JP2009132819A - Process for producing modified zirconia fine particles, coating liquid for forming transparent film containing modified zirconia fine particles and substrate with transparent film - Google Patents
Process for producing modified zirconia fine particles, coating liquid for forming transparent film containing modified zirconia fine particles and substrate with transparent film Download PDFInfo
- Publication number
- JP2009132819A JP2009132819A JP2007310706A JP2007310706A JP2009132819A JP 2009132819 A JP2009132819 A JP 2009132819A JP 2007310706 A JP2007310706 A JP 2007310706A JP 2007310706 A JP2007310706 A JP 2007310706A JP 2009132819 A JP2009132819 A JP 2009132819A
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- JP
- Japan
- Prior art keywords
- zirconia fine
- fine particles
- dispersion
- modified zirconia
- zirconia
- 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.)
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 457
- 239000010419 fine particle Substances 0.000 title claims abstract description 227
- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 239000011248 coating agent Substances 0.000 title claims abstract description 71
- 239000000758 substrate Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007788 liquid Substances 0.000 title abstract description 42
- 230000008569 process Effects 0.000 title abstract description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 143
- 239000000843 powder Substances 0.000 claims abstract description 53
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 47
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 47
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003513 alkali Substances 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 63
- 238000004519 manufacturing process Methods 0.000 claims description 39
- 238000004381 surface treatment Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 13
- 239000002585 base Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000011859 microparticle Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 37
- 239000007787 solid Substances 0.000 description 36
- 229920005989 resin Polymers 0.000 description 26
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- 239000000243 solution Substances 0.000 description 22
- 238000003917 TEM image Methods 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
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- 150000002500 ions Chemical class 0.000 description 10
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
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- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 4
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
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- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000000017 hydrogel Substances 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
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- 229920005992 thermoplastic resin Polymers 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 2
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 2
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- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 1
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- MLXDKRSDUJLNAB-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MLXDKRSDUJLNAB-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、屈折率が高く、分散性、安定性に優れた改質ジルコニア微粒子の製造方法、改質ジルコニア微粒子を含む透明被膜形成用塗布液および透明被膜付基材に関する。 The present invention relates to a method for producing modified zirconia fine particles having a high refractive index and excellent dispersibility and stability, a coating liquid for forming a transparent film containing the modified zirconia fine particles, and a substrate with a transparent film.
従来、シリカ、アルミナ、チタニア、ジルコニア、酸化亜鉛、五酸化アンチモン、酸化セリウム、酸化スズ、シリカ・アルミナ、シリカ・ジルコニアなどのコロイド粒子が、光学材料として屈折率を調整するために被膜等に配合して用いられている。 Conventionally, colloidal particles such as silica, alumina, titania, zirconia, zinc oxide, antimony pentoxide, cerium oxide, tin oxide, silica-alumina, silica-zirconia, etc. are blended into coatings etc. to adjust the refractive index as an optical material It is used as.
例えば、シリカは低屈折材料として、アルミナは中程度の屈折率材料として、チタニア、ジルコニア等は高屈折率材料として用いられている。このとき、チタニア粒子は高屈折率ではあるものの、分散安定性や、用法、用途によっては光触媒活性のために耐光性、耐候性等に問題があった。このため他の成分、例えばシリカ成分などを複合化することによって分散安定性や、耐光性、耐候性等を向上させることが行われている（特開平８−４８９４０号公報）が、複合化成分によっては屈折率を低下させることになることに加えて、光触媒活性を完全に抑制することが困難で、このため耐光性、耐候性等が不充分となることがあった（特許文献１：特開平８−４８９４０号公報）
一方、ジルコニア粒子は、光触媒活性は実質的に有しておらず、耐光性、耐候性等には優れているものの、チタニア粒子に較べて屈折率が低く、また、分散性、安定性に優れたコロイド領域のジルコニアゾルを得ることが困難であった。
For example, silica is used as a low refractive index material, alumina is used as a medium refractive index material, and titania, zirconia, and the like are used as high refractive index materials. At this time, although the titania particles had a high refractive index, there were problems in light stability, weather resistance, etc. due to dispersion stability, photocatalytic activity depending on usage and applications. For this reason, the dispersion stability, light resistance, weather resistance and the like are improved by compounding other components such as a silica component (JP-A-8-48940). In some cases, the refractive index is lowered, and it is difficult to completely suppress the photocatalytic activity. For this reason, the light resistance, weather resistance, etc. may be insufficient (Patent Document 1: Special). (Kaihei 8-48940)
On the other hand, zirconia particles have substantially no photocatalytic activity, and are excellent in light resistance, weather resistance, etc., but have a lower refractive index than titania particles, and are excellent in dispersibility and stability. It was difficult to obtain a colloidal zirconia sol.
本願出願人は、ジルコニウム塩の加水分解物をカルボン酸等の粒子成長抑制剤の存在下で水熱処理する分散性に優れたジルコニアゾルの製造方法を開示している（特許文献２：特開２００６−１４３５３５号公報）。 The present applicant has disclosed a method for producing a zirconia sol having excellent dispersibility by hydrothermally treating a hydrolyzate of a zirconium salt in the presence of a particle growth inhibitor such as a carboxylic acid (Patent Document 2: Japanese Patent Laid-Open No. 2006-2006). -143535).
また、炭酸ジルコニウムアンモニウムをカルボン酸等の存在下で加熱加水分解する安定性に優れたジルコニアゾルの製造方法が開示されている（特許文献３：特開平３−１７４３２５号公報）。 Further, a method for producing a zirconia sol excellent in stability in which ammonium zirconium carbonate is hydrolyzed by heating in the presence of carboxylic acid or the like is disclosed (Patent Document 3: Japanese Patent Application Laid-Open No. 3-174325).
一方、水酸化ジルコニウムを高温で焼成し、これを粉砕して微粒子としたジルコニア微粒子は、屈折率は高いものの粒子径が大きすぎたり、粒子径分布が不均一であったり、凝集粒子が存在して分散性に劣る等の点から透明被膜に用いるには不向きであった。また、この方法では、粉砕時にアルカリ等（粉砕助剤）を添加することによって粒子径をより小さくしたり、粒子径分布を均一化できる等の効果が知られている。
しかしながら、特許文献１〜３に開示された方法で得られるジルコニア微粒子は屈折率が必ずしも高くなく、高屈折率の透明被膜に用いるには満足のいくものではなかった。
また、従来、各種金属酸化物ゾルの分散性、安定性を向上するためにシランカップリング剤で表面処理することが行われているが、上記、焼成、粉砕して得たジルコニア微粒子は、アルカリ共存下のアルカリ領域では安定に分散するものの、洗浄や精製を行い、アルカリ成分を除去すると、表面電位が低下し分散性が著しく低下する問題があった。特に、
アルカリ存在下で処理したジルコニア微粒子はアルカリイオンの共存のために表面へのシランカップリング剤処理が不均一になるためか、得られる表面処理したジルコニア微粒子の分散性、安定性は必ずしも充分ではなかった。
However, the zirconia fine particles obtained by the methods disclosed in Patent Documents 1 to 3 do not necessarily have a high refractive index, and are not satisfactory for use in a high refractive index transparent film.
Conventionally, in order to improve the dispersibility and stability of various metal oxide sols, surface treatment with a silane coupling agent has been performed. Although it is stably dispersed in the coexisting alkali region, there is a problem that when washing and purification are performed and the alkali component is removed, the surface potential is lowered and the dispersibility is remarkably lowered. In particular,
The dispersibility and stability of the resulting surface-treated zirconia fine particles are not necessarily sufficient because the silane coupling agent treatment on the surface becomes non-uniform due to the coexistence of alkali ions in the zirconia fine particles treated in the presence of alkali. It was.
また、各種金属酸化物微粒子のシランカップリング剤との反応性を高めるためにアルカリ処理することが知られているが、ジルコニア微粒子の場合は上記した問題があり、他の方法として金属酸化物粒子の表面をＴＥＯＳなどの加水分解物で被覆して反応性を高めた後、シランカップリング剤で表面処理することもできるが、この場合は屈折率の低いシリカで被覆することになるので得られる粒子の屈折率が低下し、本発明の目的と乖離し、採用ができない。 In addition, it is known that alkali treatment is performed in order to increase the reactivity of various metal oxide fine particles with a silane coupling agent. However, in the case of zirconia fine particles, there are the above-mentioned problems, and other methods include metal oxide particles. After the surface of the coating is coated with a hydrolyzate such as TEOS to increase the reactivity, it can be surface-treated with a silane coupling agent, but in this case, it is coated with silica having a low refractive index. The refractive index of the particles decreases, deviating from the object of the present invention and cannot be employed.
本発明者等は、上記課題を鋭意検討した結果、焼成後、アルカリ存在下で粉砕処理したジルコニア微粒子を洗浄した後、ＮＨ4型イオン交換樹脂で処理すると効率的にシランカ
ップリング剤で表面処理できることを見出して本発明を完成するに至った。
As a result of diligent examination of the above problems, the present inventors have washed the zirconia fine particles that have been pulverized in the presence of alkali after firing, and then efficiently treated the surface with an NH 4 type ion exchange resin. The present invention has been completed by finding out what can be done.
すなわち本発明は、屈折率が高く、分散性、安定性に優れた改質ジルコニア微粒子の製造方法、該改質ジルコニア微粒子を含み、高屈折率で耐光性、耐候性等に優れた透明被膜を形成するための透明被膜形成用塗布液および透明被膜付基材を提供することを目的としている。 That is, the present invention provides a method for producing modified zirconia fine particles having a high refractive index and excellent dispersibility and stability, and a transparent coating film comprising the modified zirconia fine particles and having a high refractive index and excellent light resistance, weather resistance and the like. It aims at providing the coating liquid for transparent film formation for forming, and a base material with a transparent film.
本発明の要旨は、
[1]下記の工程（ａ）〜（ｆ）からなることを特徴とする改質ジルコニア微粒子の製造方
法。
（ａ）ジルコニア微粉末を３００〜８００℃で焼成する工程
（ｂ）焼成ジルコニア微粉末を、アルカリ金属を含むアルカリ存在下で粉砕する工程
（ｃ）粉砕後に洗浄する工程
（ｄ）洗浄した微粉末を分散させたジルコニア微粒子水分散液をＮＨ4型イオン交換樹脂
で処理してアルカリを除去する工程
（ｅ）脱アルカリ処理後のジルコニア微粒子分散液をアルコールに溶媒置換する工程
（ｆ）下記式(1)で表される有機ケイ素化合物で表面処理する工程
Ｒn-ＳiＸ4-n （１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：１〜３の整数）
[2]前記ジルコニア微粉末がジルコニアゾルを乾燥したものである[1]の改質ジルコニア微粒子の製造方法。
[3]前記工程（ｂ）で得られるジルコニア微粒子の平均粒子径が５〜１２０ｎｍの範囲に
ある[1]または[2]の改質ジルコニア微粒子の製造方法。
[4]前記工程（ｃ）後のジルコニア微粒子中のアルカリの含有量がＭ（Ｍ：アルカリ金属
）として１００〜１０，０００ｐｐｍの範囲にあり、前記工程（ｄ）後のジルコニア微粒子中のアルカリの含有量がＭ（Ｍ：アルカリ金属）として１〜１，０００ｐｐｍの範囲にある[1]〜[3]の改質ジルコニア微粒子の製造方法。
[5]前記工程（ｄ）における分散液のｐＨが８〜１２の範囲にあり、前記工程（ｆ）にお
ける表面処理時の分散液のｐＨが８〜１２の範囲にある[1]〜[4]の改質ジルコニア微粒子の製造方法。
[6]前記有機ケイ素化合物が（メタ）アクリル系シランカップリング剤である[1]〜[5]の
改質ジルコニア微粒子の製造方法。
[7]前記工程（ｆ）についで、下記工程（ｇ）：表面処理ジルコニア微粒子分散液を有機
溶媒置換する工程を行う[1]〜[6]の改質ジルコニア微粒子の製造方法。
[8]有機ケイ素化合物の含有量がＲnＳiＯ4-n/2で表して１〜３０重量％の範囲にある[1]
〜[7]の改質ジルコニア微粒子の製造方法。
[9]屈折率が１．８〜２．１５の範囲にある[1]〜[8]の改質ジルコニア微粒子の製造方法
。
[10][1]〜[9]の改質ジルコニア微粒子とマトリックス形成成分とからなることを特徴とする透明被膜形成用塗布液。
[11]基材と、基材の少なくとも一方の表面上に形成された透明被膜とからなり、該透明被膜が[1]〜[9]の改質ジルコニア微粒子とマトリックス成分とからなることを特徴とする透明被膜付基材。
The gist of the present invention is as follows.
[1] A method for producing modified zirconia fine particles, comprising the following steps (a) to (f):
(A) Step of calcining zirconia fine powder at 300 to 800 ° C. (b) Step of crushing calcined zirconia fine powder in the presence of alkali containing alkali metal (c) Step of washing after crushing (d) Washed fine powder The step of removing the alkali by treating the aqueous dispersion of zirconia fine particles dispersed with NH 4 type ion exchange resin (e) the step of substituting the zirconia fine particle dispersion after dealkalization treatment with alcohol for the solvent (f) Step of surface treatment with an organosilicon compound represented by 1) R n -SiX 4-n (1)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)
[2] The method for producing modified zirconia fine particles according to [1], wherein the zirconia fine powder is obtained by drying a zirconia sol.
[3] The method for producing modified zirconia fine particles according to [1] or [2], wherein the average particle size of the zirconia fine particles obtained in the step (b) is in the range of 5 to 120 nm.
[4] The alkali content in the zirconia fine particles after the step (c) is in the range of 100 to 10,000 ppm as M (M: alkali metal), and the alkali content in the zirconia fine particles after the step (d) A method for producing modified zirconia fine particles of [1] to [3] whose content is in the range of 1 to 1,000 ppm as M (M: alkali metal).
[5] The pH of the dispersion in the step (d) is in the range of 8 to 12, and the pH of the dispersion in the surface treatment in the step (f) is in the range of 8 to 12. [1] to [4 ] The manufacturing method of modified zirconia microparticles | fine-particles.
[6] The method for producing modified zirconia fine particles according to [1] to [5], wherein the organosilicon compound is a (meth) acrylic silane coupling agent.
[7] The method for producing modified zirconia fine particles according to [1] to [6], wherein the step (f) is followed by the step (g): replacing the surface-treated zirconia fine particle dispersion with an organic solvent.
[8] The content of the organic silicon compound is in the range of 1 to 30 wt% expressed in R n S i O 4-n / 2 [1]
A method for producing modified zirconia fine particles of [7].
[9] A method for producing modified zirconia fine particles of [1] to [8] having a refractive index in the range of 1.8 to 2.15.
[10] A coating solution for forming a transparent film, comprising the modified zirconia fine particles of [1] to [9] and a matrix-forming component.
[11] A substrate and a transparent film formed on at least one surface of the substrate, and the transparent film includes the modified zirconia fine particles of [1] to [9] and a matrix component A substrate with a transparent coating.
本発明によれば、高屈折率で、均一な粒子径分布を有し、分散性、安定性に優れた改質ジルコニア微粒子の製造方法、改質ジルコニア微粒子を含む透明被膜形成用塗布液および透明被膜付基材を提供することができる。 According to the present invention, a method for producing modified zirconia fine particles having a high refractive index, a uniform particle size distribution, excellent dispersibility and stability, a coating liquid for forming a transparent film containing the modified zirconia fine particles, and a transparent A coated substrate can be provided.
改質ジルコニア微粒子は透明被膜形成用塗布液中で均一に分散し、塗布液は安定性に優れ、高屈折率の透明被膜の形成に好適に用いることができ、得られる透明被膜付基材は、干渉縞が生じることもなく、基材との密着性、耐擦傷性、スクラッチ強度、鉛筆硬度等に優れるとともに耐光性、耐候性に優れている。 The modified zirconia fine particles are uniformly dispersed in the coating liquid for forming a transparent film, and the coating liquid is excellent in stability and can be suitably used for forming a transparent film having a high refractive index. In addition, no interference fringes are generated, and it is excellent in adhesion to a substrate, scratch resistance, scratch strength, pencil hardness and the like, and in light resistance and weather resistance.
以下に、まず本発明に係る改質ジルコニア微粒子の製造方法について説明する。
[改質ジルコニア微粒子の製造方法]
本発明に係る改質ジルコニア微粒子の製造方法は、下記の工程（ａ）〜（ｆ）からなることを特徴としている。
（ａ）ジルコニア微粉末を３００〜８００℃で焼成する工程
（ｂ）焼成ジルコニア微粉末を、アルカリ金属を含むアルカリ存在下で粉砕する工程
（ｃ）粉砕後に洗浄する工程
（ｄ）洗浄した微粉末を分散させたジルコニア微粒子水分散液をＮＨ4型イオン交換樹脂
で処理してアルカリを除去する工程
（ｅ）脱アルカリ処理後のジルコニア微粒子分散液をアルコールに溶媒置換する工程
（ｆ）有機ケイ素化合物で表面処理する工程
Below, the manufacturing method of the modified zirconia microparticles | fine-particles based on this invention is demonstrated first.
[Production method of modified zirconia fine particles]
The method for producing modified zirconia fine particles according to the present invention is characterized by comprising the following steps (a) to (f).
(A) Step of calcining zirconia fine powder at 300 to 800 ° C. (b) Step of crushing calcined zirconia fine powder in the presence of alkali containing alkali metal (c) Step of washing after crushing (d) Washed fine powder A step of removing the alkali by treating the aqueous dispersion of zirconia fine particles dispersed with NH 4 type ion exchange resin (e) a step of replacing the zirconia fine particle dispersion after dealkalization treatment with alcohol (f) an organosilicon compound Surface treatment process
工程（ａ）
まず、ジルコニア微粉末を３００〜８００℃、好ましくは５００〜７００℃で焼成する。
本発明に用いるジルコニア微粉末としては、従来公知のジルコニア微粉末を用いることができるが、後に粉砕を必要とすることから、できるだけ微細な粉末を用いることが好ましい。なかでも、特開２００６−１４３５３５号公報、特開平３−１７４３２５号公報等に記載されたジルコニアゾルは平均粒子径が１２０ｎｍ以下で、粒子径分布が均一なジルコニアゾルであることからこれを乾燥したジルコニア微粉末が好適に用いることができる。
Step (a)
First, the zirconia fine powder is fired at 300 to 800 ° C, preferably 500 to 700 ° C.
As the zirconia fine powder used in the present invention, a conventionally known zirconia fine powder can be used. However, since pulverization is required later, it is preferable to use a fine powder as much as possible. Among them, the zirconia sol described in JP-A-2006-143535, JP-A-3-174325 and the like is a zirconia sol having an average particle size of 120 nm or less and a uniform particle size distribution, and thus dried. Zirconia fine powder can be suitably used.
ジルコニアゾルを乾燥する方法としては従来公知の方法を採用することができ、例えば、ロータリーエバポレーターを用いて、あるいは加熱して濃縮し、通常１００℃〜２００℃で乾燥して分散媒を除去する。 As a method for drying the zirconia sol, a conventionally known method can be employed, for example, using a rotary evaporator or heating and concentrating, and usually drying at 100 ° C. to 200 ° C. to remove the dispersion medium.
この焼成工程によって、ジルコニアの結晶性が高められ、屈折率の高い粒子が得られる。
ジルコニア微粉末の焼成温度が低いと結晶化不充分なため、屈折率が充分高いものが得
られない場合があり、焼成温度が高すぎると、屈折率は高くなるが粒子径が大きくなりすぎて、後の粉砕工程で所望の微細な粉末（平均粒子径が５〜１２０ｎｍ）とすることが困難になる場合がある。また、過度に粉砕すると結晶性が低下し、屈折率の高い粒子が得られない場合がある。
By this firing step, the crystallinity of zirconia is enhanced and particles having a high refractive index are obtained.
If the calcination temperature of the zirconia fine powder is low, crystallization is insufficient, so that a product having a sufficiently high refractive index may not be obtained. If the calcination temperature is too high, the refractive index increases but the particle size becomes too large. In the subsequent pulverization step, it may be difficult to obtain a desired fine powder (average particle size of 5 to 120 nm). Moreover, when it grind | pulveres too much, crystallinity will fall and a particle | grain with a high refractive index may not be obtained.
工程（ｂ）
焼成したジルコニア微粉末を、アルカリ金属を含むアルカリ存在下で粉砕する。
アルカリとしては、ＮａＯＨ、ＫＯＨ等が用いられる。なかでも、ＫＯＨは後の洗浄、精製工程で比較的除去しやすいので好ましい。また、これらのアルカリとともに、あるいは、アルカリの代わりに4級アンモニウム塩を含むアルカリを使用してもよい。
Step (b)
The fired zirconia fine powder is pulverized in the presence of an alkali containing an alkali metal.
As the alkali, NaOH, KOH or the like is used. Of these, KOH is preferable because it is relatively easy to remove in the subsequent washing and purification steps. Moreover, you may use the alkali containing a quaternary ammonium salt with these alkalis instead of an alkali.
アルカリ存在下で粉砕することによって、凝集することなく、分散性が良く、同時に表面にOH基が増加した（活性化した）ジルコニア粒子がえられる。そして、有機ケイ素化合物による表面処理効果を高めることができる。 By pulverizing in the presence of an alkali, zirconia particles having good dispersibility without agglomeration and having increased (activated) OH groups on the surface can be obtained. And the surface treatment effect by an organosilicon compound can be heightened.
アルカリの使用量は、ジルコニア微粉末（ＺｒＯ2）１重量部当たり、アルカリをＭ2Ｏとして０．０１〜０．３重量部、さらには０．０５〜０．２重量部の範囲にあることが好ましい。 The amount of alkali, fine zirconia powder (ZrO 2) 0.01 to 0.3 parts by weight per part by weight, the alkali as M 2 O, further in the range of 0.05 to 0.2 parts by weight Is preferred.
アルカリの使用量が少ないと、粉砕効果が不充分であり、また、粒子の活性化効果が不充分で後工程の有機ケイ素化合物で表面処理効果が充分得られず、さらに、分散液のｐＨがアルカリ領域とならないことがあり、分散液の安定性が不充分となることがある。 If the amount of alkali used is small, the pulverization effect is insufficient, the particle activation effect is insufficient, and the surface treatment effect cannot be sufficiently obtained with the organosilicon compound in the subsequent step. The alkaline region may not be obtained, and the dispersion may have insufficient stability.
アルカリの使用量が多すぎると、粉砕効果、粒子の活性化効果、分散液の安定性などの問題はなくなるものの、工程（ｃ）の洗浄効率が低下したり、工程（ｄ）のＮＨ4型イオ
ン交換樹脂の使用量が増大するとともにアルカリイオンの除去効率が低下することがある。
If the amount of alkali used is too large, problems such as pulverization effect, particle activation effect, and dispersion stability are eliminated, but the cleaning efficiency in step (c) is reduced, and NH 4 type in step (d) is used. As the amount of ion exchange resin used increases, the removal efficiency of alkali ions may decrease.
粉砕方法としては、従来公知の乾式、湿式粉砕方法を採用することができるが、ボールミル粉砕機、衝撃微粉砕機、コロイドミル粉砕機などの湿式粉砕法が好適に採用される。
粉砕処理後、遠心分離等により、粉砕が不充分な粒子を除去することもできる。
Conventionally known dry and wet pulverization methods can be used as the pulverization method, but wet pulverization methods such as a ball mill pulverizer, impact fine pulverizer, and colloid mill pulverizer are preferably employed.
After the pulverization treatment, particles that are insufficiently pulverized can be removed by centrifugation or the like.
粉砕後のジルコニア微粒子の平均粒子径は５〜１２０ｎｍ、さらには１０〜１００ｎｍの範囲に調整されることが好ましい。粉砕後のジルコニア微粒子の平均粒子径が５〜１２０ｎｍの範囲を外れるものは、本発明の高屈折率の透明被膜には、透明性、ヘーズ、強度、耐擦傷性等の点から必ずしも望ましくはない。なお、平均粒子径の調整方法は、粉砕方法や粉砕条件を適宜選択したり、遠心分離などによる分級操作など公知の方法によって、調整することが可能である。 The average particle size of the zirconia fine particles after pulverization is preferably adjusted to a range of 5 to 120 nm, more preferably 10 to 100 nm. Those whose zirconia fine particles after pulverization have an average particle size outside the range of 5 to 120 nm are not necessarily desirable for the high refractive index transparent film of the present invention in terms of transparency, haze, strength, scratch resistance and the like. . The method for adjusting the average particle size can be adjusted by a known method such as a pulverization method and pulverization conditions, or a classification operation such as centrifugation.
工程（ｃ）
ついで、洗浄してアルカリをできるだけ除去する。洗浄方法としてはアルカリを低減できれば特に制限はなく、従来公知の方法を採用することができる。
Step (c)
Next, the alkali is removed as much as possible by washing. The washing method is not particularly limited as long as alkali can be reduced, and a conventionally known method can be adopted.
例えばデカンテーション法、限外濾過膜法等を採用することができる。
なお、アルカリの低減だけであれば、酸洗浄、イオン交換樹脂（Ｈ型イオン交換樹脂）の使用が可能であるが、この場合、ｐＨが酸性領域となりジルコニア微粒子が凝集することがある。
For example, a decantation method, an ultrafiltration membrane method, or the like can be employed.
In addition, acid reduction and use of an ion exchange resin (H-type ion exchange resin) are possible as long as the alkali is reduced, but in this case, the pH becomes an acidic region and zirconia fine particles may aggregate.
洗浄後のジルコニア微粒子中のアルカリの含有量はＭ（Ｍ：アルカリ金属またはアンモニウム）は、上限が１０，０００ｐｍ以下、さらには１，０００ｐｐｍ以下とすることが
好ましい。前記上限を超えると、工程（ｄ）のＮＨ4型イオン交換樹脂の使用量が増大す
るとともにアルカリイオンの除去効率が低下することがある。また、アルカリ含有量の下限は特に制限されず、少なければ少ない方がよいが、通常1ppmである。なお洗浄後のアルカリ含有量をこの範囲よりも少なくするのは難しく、また効率的でないこともある。
The alkali content in the washed zirconia fine particles is preferably set such that M (M: alkali metal or ammonium) has an upper limit of 10,000 pm or less, more preferably 1,000 ppm or less. If the upper limit is exceeded, the amount of NH 4 ion exchange resin used in step (d) may increase and the alkali ion removal efficiency may decrease. Further, the lower limit of the alkali content is not particularly limited, and is preferably as low as possible, but is usually 1 ppm. It is difficult to reduce the alkali content after washing below this range, and it may not be efficient.
工程（ｄ）
ついで、ジルコニア微粒子水分散液をＮＨ4型イオン交換樹脂で処理して残存するアル
カリを除去する。ジルコニア微粒子水分散液の濃度は、イオン交換樹脂で処理することができれば特に制限はないが、通常０．１〜２０重量％の範囲にあることが好ましい。
Step (d)
Next, the remaining alkali is removed by treating the zirconia fine particle aqueous dispersion with NH 4 type ion exchange resin. The concentration of the zirconia fine particle aqueous dispersion is not particularly limited as long as it can be treated with an ion exchange resin, but it is usually preferably in the range of 0.1 to 20% by weight.
本工程においては、分散液をアルカリ領域に維持することが重要である。そのために、本発明ではイオン交換樹脂としてはＮＨ4型イオン交換樹脂を用いる。ＮＨ4型イオン交換樹脂を用いるとアルカリイオンとＮＨ4イオンとがイオン交換してアルカリを低減できる
とともに、アルカリ領域を保持できる為、ジルコニア粒子表面の電荷が保持され、分散性が保持できる。
In this step, it is important to maintain the dispersion in the alkaline region. Therefore, in the present invention, NH 4 type ion exchange resin is used as the ion exchange resin. When NH 4 type ion exchange resin is used, alkali ions and NH 4 ions are ion-exchanged to reduce alkali, and since the alkali region can be retained, the charge on the surface of the zirconia particles is retained and dispersibility can be retained.
このように(ｄ)工程によるNH4型イオン交換樹脂処理によって、少なくとも一部のＮＨ4イオンが表面に付加されて、表面OH…NH4 +を形成していることが考えられ。OH基が有機ケイ素化合物の加水分解物のOH基と脱水反応によって結合する基点となり、ＮＨ4が有機ケ
イ素化合物の加水分解を促進する（触媒効果）と考えられ、OH(NH4 +)により、効率的に後述する工程(f)での有機ケイ素化合物の表面処理ができるものと考えられる。その結果、
分散性、安定性に優れたジルコニア微粒子を得ることができる。
Thus, it is conceivable that at least a part of NH 4 ions are added to the surface by the NH 4 type ion exchange resin treatment in the step (d) to form the surface OH... NH 4 + . The OH group becomes a base point for bonding with the OH group of the hydrolyzate of the organosilicon compound by a dehydration reaction, and NH 4 is considered to promote the hydrolysis of the organosilicon compound (catalytic effect). By OH (NH 4 + ), It is considered that the surface treatment of the organosilicon compound can be efficiently performed in the step (f) described later. as a result,
Zirconia fine particles having excellent dispersibility and stability can be obtained.
ＮＨ4型イオン交換樹脂の使用量は、ジルコニア微粒子（ＺｒＯ2）１重量部当たり、ＮＨ4型イオン交換樹脂が２〜３０重量部、さらには５〜２０重量部の範囲にあることが好
ましい。
The amount of NH 4 ion exchange resin used is preferably in the range of 2 to 30 parts by weight, more preferably 5 to 20 parts by weight of NH 4 ion exchange resin per part by weight of zirconia fine particles (ZrO 2 ).
ＮＨ4型イオン交換樹脂の使用量が少ないと、(c)工程の処理量にもよるが、アルカリ除去が不十分になるうえ、ジルコニア微粒子表面へのＮＨ4イオン付加も不充分となる。
ＮＨ4型イオン交換樹脂の使用量が多すぎてもさらにアルカリが低減することもなく、
後述する有機ケイ素化合物での表面処理効率が向上したり、得られる表面処理ジルコニア微粒子の分散性、安定性がさらに向上することもない。
When the amount of NH 4 ion exchange resin used is small, although depending on the amount of treatment in step (c), alkali removal is insufficient and addition of NH 4 ions to the surface of the zirconia fine particles is insufficient.
Even if the amount of NH 4 ion exchange resin used is too much, the alkali will not be further reduced.
The surface treatment efficiency with an organosilicon compound described later is not improved, and the dispersibility and stability of the obtained surface-treated zirconia fine particles are not further improved.
ＮＨ4型イオン交換樹脂で処理した後のジルコニア微粒子中のアルカリ含有量は、(c)工程での残存量によるが、Ｍ（Ｍ：アルカリ金属）として１〜１，０００ｐｐｍの範囲にあることが好ましい。 The alkali content in the zirconia fine particles after being treated with the NH 4 type ion exchange resin depends on the remaining amount in the step (c), but may be in the range of 1 to 1,000 ppm as M (M: alkali metal). preferable.
ジルコニア微粒子水分散液をＮＨ4型イオン交換樹脂で処理する際の分散液のｐＨは８
〜１２、さらには８．５〜１１の範囲にあることが好ましい。
ジルコニア微粒子水分散液をＮＨ4型イオン交換樹脂で処理する際の分散液のｐＨが８
未満の場合はジルコニア微粒子の表面が充分に帯電しないためジルコニア微粒子が凝集することがある。なお、必要に応じてアンモニアを用いて、pHを調整してもよい。
The pH of the dispersion when the aqueous dispersion of zirconia fine particles is treated with NH 4 type ion exchange resin is 8
It is preferable to be in the range of -12, more preferably 8.5-11.
The pH of the dispersion when the aqueous dispersion of zirconia fine particles is treated with NH 4 type ion exchange resin is 8
If it is less than 1, the surface of the zirconia fine particles is not sufficiently charged, and the zirconia fine particles may aggregate. In addition, you may adjust pH using ammonia as needed.
ジルコニア微粒子水分散液をＮＨ4型イオン交換樹脂で処理する際の分散液のｐＨが１
２を越えるとイオン交換が充分に起きないためアルカリイオンが１，０００ｐｐｍを越えて残存することがあり、最終的に得られる表面処理ジルコニア微粒子の分散性、安定性が不充分となることがある。
When the zirconia fine particle aqueous dispersion is treated with NH 4 type ion exchange resin, the pH of the dispersion is 1.
If it exceeds 2, ion exchange does not occur sufficiently, so that alkali ions may remain in excess of 1,000 ppm, and the dispersibility and stability of the finally obtained surface-treated zirconia fine particles may be insufficient. .
なお、本発明に用いるＮＨ4型イオン交換樹脂はＨ型イオン交換樹脂をＮＨ4イオン交換して用いることができ、Ｈ型イオン交換樹脂とＮＨ4イオンを同時に用いることによって
も同様の効果を得ることができる。
Incidentally, NH 4 type ion-exchange resin used in the present invention can be used with NH 4 ion exchange H type ion exchange resin, to obtain the same effect by using a H-type ion exchange resin and NH 4 ions simultaneously be able to.
また、分散液のｐＨの調製は、ＮＨ4型イオン交換樹脂の使用量、ＮＨ4型イオン交換樹脂とＨ型イオン交換樹脂の併用、あるいはＮＨ4イオンの使用量によって調整することが
できる。
Further, the preparation of the pH of the dispersion can be adjusted using the amount of NH 4 form ion exchange resin, the combination of NH 4 form ion exchange resin and H-type ion exchange resins, or by the amount of NH 4 ion.
工程（ｅ）
ついで、ジルコニア微粒子水分散液をアルコールに溶媒置換する。アルコールに分散させることで、表面処理が効率的に行うことができる。
Step (e)
Next, the zirconia fine particle aqueous dispersion is solvent-substituted with alcohol. By dispersing in alcohol, the surface treatment can be performed efficiently.
アルコールとしては、メタノール、エタノール、イソプロピルアルコール、ブタノール等を用いることができるが、通常メタノール、エタノールを用いられる。
溶媒置換する方法としてはアルコールによっても異なるが、溶媒置換できれば特に制限はなく、蒸留法、限外濾過膜法等が挙げられる。本発明では限外濾過膜法が推奨される。
As the alcohol, methanol, ethanol, isopropyl alcohol, butanol and the like can be used, but methanol and ethanol are usually used.
The method for solvent substitution varies depending on the alcohol, but there is no particular limitation as long as the solvent substitution can be performed, and examples thereof include a distillation method and an ultrafiltration membrane method. In the present invention, an ultrafiltration membrane method is recommended.
得られる、ジルコニア微粒子アルコール分散液の濃度は概ね１〜３０重量％の範囲にあることが好ましい。この範囲にあれば、工程（ｆ）の表面処理を好適に実施することができる。 The concentration of the resulting zirconia fine particle alcohol dispersion is preferably in the range of 1 to 30% by weight. If it exists in this range, the surface treatment of a process (f) can be implemented suitably.
工程（ｆ）
ついで、下記式(1)で表される有機ケイ素化合物で表面処理する。
Ｒn-ＳiＸ4-n （１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：１〜３の整数）
このような有機ケイ素化合物としては、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、イソブチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（βメトキシエトキシ）シラン、3,3,3−トリフルオロプ
ロピルトリメトキシシラン、メチル-3,3,3−トリフルオロプロピルジメトキシシラン、β-（3,4-エポキシシクロヘキシル）エチルトリメトキシシラン、γ-グリシドキシメチルトリメトキシシラン、γ-グリシドキシメチルトリエキシシラン、γ-グリシドキシエチルトリメトキシシラン、γ-グリシドキシエチルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-(β-グリシドキシエトキシ)プロピルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリエキシシラン、γ-（メタ）アクリロオキシエチルトリメトキシシラン、γ-（メタ）アクリロオキシエチルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、ブチルトリメトキシシラン、イソブチルトリエトキシシラン、ヘキシルトリエトキシシラオクチルトリエトキシシラン、デシルトリエトキシシラン、ブチルトリエトキシシラン、イソブチルトリエトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、デシルトリエトキシシラン、3-ウレイドイソプロピルプロピルトリエトキシシラン、パーフルオロオクチルエチルトリメトキシシラン、パーフルオロオクチルエチルトリエトキシシラン、パーフルオロオクチルエチルトリイソプロポキシシラン、トリフルオロプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、トリメチルシラノール、メチルトリクロロシラン等、およびこれらの混合物が挙げられる。
Step (f)
Next, surface treatment is performed with an organosilicon compound represented by the following formula (1).
R n -SiX 4-n (1 )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)
Such organosilicon compounds include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxy. Silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyl Liethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycyl Sidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (Meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (Meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane , Isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropyl Propyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltri A chlorosilane etc., and these mixtures are mentioned.
有機ケイ素化合物の使用量は、得られる改質ジルコニア微粒子中の有機ケイ素化合物がＲn-ＳiＯ4-n/2として１〜５０重量％、さらには２〜３０重量％となる範囲にあることが好ましい。 The amount of the organosilicon compound used is such that the organosilicon compound in the resulting modified zirconia fine particles is in the range of 1 to 50 wt%, more preferably 2 to 30 wt% as R n —SiO 4 -n / 2. preferable.
有機ケイ素化合物の使用量が少ないと、表面処理が不充分で、分散安定性向上効果が充分得られないことがある。有機ケイ素化合物の使用量が多すぎても分散安定性は良くなるものの、得られる改質ジルコニア微粒子の屈折率が低下し、屈折率が所望の範囲以下となることがあり、屈折率が低い粒子であれば本発明によらずとも従来公知の方法で容易に得ることができる。 If the amount of the organosilicon compound used is small, the surface treatment may be insufficient and the dispersion stability improving effect may not be sufficiently obtained. Although the dispersion stability is improved even when the amount of the organosilicon compound used is too large, the refractive index of the resulting modified zirconia fine particles is lowered, and the refractive index may be below the desired range, so that the refractive index is low. If it is, it can obtain easily by a conventionally well-known method irrespective of this invention.
ジルコニア微粒子のアルコール分散液に、所定量の有機ケイ素化合物または有機ケイ素化合物のアルコール溶液を加え、これに、水を加え、必要に応じて加水分解触媒を加え、有機ケイ素化合物を加水分解する。 A predetermined amount of an organosilicon compound or an alcohol solution of an organosilicon compound is added to an alcohol dispersion of zirconia fine particles, water is added thereto, and a hydrolysis catalyst is added as necessary to hydrolyze the organosilicon compound.
水の添加量は水のモル数（ＭH）と有機ケイ素化合物の（加水分解性官能基の）モル数
（ＭO）とのモル比（ＭH）／（ＭO）が１〜５０、さらには５〜２０の範囲にあることが
好ましい。
モル比（ＭH）／（ＭO）が１未満の場合は、加水分解が不充分となり表面処理が充分できないため得られるジルコニア微粒子の分散性、安定性が不充分となる。
モル比（ＭH）／（ＭO）が５０を越えても、さらに加水分解が進むこともなく、過剰の水であることから不要である。
The amount of water added is such that the molar ratio (M H ) / (M O ) between the number of moles of water (M H ) and the number of moles (M O ) of the organosilicon compound (M O ) is 1-50, Furthermore, it is preferable that it exists in the range of 5-20.
When the molar ratio (M H ) / (M O ) is less than 1, the hydrolysis is insufficient and the surface treatment cannot be performed sufficiently, so that the dispersibility and stability of the resulting zirconia fine particles are insufficient.
Even if the molar ratio (M H ) / (M O ) exceeds 50, the hydrolysis does not proceed further and is unnecessary because it is an excess of water.
有機ケイ素化合物で表面処理する際の分散液のｐＨは８〜１２、さらには８．５〜１０の範囲にあることが好ましい。ｐＨが低いと、ジルコニア微粒子が凝集することがあり、ジルコニア微粒子表面に均一な表面処理を施すことができない場合がある。ｐＨが高いと、有機ケイ素化合物の加水分解が早くなりすぎるためか得られる表面処理ジルコニア微粒子の分散性、安定性が不充分となることがある。このようにして本発明の改質ジルコニア微粒子は製造することができる。 The pH of the dispersion upon surface treatment with the organosilicon compound is preferably in the range of 8 to 12, more preferably 8.5 to 10. When the pH is low, the zirconia fine particles may aggregate, and the surface of the zirconia fine particles may not be uniformly treated. When the pH is high, the dispersibility and stability of the surface-treated zirconia fine particles obtained may be insufficient because the hydrolysis of the organosilicon compound becomes too fast. In this way, the modified zirconia fine particles of the present invention can be produced.
工程（ｇ）
本発明では、必要に応じて、表面処理ジルコニア微粒子分散液を所望の有機溶媒置換することができる。有機溶媒としては、従来公知の有機溶媒を用いることができ、具体的には、メタノール、エタノール、プロパノール、2-プロパノール（ＩＰＡ）、ブタノール、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコール、エチレングリコール、ヘキシレングリコール、イソプロピルグリコールなどのアルコール類；酢酸メチルエステル、酢酸エチルエステル、酢酸ブチルなどのエステル類；ジエチルエーテル、エチ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モノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルなどのエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセト酢酸エステルなどのケトン類、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、トルエン、シクロヘキサノン、イソホロン等およびこれらの混合溶媒が挙げられる。
Step (g)
In the present invention, the surface-treated zirconia fine particle dispersion can be substituted with a desired organic solvent as necessary. As the organic solvent, conventionally known organic solvents can be used. Specifically, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene Alcohols such as glycol, hexylene glycol and isopropyl glycol; esters such as acetic acid methyl ester, ethyl acetate, butyl acetate; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether , Ethers such as diethylene glycol monoethyl ether and propylene glycol monomethyl ether; acetone, methyl ethyl ketone Emissions, methyl isobutyl ketone, acetylacetone, ketones such as acetoacetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone and the like and mixed solvents thereof.
本発明では、後述する透明被膜形成用塗布液の溶媒と同様の有機溶媒を用いることが好ましく、イソプロピルアルコール、メチルイソブチルケトン、メチルエチルケトン、酢酸エチル等が好適に用いられる。 In the present invention, it is preferable to use the same organic solvent as the solvent of the coating liquid for forming a transparent film described later, and isopropyl alcohol, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate, etc. are preferably used.
溶媒置換する方法としては有機溶媒によっても異なるが、溶媒置換できれば特に制限は
なく、蒸留法、限外濾過膜法、ロータリーエバポレーター等が挙げられる。本発明では限外濾過膜法が推奨される。得られる改質ジルコニア微粒子分散液の濃度は、目的及び用途に応じて適宜選択されるが、固形分として１〜５０重量％、さらには２〜４０重量％の範囲にあることが好ましい。
The method for solvent replacement varies depending on the organic solvent, but is not particularly limited as long as the solvent replacement can be performed, and examples thereof include a distillation method, an ultrafiltration membrane method, and a rotary evaporator. In the present invention, an ultrafiltration membrane method is recommended. The concentration of the resulting modified zirconia fine particle dispersion is appropriately selected depending on the purpose and application, but is preferably in the range of 1 to 50% by weight, more preferably 2 to 40% by weight as the solid content.
このようにして得られる改質ジルコニア微粒子は、有機ケイ素化合物の含有量がＲnＳiＯ4-n/2で表して１〜５０、さらには２〜３０重量％の範囲にあることが好ましい。
また、改質ジルコニア微粒子の屈折率は１．８〜２．１５、さらには１．９〜２．１５の範囲にある。屈折率は、有機ケイ素化合物の量、粉砕工程における焼成温度、粉砕の程度（粒子径）を調整することによって調整できる。
ついで、本発明に係る透明被膜形成用塗布液について説明する。
Modified zirconia particles obtained in this way is from 1 to 50 the content of the organic silicon compound represented by R n S i O 4-n / 2, and more preferably in the range of 2 to 30 wt% .
The refractive index of the modified zirconia fine particles is in the range of 1.8 to 2.15, and further 1.9 to 2.15. The refractive index can be adjusted by adjusting the amount of the organosilicon compound, the firing temperature in the pulverization step, and the degree of pulverization (particle diameter).
Next, the coating liquid for forming a transparent film according to the present invention will be described.
[透明被膜形成用塗布液]
本発明に係る透明被膜形成用塗布液は、前記調製した改質ジルコニア微粒子とマトリックス形成成分とからなることを特徴としている。
[Transparent coating solution]
The coating liquid for forming a transparent film according to the present invention is characterized by comprising the prepared modified zirconia fine particles and a matrix-forming component.
マトリックス形成成分
マトリックス形成成分としては有機樹脂マトリックスが用いられる。
有機樹脂マトリックス形成成分として、具体的には塗料用樹脂として公知の熱硬化性樹脂、熱可塑性樹脂等のいずれも採用することができる。たとえば、従来から用いられているポリエステル樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリフェニレンオキサイド樹脂、熱可塑性アクリル樹脂、塩化ビニル樹脂、フッ素樹脂、酢酸ビニル樹脂、シリコーンゴムなどの熱可塑性樹脂、ウレタン樹脂、メラミン樹脂、ケイ素樹脂、ブチラール樹脂、反応性シリコーン樹脂、フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、熱硬化性アクリル樹脂などの熱硬化性樹脂、ＵＶ硬化性樹脂などが挙げられる。さらにはこれら樹脂の２種以上の共重合体や変性体であってもよい。なお、熱硬化性樹脂の場合、マトリックス形成成分は、硬化前のモノマー、プレポリマーが使用され、さらに、反応開示剤、安定剤などが含まれていても良い。
Matrix-forming component An organic resin matrix is used as the matrix-forming component.
As the organic resin matrix forming component, specifically, any of thermosetting resins and thermoplastic resins known as coating resins can be employed. For example, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, silicone rubber and other thermoplastic resins, urethane resins, melamine resins , Silicon resins, butyral resins, reactive silicone resins, phenol resins, epoxy resins, unsaturated polyester resins, thermosetting resins such as thermosetting acrylic resins, and UV curable resins. Further, it may be a copolymer or modified body of two or more of these resins. In the case of a thermosetting resin, the matrix-forming component is a monomer or prepolymer before curing, and may further contain a reaction disclosure agent, a stabilizer, and the like.
分散媒
本発明に用いる分散媒としては前記マトリックス形成成分、必要に応じて用いる重合開始剤を溶解あるいは分散できるとともに改質ジルコニア微粒子を均一に分散することができれば特に制限はなく、従来公知の溶媒を用いることができる。
Dispersion medium The dispersion medium used in the present invention is not particularly limited as long as it can dissolve or disperse the matrix-forming component and, if necessary, the polymerization initiator and uniformly disperse the modified zirconia fine particles. Can be used.
具体的には、メタノール、エタノール、プロパノール、2-プロパノール（ＩＰＡ）、ブタノール、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコール、エチレングリコール、ヘキシレングリコール、イソプロピルグリコールなどのアルコール類；酢酸メチルエステル、酢酸エチルエステル、酢酸ブチルなどのエステル類；ジエチルエーテル、エチ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モノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルなどのエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセト酢酸エステルなどのケトン類、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、トルエン、シクロヘキサノン、イソホロン等が挙げられる。 Specifically, alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; methyl acetate , Esters such as ethyl acetate, butyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether; acetone , Methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, aceto vinegar Ketones such as esters, methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone and the like.
これらは単独で使用してもよく、また２種以上混合して使用することもできる。
透明被膜形成用塗布液は、改質ジルコニア微粒子とマトリックス形成成分との合計濃度が固形分として１〜５０重量％、さらには２０〜４０重量％の範囲にあることが好ましい。合計濃度が少ないと一回の塗布で所望の厚みの透明被膜を得ることができない場合があり、多すぎても、均一な膜を得ることが困難であったり、膜にムラ・白化等が発生する場合がある。
These may be used alone or in combination of two or more.
In the coating solution for forming a transparent film, the total concentration of the modified zirconia fine particles and the matrix-forming component is preferably in the range of 1 to 50% by weight, more preferably 20 to 40% by weight as the solid content. If the total concentration is low, it may not be possible to obtain a transparent film with the desired thickness by a single application. If it is too large, it may be difficult to obtain a uniform film, or the film may be uneven or whitened. There is a case.
また、透明被膜形成用塗布液中の改質ジルコニア微粒子の濃度は、透明被膜中の改質ジルコニア微粒子の濃度が１〜８０重量％、好ましくは２〜５０重量％となるように用いるが、固形分として０．１〜３６重量％、さらには０．５〜３２重量％の範囲にあることが好ましい。改質ジルコニア微粒子の濃度が少ないと、耐擦傷性、膜の強度が不充分となったり所望の屈折率を有する透明被膜を得ることができない場合があり、改質ジルコニア微粒子の濃度が高すぎても透明被膜の透明性、平滑性が不充分となったり透明被膜の強度や耐擦傷性が不充分となる場合がある。 The concentration of the modified zirconia fine particles in the coating solution for forming the transparent film is used so that the concentration of the modified zirconia fine particles in the transparent film is 1 to 80% by weight, preferably 2 to 50% by weight. It is preferable that the content is in the range of 0.1 to 36% by weight, more preferably 0.5 to 32% by weight. If the concentration of the modified zirconia fine particles is low, the scratch resistance, the film strength may be insufficient, or a transparent film having a desired refractive index may not be obtained, and the concentration of the modified zirconia fine particles is too high. However, the transparency and smoothness of the transparent film may be insufficient, and the strength and scratch resistance of the transparent film may be insufficient.
透明被膜形成用塗布液中のマトリックス形成成分の濃度は、樹脂を固形分として１〜４０重量％、さらには２〜３０重量％の範囲にあることが好ましい。マトリックス形成成分濃度が少ないと一回の塗布では所定の膜厚が得られないことがあり、塗布、乾燥を繰り返すと密着性等が不充分となったり、経済性が不十分となることがある。マトリックス形成成分の濃度が多すぎても、得られる透明被膜の厚さが不均一になる傾向がある。 The concentration of the matrix-forming component in the coating liquid for forming a transparent film is preferably in the range of 1 to 40% by weight, more preferably 2 to 30% by weight, based on the resin. If the concentration of the matrix-forming component is low, a predetermined film thickness may not be obtained by a single coating, and if coating and drying are repeated, the adhesion may become insufficient or the economy may be insufficient. . Even if the concentration of the matrix forming component is too high, the thickness of the resulting transparent film tends to be non-uniform.
上記した透明被膜形成用塗布液をディップ法、スプレー法、スピナー法、ロールコート法、バーコート法、グラビア印刷法、マイクログラビア印刷法等の周知の方法で基材に塗布し、乾燥し、紫外線照射、加熱処理等常法によって硬化させることによって透明被膜を形成することができる。
ついで、本発明に係る透明被膜付基材について説明する。
The above-mentioned coating liquid for forming a transparent film is applied to a substrate by a known method such as a dipping method, a spray method, a spinner method, a roll coating method, a bar coating method, a gravure printing method, or a micro gravure printing method, dried, and then irradiated with ultraviolet rays. A transparent film can be formed by curing by conventional methods such as irradiation and heat treatment.
Next, the transparent film-coated substrate according to the present invention will be described.
[透明被膜付基材]
本発明に係る透明被膜付基材は、基材と、基材の少なくとも一方の表面上に形成された透明被膜とを含み、該透明被膜が前記とマトリックス成分とからなることを特徴としている。
[Base material with transparent coating]
The substrate with a transparent coating according to the present invention includes a substrate and a transparent coating formed on at least one surface of the substrate, and the transparent coating comprises the above and a matrix component.
基材
本発明に用いる基材としては、特に制限されるものではなく、従来公知のガラス、ポリカーボネート、アクリル樹脂、ＰＥＴ、ＴＡＣ等のプラスチックシート、プラスチックフィルム等、プラスチックパネル等を用いることができる。これらのうち、透明性、加工性の面からＰＥＴ、ＴＡＣのプラスチックシートが好適に用いられる。また、本発明では、眼鏡レンズを基材とすることも好適である。
Substrate The substrate used in the present invention is not particularly limited, and conventionally known glass, polycarbonate, acrylic resin, plastic sheets such as PET and TAC, plastic films, plastic panels, and the like can be used. Among these, PET and TAC plastic sheets are preferably used in terms of transparency and processability. In the present invention, it is also preferable to use a spectacle lens as a base material.
透明被膜
改質ジルコニア微粒子としては前記した改質ジルコニア微粒子が用いられる。
マトリックス成分としては、前記したマトリックス形成成分から誘導されるものがあげられる。熱可塑性樹脂の場合は、前記したマトリックス形成成分がそのままマトリックス成分となり、熱硬化性樹脂の場合、重合体となっている。なおマトリックス成分は、2種
以上組合わせても良く、さらにこれら樹脂の２種以上の共重合体や変性体であってもよい。
As the transparent film- modified zirconia fine particles, the modified zirconia fine particles described above are used.
Examples of the matrix component include those derived from the matrix-forming component described above. In the case of a thermoplastic resin, the above-described matrix forming component is directly used as a matrix component, and in the case of a thermosetting resin, it is a polymer. Two or more kinds of matrix components may be combined, and two or more kinds of copolymers or modified products of these resins may be used.
透明被膜中の改質ジルコニア微粒子の含有量は１〜８０重量％、さらには２〜５０重量％の範囲にあることが好ましい。
透明被膜中の改質ジルコニア微粒子の含有量が１重量％未満の場合は、所望の屈折率を有する透明被膜を得ることができない場合があり、透明被膜中の改質ジルコニア微粒子の含有量が８０重量％を越えると透明性、平滑性が不充分となったり透明被膜の強度や耐擦傷性が不充分となる場合がある。
The content of the modified zirconia fine particles in the transparent coating is preferably in the range of 1 to 80% by weight, more preferably 2 to 50% by weight.
When the content of the modified zirconia fine particles in the transparent coating is less than 1% by weight, a transparent coating having a desired refractive index may not be obtained, and the content of the modified zirconia fine particles in the transparent coating is 80. If it exceeds wt%, the transparency and smoothness may be insufficient, and the strength and scratch resistance of the transparent film may be insufficient.
透明被膜中のマトリックス成分の含有量は２０〜９９重量％、さらには５０〜９８重量％の範囲にあることが好ましい。マトリックス成分の含有量が少ないと、透明被膜の基材との密着性、強度や耐擦傷性が不充分となる場合があり、マトリックス成分の含有量が多いと耐擦傷性、膜の強度が不充分となったり所望の屈折率を有する透明被膜を得ることができない場合がある。 The content of the matrix component in the transparent film is preferably in the range of 20 to 99% by weight, more preferably 50 to 98% by weight. If the content of the matrix component is low, the adhesion, strength and scratch resistance of the transparent film to the substrate may be insufficient, and if the content of the matrix component is high, the scratch resistance and film strength will be insufficient. In some cases, a transparent film having a sufficient refractive index cannot be obtained.
また、透明被膜の膜厚は、用途によっても異なるが、例えば、ハードコート膜である場合は、０.１〜３０μｍ、さらには０.２〜２０μｍ、特に０.２〜１０μｍの範囲にある
ことが好ましい。
The film thickness of the transparent film varies depending on the use, but for example, in the case of a hard coat film, it should be in the range of 0.1 to 30 μm, further 0.2 to 20 μm, particularly 0.2 to 10 μm. Is preferred.
ハードコート膜の厚さが前記範囲の下限未満の場合は、ハードコート膜が薄いためにハードコート膜表面に加わる応力を充分吸収することがでないために、ハードコート機能が不充分となる。ハードコート膜の厚さが前記範囲の上限を越えると、膜の厚さが均一になるように塗布したり、均一に乾燥することが困難となり、さらに収縮が大きくなるのでカーリング（ハードコート膜付基材が湾曲）が生じることがある。また、膜厚が厚すぎて透明性が不充分となることがある。 When the thickness of the hard coat film is less than the lower limit of the above range, since the hard coat film is thin, the stress applied to the hard coat film surface cannot be sufficiently absorbed, and the hard coat function is insufficient. When the thickness of the hard coat film exceeds the upper limit of the above range, it becomes difficult to apply the film so that the film thickness becomes uniform or to dry uniformly, and further shrinkage increases, so curling (with hard coat film) The substrate may be curved). Also, the film thickness may be too thick and the transparency may be insufficient.
このようなハードコート膜の屈折率は基材の屈折率と同程度であることが好ましく、少なくとも屈折率の差が０．３以下、さらには０．２以下であることが好ましい。ハードコート膜の屈折率と基材の屈折率との差が０．３を越えると干渉縞を生じる問題がある。 The refractive index of such a hard coat film is preferably about the same as the refractive index of the substrate, and at least the difference in refractive index is preferably 0.3 or less, more preferably 0.2 or less. If the difference between the refractive index of the hard coat film and the refractive index of the substrate exceeds 0.3, there is a problem that interference fringes are generated.
本発明では、特定の製造方法で得られた改質ジルコニア微粒子が使用されているので、いままで得られなかったような、ジルコニア微粒子が透明被膜形成用塗布液中で均一に分散でき、このため、塗布液は安定性に優れ、特に高屈折率の透明被膜の形成に好適に用いることができる。そして、得られる透明被膜は、高屈折率基材に対して干渉縞を生じることもないという、従来のジルコニア微粒子では考えらないような性質を有している。 In the present invention, since modified zirconia fine particles obtained by a specific production method are used, zirconia fine particles, which have not been obtained so far, can be uniformly dispersed in a coating liquid for forming a transparent film. The coating solution is excellent in stability and can be suitably used particularly for the formation of a transparent film having a high refractive index. And the obtained transparent film has the property which is not considered with the conventional zirconia microparticles | fine-particles that an interference fringe does not produce with respect to a high refractive index base material.
[実施例]
以下、実施例により説明するが、本発明はこれらの実施例により限定されるものではない。
[Example]
Hereinafter, although an example explains, the present invention is not limited by these examples.
[実施例1]
改質ジルコニア微粒子(1)分散液の調製
焼成ジルコニア粉末(1)の調製
純水１，３０２ｇにオキシ塩化ジルコニウム８水和物（ZrOCl2・8H2O）３５ｇを溶解し、これに濃度１０重量％のＫＯＨ水溶液１２２．８ｇを添加してジルコニウム水酸化物ヒドロゲル（ZrO2濃度1重量％）を調製した。ついで、限外濾過膜法で電導度が０．５μＳ／ｃｍ以下になるまで洗浄した。
[Example 1]
Preparation of modified zirconia fine particles (1) dispersion
Preparation of calcined zirconia powder (1) 35 g of zirconium oxychloride octahydrate (ZrOCl 2 .8H 2 O) was dissolved in 1,302 g of pure water, and 122.8 g of a 10 wt% KOH aqueous solution was added thereto. Zirconium hydroxide hydrogel (ZrO 2 concentration 1 wt%) was prepared. Subsequently, it was washed by an ultrafiltration membrane method until the electric conductivity became 0.5 μS / cm or less.
得られたジルコニウム水酸化物ヒドロゲルに酒石酸０．９６ｇを加えて充分に攪拌を行った。ついで、ｐＨ１１．０になるまで濃度１０重量％のＫＯＨ水溶液を加え、超音波を1時間照射してヒドロゲルの分散処理をした後、限外濾過膜を用いて電導度が０．３５ｍｓ／ｃｍ以下になるまで洗浄した。つぎに、陰イオン交換樹脂（ROHM AND HAAS社製：DUOLITE UP5000）を２．６ｇ加え、洗浄を行った。ついで、樹脂を分離した後、得られたジルコニウム水酸化物ヒドロゲル（固形分濃度５．０重量％）をオートクレーブに充填し、１６５℃で６時間水熱処理を行った。このときｐＨは１０．７であった。ついで、水熱処理して得られた分散液を乾燥した後６５０℃で２時間焼成して焼成ジルコニア粉末(1)を得た。得られた焼成ジルコニア粉末(1)は立方晶，単斜晶の混晶体であった。 0.96 g of tartaric acid was added to the obtained zirconium hydroxide hydrogel and sufficiently stirred. Next, a 10% strength by weight KOH aqueous solution was added until the pH reached 11.0, and after ultrasonic treatment was applied for 1 hour to disperse the hydrogel, the conductivity was 0.35 ms / cm or less using an ultrafiltration membrane. Washed until Next, 2.6 g of anion exchange resin (manufactured by ROHM AND HAAS: DUOLITE UP5000) was added and washed. Next, after separating the resin, the obtained zirconium hydroxide hydrogel (solid content concentration 5.0% by weight) was filled in an autoclave and hydrothermally treated at 165 ° C. for 6 hours. At this time, the pH was 10.7. Subsequently, the dispersion obtained by hydrothermal treatment was dried and then calcined at 650 ° C. for 2 hours to obtain calcined zirconia powder (1). The obtained calcined zirconia powder (1) was a cubic and monoclinic mixed crystal.
ジルコニア微粒子分散液(1)の調製
純水１６１．９ｇに酒石酸４．４ｇを溶解した水溶液に焼成ジルコニア粉末(1)３６ｇ
を加え、ついで、濃度１０重量％のＫＯＨ水溶液３０ｇを加えてｐＨ１２．３のジルコニア粉末分散液とした。ジルコニア粉末(1)分散液を分散機（カンペ（株)製：BATCH SAND）にて分散させた後、限外濾過膜を用いて電導度が１００μｓ／ｃｍ程度になるまで洗浄し、ついで、陰イオン交換樹脂（ROHM AND HAAS社製：DUOLITE UP5000）４０ｇを加えて洗浄処理を行い、樹脂を分離し、ＺｒＯ2濃度２重量％のジルコニア微粒子分散液(1)を調製した。
Preparation of zirconia fine particle dispersion (1) 36 g of calcined zirconia powder (1) in an aqueous solution of 4.4 g of tartaric acid dissolved in 161.9 g of pure water
Next, 30 g of a 10% strength by weight aqueous KOH solution was added to obtain a zirconia powder dispersion having a pH of 12.3. After dispersing the zirconia powder (1) dispersion with a disperser (manufactured by Campe Co., Ltd .: BATCH SAND), the dispersion was washed with an ultrafiltration membrane until the conductivity reached about 100 μs / cm, and then the negative 40 g of ion exchange resin (ROHM AND HAAS: DUOLITE UP5000) was added for washing treatment, and the resin was separated to prepare a zirconia fine particle dispersion (1) having a ZrO 2 concentration of 2% by weight.
ジルコニア微粒子を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子等は無
く、平均粒子径３０ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶、単斜晶の混晶体であった。また、屈折率は２．１であった。
When the zirconia fine particles were observed with a transmission electron micrograph (TEM), there were no coarse particles and the like, and the zirconia fine particles had an average particle diameter of 30 nm. The zirconia fine particles were cubic and monoclinic mixed crystals. The refractive index was 2.1.
ＮＨ 4 型イオン交換樹脂で処理
ＺｒＯ2濃度２重量％のジルコニア微粒子分散液(1)１００ｇにＮＨ4 +型イオン交換樹脂（三菱化学（株）製：ＳＫ−１ＢＨをアンモニアで処理した樹脂）を２８ｇ加え、３０分間攪拌を行った後、樹脂を分離した。得られたゾルのｐＨは１１．０であった。ついで、限外濾過膜を用いて溶媒をメタノールに置換し、固形分濃度５重量％のジルコニア微粒子アルコール分散液(1)を得た。
NH 4 type ion exchange resin treated ZrO 2 concentration 2 wt% zirconia fine particle dispersion (1) 100 g NH 4 + type ion exchange resin (Mitsubishi Chemical Co., Ltd .: SK-1BH treated with ammonia) After adding 28 g and stirring for 30 minutes, the resin was separated. The pH of the obtained sol was 11.0. Subsequently, the solvent was replaced with methanol using an ultrafiltration membrane to obtain a zirconia fine particle alcohol dispersion (1) having a solid content concentration of 5% by weight.
表面処理
つぎに、固形分濃度５重量％のジルコニア微粒子アルコール分散液(1)１１９ｇにγ-メタアクリロオキシプロピルトリメトキシシラン（信越化学（株）製：KBM-503）０．６０
ｇを加え、５０℃で１６時間熟成し、固形分濃度５重量％の改質ジルコニア微粒子(1)分
散液を調製した。得られた改質ジルコニア微粒子(1)の平均粒子径および屈折率を以下の
方法で測定し、結果を表に示した。
Surface treatment Next, 119 g of zirconia fine particle alcohol dispersion (1) having a solid content concentration of 5% by weight was added to 119 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) 0.60.
g was added and aged at 50 ° C. for 16 hours to prepare a modified zirconia fine particle (1) dispersion having a solid concentration of 5% by weight. The average particle diameter and refractive index of the obtained modified zirconia fine particles (1) were measured by the following methods, and the results are shown in the table.
平均粒子径
透過型電子顕微鏡写真（TEM）で観察し、改質ジルコニア微粒子(1)３０個の粒子径を測定して平均値を求め、平均粒子径とした。
Average particle diameter Observed with a transmission electron micrograph (TEM), the particle diameter of 30 modified zirconia fine particles (1) was measured to determine the average value, and the average particle diameter was determined.
屈折率
屈折率は標準屈折液としてCARGILL製のSeriesＡ、ＡＡを用い、以下の方法で測定し、
結果を表に示した。
（１）改質ジルコニア微粒子(1)分散液をエバポレーターに採り、分散媒を蒸発させる。
（２）これを８０℃で１２時間乾燥し、粉末とする。
（３）屈折率が既知の標準屈折液を２、３滴ガラス板上に滴下し、これに上記粉末を混合する。
（４）上記（３）の操作を種々の標準屈折液で行い、混合液が透明になったときの標準屈折液の屈折率を改質ジルコニア微粒子(1)の屈折率とする。
Refractive index The refractive index is measured by the following method using CARGILL Series A and AA as the standard refractive liquid.
The results are shown in the table.
(1) Modified zirconia fine particles (1) Take the dispersion liquid in an evaporator and evaporate the dispersion medium.
(2) This is dried at 80 ° C. for 12 hours to obtain a powder.
(3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.
(4) The operation of (3) is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is set as the refractive index of the modified zirconia fine particles (1).
ハードコート膜形成用塗布液(1)の調製
アクリル系樹脂（大日本インキ（株）製：17-824-9、樹脂濃度：７９.８重量％、溶媒
：酢酸ブチル）をイソプロピルアルコール/メチルイソブチルケトン＝1：1で希釈して樹
脂濃度３０重量％のハードコート膜形成用樹脂成分(1)を調製した。
このハードコート膜形成用樹脂成分（1）１０ｇに、改質ジルコニア微粒子(1)分散液１０ｇを混合してハードコート膜形成用塗布液(1)を調製した。
Preparation of coating liquid for hard coat film formation (1) Acrylic resin (Dainippon Ink Co., Ltd .: 17-824-9, resin concentration: 79.8% by weight, solvent: butyl acetate) isopropyl alcohol / methyl isobutyl The resin component (1) for forming a hard coat film having a resin concentration of 30% by weight was prepared by diluting with ketone = 1: 1.
A hard coating film forming coating solution (1) was prepared by mixing 10 g of the hard coating film forming resin component (1) with 10 g of the modified zirconia fine particle (1) dispersion.
ハードコート膜付基材(1)の製造
ハードコート膜形成用塗布液(1)を、ＰＥＴフィルム（東洋紡製コスモシャイン Ａ４１００、厚さ：１８８μｍ、屈折率：１.６７、基材ヘーズ0.8％）にバーコーター法（＃１０）で塗布し、８０℃で１２０秒間乾燥した後、６００ｍＪ／ｃｍ2の紫外線を照射して硬化させてハードコート膜付基材(1)を製造した。このときのハードコート膜の厚さは３μｍであった。
Production of base material with hard coat film (1) Coating liquid for hard coat film formation (1) was obtained by applying PET film (Toyobo Cosmo Shine A4100, thickness: 188 μm, refractive index: 1.67, base material haze 0.8%) The substrate was coated by the bar coater method (# 10), dried at 80 ° C. for 120 seconds, and then cured by irradiating with 600 mJ / cm 2 of ultraviolet rays to produce a substrate (1) with a hard coat film. At this time, the thickness of the hard coat film was 3 μm.
得られたハードコート膜の全光線透過率およびヘーズをヘーズメーター（スガ試験機（株）製）により測定し結果を表１に示した。さらに、耐擦傷性を以下の方法で測定し、結果を表に示した。 The total light transmittance and haze of the obtained hard coat film were measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the results are shown in Table 1. Further, the scratch resistance was measured by the following method, and the results are shown in the table.
耐擦傷性の測定
＃００００スチールウールを用い、荷重１０００ｇ／ｃｍ2で２０回摺動し、膜の表面
を目視観察し、以下の基準で評価し、結果を表に示した。
評価基準：
筋条の傷が認められない ：◎
筋条に傷が僅かに認められる ：○
筋条に傷が多数認められる ：△
面が全体的に削られている ：×
Measurement of scratch resistance Using # 0000 steel wool, sliding 20 times at a load of 1000 g / cm 2, visually observing the surface of the film, and evaluating according to the following criteria, the results are shown in the table.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×
分散性
ヘーズおよび透明被膜の外観観察結果から改質ジルコニア微粒子の透明被膜中の分散性を下記のように評価した。
The dispersibility of the modified zirconia fine particles in the transparent film was evaluated as follows from the results of the dispersibility haze and the appearance observation of the transparent film.
評価基準
基材のヘーズと同等 ：◎
若干ヘーズが増加するが、目視では区別できない ：○
ヘーズが増加し、目視で白化が認められる ：△
ヘーズが大きく増加し、目視で顕著な白化が認められる ：×
Equivalent to haze of evaluation base material: ◎
Slightly increased haze, but cannot be distinguished visually: ○
Haze increases and whitening is observed visually: △
Haze increases greatly, and noticeable whitening is recognized visually: ×
[実施例２]
改質ジルコニア微粒子(2)分散液の調製
ジルコニア微粒子分散液(2)の調製
実施例１において、濃度１０重量％のＫＯＨ水溶液６０ｇを加えてｐＨ１３．０のジルコニア粉末分散液とした以外は同様にしてＺｒＯ2濃度２重量％のジルコニア微粒子分散
液(2)を調製した。
[Example 2]
Preparation of modified zirconia fine particle (2) dispersion
Preparation of Zirconia Fine Particle Dispersion (2) Dispersion of ZrO 2 fine particles having a ZrO 2 concentration of 2 wt% in the same manner as in Example 1, except that 60 g of a 10 wt% KOH aqueous solution was added to form a zirconia powder dispersion having a pH of 13.0. Liquid (2) was prepared.
ジルコニア微粒子(2)を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子等は無く、平均粒子径３０ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶、単斜晶の混晶体であった。また、屈折率は２．１であった。 When the zirconia fine particles (2) were observed with a transmission electron micrograph (TEM), there were no coarse particles, and the zirconia fine particles had an average particle size of 30 nm. The zirconia fine particles were cubic and monoclinic mixed crystals. The refractive index was 2.1.
ＮＨ 4 型イオン交換樹脂で処理
ＺｒＯ2濃度２重量％のジルコニア微粒子分散液(2) １００ｇを用いた以外は実施例１
と同様にして固形分濃度５重量％のジルコニア微粒子アルコール分散液(2)を得た。
Example 1 except that 100 g of zirconia fine particle dispersion (2) having a ZrO 2 concentration of 2% by weight treated with NH 4 type ion exchange resin was used.
In the same manner as above, a zirconia fine particle alcohol dispersion (2) having a solid concentration of 5% by weight was obtained.
表面処理
固形分濃度５重量％のジルコニア微粒子アルコール分散液(2)を用いた以外は実施例１
と同様にして固形分濃度５重量％の改質ジルコニア微粒子(2)分散液を調製した。
Example 1 except that the zirconia fine particle alcohol dispersion (2) having a surface treatment solid content concentration of 5% by weight was used.
In the same manner, a modified zirconia fine particle (2) dispersion having a solid content concentration of 5% by weight was prepared.
粒子の評価
得られた改質ジルコニア微粒子(2)について平均粒子径および屈折率を測定し、結果を
表１に示した。
Evaluation of Particles The average particle diameter and refractive index of the obtained modified zirconia fine particles (2) were measured, and the results are shown in Table 1.
ハードコート膜形成用塗布液(2)の調製
実施例１において、改質ジルコニア微粒子(2)分散液１０ｇを用いた以外は同様にして
ハードコート膜形成用塗布液(2)を調製した。
Preparation of Hard Coat Film Forming Coating Liquid (2) A hard coat film forming coating liquid (2) was prepared in the same manner as in Example 1 except that 10 g of the modified zirconia fine particle (2) dispersion was used.
ハードコート膜付基材(2)の製造
実施例１において、ハードコート膜形成用塗布液(2)を用いた以外は同様にしてハード
コート膜付基材(2)を製造した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜(2)の全光線透過率、ヘーズ、耐擦傷性および分散安定性を評
価し、結果を表１に示した。
Production of Substrate with Hard Coat Film (2) A substrate with hard coat film (2) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (2) was used. At this time, the thickness of the hard coat film was 3 μm.
The total light transmittance, haze, scratch resistance and dispersion stability of the obtained hard coat film (2) were evaluated, and the results are shown in Table 1.
[実施例3]
改質ジルコニア微粒子(3)分散液の調製
ジルコニア微粒子分散液(3)の調製
実施例１において、濃度１０重量％のＫＯＨ水溶液１５ｇを加えてｐＨ１０．０のジルコニア粉末分散液とした以外は同様にしてＺｒＯ2濃度２重量％のジルコニア微粒子分散
液(3)を調製した。
[Example 3]
Preparation of modified zirconia fine particle (3) dispersion
Preparation of zirconia fine particle dispersion (3) In the same manner as in Example 1, except that 15 g of 10% by weight aqueous KOH solution was added to obtain a zirconia powder dispersion having a pH of 10.0, zirconia fine particle dispersion having a ZrO 2 concentration of 2% by weight was prepared. Liquid (3) was prepared.
ジルコニア微粒子(3)を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子等は無く、平均粒子径４０ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶、単斜晶の混晶体であった。また、屈折率は２．１であった。 When the zirconia fine particles (3) were observed with a transmission electron micrograph (TEM), there were no coarse particles and the like, and the zirconia fine particles had an average particle diameter of 40 nm. The zirconia fine particles were cubic and monoclinic mixed crystals. The refractive index was 2.1.
ＮＨ 4 型イオン交換樹脂で処理
ＺｒＯ2濃度２重量％のジルコニア微粒子分散液(3) １００ｇを用いた以外は実施例１
と同様にして固形分濃度５重量％のジルコニア微粒子アルコール分散液(2)を得た。
Example 1 except that 100 g of zirconia fine particle dispersion (3) treated with NH 4 type ion exchange resin and having a ZrO 2 concentration of 2% by weight was used.
In the same manner as above, a zirconia fine particle alcohol dispersion (2) having a solid concentration of 5% by weight was obtained.
表面処理
固形分濃度５重量％のジルコニア微粒子アルコール分散液(3)を用いた以外は実施例１
と同様にして固形分濃度５重量％の改質ジルコニア微粒子(3)分散液を調製した。
Example 1 except that a zirconia fine particle alcohol dispersion (3) having a surface treatment solid content concentration of 5% by weight was used.
In the same manner, a modified zirconia fine particle (3) dispersion having a solid content concentration of 5% by weight was prepared.
粒子の評価
得られた改質ジルコニア微粒子(3)について平均粒子径および屈折率を測定し、結果を
表１に示した。
Evaluation of Particles The average particle diameter and refractive index of the obtained modified zirconia fine particles (3) were measured, and the results are shown in Table 1.
ハードコート膜形成用塗布液(3)の調製
実施例１において、改質ジルコニア微粒子(3)分散液１０ｇを用いた以外は同様にして
ハードコート膜形成用塗布液(3)を調製した。
Preparation of Hard Coat Film Forming Coating Liquid (3) A hard coat film forming coating liquid (3) was prepared in the same manner as in Example 1 except that 10 g of the modified zirconia fine particle (3) dispersion was used.
ハードコート膜付基材(3)の製造
実施例１において、ハードコート膜形成用塗布液(3)を用いた以外は同様にしてハード
コート膜付基材(3)を製造した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜(3)の全光線透過率、ヘーズ、耐擦傷性および分散安定性を評
価し、結果を表１に示した。
Production of substrate with hard coat film (3) A substrate with hard coat film (3) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (3) was used. At this time, the thickness of the hard coat film was 3 μm.
The total light transmittance, haze, scratch resistance and dispersion stability of the obtained hard coat film (3) were evaluated, and the results are shown in Table 1.
[実施例4]
ＮＨ 4 型イオン交換樹脂で処理
実施例１と同様にしてＮＨ4 +型イオン交換樹脂で処理し、ついで、樹脂を分離した後、Ｈ+型イオン交換樹脂（三菱化学（株）製：ＳＫ−１ＢＨ）１０ｇを加え、３０分間撹拌
を行った。得られたゾルのｐＨは８．５であった。ついで、限外濾過膜を用いて溶媒をメタノールに置換し、固形分濃度５重量％のジルコニア微粒子アルコール分散液(4)を得た
。
[Example 4]
Treatment with NH 4 type ion exchange resin Treatment with NH 4 + type ion exchange resin in the same manner as in Example 1, and then separating the resin, followed by H + type ion exchange resin (manufactured by Mitsubishi Chemical Corporation: SK- 1BH) 10 g was added and stirred for 30 minutes. The obtained sol had a pH of 8.5. Subsequently, the solvent was replaced with methanol using an ultrafiltration membrane to obtain a zirconia fine particle alcohol dispersion (4) having a solid content concentration of 5% by weight.
表面処理
固形分濃度５重量％のジルコニア微粒子アルコール分散液(4)を用いた以外は実施例１
と同様にして固形分濃度５重量％の改質ジルコニア微粒子(4)分散液を調製した。
Example 1 except that a zirconia fine particle alcohol dispersion (4) having a surface treatment solid content concentration of 5% by weight was used.
In the same manner, a modified zirconia fine particle (4) dispersion having a solid content concentration of 5% by weight was prepared.
粒子の評価
得られた改質ジルコニア微粒子(4)について平均粒子径および屈折率を測定し、結果を
表１に示した。
Evaluation of Particles The average particle diameter and refractive index of the obtained modified zirconia fine particles (4) were measured, and the results are shown in Table 1.
ハードコート膜形成用塗布液(4)の調製
実施例１において、改質ジルコニア微粒子(4)分散液１０ｇを用いた以外は同様にして
ハードコート膜形成用塗布液(4)を調製した。
Preparation of hard coat film forming coating solution (4) A hard coat film forming coating solution (4) was prepared in the same manner as in Example 1, except that 10 g of the modified zirconia fine particle (4) dispersion was used.
ハードコート膜付基材(4)の製造
実施例１において、ハードコート膜形成用塗布液(4)を用いた以外は同様にしてハード
コート膜付基材(4)を製造した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜(4)の全光線透過率、ヘーズ、耐擦傷性および分散安定性を評
価し、結果を表１に示した。
Production of Substrate with Hard Coat Film (4) A substrate with hard coat film (4) was produced in the same manner as in Example 1, except that the coating liquid for forming a hard coat film (4) was used. At this time, the thickness of the hard coat film was 3 μm.
The total light transmittance, haze, scratch resistance and dispersion stability of the obtained hard coat film (4) were evaluated, and the results are shown in Table 1.
[実施例5]
改質ジルコニア微粒子(5)分散液の調製
焼成ジルコニア粉末(5)の調製
実施例１において、水熱処理して得られた分散液を乾燥した後、４５０℃で２時間焼成した以外は同様にして焼成ジルコニア粉末(5)を得た。得られた焼成ジルコニア粉末(5)は立方晶，単斜晶の混晶体であった。
[Example 5]
Preparation of modified zirconia fine particle (5) dispersion
Preparation of calcined zirconia powder (5) A calcined zirconia powder (5) was obtained in the same manner as in Example 1, except that the dispersion obtained by hydrothermal treatment was dried and then calcined at 450 ° C for 2 hours. The obtained calcined zirconia powder (5) was a cubic and monoclinic mixed crystal.
ジルコニア微粒子分散液(5)の調製
実施例１において、焼成ジルコニア粉末(5)を用いた以外は同様にしてＺｒＯ2濃度2重
量％のジルコニア微粒子分散液(5)を調製した。
ジルコニア微粒子を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子等は無
く、平均粒子径２０ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶、単斜晶の混晶体であった。また、屈折率は２．０であった。
Preparation of zirconia fine particle dispersion (5) A zirconia fine particle dispersion (5) having a ZrO 2 concentration of 2% by weight was prepared in the same manner as in Example 1 except that the calcined zirconia powder (5) was used.
When the zirconia fine particles were observed with a transmission electron micrograph (TEM), there were no coarse particles and the like, and the zirconia fine particles had an average particle diameter of 20 nm. The zirconia fine particles were cubic and monoclinic mixed crystals. The refractive index was 2.0.
ＮＨ 4 型イオン交換樹脂で処理
ＺｒＯ2濃度２重量％のジルコニア微粒子分散液(5) １００ｇを用いた以外は実施例１
と同様にして固形分濃度５重量％のジルコニア微粒子アルコール分散液(5)を得た。
Example 1 except that 100 g of zirconia fine particle dispersion (5) treated with NH 4 type ion exchange resin and having a ZrO 2 concentration of 2% by weight was used.
In the same manner as above, a zirconia fine particle alcohol dispersion (5) having a solid content concentration of 5% by weight was obtained.
表面処理
固形分濃度５重量％のジルコニア微粒子アルコール分散液(5)を用いた以外は実施例１
と同様にして固形分濃度５重量％の改質ジルコニア微粒子(5)分散液を調製した。
Example 1 except that the zirconia fine particle alcohol dispersion (5) having a surface treatment solid content concentration of 5% by weight was used.
In the same manner, a modified zirconia fine particle (5) dispersion having a solid content concentration of 5% by weight was prepared.
粒子の評価
得られた改質ジルコニア微粒子(5)について平均粒子径および屈折率を測定し、結果を
表にした。
Evaluation of Particles The average particle diameter and refractive index of the modified zirconia fine particles (5) obtained were measured, and the results were tabulated.
ハードコート膜形成用塗布液(5)の調製
実施例１において、改質ジルコニア微粒子(5)分散液１０ｇを用いた以外は同様にして
ハードコート膜形成用塗布液(5)を調製した。
Preparation of hard coat film forming coating solution (5) A hard coat film forming coating solution (5) was prepared in the same manner as in Example 1, except that 10 g of the modified zirconia fine particle (5) dispersion was used.
ハードコート膜付基材(5)の製造
実施例１において、ハードコート膜形成用塗布液(5)を用いた以外は同様にしてハード
コート膜付基材(5)を製造した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜(5)の全光線透過率、ヘーズ、耐擦傷性および分散安定性を評
価し、結果を表１に示した。
Production of Substrate with Hard Coat Film (5) A substrate with hard coat film (5) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (5) was used. At this time, the thickness of the hard coat film was 3 μm.
The total light transmittance, haze, scratch resistance and dispersion stability of the obtained hard coat film (5) were evaluated, and the results are shown in Table 1.
[実施例6]
改質ジルコニア微粒子(6)分散液の調製
焼成ジルコニア粉末(6)の調製
実施例１において、水熱処理して得られた分散液を乾燥した後７５０℃で２時間焼成した以外は同様にして焼成ジルコニア粉末(6)を得た。得られた焼成ジルコニア粉末(6)は立方晶，単斜晶の混晶体であった。
[Example 6]
Preparation of modified zirconia fine particle (6) dispersion
Preparation of calcined zirconia powder (6) A calcined zirconia powder (6) was obtained in the same manner as in Example 1 except that the dispersion obtained by hydrothermal treatment was dried and then calcined at 750 ° C for 2 hours. The obtained calcined zirconia powder (6) was a cubic and monoclinic mixed crystal.
ジルコニア微粒子分散液(6)の調製
実施例１において、焼成ジルコニア粉末(6)を用いた以外は同様にしてＺｒＯ2濃度2重
量％のジルコニア微粒子分散液(6)を調製した。
Preparation of zirconia fine particle dispersion (6) A zirconia fine particle dispersion (6) having a ZrO 2 concentration of 2% by weight was prepared in the same manner as in Example 1 except that the calcined zirconia powder (6) was used.
ジルコニア微粒子を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子等は無
く、平均粒子径５０ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶、単斜晶の混晶体であった。また、屈折率は２．２であった。
When the zirconia fine particles were observed with a transmission electron micrograph (TEM), there were no coarse particles and the like, and the zirconia fine particles had an average particle diameter of 50 nm. The zirconia fine particles were cubic and monoclinic mixed crystals. The refractive index was 2.2.
ＮＨ 4 型イオン交換樹脂で処理
ＺｒＯ2濃度２重量％のジルコニア微粒子分散液(6) １００ｇを用いた以外は実施例１
と同様にして固形分濃度５重量％のジルコニア微粒子アルコール分散液(6)を得た。
Example 1 except that 100 g of zirconia fine particle dispersion (6) having a ZrO 2 concentration of 2% by weight treated with NH 4 type ion exchange resin was used.
In the same manner as above, a zirconia fine particle alcohol dispersion (6) having a solid content concentration of 5% by weight was obtained.
表面処理
固形分濃度５重量％のジルコニア微粒子アルコール分散液(6)を用いた以外は実施例１
と同様にして固形分濃度５重量％の改質ジルコニア微粒子(6)分散液を調製した。
Example 1 except that a zirconia fine particle alcohol dispersion (6) having a surface treatment solid content concentration of 5% by weight was used.
In the same manner, a modified zirconia fine particle (6) dispersion having a solid content concentration of 5% by weight was prepared.
粒子の評価
得られた改質ジルコニア微粒子(6)について平均粒子径および屈折率を測定し、結果を
表１に示した。
Evaluation of Particles The average particle diameter and refractive index of the obtained modified zirconia fine particles (6) were measured, and the results are shown in Table 1.
ハードコート膜形成用塗布液(6)の調製
実施例１において、改質ジルコニア微粒子(6)分散液１０ｇを用いた以外は同様にして
ハードコート膜形成用塗布液(6)を調製した。
Preparation of hard coat film forming coating solution (6) A hard coat film forming coating solution (6) was prepared in the same manner as in Example 1, except that 10 g of the modified zirconia fine particle (6) dispersion was used.
ハードコート膜付基材(6)の製造
実施例１において、ハードコート膜形成用塗布液(6)を用いた以外は同様にしてハード
コート膜付基材(6)を製造した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜(6)の全光線透過率、ヘーズ、耐擦傷性および分散安定性を評
価し、結果を表１に示した。
Production of Substrate with Hard Coat Film (6) A substrate with hard coat film (6) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (6) was used. At this time, the thickness of the hard coat film was 3 μm.
The total light transmittance, haze, scratch resistance and dispersion stability of the obtained hard coat film (6) were evaluated, and the results are shown in Table 1.
[実施例7]
改質ジルコニア微粒子(7)分散液の調製
ＮＨ 4 型イオン交換樹脂で処理
実施例１と同様にして調製したＺｒＯ2濃度２重量％のジルコニア微粒子分散液(1) １
００ｇにＮＨ4 +型イオン交換樹脂５６ｇ加え、３０分間攪拌を行った後、樹脂を分離した。得られたゾルのｐＨは１１．６であった。ついで、限外濾過膜を用いて溶媒をメタノールに置換し、固形分濃度５重量％のジルコニア微粒子アルコール分散液(7)を得た。
[Example 7]
Preparation of modified zirconia fine particle (7) dispersion
Treatment with NH 4 type ion exchange resin ZrO 2 fine particle dispersion (1) 1 having a ZrO 2 concentration of 2% by weight prepared in the same manner as in Example 1.
After adding 56 g of NH 4 + type ion exchange resin to 00 g and stirring for 30 minutes, the resin was separated. The obtained sol had a pH of 11.6. Subsequently, the solvent was replaced with methanol using an ultrafiltration membrane to obtain a zirconia fine particle alcohol dispersion (7) having a solid concentration of 5% by weight.
表面処理
固形分濃度５重量％のジルコニア微粒子アルコール分散液(7)を用いた以外は実施例１
と同様にして固形分濃度５重量％の改質ジルコニア微粒子(7)分散液を調製した。
Example 1 except that a zirconia fine particle alcohol dispersion (7) having a surface treatment solid content concentration of 5% by weight was used.
In the same manner, a modified zirconia fine particle (7) dispersion having a solid content concentration of 5% by weight was prepared.
粒子の評価
得られた改質ジルコニア微粒子(7)について平均粒子径および屈折率を測定し、結果を
表１に示した。
Evaluation of Particles The average particle diameter and refractive index of the obtained modified zirconia fine particles (7) were measured, and the results are shown in Table 1.
ハードコート膜形成用塗布液(7)の調製
実施例１において、改質ジルコニア微粒子(7)分散液１０ｇを用いた以外は同様にして
ハードコート膜形成用塗布液(7)を調製した。
Preparation of Hard Coat Film Forming Coating Liquid (7) A hard coat film forming coating liquid (7) was prepared in the same manner as in Example 1 except that 10 g of the modified zirconia fine particle (7) dispersion was used.
ハードコート膜付基材(7)の製造
実施例１において、ハードコート膜形成用塗布液(7)を用いた以外は同様にしてハード
コート膜付基材(7)を製造した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜(7)の全光線透過率、ヘーズ、耐擦傷性および分散安定性を評
価し、結果を表１に示した。
Production of substrate with hard coat film (7) A substrate with hard coat film (7) was produced in the same manner as in Example 1, except that the coating liquid for forming a hard coat film (7) was used. At this time, the thickness of the hard coat film was 3 μm.
The total light transmittance, haze, scratch resistance and dispersion stability of the obtained hard coat film (7) were evaluated, and the results are shown in Table 1.
[実施例8]
改質ジルコニア微粒子(8)分散液の調製
ジルコニア微粒子分散液(8)の調製
実施例１において、濃度１０重量％のＮａＯＨ水溶液２１．４ｇを加えてｐＨ１２．３のジルコニア粉末分散液とした以外は同様にしてＺｒＯ2濃度２重量％のジルコニア微粒
子分散液(8)を調製した。
[Example 8]
Preparation of modified zirconia fine particle (8) dispersion
Preparation of zirconia fine particle dispersion (8) In Example 1, except that 21.4 g of NaOH aqueous solution having a concentration of 10% by weight was added to obtain a zirconia powder dispersion having a pH of 12.3, zirconia having a ZrO 2 concentration of 2% by weight. A fine particle dispersion (8) was prepared.
ジルコニア微粒子を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子等は無
く、平均粒子径３０ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶、単斜晶の混晶体であった。また、屈折率は２．１であった。
When the zirconia fine particles were observed with a transmission electron micrograph (TEM), there were no coarse particles and the like, and the zirconia fine particles had an average particle diameter of 30 nm. The zirconia fine particles were cubic and monoclinic mixed crystals. The refractive index was 2.1.
ＮＨ 4 型イオン交換樹脂で処理
ＺｒＯ2濃度２重量％のジルコニア微粒子分散液(8) １００ｇを用いた以外は実施例１
と同様にして固形分濃度５重量％のジルコニア微粒子アルコール分散液(8)を得た。
Example 1 except that 100 g of a zirconia fine particle dispersion (8) treated with NH 4 type ion exchange resin and having a ZrO 2 concentration of 2% by weight was used.
In the same manner as above, a zirconia fine particle alcohol dispersion (8) having a solid content concentration of 5% by weight was obtained.
表面処理
固形分濃度５重量％のジルコニア微粒子アルコール分散液(8)を用いた以外は実施例１と
同様にして固形分濃度５重量％の改質ジルコニア微粒子(8)分散液を調製した。
Surface treatment A modified zirconia fine particle (8) dispersion having a solid content concentration of 5% by weight was prepared in the same manner as in Example 1 except that the zirconia fine particle alcohol dispersion (8) having a solid content concentration of 5% by weight was used. Prepared.
粒子の評価
得られた改質ジルコニア微粒子(8)について平均粒子径および屈折率を測定し、結果を
表１に示した。
Evaluation of Particles The average particle diameter and refractive index of the obtained modified zirconia fine particles (8) were measured, and the results are shown in Table 1.
ハードコート膜形成用塗布液(8)の調製
実施例１において、改質ジルコニア微粒子(8)分散液１０ｇを用いた以外は同様にして
ハードコート膜形成用塗布液(8)を調製した。
Preparation of Hard Coat Film Forming Coating Liquid (8) A hard coat film forming coating liquid (8) was prepared in the same manner as in Example 1 except that 10 g of the modified zirconia fine particle (8) dispersion was used.
ハードコート膜付基材(8)の製造
実施例１において、ハードコート膜形成用塗布液(8)を用いた以外は同様にしてハード
コート膜付基材(8)を製造した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜(8)の全光線透過率、ヘーズ、耐擦傷性および分散安定性を評
価し、結果を表１に示した。
Production of substrate with hard coat film (8) A substrate with hard coat film (8) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (8) was used. At this time, the thickness of the hard coat film was 3 μm.
The total light transmittance, haze, scratch resistance and dispersion stability of the obtained hard coat film (8) were evaluated, and the results are shown in Table 1.
[比較例1]
改質ジルコニア微粒子(R1)分散液の調製
ジルコニア粉末(R1)の調製
実施例１において、６５０℃で２時間焼成することなく、水熱処理して得られた分散液を乾燥してジルコニア粉末(R1)を得た。得られたジルコニア粉末(R1)は立方晶であった。
[Comparative Example 1]
Preparation of modified zirconia fine particle (R1) dispersion
Preparation of zirconia powder (R1) In Example 1, the dispersion obtained by hydrothermal treatment was dried without firing at 650 ° C. for 2 hours to obtain zirconia powder (R1). The obtained zirconia powder (R1) was cubic.
ジルコニア微粒子分散液(R1)の調製
実施例１において、ジルコニア粉末(R1)３６ｇを用いた以外は同様にしてＺｒＯ2濃度
２重量％のジルコニア微粒子分散液(R1)を調製した。
ジルコニア微粒子を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子等は無
く、平均粒子径１０ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶であった。また、屈折率は１．８であった。
Preparation of zirconia fine particle dispersion (R1) A zirconia fine particle dispersion (R1) having a ZrO 2 concentration of 2% by weight was prepared in the same manner as in Example 1 except that 36 g of zirconia powder (R1) was used.
When the zirconia fine particles were observed with a transmission electron micrograph (TEM), there were no coarse particles and the like, and the zirconia fine particles had an average particle diameter of 10 nm. The zirconia fine particles were cubic. The refractive index was 1.8.
ＮＨ 4 型イオン交換樹脂で処理
ＺｒＯ2濃度２重量％のジルコニア微粒子分散液(R1) １００ｇを用いた以外は実施例１と同様にして固形分濃度５重量％のジルコニア微粒子アルコール分散液(R1)を得た。
Treated with NH 4 type ion exchange resin ZrO 2 fine particle dispersion (R1) having a ZrO 2 concentration of 2% by weight In the same manner as in Example 1 except that 100 g of zirconia fine particle dispersion (R1) having a solid content of 5% by weight was used. Got.
表面処理
固形分濃度５重量％のジルコニア微粒子アルコール分散液(R1)を用いた以外は実施例１と同様にして固形分濃度５重量％の改質ジルコニア微粒子(R1)分散液を調製した。
A modified zirconia fine particle (R1) dispersion having a solid content concentration of 5% by weight was prepared in the same manner as in Example 1 except that the surface-treated solid content concentration of 5% by weight of zirconia fine particle alcohol dispersion (R1) was used.
粒子の評価
得られた改質ジルコニア微粒子(R1)について平均粒子径および屈折率を測定し、結果を表１に示した。
Evaluation of Particles The average particle diameter and refractive index of the obtained modified zirconia fine particles (R1) were measured, and the results are shown in Table 1.
ハードコート膜形成用塗布液(R1)の調製
実施例１において、改質ジルコニア微粒子(R1)分散液１０ｇを用いた以外は同様にしてハードコート膜形成用塗布液(R1)を調製した。
Preparation of hard coat film forming coating solution (R1) A hard coat film forming coating solution (R1) was prepared in the same manner as in Example 1, except that 10 g of the modified zirconia fine particle (R1) dispersion was used.
ハードコート膜付基材(R1)の製造
実施例１において、ハードコート膜形成用塗布液(R1)を用いた以外は同様にしてハードコート膜付基材(R1)を製造した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜(R1)の全光線透過率、ヘーズ、耐擦傷性および分散安定性を評価し、結果を表１に示した。
Production of Substrate with Hard Coat Film (R1) A substrate with hard coat film (R1) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (R1) was used. At this time, the thickness of the hard coat film was 3 μm.
The total light transmittance, haze, scratch resistance and dispersion stability of the obtained hard coat film (R1) were evaluated, and the results are shown in Table 1.
[比較例２]
改質ジルコニア微粒子(R2)分散液の調製
焼成ジルコニア粉末(R2)の調製
実施例１において、水熱処理して得られた分散液を乾燥した後、１０００℃で２時間焼成した以外は同様にして焼成ジルコニア粉末(R2)を得た。得られた焼成ジルコニア粉末(R2)は立方晶，単斜晶の混晶体であった。
[Comparative Example 2]
Preparation of modified zirconia fine particle (R2) dispersion
Preparation of calcined zirconia powder (R2) A calcined zirconia powder (R2) was obtained in the same manner as in Example 1 except that the dispersion obtained by hydrothermal treatment was dried and then calcined at 1000 ° C for 2 hours. The obtained calcined zirconia powder (R2) was a cubic and monoclinic mixed crystal.
ジルコニア微粒子分散液(R2)の調製
純水１６１．９ｇに酒石酸４．４ｇを溶解した水溶液にジルコニア粉末(R2)３６ｇを加え、ついで、濃度１０重量％のＫＯＨ水溶液３０ｇを加えてｐＨ１２．３のジルコニア粉末分散液とした。ジルコニア粉末(R2)分散液を分散機（カンペ（株)製：BATCH SAND）に
て分散させた後、遠心分離器にセットし、２，５００ｒｐｍで5分間遠心分離処理を行な
った後、限外濾過膜を用いて電導度が１００μｓ／ｃｍ程度になるまで洗浄し、ついで、陰イオン交換樹脂（ROHM AND HAAS社製：DUOLITE UP5000）４０ｇを加えて洗浄処理を行
い、樹脂を分離し、ＺｒＯ2濃度２重量％のジルコニア微粒子分散液(R2)を調製した。
Preparation of zirconia fine particle dispersion (R2) 36 g of zirconia powder (R2) was added to an aqueous solution in which 4.4 g of tartaric acid was dissolved in 161.9 g of pure water, and then 30 g of a 10 wt% KOH aqueous solution was added to adjust the pH to 12.3. A zirconia powder dispersion was obtained. Disperse the zirconia powder (R2) dispersion with a disperser (manufactured by Campe Co., Ltd .: BATCH SAND), set in a centrifuge, and centrifuge at 2,500 rpm for 5 minutes. Washing is performed using a filtration membrane until the electric conductivity reaches about 100 μs / cm, and then 40 g of anion exchange resin (ROHM AND HAAS: DUOLITE UP5000) is added for washing treatment to separate the resin, and ZrO 2 A zirconia fine particle dispersion (R2) having a concentration of 2% by weight was prepared.
ジルコニア微粒子を透過型電子顕微鏡写真（TEM）で観察したところ、粗大粒子が存在
し、平均粒子径１００ｎｍのジルコニア微粒子であった。また、ジルコニア微粒子は立方晶、単斜晶の混晶体であった。また、屈折率は２．１５であった。
When the zirconia fine particles were observed with a transmission electron micrograph (TEM), coarse particles were present and the zirconia fine particles had an average particle diameter of 100 nm. The zirconia fine particles were cubic and monoclinic mixed crystals. The refractive index was 2.15.
ＮＨ 4 型イオン交換樹脂で処理
ＺｒＯ2濃度２重量％のジルコニア微粒子分散液(R2)１００ｇを用いた以外は実施例１
と同様にして固形分濃度５重量％のジルコニア微粒子アルコール分散液(R2)を得た。
Example 1 except that 100 g of zirconia fine particle dispersion (R2) having a ZrO 2 concentration of 2% by weight treated with NH 4 type ion exchange resin was used.
In the same manner as above, a zirconia fine particle alcohol dispersion (R2) having a solid content concentration of 5% by weight was obtained.
表面処理
固形分濃度５重量％のジルコニア微粒子アルコール分散液(R2)を用いた以外は実施例１と同様にして固形分濃度５重量％の改質ジルコニア微粒子(R2)分散液を調製した。
A modified zirconia fine particle (R2) dispersion having a solid content concentration of 5% by weight was prepared in the same manner as in Example 1 except that the zirconia fine particle alcohol dispersion (R2) having a surface treatment solid content concentration of 5% by weight was used.
粒子の評価
得られた改質ジルコニア微粒子(R2)について平均粒子径および屈折率を測定し、結果を表１に示した。
Evaluation of Particles The average particle diameter and refractive index of the obtained modified zirconia fine particles (R2) were measured, and the results are shown in Table 1.
ハードコート膜形成用塗布液(R2)の調製
実施例１において、改質ジルコニア微粒子(R2)分散液１０ｇを用いた以外は同様にしてハードコート膜形成用塗布液(R2)を調製した。
Preparation of hard coat film forming coating solution (R2) A hard coat film forming coating solution (R2) was prepared in the same manner as in Example 1, except that 10 g of the modified zirconia fine particle (R2) dispersion was used.
ハードコート膜付基材(R2)の製造
実施例１において、ハードコート膜形成用塗布液(R2)を用いた以外は同様にしてハードコート膜付基材(R2)を製造した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜(R2)の全光線透過率、ヘーズ、耐擦傷性および分散安定性を評価し、結果を表１に示した。
Production of Substrate with Hard Coat Film (R2) A substrate with hard coat film (R2) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (R2) was used. At this time, the thickness of the hard coat film was 3 μm.
The total light transmittance, haze, scratch resistance and dispersion stability of the obtained hard coat film (R2) were evaluated, and the results are shown in Table 1.
[比較例3]
改質ジルコニア微粒子(R3)分散液の調製
実施例１と同様にして調製したＺｒＯ2濃度２重量％のジルコニア微粒子分散液(1)を、ＮＨ4型イオン交換樹脂で処理することなく、限外濾過膜を用いて溶媒をメタノールに置
換し、固形分濃度５重量％のジルコニア微粒子アルコール分散液（R3）を得た。
[Comparative Example 3]
Preparation of Modified Zirconia Fine Particle (R3) Dispersion A zirconia fine particle dispersion (1) having a ZrO 2 concentration of 2% by weight prepared in the same manner as in Example 1 was treated without treatment with NH 4 type ion exchange resin. The solvent was replaced with methanol using a filtration membrane to obtain a zirconia fine particle alcohol dispersion (R3) having a solid content concentration of 5% by weight.
表面処理
固形分濃度５重量％のジルコニア微粒子アルコール分散液(R3)を用いた以外は実施例１と同様にして固形分濃度５重量％の改質ジルコニア微粒子(R3)分散液を調製した。
A modified zirconia fine particle (R3) dispersion having a solid content concentration of 5% by weight was prepared in the same manner as in Example 1 except that the zirconia fine particle alcohol dispersion (R3) having a surface treatment solid content of 5% by weight was used.
粒子の評価
得られた改質ジルコニア微粒子(R3)について平均粒子径および屈折率を測定し、結果を表１に示した。
Evaluation of Particles The average particle diameter and refractive index of the obtained modified zirconia fine particles (R3) were measured, and the results are shown in Table 1.
ハードコート膜形成用塗布液(R3)の調製
実施例１において、改質ジルコニア微粒子(R3)分散液１０ｇを用いた以外は同様にしてハードコート膜形成用塗布液(R3)を調製した。
Preparation of hard coat film forming coating solution (R3) A hard coat film forming coating solution (R3) was prepared in the same manner as in Example 1, except that 10 g of the modified zirconia fine particle (R3) dispersion was used.
ハードコート膜付基材(R3)の製造
実施例１において、ハードコート膜形成用塗布液(R3)を用いた以外は同様にしてハードコート膜付基材(R3)を製造した。このときのハードコート膜の厚さは３μｍであった。
得られたハードコート膜(R3)の全光線透過率、ヘーズ、耐擦傷性および分散安定性を評
価し、結果を表１に示した。
Production of Substrate with Hard Coat Film (R3) A substrate with hard coat film (R3) was produced in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (R3) was used. At this time, the thickness of the hard coat film was 3 μm.
The total light transmittance, haze, scratch resistance, and dispersion stability of the obtained hard coat film (R3) were evaluated. The results are shown in Table 1.
[比較例4]
改質ジルコニア微粒子(R4)分散液の調製
Ｈ型イオン交換樹脂で処理
実施例１と同様にして調製したＺｒＯ2濃度２重量％のジルコニア微粒子分散液(1) １
００ｇにＨ+型イオン交換樹脂（三菱化学（株）製：ダイヤイオン ＳＫ−１ＢＨ）を２
８ｇ加え、３０分間攪拌を行った。ついで、樹脂を分離したが、分散液のｐＨは３．５となり、ジルコニア微粒子は凝集・沈降した。このため、以下、表面処理、ハードコート膜形成用塗布液の調製、ハードコート膜付基材の製造およびこれらの評価は実施しなかった。
[Comparative Example 4]
Preparation of modified zirconia fine particle (R4) dispersion
Treatment with H-type ion exchange resin ZrO 2 concentration 2% by weight of zirconia fine particle dispersion (1) 1
00 g of H + type ion exchange resin (Mitsubishi Chemical Corporation: Diaion SK-1BH) 2
8 g was added and stirred for 30 minutes. Subsequently, the resin was separated, but the pH of the dispersion became 3.5, and the zirconia fine particles aggregated and settled. For this reason, surface treatment, preparation of a coating solution for forming a hard coat film, production of a substrate with a hard coat film, and evaluation thereof were not performed.
Claims (11)
（ａ）ジルコニア微粉末を３００〜８００℃で焼成する工程
（ｂ）焼成ジルコニア微粉末を、アルカリ金属を含むアルカリ存在下で粉砕する工程
（ｃ）粉砕後に洗浄する工程
（ｄ）洗浄した微粉末を分散させたジルコニア微粒子水分散液をＮＨ4型イオン交換樹脂
で処理してアルカリを除去する工程
（ｅ）脱アルカリ処理後のジルコニア微粒子分散液をアルコールに溶媒置換する工程
（ｆ）下記式(1)で表される有機ケイ素化合物で表面処理する工程
Ｒn-ＳiＸ4-n （１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：１〜３の整数） A method for producing modified zirconia fine particles, comprising the following steps (a) to (f).
(A) Step of calcining zirconia fine powder at 300 to 800 ° C. (b) Step of crushing calcined zirconia fine powder in the presence of alkali containing alkali metal (c) Step of washing after crushing (d) Washed fine powder The step of removing the alkali by treating the aqueous dispersion of zirconia fine particles dispersed with NH 4 type ion exchange resin (e) the step of substituting the zirconia fine particle dispersion after dealkalization treatment with alcohol for the solvent (f) Step of surface treatment with an organosilicon compound represented by 1) R n -SiX 4-n (1)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n: an integer of 1 to 3)
を特徴とする請求項１〜７のいずれかに記載の改質ジルコニア微粒子の製造方法。 The content of the organic silicon compound is modified zirconia fine particles according to any one of claims 1 to 7, characterized in that in the range of 1 to 30 wt% expressed in R n S i O 4-n / 2 Production method.
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| JP2014105133A (en) * | 2012-11-28 | 2014-06-09 | Japan Fine Ceramics Center | Method for producing ceria-zirconia composite oxide material and ceria-zirconia composite oxide material obtained thereby |
| KR20140078995A (en) | 2012-12-18 | 2014-06-26 | 니끼 쇼꾸바이 카세이 가부시키가이샤 | Reformed zirconia fine particle, dispersion sol of reformed zirconia fine particle and its preparation method |
| TWI568677B (en) * | 2013-01-17 | 2017-02-01 | 日揮觸媒化成股份有限公司 | Modified zirconia fine particle powder, modified zirconia fine particle powder dispersion gel and manufacturing method thereof |
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