JP2011207751A5

JP2011207751A5 -

Info

Publication number: JP2011207751A5
Application number: JP2011051537A
Authority: JP
Filing date: 2011-03-09
Publication date: 2014-04-24
Anticipated expiration: 2031-03-09

Description

本発明は、このような知見に基いて達成されたものであり、本発明の第一の要旨は、シリカ系多孔質膜の製造方法において、アルコキシシラン類、その加水分解物及び部分縮合物からなるアルコキシシラン類群より選ばれる少なくとも１種のアルコキシシラン化合物と、界面活性剤と、炭素数１〜３の低級アルコールと、沸点１２５〜１８０℃で２０℃又は２５℃の蒸気圧が２．０ｋＰａ以下の有機溶媒と、水とを含むシリカ系組成物を霧状に噴出させることにより、透光基材上にシリカ系前駆体を製膜する製膜工程、及び、該シリカ系前駆体を加熱してシリカ系多孔質膜とする加熱工程を含むことを特徴とするシリカ系多孔質膜の製造方法、に存する（請求項１，３）。 The present invention has been achieved on the basis of such knowledge, and the first gist of the present invention is that in the method for producing a silica-based porous film, from alkoxysilanes, hydrolysates thereof and partial condensates thereof. And at least one alkoxysilane compound selected from the group consisting of alkoxysilanes, a surfactant, a lower alcohol having 1 to 3 carbon atoms, and a vapor pressure of 20 ° C or 25 ° C at a boiling point of 125 to 180 ° C of 2.0 kPa or less. The silica-based composition containing the organic solvent and water is sprayed in the form of a mist to form a silica-based precursor on the light-transmitting substrate, and the silica-based precursor is heated. method for producing a silica-based porous membrane which comprises a heating step of a silica-based porous membrane Te resides in, (claim 1, 3).

本発明において、炭素数１〜３の低級アルコールと沸点１２５〜１８０℃で２０℃又は２５℃の蒸気圧が２．０ｋＰａ以下の有機溶媒とは、炭素数１〜３の低級アルコールに対する沸点１２５〜１８０℃で蒸気圧が２．０ｋＰａ以下の有機溶媒のモル比が、０．１〜５０（ｍｏｌ／ｍｏｌ）となるように用いることが好ましい（請求項２，４）。 In the present invention, the lower alcohol having 1 to 3 carbon atoms and the organic solvent having a boiling point of 125 to 180 ° C. and a vapor pressure of 20 ° C. or 25 ° C. of 2.0 kPa or less are the boiling points of 125 to molar ratio the vapor pressure of the following organic solvents 2.0kPa at 180 ° C. is preferably used so that 0.1~50 (mol / mol) (claim 2, 4).

また、界面活性剤としては、アルキレンオキサイド部位を有する非イオン性高分子が好ましい（請求項５）。 As the surfactant, a nonionic polymer having an alkylene oxide moiety is preferably (claim 5).

また、アルコキシシラン化合物としては、下記アルコキシシラン類群Ｉより選ばれる少なくとも１種のアルコキシシラン化合物と下記アルコキシシラン類群IIより選ばれる少なくとも１種のアルコキシシラン化合物、或いは、下記アルコキシシラン類群IIIより選ばれる少なくとも１種のアルコキシシラン化合物、或いは、下記アルコキシシラン類群Ｉより選ばれる少なくとも１種のアルコキシシラン化合物及び／又は下記アルコキシシラン類群IIより選ばれる少なくとも１種のアルコキシシラン化合物と下記アルコキシシラン類群IIIより選ばれる少なくとも１種のアルコキシシラン化合物を用いることが好ましい（請求項６）。
アルコキシシラン類群Ｉ：テトラアルコキシシラン類、その加水分解物及び部分縮合物からなるテトラアルコキシシラン類群
アルコキシシラン類群II：上記テトラアルコキシシラン類以外のアルコキシシラン類、その加水分解物及び部分縮合物からなるその他のアルコキシシラン類群
アルコキシシラン類群III：上記テトラアルコキシシラン類群Ｉより選ばれる少なくとも１種のアルコキシシラン化合物と上記他のアルコキシシラン類群IIより選ばれる少なくとも１種のアルコキシシラン化合物との部分縮合物群 The alkoxysilane compound is selected from at least one alkoxysilane compound selected from the following alkoxysilanes group I and at least one alkoxysilane compound selected from the following alkoxysilanes group II, or from the following alkoxysilanes group III: At least one alkoxysilane compound, or at least one alkoxysilane compound selected from the following alkoxysilanes group I and / or at least one alkoxysilane compound selected from the following alkoxysilanes group II and the following alkoxysilanes group III: it is preferred to use at least one alkoxysilane compound selected (claim 6).
Alkoxysilanes group I: Tetraalkoxysilanes, tetraalkoxysilanes group consisting of hydrolysates and partial condensates Alkoxysilanes group II: Alkoxysilanes other than the above tetraalkoxysilanes, hydrolysates and partial condensates Other Alkoxysilanes Group Alkoxysilanes Group III: Partial condensate group of at least one alkoxysilane compound selected from tetraalkoxysilanes group I and at least one alkoxysilane compound selected from other alkoxysilanes group II

また、製膜工程においては、５ｋＰａ以上５００ｋＰａ以下の気体によりシリカ系組成物を霧状に噴出させるノズルを用い、かつ該ノズルと前記透光基材との距離を３ｃｍ以上１００ｃｍ以下としてシリカ系組成物を噴出させることが好ましい（請求項７）。
また、製膜工程の後に粗乾燥工程を行い、該粗乾燥工程後の前記シリカ系前駆体の膜厚が１０μｍ以下であることが好ましい（請求項８）。 Further, in the film forming process, a silica-based composition is used in which a nozzle for ejecting the silica-based composition in a mist form with a gas of 5 kPa or more and 500 kPa or less is used, and the distance between the nozzle and the translucent substrate is 3 cm or more and 100 cm or less. It is preferable to eject an object (claim 7 ).
Also performs rough drying step after the film forming step, it is preferable thickness of the silica precursor after crude drying step is 10μm or less (claim 8).

本発明のシリカ系多孔質膜の製造方法により製造されるシリカ系多孔質膜は、光学フィルター、特に、反射防止膜であることが好ましく（請求項９，１０）、とりわけ、太陽電池用反射防止膜であることが好ましい（請求項１１）。 The silica-based porous film produced by the method for producing a silica-based porous film of the present invention is preferably an optical filter, particularly an antireflection film (claims 9 and 10 ), and in particular, an antireflection film for solar cells. A membrane is preferred (claim 11 ).

本発明の第二の要旨は、アルコキシシラン類、その加水分解物及び部分縮合物からなるアルコキシシラン類群より選ばれる少なくとも１種のアルコキシシラン化合物と、界面活性剤と、炭素数１〜３の低級アルコールと、その他の有機溶媒と、水とを含むシリカ系組成物であって、該その他の有機溶媒が、沸点１２５〜１８０℃、２０℃又は２５℃の蒸気圧２．０ｋＰａ以下で、分子量が１００以上であることを特徴とするシリカ系組成物、に存する（請求項１２，１３）。 The second gist of the present invention is that at least one alkoxysilane compound selected from the group of alkoxysilanes consisting of alkoxysilanes, hydrolysates and partial condensates thereof, surfactants, and lower ones having 1 to 3 carbon atoms. A silica-based composition containing alcohol, another organic solvent, and water, wherein the other organic solvent has a boiling point of 125 to 180 ° C, a vapor pressure of 2.0 kPa or less at 20 ° C or 25 ° C, and a molecular weight. It exists in the silica type composition characterized by being 100 or more (Claims 12 and 13 ).

Claims

In the method for producing a silica-based porous membrane,
At least one alkoxysilane compound selected from the alkoxysilane group consisting of alkoxysilanes, hydrolysates and partial condensates thereof, a surfactant, a lower alcohol having 1 to 3 carbon atoms, and a boiling point of 125 to 180 ° C. A film forming step of forming a silica-based precursor on a light-transmitting substrate by spraying a silica-based composition containing an organic solvent having a vapor pressure of 20 kPa or less at 20 ° C. and water in a mist form;
And the manufacturing method of the silica type porous membrane characterized by including the heating process which heats this silica type precursor and makes it a silica type porous membrane.

The molar ratio of the organic solvent having a boiling point of 125 to 180 ° C and a vapor pressure of 20 ° C of 2.0 kPa or less with respect to the lower alcohol having 1 to 3 carbon atoms is 0.1 to 50 (mol / mol). The manufacturing method of the silica type porous membrane of description.

In the method for producing a silica-based porous membrane,
At least one alkoxysilane compound selected from the alkoxysilane group consisting of alkoxysilanes, hydrolysates and partial condensates thereof, a surfactant, a lower alcohol having 1 to 3 carbon atoms, and a boiling point of 125 to 180 ° C. A film-forming step of forming a silica-based precursor on a light-transmitting substrate by ejecting a silica-based composition containing an organic solvent having a vapor pressure of 2.0 kPa or less at 25 ° C. and water,
And the manufacturing method of the silica type porous membrane characterized by including the heating process which heats this silica type precursor and makes it a silica type porous membrane.

Molar ratio of 25 ° C. The organic solvent having a vapor pressure below 2.0kPa at boiling point 125 to 180 ° C. for a lower alcohol of the 1 to 3 carbon atoms, to claim 3 which is 0.1~50 (mol / mol) The manufacturing method of the silica type porous membrane of description.

The method for producing a silica-based porous film according to any one of claims 1 to 4, wherein the surfactant is a nonionic polymer having an alkylene oxide moiety.

The alkoxysilane compound is at least one alkoxysilane compound selected from the following alkoxysilanes group I and at least one alkoxysilane compound selected from the following alkoxysilanes group II, or at least one selected from the following alkoxysilanes group III A kind of alkoxysilane compound, or at least one alkoxysilane compound selected from the following alkoxysilanes group I and / or at least one alkoxysilane compound selected from the following alkoxysilanes group II and the following alkoxysilanes group III The method for producing a silica-based porous film according to any one of claims 1 to 5 , comprising at least one alkoxysilane compound.
Alkoxysilanes group I: Tetraalkoxysilanes, tetraalkoxysilanes group consisting of hydrolysates and partial condensates Alkoxysilanes group II: Alkoxysilanes other than the above tetraalkoxysilanes, hydrolysates and partial condensates Other Alkoxysilanes Group Alkoxysilanes Group III: Partial condensate group of at least one alkoxysilane compound selected from tetraalkoxysilanes group I and at least one alkoxysilane compound selected from other alkoxysilanes group II

In the film forming step, the silica-based composition is used by using a nozzle that sprays the silica-based composition in a mist form with a gas of 5 kPa or more and 500 kPa or less, and the distance between the nozzle and the translucent substrate is 3 cm or more and 100 cm or less. The method for producing a silica-based porous film according to any one of claims 1 to 6 , wherein an object is ejected.

The silica according to any one of claims 1 to 7 , wherein a rough drying step is performed after the film forming step, and a film thickness of the silica precursor after the rough drying step is 10 µm or less. Of a porous porous membrane.

The method for producing a silica-based porous film according to any one of claims 1 to 8 , wherein the silica-based porous film is an optical filter.

The method for producing a silica-based porous film according to claim 9 , wherein the optical filter is an antireflection film.

The method for producing a silica-based porous film according to claim 10 , wherein the antireflection film is a solar cell antireflection film.

At least one alkoxysilane compound selected from the alkoxysilane group consisting of alkoxysilanes, hydrolysates and partial condensates thereof, a surfactant, a lower alcohol having 1 to 3 carbon atoms, and other organic solvents, A silica-based composition comprising water,
A silica-based composition characterized in that the other organic solvent has a boiling point of 125 to 180 ° C, a vapor pressure of 2.0 kPa or less at 20 ° C, and a molecular weight of 100 or more.

At least one alkoxysilane compound selected from the alkoxysilane group consisting of alkoxysilanes, hydrolysates and partial condensates thereof, a surfactant, a lower alcohol having 1 to 3 carbon atoms, and other organic solvents, A silica-based composition comprising water,
A silica-based composition, wherein the other organic solvent has a boiling point of 125 to 180 ° C, a vapor pressure of 2.0 kPa or less at 25 ° C, and a molecular weight of 100 or more.