JP6733235B2 - Liquid composition for forming a low refractive index film - Google Patents
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- JP6733235B2 JP6733235B2 JP2016053200A JP2016053200A JP6733235B2 JP 6733235 B2 JP6733235 B2 JP 6733235B2 JP 2016053200 A JP2016053200 A JP 2016053200A JP 2016053200 A JP2016053200 A JP 2016053200A JP 6733235 B2 JP6733235 B2 JP 6733235B2
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- 239000000203 mixture Substances 0.000 title claims description 61
- 239000007788 liquid Substances 0.000 title claims description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 73
- 239000002245 particle Substances 0.000 claims description 66
- 239000008119 colloidal silica Substances 0.000 claims description 50
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 38
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 25
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- -1 silicon alkoxide Chemical class 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- 238000000576 coating method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- 239000002612 dispersion medium Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- IEJKFDMRQARVHW-UHFFFAOYSA-N butan-2-one;1-methoxypropan-2-ol Chemical compound CCC(C)=O.COCC(C)O IEJKFDMRQARVHW-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Description
本発明は、ディスプレイパネルや太陽電池、光学レンズ、カメラモジュール、センサーモジュール、ミラー、メガネ等に用いられる低屈折率膜を形成するための液組成物に関する。更に詳しくは、凹凸が少なく段差性に優れた低屈折率膜を形成するための液組成物に関するものである。 The present invention relates to a liquid composition for forming a low refractive index film used for display panels, solar cells, optical lenses, camera modules, sensor modules, mirrors, glasses and the like. More specifically, the present invention relates to a liquid composition for forming a low-refractive-index film having little unevenness and excellent step difference.
ガラスやプラスチック等の透明基材の表面に形成された低屈折率の膜は、ブラウン管、液晶、有機ＥＬ等のディスプレイパネルや太陽電池、光学レンズ、ショーケース用ガラス等において、入射する光の反射を防止するための反射防止膜として利用されている。例えば、ディスプレイパネルの表示面側には視認性を向上させるための反射防止膜が設けられたり、また、太陽電池の分野では、入射する太陽光の反射を防止して光の吸収率を上げるために、ガラス基材の表面等に低屈折率の膜を反射防止膜として形成する等の対策がなされている。 A low-refractive index film formed on the surface of a transparent substrate such as glass or plastic reflects incident light on display panels such as cathode ray tubes, liquid crystals, organic EL, solar cells, optical lenses, and glass for showcases. It is used as an antireflection film for preventing For example, an antireflection film is provided on the display surface side of the display panel to improve visibility, or in the field of solar cells, to prevent reflection of incident sunlight and increase the light absorption rate. In addition, measures such as forming a film having a low refractive index as an antireflection film on the surface of a glass substrate are taken.
このような反射を防止するための膜としては、従来、真空蒸着法やスパッタリング法等の気相法により形成したＭｇＦ２や氷晶石等からなる単層膜が実用化されている。また、ＳｉＯ２等の低屈折率被膜と、ＴｉＯ２やＺｒＯ２等の高屈折率被膜を、基材上に交互に積層して形成された多層膜等も、高い反射防止効果が得られることが知られている。しかし、真空蒸着法やスパッタリング法等の気相法では、装置等が高価であることから製造コスト等の面で問題がある。また、低屈折率被膜と高屈折率被膜を交互に積層して多層膜を形成する方法では、製造工程が煩雑で、時間と手間が掛かることからあまり実用的ではない。 As a film for preventing such reflection, a single-layer film made of MgF 2 or cryolite formed by a vapor phase method such as a vacuum deposition method or a sputtering method has been put into practical use. Further, a multilayer film formed by alternately laminating a low-refractive-index film such as SiO 2 and a high-refractive-index film such as TiO 2 or ZrO 2 on a base material also has a high antireflection effect. It has been known. However, a vapor phase method such as a vacuum vapor deposition method or a sputtering method has a problem in terms of manufacturing cost and the like because an apparatus and the like are expensive. Further, the method of forming a multilayer film by alternately laminating a low refractive index coating and a high refractive index coating is not very practical because the manufacturing process is complicated and it takes time and labor.
そのため、最近では、製造コスト等の面から、ゾルゲル法等の塗布法が注目されている。しかし、ゾルゲル法では、一般に、ゾルゲル液を調製し、これをガラス等の透明基板に塗布した後、乾燥や焼成等を行うことにより膜の形成を行うが、ゾルゲル法によって形成された膜は、真空蒸着法等の気相法で形成された膜に比べて所望の低屈折率が得られなかったり、基板との密着性不良やクラックの発生といった様々な課題が残されていた。 Therefore, recently, a coating method such as a sol-gel method has been drawing attention from the viewpoint of manufacturing cost and the like. However, in the sol-gel method, generally, a sol-gel solution is prepared, and after applying this to a transparent substrate such as glass, the film is formed by performing drying or firing, but the film formed by the sol-gel method is As compared with a film formed by a vapor phase method such as vacuum deposition, a desired low refractive index cannot be obtained, and various problems such as poor adhesion to a substrate and generation of cracks remain.
このようなゾルゲル法を利用した低屈折率膜として、所定の平均粒径を有するシリカ粒子が分散するシリカゾル（ａ）と、アルコキシシランの加水分解物、金属アルコキシドの加水分解物及び金属塩からなる群より選ばれた少なくとも１種の成分（ｂ）からなり、これらが所望の割合で有機溶媒に含有する組成物を、基材に塗布した後、硬化させた低屈折率反射防止膜が開示されている（例えば、特許文献１参照。）。上記塗布におけるシリカゾルとして、水性シリカゾル中の水を蒸留法等により有機溶剤に置換することにより得られる有機溶剤系シリカゾル（オルガノシリカゾル）が示され、その有機溶剤として好ましくは、メタノール、エタノール、イソプロパノール、ブタノール等のアルコール類、エチルセロソルブ、ブチルセロソルブ、エチルカルビトール、ブチルカルビトール、ジエチルセロソルブ、ジエチルカルビトール等のグリコールエーテル類や、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類の親水性溶剤が用いられる。
しかし、特許文献１に示された組成物は、球状のシリカ粒子のみを含み、数珠状シリカ粒子を含まないため、塗膜の屈折率が十分に低下しないという課題があった。
A low refractive index film using such a sol-gel method is composed of silica sol (a) in which silica particles having a predetermined average particle size are dispersed, an alkoxysilane hydrolyzate, a metal alkoxide hydrolyzate, and a metal salt. Disclosed is a low-refractive-index antireflection film obtained by applying a composition comprising at least one component (b) selected from the group, which is contained in an organic solvent in a desired ratio, and then curing the composition. (See, for example, Patent Document 1). As the silica sol in the coating, an organic solvent-based silica sol (organo silica sol) obtained by substituting water in an aqueous silica sol with an organic solvent by a distillation method or the like is shown, and the organic solvent is preferably methanol, ethanol or isopropanol. Hydrophilic solvents such as alcohols such as butanol, glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve and diethyl carbitol, and ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone are used. ..
However, since the composition disclosed in Patent Document 1 contains only spherical silica particles and does not contain beaded silica particles, there is a problem that the refractive index of the coating film is not sufficiently lowered.
そこで、ケイ素アルコキシドとしてのテトラメトキシシラン又はテトラエトキシシランのアルコール溶液に水と硝酸との混合物を添加して攪拌することにより生成されたケイ素アルコキシドの加水分解物と、球状コロイダルシリカ粒子及び数珠状コロイダルシリカ粒子が液体媒体中に分散したシリカゾルとを混合し、水に分散された組成物が開示され、水性有機溶媒に分散された組成物が示唆されている（特許文献２参照。）。 Therefore, a hydrolyzate of silicon alkoxide produced by adding a mixture of water and nitric acid to an alcohol solution of tetramethoxysilane or tetraethoxysilane as a silicon alkoxide and stirring, spherical colloidal silica particles and beaded colloidal A composition in which silica particles are mixed with silica sol dispersed in a liquid medium and dispersed in water is disclosed, and a composition dispersed in an aqueous organic solvent is suggested (see Patent Document 2).
しかしながら、特許文献２に示された低屈折率膜を形成する組成物（低屈折率膜形成用液組成物）は、溶媒を選択しないと、成膜したときの低屈折率膜に凹凸があり段差性に劣り、使用するのに不十分であった。 However, the composition for forming a low refractive index film (liquid composition for forming a low refractive index film) disclosed in Patent Document 2 has unevenness in the low refractive index film when formed unless a solvent is selected. The step property was inferior and it was insufficient for use.
本発明の目的は、上記課題を解決するもので、成膜した時に得られる低屈折率膜に凹凸が少なく段差性に優れた膜となる液組成物を提供することにある。 An object of the present invention is to solve the above-mentioned problems, and to provide a liquid composition which is a film having a low refractive index film which is obtained when it is formed and which has little unevenness and is excellent in step difference.
本発明者らは、あまたある溶媒の中から、プロピレングリコールモノメチルエーテルを選択すると、塗膜形成時の溶媒の揮発速度が適切であるという理由により、成膜した時の低屈折率膜の凹凸が少なく段差性に優れた膜が得られるという知見を見出し、本発明を完成した。 The inventors of the present invention selected propylene glycol monomethyl ether from among other solvents, and because the evaporation rate of the solvent at the time of coating film formation was appropriate, the unevenness of the low refractive index film when formed was The present inventors have completed the present invention by finding the finding that a film having a small number of steps can be obtained.
塗膜形成時の溶媒の揮発速度が適切であると成膜した時の低屈折率膜の凹凸が少なく段差性に優れた膜が得られる理由は以下の通りである。
溶媒の揮発速度が速いものを選択した場合、塗膜の表面は溶媒の揮発により冷却される。その際に室内の湿度により水分が凝縮される。凝縮した水分とケイ素アルコキシドとの反応による部分的な反応性の違いや、また、水分が組成物に含まれることによる表面張力の変化等により、膜表面に凹凸が発生しやすく、段差の大きな膜となる。
一方、溶媒の揮発速度が遅いものを選択した場合、塗膜がゆっくりと乾燥し、その間、塗膜の流動時間が長くなる。その際に塗膜中で分散粒子が凝集したり、分離することが、特に分散液と異なる溶媒種を混合した際に、見られる。塗膜中において、溶媒の揮発速度が大きく異なる時、部分的な流動しやすさや、流動している時間に差異が出てくるため、分散粒子が偏って凝集するような現象が生じ、これに起因して、膜表面に凹凸が発生しやすく、段差の大きな膜となる。
The reason why a film having excellent unevenness with little unevenness of the low refractive index film when formed is obtained when the evaporation rate of the solvent at the time of forming the film is appropriate is as follows.
When a solvent having a high evaporation rate is selected, the surface of the coating film is cooled by evaporation of the solvent. At that time, moisture is condensed due to indoor humidity. Due to the difference in partial reactivity due to the reaction between condensed water and silicon alkoxide, and the change in surface tension due to the inclusion of water in the composition, unevenness is likely to occur on the film surface, resulting in a film with large steps. Becomes
On the other hand, when a solvent with a low volatilization rate is selected, the coating film dries slowly, and the flow time of the coating film becomes long during that period. At that time, it is observed that dispersed particles aggregate or separate in the coating film, especially when a solvent species different from the dispersion liquid is mixed. In the coating film, when the volatilization rate of the solvent is greatly different, partial easiness of flow and difference in the time during which it is flowing occur, resulting in a phenomenon in which dispersed particles are unevenly aggregated. As a result, unevenness is likely to occur on the film surface, resulting in a film having a large step.
本発明の第１の観点は、ケイ素アルコキシドとしてのテトラメトキシシラン又はテトラエトキシシランのアルコール溶液に水と硝酸との混合物を添加して攪拌することによりケイ素アルコキシドの加水分解物を生成し、前記生成された加水分解物と、球状コロイダルシリカ粒子及び数珠状コロイダルシリカ粒子が質量比で５：９５〜５０：５０の割合でプロピレングリコールモノメチルエーテル中に分散したシリカゾルとを、前記加水分解物中のＳｉＯ2分１質量部に対してシリカゾル中のＳｉＯ2分が３〜４５質量部となる割合で混合し、更にプロピレングリコールモノメチルエーテルを、前記加水分解物中のＳｉＯ2分１質量部に対して１５〜４５質量部の割合で有機溶媒として混合する低屈折率膜形成用液組成物の製造方法である。
A first aspect of the present invention is to form a hydrolyzate of silicon alkoxide by adding a mixture of water and nitric acid to an alcohol solution of tetramethoxysilane or tetraethoxysilane as a silicon alkoxide and stirring the mixture, And the silica sol in which the spherical colloidal silica particles and the beaded colloidal silica particles are dispersed in propylene glycol monomethyl ether in a mass ratio of 5:95 to 50:50. SiO 2 minutes in the silica sol are mixed in a ratio to be 3 to 45 parts by weight with respect to 2 minutes 1 part by weight, 15 further propylene glycol monomethyl ether, with respect to SiO 2 minutes 1 part by weight of the hydrolyzate It is a method for producing a liquid composition for forming a low refractive index film, which is mixed as an organic solvent at a ratio of about 45 parts by mass.
本発明の第２の観点は、第１の観点の製造方法により得られた低屈折率膜形成用液組成物を用いて低屈折率膜を形成する方法である。 A second aspect of the present invention is a method of forming a low refractive index film using the liquid composition for forming a low refractive index film obtained by the production method of the first aspect.
本発明の第１の観点の液組成物によれば、塗膜形成時の溶媒の揮発速度が適切であるという理由により、成膜したときに凹凸が少なく段差性に優れた低屈折率膜が得られるという効果がある。
本発明の第２の観点の方法によれば、第１の観点の低屈折率膜形成用液組成物を用いて、凹凸が少なく段差性に優れた低屈折率膜を形成することができる。
According to the liquid composition of the first aspect of the present invention, a low-refractive-index film having less unevenness and excellent step difference when formed is formed because the evaporation rate of the solvent at the time of film formation is appropriate. It has the effect of being obtained.
According to the method of the second aspect of the present invention, it is possible to form a low refractive index film having less unevenness and excellent step difference by using the liquid composition for forming a low refractive index film of the first aspect.
次に本発明を実施するための形態を説明する。 Next, modes for carrying out the present invention will be described.
本発明の低屈折率膜形成用液組成物の製造方法は、ケイ素アルコキシドとしてのテトラメトキシシラン又はテトラエトキシシランのアルコール溶液に水と硝酸との混合物を添加して攪拌することにより生成されたケイ素アルコキシドの加水分解物と、球状コロイダルシリカ粒子及び数珠状コロイダルシリカ粒子が液体媒体中に分散したシリカゾルとを混合し、更にプロピレングリコールモノメチルエーテルを有機溶媒として混合して調製される。 The method for producing a liquid composition for forming a low refractive index film of the present invention is a silicon produced by adding a mixture of water and nitric acid to an alcohol solution of tetramethoxysilane or tetraethoxysilane as a silicon alkoxide and stirring the mixture. It is prepared by mixing a hydrolyzate of an alkoxide, a silica sol in which spherical colloidal silica particles and beads-shaped colloidal silica particles are dispersed in a liquid medium, and further mixing propylene glycol monomethyl ether as an organic solvent.
本発明の低屈折率膜形成用液組成物を製造するには、先ず、ケイ素アルコキシドとしてのテトラメトキシシラン又はテトラエトキシシラン１質量部に対して、０．５〜８．０質量部となる量のエタノール、イソプロパノール（ＩＰＡ）、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）等の有機溶媒を添加して、好ましくは３０〜４０℃の温度で５〜２０分間撹拌することにより第１液を調製する。ケイ素アルコキシドとしては、汎用性および原料の安全性の面から、テトラエトキシシランが好ましい。 In order to produce the liquid composition for forming a low refractive index film of the present invention, first, an amount of 0.5 to 8.0 parts by mass relative to 1 part by mass of tetramethoxysilane or tetraethoxysilane as a silicon alkoxide. The first liquid is prepared by adding an organic solvent such as ethanol, isopropanol (IPA), propylene glycol monomethyl ether (PGME) and stirring the mixture at a temperature of 30 to 40° C. for 5 to 20 minutes. As the silicon alkoxide, tetraethoxysilane is preferable in terms of versatility and safety of raw materials.
一方、この第１液とは別に、上記ケイ素アルコキシド１質量部に対して、水を０．５〜５．０質量部、硝酸を０．００５〜０．５質量部の割合で添加し、３０〜４０℃の温度で５〜２０分間攪拌することにより第２液を調製する。 On the other hand, separately from the first liquid, 0.5 to 5.0 parts by mass of water and 0.005 to 0.5 parts by mass of nitric acid were added to 1 part by mass of the silicon alkoxide, The second liquid is prepared by stirring at a temperature of -40°C for 5 to 20 minutes.
次に、上記調製した第１液を、ウォーターバス等を用いて好ましくは３０〜８０℃の温度に保持してから、第１液に第２液を添加し、上記温度を保持した状態で好ましくは３０〜１８０分間撹拌する。これにより、上記ケイ素アルコキシドの加水分解物が生成される。 Next, the first liquid prepared above is preferably maintained at a temperature of 30 to 80° C. using a water bath or the like, and then the second liquid is added to the first liquid, and the above temperature is preferably maintained. Stir for 30-180 minutes. As a result, a hydrolyzate of the silicon alkoxide is produced.
球状コロイダルシリカ粒子と数珠状コロイダルシリカ粒子を質量比で５：９５〜５０：５０の割合でエタノール、イソプロピルアルコール、メチルエチルケトンプロピレングリコールモノメチルエーテル、エチレングリコール等の分散媒に分散させたシリカゾルを得る。
次に、上記得られた加水分解物と、球状コロイダルシリカ粒子及び数珠状コロイダルシリカ粒子が分散したシリカゾルを、加水分解物中のＳｉＯ2分１質量部に対するシリカゾル中のＳｉＯ2分が３〜４５質量部となる割合で、撹拌して混合し、更にプロピレングリコールモノメチルエーテルを上記加水分解物中のＳｉＯ2分１質量部に対して、１５〜４５質量部となる割合で添加混合し攪拌することにより、本発明の低屈折率膜形成用液組成物が得られる。
A silica sol is obtained in which spherical colloidal silica particles and beaded colloidal silica particles are dispersed in a dispersion medium such as ethanol, isopropyl alcohol, methyl ethyl ketone propylene glycol monomethyl ether, and ethylene glycol at a mass ratio of 5:95 to 50:50 .
Next, a silica sol in which the above-obtained hydrolyzate and spherical colloidal silica particles and beaded colloidal silica particles were dispersed was used, and the SiO 2 content in the silica sol was 3 to 45 parts with respect to 1 part by mass of SiO 2 content in the hydrolyzate. The mixture is stirred and mixed at a ratio of 15 parts by mass, and propylene glycol monomethyl ether is further added and mixed at a ratio of 15 to 45 parts by mass with respect to 1 part by mass of SiO 2 in the hydrolyzate. As a result, the liquid composition for forming a low refractive index film of the present invention can be obtained.
本発明の低屈折率膜形成用液組成物に含まれるシリカゾルは、球状コロイダルシリカ粒子と数珠状コロイダルシリカ粒子が液体媒体中に分散したゾルである。一般に、シリカゾルに含まれるシリカ粒子としては、数珠状の他に、球状、針状又は板状のもの等が広く知られているが、本発明では、球状コロイダルシリカ粒子及び数珠状コロイダルシリカ粒子の双方が分散したシリカゾルを用いる。球状コロイダルシリカ粒子だけを用いると、塗膜の屈折率が十分に下がらず、数珠状コロイダルシリカ粒子だけを用いると、膜の強度が低い塗膜となる。 The silica sol contained in the liquid composition for forming a low refractive index film of the present invention is a sol in which spherical colloidal silica particles and beaded colloidal silica particles are dispersed in a liquid medium. In general, as the silica particles contained in the silica sol, other than beads, spherical, needle-shaped or plate-like ones are widely known, but in the present invention, spherical colloidal silica particles and beads-shaped colloidal silica particles are included. A silica sol in which both are dispersed is used. When only spherical colloidal silica particles are used, the refractive index of the coating film is not sufficiently lowered, and when only beaded colloidal silica particles are used, the coating film has low strength.
球状コロイダルシリカ粒子は、平均粒径２〜８０ｎｍが好ましい。２ｎｍ以下だと単一分散状態で存在し難く、凝集した形態をとりやすくなり、８０ｎｍ以上だと塗膜の表面の凹凸が大きくなり、膜のヘイズが増大しやすくなる。
一方、上記数珠状コロイダルシリカ粒子は、平均粒子径が５〜５０ｎｍの複数の球状コロイダルシリカ粒子が、金属酸化物含有シリカによって接合されたものである。ここで、数珠状コロイダルシリカ粒子を構成する複数の球状コロイダルシリカ粒子の平均粒子径を上記範囲が好ましいのは、平均粒子径が下限値未満では形成後の膜の屈折率が十分に低下しにくくなり、一方、上限値を越えると膜表面の凹凸により膜のヘイズが増大しやすくなるからである。このうち、上記数珠状コロイダルシリカ粒子を構成する複数の球状コロイダルシリカ粒子の平均粒子径は５〜３０ｎｍの範囲であることが更に好ましい。なお、上記球状コロイダルシリカ粒子の平均粒子径とは、ＴＥＭ観察により得られた粒子形状を２００点計測した平均値を用いた。また、球状コロイダルシリカ粒子を接合する金属酸化物含有シリカとしては、例えば非晶質のシリカ、又は、非晶質のアルミナ等が例示される。
The spherical colloidal silica particles preferably have an average particle size of 2 to 80 nm. If it is 2 nm or less, it is difficult to exist in a monodispersed state, and it tends to take an aggregated form.
On the other hand, the beaded colloidal silica particles are obtained by bonding a plurality of spherical colloidal silica particles having an average particle diameter of 5 to 50 nm with a metal oxide-containing silica. Here, the average particle diameter of the plurality of spherical colloidal silica particles constituting the beaded colloidal silica particles is preferably in the above range, because the average particle diameter is less than the lower limit, the refractive index of the film after formation is difficult to sufficiently decrease. On the other hand, when the value exceeds the upper limit, the haze of the film tends to increase due to the unevenness of the film surface. Among these, it is more preferable that the plurality of spherical colloidal silica particles forming the beaded colloidal silica particles have an average particle diameter of 5 to 30 nm. The average particle diameter of the spherical colloidal silica particles was an average value of 200 particle shapes obtained by TEM observation. Examples of the metal oxide-containing silica for bonding the spherical colloidal silica particles include amorphous silica and amorphous alumina.
使用するシリカゾルのＳｉＯ２濃度が５〜４０質量％であるものが好ましい。使用するシリカゾルのＳｉＯ２濃度が低すぎると形成後の膜の屈折率が十分に低下しない場合があり、一方、高すぎるとシリカゾル中のＳｉＯ２が凝集しやすく液が不安定となる場合がある。
本発明の低屈折率膜形成用液組成物に含まれるシリカゾルは、球状コロイダルシリカ粒子については、ケイ酸ソーダをイオン交換し、活性ケイ酸を調製後、これを加熱下において、ＮａＯＨでｐＨ調整した種粒子含有水溶液中に添加し、粒子成長させる水ガラス法にて作製することが出来る。例えば、特開昭６１−１５８８１０号公報に記載されているシリカゾル等を使用することも出来る。
また、いわゆるStoeber法と呼ばれる、ケイ酸アルキル（テトラアルコキシシラン）を塩基性触媒の存在下で加水分解すると同時に縮合・粒子成長を行いながらシリカ粒子を製造するアルコキシド法でも、球状コロイダルシリカ粒子を作製できる。例えば、特開昭６３−２９１８０７号公報に記載されているシリカゾル等を使用することも出来る。
数珠状のコロイダルシリカ粒子は、具体的には、複数の球状シリカ粒子が、金属酸化物含有シリカ等の接合部によって接合されたものであることが好ましい。数珠状のコロイダルシリカ粒子は、先に作製した球状のコロイダルシリカ粒子を含有する酸性ゾルを用い、更に水ガラス法による球状シリカ粒子を製造する過程を経ることで、球状シリカ粒子が金属酸化物含有のシリカ等によって接合されたものを得ることが出来る。このような数珠状コロイダルシリカ粒子が分散したシリカゾルとしては、例えば特許第４３２８９３５号に記載されているシリカゾル等を使用することができる。
The silica sol used preferably has a SiO 2 concentration of 5 to 40 mass %. If the SiO 2 concentration of the silica sol used is too low, the refractive index of the formed film may not be sufficiently lowered, while if it is too high, the SiO 2 in the silica sol may easily aggregate and the liquid may become unstable. ..
The silica sol contained in the liquid composition for forming a low refractive index film of the present invention, for the spherical colloidal silica particles, is subjected to ion exchange with sodium silicate to prepare active silicic acid, which is then heated to adjust the pH with NaOH. It can be prepared by a water glass method in which the seed particles are added to the aqueous solution containing seed particles to grow the particles. For example, silica sol described in JP-A-61-158810 can be used.
In addition, spherical colloidal silica particles are also produced by the so-called Stoeber method, which is an alkoxide method in which an alkyl silicate (tetraalkoxysilane) is hydrolyzed in the presence of a basic catalyst, and at the same time condensation and particle growth are performed to produce silica particles. it can. For example, silica sol described in JP-A-63-291807 can be used.
Specifically, the beaded colloidal silica particles are preferably those in which a plurality of spherical silica particles are bonded by a bonding portion such as silica containing metal oxide. Bead-shaped colloidal silica particles, using the acidic sol containing the spherical colloidal silica particles prepared above, further through the process of producing spherical silica particles by the water glass method, spherical silica particles containing metal oxides It is possible to obtain a product bonded by silica or the like. As the silica sol in which such beaded colloidal silica particles are dispersed, for example, the silica sol described in Japanese Patent No. 4328935 can be used.
本発明の低屈折率膜形成用液組成物において、上記加水分解物と上記シリカゾルは、加水分解物中のＳｉＯ２分を１質量部とするときに、上記シリカゾルのＳｉＯ２分が３〜４５質量部となるように混合して調製される。シリカゾルの割合が下限値未満では形成後の膜の屈折率が十分に低下せず、一方、上限値を越えると膜厚が不均一になることで膜表面の凹凸が大きくなりヘイズが増大するからである。このうち、シリカゾルの割合は、加水分解物中のＳｉＯ２分１質量部に対するシリカゾルのＳｉＯ２分が１０〜３０質量部となる割合とするのが好ましい。 In the liquid composition for forming a low refractive index film of the present invention, the hydrolyzate and the silica sol have a SiO 2 content of 3 to 45 when the SiO 2 content in the hydrolyzate is 1 part by mass. It is prepared by mixing so as to be a mass part. If the proportion of silica sol is less than the lower limit, the refractive index of the film after formation will not be sufficiently reduced, while if it exceeds the upper limit, the unevenness of the film surface will increase due to uneven film thickness, and haze will increase. Is. Among these, the ratio of silica sol is preferably such that the SiO 2 content of silica sol is 10 to 30 parts by mass with respect to 1 part by mass of SiO 2 in the hydrolyzate.
本発明では、プロピレングリコールモノメチルエーテルを用いる。塗膜形成時の溶媒の揮発速度が適切であるという理由により、成膜した時に凹凸が少なく非常に優れた段差性を示す。 In the present invention, propylene glycol monomethyl ether is used. Due to the reason that the evaporation rate of the solvent at the time of forming the coating film is appropriate, there is little unevenness when the film is formed, and excellent step difference is exhibited.
続いて、本発明の低屈折率膜を形成する方法について説明する。本発明の低屈折率膜の形成方法では、先ず、ガラスやプラスチック等の基材を用意し、この基材表面に、上述した本発明の低屈折率膜形成用液組成物を、例えばスピンコート法、ダイコート法又はスプレー法等により塗布する。塗布した後は、ホットプレートや雰囲気焼成炉等を用いて、好ましくは５０〜１００℃の温度で５〜６０分間乾燥した後、ホットプレートや雰囲気焼成炉等を用いて、好ましくは１００〜３００℃の温度で５〜１２０分間焼成して硬化させる。このように形成された膜は、０．１μｍ以下の段差性を示す。そのため、例えばブラウン管、液晶、有機ＥＬ等のディスプレイパネルや太陽電池、ショーケース用ガラス等において入射光の反射を防止するために用いられる反射防止膜、或いはセンサーやカメラモジュール等に用いられる屈折率差を利用した中間膜等の形成に好適に使用することができる。更に防曇性に優れため、ミラー、メガネ等のコーティング用の膜に好適に用いることができる。 Next, a method for forming the low refractive index film of the present invention will be described. In the method for forming a low refractive index film of the present invention, first, a base material such as glass or plastic is prepared, and the liquid composition for forming a low refractive index film of the present invention is spin-coated on the surface of the base material. Method, die coating method, spray method or the like. After coating, it is dried at a temperature of 50 to 100° C. for 5 to 60 minutes using a hot plate or an atmosphere baking furnace, and then at a temperature of 50 to 100° C., preferably at a temperature of 100 to 300° C. It is baked at the temperature of 5 to 120 minutes to cure. The film thus formed exhibits a step difference of 0.1 μm or less. Therefore, for example, an antireflection film used for preventing reflection of incident light in a display panel such as a cathode ray tube, liquid crystal, organic EL, a solar cell, a glass for a showcase, or a refractive index difference used in a sensor or a camera module. It can be preferably used for forming an intermediate film using the. Further, since it has excellent anti-fogging property, it can be suitably used as a coating film for mirrors, glasses and the like.
次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
＜実施例１＞
先ず、ケイ素アルコキシドとしてテトラエキシシラン（ＴＥＯＳ）を用意し、セパラブルフラスコ内に投入した。このケイ素アルコキシド１質量部に対して１．０質量部となる量のエタノールを添加し、３０℃の温度で１５分間撹拌することにより第１液を調製した。
<Example 1>
First, tetraexisilane (TEOS) was prepared as a silicon alkoxide and put into a separable flask. A first liquid was prepared by adding 1.0 part by mass of ethanol to 1 part by mass of this silicon alkoxide and stirring the mixture at a temperature of 30° C. for 15 minutes.
また、この第１液とは別に、ケイ素アルコキシド１質量部に対して０．８質量部となる量のイオン交換水と、０．０１質量部となる量の硝酸をビーカー内に投入して混合し、３０℃の温度で１５分間撹拌することにより第２液を調製した。次に、上記調製した第１液を、ウォーターバスにて５５℃の温度に保持してから、この第１液に第２液を添加し、上記温度を保持した状態で６０分間撹拌した。これにより、上記ケイ素アルコキシドの加水分解物を得た。 Separately from the first liquid, 0.8 parts by mass of ion-exchanged water and 0.01 part by mass of nitric acid are put into a beaker and mixed with 1 part by mass of silicon alkoxide. Then, the second liquid was prepared by stirring at a temperature of 30° C. for 15 minutes. Next, the above-prepared first liquid was kept at a temperature of 55° C. in a water bath, then the second liquid was added to the first liquid, and the mixture was stirred for 60 minutes while keeping the above temperature. As a result, a hydrolyzate of the silicon alkoxide was obtained.
球状コロイダルシリカ粒子については、ケイ酸ソーダをイオン交換し、活性ケイ酸を調製後、これを加熱下において、ＮａＯＨでｐＨ調整した種粒子含有水溶液中に添加し、粒子成長させる水ガラス法にて作製して得た。
また、数珠状のコロイダルシリカ粒子は、先に作製した球状のコロイダルシリカ粒子を含有する酸性ゾルを用い、更に水ガラス法による球状シリカ粒子を製造する過程を経ることで、球状シリカ粒子が金属酸化物含有のシリカ等によって接合されることで得た。
そして、上記得られた加水分解物と、球状コロイダルシリカ粒子と数珠状コロイダルシリカ粒子（重量比１０：９０）がプロピレングリコールモノメチルエーテルに分散したシリカゾルを、加水分解物中のＳｉＯ２分１質量部に対するシリカゾル中のＳｉＯ２分が２０質量部となる割合で、撹拌して混合し、さらに、プロピレングリコールモノメチルエーテルを上記加水分解物中のＳｉＯ２分１質量部に対して、２２質量部となる割合で撹拌混合し、液組成物を得た。
Regarding the spherical colloidal silica particles, sodium silicate is ion-exchanged to prepare active silicic acid, which is then added to a seed particle-containing aqueous solution whose pH has been adjusted with NaOH under heating, by a water glass method for particle growth. It was made and obtained.
Further, the beaded colloidal silica particles use an acidic sol containing the spherical colloidal silica particles prepared above, and further undergo a process of producing spherical silica particles by the water glass method, whereby the spherical silica particles are metal-oxidized. It was obtained by joining with silica containing a substance.
Then, the hydrolyzate obtained above, a silica sol in which the spherical colloidal silica particles and the beaded colloidal silica particles (weight ratio 10:90) are dispersed in propylene glycol monomethyl ether, are added in an amount of 1 part by mass of SiO 2 in the hydrolyzate. SiO 2 content in the silica sol is 20 parts by mass and mixed by stirring, and propylene glycol monomethyl ether is 22 parts by mass with respect to 1 part by mass of SiO 2 in the hydrolyzate. The mixture was stirred and mixed in a ratio to obtain a liquid composition.
＜実施例２＞
球状コロイダルシリカ粒子と数珠状コロイダルシリカ粒子（重量比３０：７０）とした以外は、実施例１と同様にして液組成物を調製した。
<Example 2>
A liquid composition was prepared in the same manner as in Example 1 except that the spherical colloidal silica particles and the beaded colloidal silica particles (weight ratio 30:70) were used.
＜実施例３＞
球状コロイダルシリカ粒子と数珠状コロイダルシリカ粒子（重量比５：９５）としたこと、及び上記シリカゾルの分散媒をイソプロピルアルコールに変更したこと以外は、実施例１と同様にして液組成物を調製した。
<Example 3>
A liquid composition was prepared in the same manner as in Example 1 except that spherical colloidal silica particles and beaded colloidal silica particles (weight ratio 5:95) were used, and the dispersion medium of the silica sol was changed to isopropyl alcohol. ..
＜実施例４＞
プロピレングリコールモノメチルエーテルを加水分解物中のＳｉＯ２分１質量部に対して、３３質量部となる割合で撹拌混合した以外は、実施例１と同様にして液組成物を調製した。
<Example 4>
A liquid composition was prepared in the same manner as in Example 1 except that propylene glycol monomethyl ether was stirred and mixed at a ratio of 33 parts by mass with respect to 1 part by mass of SiO 2 in the hydrolyzate.
＜実施例５＞
球状コロイダルシリカ粒子と数珠状コロイダルシリカ粒子を含むシリカゾルの分散媒をエチレングリコールとしたこと及び、プロピレングリコールモノメチルエーテルを加水分解物中のＳｉＯ２分１質量部に対して、４０質量部となる割合で撹拌混合した以外は、実施例１と同様にして液組成物を調製した。
<Example 5>
Ethylene glycol was used as the dispersion medium for the silica sol containing spherical colloidal silica particles and beaded colloidal silica particles, and propylene glycol monomethyl ether was 40 parts by mass with respect to 1 part by mass of SiO 2 in the hydrolyzate. A liquid composition was prepared in the same manner as in Example 1 except that the mixture was stirred and mixed in.
＜実施例６＞
球状コロイダルシリカ粒子と数珠状コロイダルシリカ粒子（重量比２０：８０）としたこと、及び上記シリカゾルの分散媒をイソプロピルアルコールに変更したこと及び、プロピレングリコールモノメチルエーテルを加水分解物のＳｉＯ２分１質量部に対して、４０質量部となる割合で撹拌混合した以外は、実施例１と同様にして液組成物を調製した。
<Example 6>
Spherical colloidal silica particles and beaded colloidal silica particles (weight ratio 20:80) were used, the dispersion medium of the silica sol was changed to isopropyl alcohol, and propylene glycol monomethyl ether was a hydrolyzate having a SiO 2 content of 1 mass. A liquid composition was prepared in the same manner as in Example 1 except that the mixture was stirred and mixed at a ratio of 40 parts by mass with respect to parts by mass.
＜実施例７＞
球状コロイダルシリカ粒子と数珠状コロイダルシリカ粒子（重量比２５：７５）としたこと、及び上記シリカゾルの分散媒をメチルエチルケトンに変更したこと及び、プロピレングリコールモノメチルエーテルを加水分解物のＳｉＯ２分１質量部に対して、３３質量部となる割合で撹拌混合した以外は、実施例１と同様にして液組成物を調製した。
<Example 7>
Spherical colloidal silica particles and beaded colloidal silica particles (weight ratio 25:75), the dispersion medium of the silica sol was changed to methyl ethyl ketone, and propylene glycol monomethyl ether was a hydrolyzate of SiO 2 per 1 part by mass. On the other hand, a liquid composition was prepared in the same manner as in Example 1 except that the mixture was stirred and mixed at a ratio of 33 parts by mass.
＜実施例８＞
球状コロイダルシリカ粒子と数珠状コロイダルシリカ粒子（重量比２５：７５）としたこと、及び上記シリカゾルの分散媒をイソプロピルアルコールに変更したこと及び、プロピレングリコールモノメチルエーテルを加水分解物のＳｉＯ２分１質量部に対して、１５質量部となる割合で撹拌混合した以外は、実施例１と同様にして液組成物を調製した。
<Example 8>
Spherical colloidal silica particles and beaded colloidal silica particles (weight ratio 25:75), the dispersion medium of the silica sol was changed to isopropyl alcohol, and propylene glycol monomethyl ether was a hydrolyzate having a SiO 2 content of 1 mass. A liquid composition was prepared in the same manner as in Example 1 except that the mixture was stirred and mixed at a ratio of 15 parts by mass with respect to parts by mass.
＜実施例９＞
球状コロイダルシリカ粒子と数珠状コロイダルシリカ粒子（重量比５０：５０）としたこと、及び上記シリカゾルの分散媒をイソプロピルアルコールに変更したこと及び、プロピレングリコールモノメチルエーテルを加水分解物のＳｉＯ２分１質量部に対して、４５質量部となる割合で撹拌混合した以外は、実施例１と同様にして液組成物を調製した。
<Example 9>
Spherical colloidal silica particles and beaded colloidal silica particles (weight ratio 50:50), the dispersion medium of the silica sol was changed to isopropyl alcohol, and propylene glycol monomethyl ether was a hydrolyzate having a SiO 2 content of 1 mass. A liquid composition was prepared in the same manner as in Example 1 except that the mixture was stirred and mixed at a ratio of 45 parts by mass with respect to parts by mass.
＜比較例１＞
プロピレングリコールモノメチルエーテルの代わりにイソプロピルアルコールを用いた以外は、実施例１と同様にして液組成物を調製した。
<Comparative Example 1>
A liquid composition was prepared in the same manner as in Example 1 except that isopropyl alcohol was used instead of propylene glycol monomethyl ether.
＜比較例２＞
プロピレングリコールモノメチルエーテルの代わりにブチルカルビトールアセテートを用いた以外は、実施例１と同様にして液組成物を調製した。
<Comparative example 2>
A liquid composition was prepared in the same manner as in Example 1 except that butyl carbitol acetate was used instead of propylene glycol monomethyl ether.
＜比較例３＞
プロピレングリコールモノメチルエーテルの代わりにメタノールを用いた以外は、実施例１と同様にして液組成物を調製した。
<Comparative example 3>
A liquid composition was prepared in the same manner as in Example 1 except that methanol was used instead of propylene glycol monomethyl ether.
＜比較例４＞
プロピレングリコールモノメチルエーテルの代わりにメチルエチルケトンを用いた以外は、実施例１と同様にして液組成物を調製した。
<Comparative example 4>
A liquid composition was prepared in the same manner as in Example 1 except that methyl ethyl ketone was used instead of propylene glycol monomethyl ether.
＜比較例５＞
プロピレングリコールモノメチルエーテルの代わりにエチルセロソルブを用いた以外は、実施例１と同様にして液組成物を調製した。
<Comparative Example 5>
A liquid composition was prepared in the same manner as in Example 1 except that ethyl cellosolve was used instead of propylene glycol monomethyl ether.
＜比較例６＞
プロピレングリコールモノメチルエーテルの代わりにイソプロピルアルコールを用いた以外は、実施例３と同様にして液組成物を調製した。
<Comparative example 6>
A liquid composition was prepared in the same manner as in Example 3 except that isopropyl alcohol was used instead of propylene glycol monomethyl ether.
＜比較試験及び評価＞
実施例１〜９及び比較例１〜６で調製した液組成物を用いて成膜して得られた低屈折率膜の段差性評価試験は次の方法により行った。
また、成膜条件は、５ｃｍ角のガラス基板に、液組成物を９００μｌ塗布後、スピンコーターを用いて、１０００ｒｐｍで６０ｓｅｃ回転させた後、得られた塗膜を１２０℃で３０分硬化させ、評価用ガラス基板を得た。
<Comparison test and evaluation>
The step evaluation test of the low refractive index films obtained by forming films using the liquid compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 6 was performed by the following method.
In addition, the film forming conditions were as follows: 900 μl of the liquid composition was applied to a 5 cm square glass substrate, the mixture was rotated at 1000 rpm for 60 seconds using a spin coater, and the obtained coating film was cured at 120° C. for 30 minutes. A glass substrate for evaluation was obtained.
段差性は、最大高低差で評価した。最大高低差は、走査型プローブ顕微鏡（エスアイアイ・ナノテクノロジー製「Ｎａｎｏｃｕｔｅ」）を用いて、評価用ガラス基板中心１０μｍ角の凹凸形状を測定したのち、断面解析を行って得た。断面解析では、測定範囲の中心線の一走査分の凹凸の最大箇所の標高から、最小箇所の標高を差し引いて、その段差（高低差）を算出した。このうち最大高低差の算出結果を下記表１に示す。 The step difference was evaluated by the maximum height difference. The maximum height difference was obtained by measuring the uneven shape of the evaluation glass substrate center 10 μm square using a scanning probe microscope (“Nanocute” manufactured by SII Nanotechnology), and then performing a cross-sectional analysis. In the cross-sectional analysis, the level difference (height difference) was calculated by subtracting the altitude of the minimum position from the altitude of the maximum position of the unevenness for one scan of the center line of the measurement range. Table 1 below shows the calculation results of the maximum height difference.
表１から明らかなように、プロピレングリコールモノメチルエーテルを用いた実施例１〜９は最大高低差が小さく段差性に優れていることがわかった。一方、それ以外の溶媒を用いた比較例１〜６は最大高低差が大きく段差性に劣っていることがわかった。 As is clear from Table 1, it was found that Examples 1 to 9 using propylene glycol monomethyl ether had a small maximum height difference and excellent step difference. On the other hand, it was found that Comparative Examples 1 to 6 using other solvents had a large maximum height difference and were inferior in step difference.
本発明の液組成物は、ディスプレイパネルや太陽電池、光学レンズ、カメラモジュール、センサーモジュール、ミラー、メガネ等に用いられる低屈折率膜を形成することに利用できる。 The liquid composition of the present invention can be used for forming a low refractive index film used for display panels, solar cells, optical lenses, camera modules, sensor modules, mirrors, glasses and the like.
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