysilane is produced by hydrolyzing alkoxysilane in an alcoholic solution. True spherical type spherical silica (
By adding 0.01 to 2% by weight of spherical silica (hereinafter referred to as "surface uneven spherical silica") to a resin such as polyester, an anchoring effect to the resin based on the unevenness of this spherical silica is exhibited, and this resin The present invention has been completed based on the discovery that the slipperiness of the resin film formed by the method and the falling off of the silica particles from the film can be prevented as much as possible, and that the slipperiness and durability can be improved at the same time.
【０００６】従って、本発明の目的は、球状シリカが持
つ利点である滑り性改良効果を維持したまま、優れた耐
久性を有する、すなわちシリカ粒子が樹脂から脱落する
のを可及的に防止できる、という優れた表面特性を有す
る滑剤入りの樹脂フィルムを提供することにある。Therefore, an object of the present invention is to maintain the slipperiness improvement effect which is an advantage of spherical silica, and to have excellent durability, that is, to prevent silica particles from falling off from the resin as much as possible. The object of the present invention is to provide a lubricant-containing resin film having excellent surface properties.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明は、二
次粒子表面に１０〜３０ｎｍのサイズの一次粒子による
凹凸を有し、かつ、サブミクロン単分散球状を示す該二
次粒子の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 a method for producing spherical silica particles of secondary particles having irregularities on the surface of the secondary particles due to the primary particles having a size of 10 to 30 nm and exhibiting a submicron monodisperse spherical shape. 0.01 to 2% by weight based on the resin
This is the added resin film.
【０００８】本発明において使用する球状シリカを製造
するためのアルコキシシランとしては、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。As the alkoxysilane for producing the spherical silica used in the present invention, tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropylorthosilicate, etc. can be used, but tetramethylorthosilicate, which is industrially easily available, Silicates and tetraethyl orthosilicate are preferred.
【０００９】また、このようなアルコキシシランを加水
分解する際に使用する溶媒としては、メタノール、エタ
ノール、イソプロパノール等の水と相溶性があるアルコ
ール等がよい。[0009] The solvent used for hydrolyzing such an alkoxysilane is preferably an alcohol that is compatible with water, such as methanol, ethanol, or isopropanol.
【００１０】本発明で使用する球状シリカを製造する際
の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３〜１５モルの範囲である。水の使用量が３
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、１５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。The amount of water used for hydrolysis in producing the spherical silica used in the present invention is in the range of 3 to 15 moles per mole of silicon alkoxide. Water usage is 3
If it is less than 15 moles, no silica particles will be produced and the entire reaction solution will become gel-like, and if it is more than 15 moles, it will be difficult to control the reaction and irregularly aggregated particles will be produced.
【００１１】また、アルコール溶媒の使用量は、特に制
限されるものではないが、例えばメタノールの場合には
５〜２０モルの範囲である。溶媒の使用量が５モルに満
たない場合は反応の制御が困難になって不規則に凝集し
た粒子が生成し、２０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, the amount of alcohol solvent used is not particularly limited, but for example, in the case of methanol, it is in the range of 5 to 20 moles. If the amount of the solvent used is less than 5 moles, it becomes difficult to control the reaction and irregularly agglomerated particles are produced, while if it is more than 20 moles, the concentration of the silica particles produced will be low, which is unfavorable in terms of production efficiency.
【００１２】また、球状シリカの製造の際に、必要に応
じて、反応触媒としてアンモニアを添加する。このアン
モニアの量は、アルコキシシラン１モルに対して０．５
〜２．０モルの範囲である。アンモニアの添加量が０．
５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その水溶液中に含まれる水
は上記加水分解用の水として計算される。[0012] Furthermore, during the production of spherical silica, ammonia is added as a reaction catalyst, if necessary. The amount of ammonia is 0.5 per mole of alkoxysilane.
~2.0 mol. The amount of ammonia added is 0.
If the amount is less than 5 moles, 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 the aqueous solution is calculated as the water for hydrolysis.
【００１３】本発明における反応温度は、３０〜５５℃
の範囲が適当であるが、反応温度が高いほど、生成する
シリカ１次粒子径が大きくなり、従って２次粒子表面の
凹凸が大きくなる傾向があり、また、反応温度が高すぎ
ると溶媒であるアルコールとアンモニアの蒸発が激しく
なるので、好ましくは４０〜５０℃の温度範囲の一定温
度で行うのがよい。[0013] The reaction temperature in the present invention is 30 to 55°C.
However, the higher the reaction temperature, the larger the diameter of the primary silica particles produced, which tends to increase the unevenness of the surface of the secondary particles, and if the reaction temperature is too high, the solvent Since alcohol and ammonia evaporate rapidly, it is preferable to carry out the process at a constant temperature in the range of 40 to 50°C.
【００１４】アルコキシシランの加水分解反応は、水、
アルコール、アンモニア混合溶液中にシリコンアルコキ
シドを滴下し、攪拌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、表面凹凸球状シリカを得るこ
とが出来る。また、フィルム成形時にこの表面凹凸球状
シリカを樹脂中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することなく直接溶媒をグリコー
ルに置換し、表面凹凸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 alkoxysilane is carried out using water,
This can be done by dropping silicon alkoxide into a mixed solution of alcohol and ammonia and stirring. Note that silicon alkoxide may be diluted with alcohol if necessary. After the reaction is completed, it is dried using an evaporator or the like to obtain spherical silica with an uneven surface. Also, considering that this spherical silica with an uneven surface is added to the resin during film forming, the solvent can be directly replaced with glycol without drying after the hydrolysis reaction is completed, and a glycol dispersion product of spherical silica with an uneven surface can be obtained. This is desirable. What is the glycol mentioned here?
Ethylene glycol, propylene glycol, 1,4-
Glycols such as butanediol.
【００１５】表面凹凸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高くするか、ア
ルコキシシランの添加量を増す事により、また、アルコ
キシシランの滴下速度を速くする事により粒径を大きく
する事が出来る。極端な例としてシリコンアルコキシド
を一括添加しても構わない。また通常の方法で得られる
真球状シリカを種子として、種子を生成した反応温度条
件より高い温度で引き続き加水分解を行う事により、真
球状粒子の表面に真球状粒子を構成する１次粒子より大
きい１次粒子を付着せしめる事により表面の凹凸を形成
する事も可能である。The particle size of the spherical silica having an uneven surface 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, by increasing the amount of alkoxysilane added, or by increasing the dropping rate of alkoxysilane. As an extreme example, silicon alkoxide may be added all at once. In addition, by using spherical silica obtained by a normal method as a seed and continuing to hydrolyze it at a temperature higher than the reaction temperature conditions that produced the seed, the surface of the spherical particles is larger than the primary particles that make up the spherical particles. It is also possible to form surface irregularities by attaching primary particles.
【００１６】この様にして得られる表面凹凸球状シリカ
は、その特異な凹凸表面の為に樹脂への食い込み、いわ
ゆるアンカー効果を有し、ポリエステルフィルムのフィ
ラーとして用いた際に、フィルムの引っ張り応力にもボ
イドを生じ難く、そのためフィルムからの脱落が生じ難
いという効果をもたらす。The spherical silica with an uneven surface obtained in this way has a unique uneven surface that bites into the resin and has a so-called anchor effect. It also has the effect that it is less likely to cause voids and therefore less likely to fall off from the film.
【００１７】また、樹脂としては、それがフィルムに成
形できるものであればよいが、好ましくはポリエステル
であり、このポリエステルとしては、テレフタル酸又は
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
リコール又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等である。[0017] The resin may be any resin as long as it can be formed into a film, but polyester is preferred, and this polyester contains terephthalic acid or its ester-forming derivative as the main dicarboxylic acid component and ethylene glycol. , polyesters whose main glycol component is a glycol such as propylene glycol or an ester-forming derivative thereof.
【００１８】表面凹凸球状シリカを樹脂、例えばポリエ
ステル中に添加する時期は、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、樹脂フィルムと表面凹凸球状シリカとの親
和性を向上させるため、生成した表面凹凸球状シリカの
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。The spherical silica with uneven surfaces can be added to the resin, for example, polyester, by a generally known method, such as at the beginning of the polyester polycondensation reaction. Furthermore, in order to improve the affinity between the resin film and the spherical silica having an uneven surface, the surface of the produced spherical silica having an uneven surface may be subjected to a silane coupling treatment by a known method.
【００１９】[0019]
【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。[Examples] The present invention will be explained in detail below based on Examples and Comparative Examples.
【００２０】実施例
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
ルを１１モル、水を４．６モル、アンモニアを１．０モ
ルの割合で反応容器に仕込み、攪拌下に４５℃に保ちな
がらそこにテトラメチルオルソシリケートを４時間で滴
下し、シリカ粒子を製造した。Example 11 moles of methanol, 4.6 moles of water, and 1.0 moles of ammonia per mole of tetramethylorthosilicate were charged into a reaction vessel, and the mixture was poured into the reaction vessel while maintaining the temperature at 45°C with stirring. Tetramethyl orthosilicate was added dropwise over 4 hours to produce silica particles.
【００２１】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、図１に示すように、約２０ｎｍの１次
粒子からなる約１．１５μｍの２次球状粒子が観察され
、その表面には１次粒子による凹凸が存在することが確
認された。When the obtained silica particles were observed with a scanning electron microscope, secondary spherical particles of approximately 1.15 μm consisting of primary particles of approximately 20 nm were observed as shown in FIG. It was confirmed that there were irregularities due to primary particles.
【００２２】この様にして得られた表面凹凸球状シリカ
をポリエステル中に０．５重量％添加してフィルムを成
形し、得られたフィルムについて走行テストを行い、フ
ィルムの走行面を顕微鏡で観察した結果、フィルムの傷
つき及びシリカ粒子の脱落は殆ど認められなかった。0.5% by weight of the thus obtained spherical silica with uneven surfaces was added to polyester to form a film, a running test was conducted on the obtained film, and the running surface of the film was observed under a microscope. As a result, almost no scratches on the film or falling off of silica particles were observed.
【００２３】比較例
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
ルを１０モル、水を５．３モル、アンモニアを１．０モ
ルの割合で反応容器に仕込み、攪拌下に２０℃に保ちな
がらテトラメチルオルソシリケートを４時間で滴下し、
シリカ粒子を製造した。Comparative Example A reaction vessel was charged with 10 moles of methanol, 5.3 moles of water, and 1.0 moles of ammonia per mole of tetramethyl orthosilicate, and while stirring and maintaining the temperature at 20°C, tetramethyl Drop orthosilicate in 4 hours,
Silica particles were produced.
【００２４】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、各粒子は約０．２μｍの真球状のシリ
カであり、それを構成する１次粒子の大きさは、走査型
電子顕微鏡写真では確認出来ないほど小さく、粒子表面
は滑らかであった。When the obtained silica particles were observed with a scanning electron microscope, each particle was a true spherical silica particle with a diameter of about 0.2 μm, and the size of the primary particles constituting the particles was determined by scanning electron micrographs. The particles were so small that they could not be confirmed, and the particle surfaces were smooth.
【００２５】このようにして得られた真球状シリカを上
記実施例と同様にポリエステル中に０．５重量％添加し
てフィルムを成形し、このフィルムについて走行テスト
を行なった結果、フィルムの傷及びシリカ粒子の脱落が
かなり認められた。0.5% by weight of the spherical silica thus obtained was added to polyester in the same manner as in the above example, a film was formed, and a running test was conducted on this film. A considerable amount of silica particles were observed to fall off.
【００２６】[0026]
【発明の効果】本発明によれば、２次粒子の表面に１０
〜３０ｎｍの１次粒子による凹凸を有する球状シリカが
ポリエステル等の樹脂フィルムの表面の滑り性や平坦性
を改善すると共に、この球状シリカは樹脂フィルム中で
アンカー効果を発揮し、このフィルムから脱落するのが
可及的に防止され、その耐久性が向上する。このため、
本発明の樹脂フィルムは、磁気テープ用、光学写真用、
蒸着用、コンデンサー用、包装用等の用途に特に有用で
ある。Effects of the Invention According to the present invention, the surface of the secondary particles has 10
Spherical silica with irregularities due to ~30 nm primary particles improves the slipperiness and flatness of the surface of resin films such as polyester, and this spherical silica also exerts an anchoring effect in the resin film and falls off from the film. is prevented as much as possible, and its durability is improved. For this reason,
The resin film of the present invention is suitable for use in magnetic tapes, optical photography,
It is particularly useful for applications such as vapor deposition, condensers, and packaging.
【図１】本発明の実施例で得られたシリカ粒子の顕微鏡
写真である。FIG. 1 is a micrograph of silica particles obtained in an example of the present invention.
Claims (1)
ズの一次粒子による凹凸を有し、かつ、サブミクロン単
分散球状を示すこの二次粒子の球状シリカを、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。Claim 1: The spherical silica of the secondary particles, which have irregularities on the surface of the secondary particles due to the primary particles with a size of 10 to 30 nm and exhibit a submicron monodisperse spherical shape, is added to the resin at a rate of 0.01 to 30 nm. A resin film characterized by adding 2% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41801490A JPH04249541A (en) | 1990-12-28 | 1990-12-28 | Resin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41801490A JPH04249541A (en) | 1990-12-28 | 1990-12-28 | Resin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04249541A true JPH04249541A (en) | 1992-09-04 |
Family
ID=18525986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP41801490A Withdrawn JPH04249541A (en) | 1990-12-28 | 1990-12-28 | Resin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04249541A (en) |
-
1990
- 1990-12-28 JP JP41801490A patent/JPH04249541A/en not_active Withdrawn
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 | |
| WO2010052945A1 (en) | Aspherical silica sol, process for producing the same, and composition for polishing | |
| JP2009149493A (en) | Nonspherical silica sol, method for producing the same and polishing composition | |
| US9708191B2 (en) | Silica composite particles and method of preparing the same | |
| JPS62207356A (en) | Method of improving slipperiness | |
| JP6207345B2 (en) | Method for producing silica particles | |
| JPH0232151A (en) | Polyester composition | |
| JPH054812A (en) | Finely particulate semi-spherical silica, production thereof and resin film using same | |
| JP2007153692A (en) | Method for manufacturing anisotropic-shape silica sol | |
| JP4949209B2 (en) | Non-spherical alumina-silica composite sol, method for producing the same, and polishing composition | |
| JPH04238807A (en) | Fine particulate semi-spherical silica and production thereof and resin film using the same | |
| JP3286304B2 (en) | Polyester resin composition for film production | |
| JPH04249541A (en) | Resin film | |
| EP0522415A1 (en) | Ethylene glycol dispersion of crystalline calcium carbonate, crystalline calcium carbonate, and plastic molded product and polyester film containing the same | |
| JP5346167B2 (en) | Particle-linked alumina-silica composite sol and method for producing the same | |
| JPH0477309A (en) | Production of silica particles | |
| JPH0474379B2 (en) | ||
| JPS62260834A (en) | Polyester film | |
| JPH0324493B2 (en) | ||
| JPH0515746B2 (en) | ||
| JP2009091197A (en) | Warty-surfaced sphere-form inorganic oxide sol, method for producing same, and abrasive containing the sol | |
| JPH04309523A (en) | Production of polyester composition | |
| JPH01153717A (en) | Production of polyester | |
| JP3260881B2 (en) | Polyester composition | |
| JPH0791400B2 (en) | Polyester film for magnetic tape |
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 |