JP2010168268A - Micro ring-like inorganic oxide particle having through-hole, base material with transparent coating film using the same and coating liquid for forming transparent coating film - Google Patents
Micro ring-like inorganic oxide particle having through-hole, base material with transparent coating film using the same and coating liquid for forming transparent coating film Download PDFInfo
- Publication number
- JP2010168268A JP2010168268A JP2009228070A JP2009228070A JP2010168268A JP 2010168268 A JP2010168268 A JP 2010168268A JP 2009228070 A JP2009228070 A JP 2009228070A JP 2009228070 A JP2009228070 A JP 2009228070A JP 2010168268 A JP2010168268 A JP 2010168268A
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- inorganic oxide
- microring
- oxide particles
- transparent film
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- 239000005055 methyl trichlorosilane Substances 0.000 description 1
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
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- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- 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
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- QNKXRZAXBKSFQC-UHFFFAOYSA-N trimethoxy-[3-[2-(oxiran-2-ylmethoxy)ethoxy]propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCCOCC1CO1 QNKXRZAXBKSFQC-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、新規な内部に貫通孔を有するマイクロリング状無機酸化物粒子、該粒子を用いた透明被膜付基材および透明被膜形成用塗布液に関する。 The present invention relates to a novel microring-shaped inorganic oxide particle having a through-hole inside, a substrate with a transparent coating using the particle, and a coating solution for forming a transparent coating.
従来より、ガラス、プラスチックシート、プラスチックレンズ等の基材表面の耐擦傷性を向上させるため、基材表面にハードコート機能を有する透明被膜を形成することが知られており、このような透明被膜として有機樹脂膜あるいは無機膜をガラスやプラスチック等の表面に形成することが行われている。さらに、有機樹脂膜あるいは無機膜中に樹脂粒子あるいはシリカ等の無機粒子を配合してさらに耐擦傷性を向上させることが行われている。 Conventionally, it has been known that a transparent film having a hard coat function is formed on the surface of the base material in order to improve the scratch resistance of the surface of the base material such as glass, plastic sheet, and plastic lens. For example, an organic resin film or an inorganic film is formed on the surface of glass or plastic. Furthermore, it is practiced to further improve the scratch resistance by blending resin particles or inorganic particles such as silica in an organic resin film or an inorganic film.
しかしながら、透明被膜形成用塗布液に微粒子を分散させる際に、マトリックス成分または分散媒と粒子の親和性が低いと、粒子が凝集したり、塗布液の安定性が低下し、得られる透明被膜の透明性、ヘーズ等の他、耐擦傷性、膜強度、密着性等が不充分となることがあった。 However, when the fine particles are dispersed in the coating liquid for forming a transparent film, if the affinity between the matrix component or the dispersion medium and the particles is low, the particles may aggregate or the stability of the coating liquid may be reduced. In addition to transparency, haze, etc., scratch resistance, film strength, adhesion, etc. may be insufficient.
さらに、透明被膜に応力が加わった場合に、用いる粒子が大きいと粒子とマトリックスとが剥離してボイドが生じる場合があった。また、基材が可撓性のあるプラスチック基材の場合は粒子が小さい場合でもボイドが生じ透明被膜の透明性、ヘーズが悪化する場合があった。 Furthermore, when a stress is applied to the transparent coating, if the particles used are large, the particles and the matrix may be separated and voids may be generated. Further, when the base material is a flexible plastic base material, voids may occur even when the particles are small, and the transparency and haze of the transparent film may be deteriorated.
また、本出願人は、特許文献1(国際公開公報WO95/33787号)にて、熱可塑性フィルムにシリカとシリカ以外の複合酸化物からなる微粒子を添加することを開示している。しかし、この微粒子は通常の球状粒子であり、本発明のようなリング状の粒子について何ら示唆していない。 Further, the present applicant discloses in Patent Document 1 (International Publication No. WO95 / 33787) that fine particles composed of silica and a composite oxide other than silica are added to a thermoplastic film. However, this fine particle is a normal spherical particle and does not suggest any ring-shaped particle as in the present invention.
本出願人は、このような問題点に鑑み鋭意検討した結果、従来の形状とは異なり、中心部に貫通孔を有する粒子を使用すれば、貫通孔にマトリックス成分が浸入できるため、粒子とマトリックス成分とが剥離することもなく、上記課題を解決できると考えた。 As a result of intensive studies in view of such problems, the present applicant has found that, unlike a conventional shape, if a particle having a through hole in the central portion is used, a matrix component can enter the through hole, so that the particle and the matrix It was thought that the above-mentioned problems could be solved without peeling off the components.
このような新規なリング状粒子について、さらに検討したところ、シリカゾルを特定の条件で噴霧乾燥したのち、特定の処理をするかあるいは微粒子形成時に特定成分を溶出させ、さらに酸・アルカリ処理したのち水熱処理すると、貫通孔を有するマイクロリング状粒子が得られることを発見した。このようにして得られた貫通孔を有するマイクロリング状粒子を用いた透明被膜は耐擦傷性、膜強度、密着性等に優れるとともに応力を加えた場合にもボイドを生じにくく、このため透明性、ヘーズが悪化しないことを見出して本発明を完成するに至った。 Further examination of such new ring-shaped particles revealed that after silica sol was spray-dried under specific conditions, it was subjected to specific treatment or specific components were eluted during the formation of fine particles, followed by acid / alkali treatment and water. It has been found that microring-like particles having through-holes can be obtained by heat treatment. The transparent film using the microring-shaped particles having through-holes obtained in this way is excellent in scratch resistance, film strength, adhesion, etc. and is less susceptible to voids when stress is applied. The present invention was completed by finding that haze does not deteriorate.
なお、従来本発明のようなリング状粒子は知られていなかった。たとえば、特開2006-7205号公報では、リング状の成形体が例示されているものの、これは、粒子を成形体に成形したものであり、粒子そのものではない。 Conventionally, ring-like particles as in the present invention have not been known. For example, in Japanese Patent Laid-Open No. 2006-7205, a ring-shaped molded body is exemplified, but this is formed by molding particles into a molded body, not the particles themselves.
本発明の要件は以下の通りである。
[1]平均外径(DO)が10nm〜20μmの範囲にあり、貫通孔の平均径(DI)が1nm〜12μmの範囲にあり、リング幅(WR)と平均外径(DO)との比(WR)/(DO)が0.2〜0.45の範囲にあるマイクロリング状無機酸化物粒子。
[2]前記無機酸化物がシリカ系無機酸化物であり[1]の性質を有するマイクロリング状無機酸化物粒子。
[3]下記式(1)で表される有機ケイ素化合物で表面処理されている[1]または[2]のマイクロリング状無機酸化物粒子。
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:0〜3の整数)
The requirements of the present invention are as follows.
[1] The average outer diameter (D O ) is in the range of 10 nm to 20 μm, the average diameter (D I ) of the through holes is in the range of 1 nm to 12 μm, the ring width (W R ) and the average outer diameter (D O ) And microring-shaped inorganic oxide particles having a ratio (W R ) / (D O ) in the range of 0.2 to 0.45.
[2] Microring-shaped inorganic oxide particles having the property [1], wherein the inorganic oxide is a silica-based inorganic oxide.
[3] The microring-shaped inorganic oxide particles according to [1] or [2], which are surface-treated 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 0 to 3)
[4]前記Rが、ハロゲン置換されていてもよいアルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、アミノ基、アミド基、アルコキシ基、エポキシ基、カルボキシル基、ケトン基、エーテル基、アリール基、ヘテロアリール基、ホスフェート基、ハロゲン基、チオール基、スルホニル基から選ばれる少なくとも1種以上の有機官能基を含む[3]のマイクロリング状無機酸化物粒子。
[5]平均粒子径が3〜100nmの無機酸化物ゾルを噴霧乾燥することで得られた粒子を、酸または塩基で処理することにより、貫通孔を形成することを特徴とするマイクロリング状無機酸化物粒子の製造方法。
[6]シリカとシリカ以外の無機酸化物とからなる複合酸化物微粒子を使用し、シリカ以外の無機酸化物を酸にて除去したのち、酸または塩基で処理するか、水熱処理して貫通孔を形成することを特徴とするマイクロリング状無機酸化物粒子の製造方法。
[7]得られたマイクロリング状無機酸化物粒子を下記式(1)で表される有機ケイ素化合物で表面処理する[5]または[6]のマイクロリング状無機酸化物粒子の製造方法。
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:0〜3の整数)
[4] R may be halogen-substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, amino group, amide group, alkoxy group, epoxy group, carboxyl group, ketone group, ether [3] The microring-shaped inorganic oxide particle according to [3], which contains at least one organic functional group selected from a group, an aryl group, a heteroaryl group, a phosphate group, a halogen group, a thiol group, and a sulfonyl group.
[5] A microring-like inorganic material characterized in that through holes are formed by treating particles obtained by spray-drying an inorganic oxide sol having an average particle size of 3 to 100 nm with an acid or a base. A method for producing oxide particles.
[6] Using composite oxide fine particles composed of silica and an inorganic oxide other than silica, and removing inorganic oxides other than silica with an acid, then treating with an acid or base, or hydrothermally treating the through-hole A process for producing microring-shaped inorganic oxide particles, characterized in that
[7] The method for producing microring-shaped inorganic oxide particles according to [5] or [6], wherein the obtained microring-shaped inorganic oxide particles are surface-treated 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 0 to 3)
[8]前記Rが、ハロゲン置換されていてもよいアルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、アミノ基、アミド基、アルコキシ基、エポキシ基、カルボキシル基、ケトン基、エーテル基、アリール基、ヘテロアリール基、ホスフェート基、ハロゲン基、チオール基、スルホニル基から選ばれる少なくとも1種以上の有機官能基を含む[7]のマイクロリング状無機酸化物粒子の製造方法。
[9]基材上に透明被膜が形成された透明被膜付基材であって、該透明被膜が[1]〜[4]のマイクロリング状無機酸化物粒子とマトリックス成分とからなり、透明被膜中のマイクロリング状無機酸化物粒子の含有量が固形分として0.01〜80質量%の範囲にあることを特徴とする透明被膜付基材。
[10]前記透明被膜の膜厚(Th)が50nm〜20μmの範囲にある[9]の透明被膜付基材。
[11]前記透明被膜の膜厚(Th)が50nm〜20μmの範囲にあり、前記平均外径(DO)が10nm〜20μmの範囲にあり、平均外径(DO)と膜厚(Th)との比(DO)/(Th)が0.3〜1.0の範囲にある[9]〜[10]の透明被膜付基材。
[12]前記マトリックス成分が有機樹脂系マトリックス成分である[9]〜[11]の透明被膜付基材。
[13]前記有機樹脂系マトリックス成分が、(メタ)アクリル酸類、γ‐グリシルオキシ類、ウレタン類、ビニル類から選ばれる少なくとも1種以上の紫外線硬化性官能基を有する[9]〜[12]の透明被膜付基材。
[14]前記[1]〜[4]のマイクロリング状無機酸化物粒子とマトリックス形成成分と有機溶媒とからなることを特徴とする透明被膜形成用塗布液。
[15]前記マトリックス形成成分が有機樹脂系マトリックス形成成分である[14]の透明被膜形成用塗布液。
[16]前記有機樹脂系マトリックス形成成分が、(メタ)アクリル酸類、γ‐グリシルオキシ類、ウレタン類、ビニル類から選ばれる少なくとも1種以上の紫外線硬化性官能基を有する[14]〜[15]の透明被膜形成用塗布液。
[8] R may be halogen-substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, amino group, amide group, alkoxy group, epoxy group, carboxyl group, ketone group, ether [7] The method for producing microring-shaped inorganic oxide particles according to [7], comprising at least one organic functional group selected from a group, an aryl group, a heteroaryl group, a phosphate group, a halogen group, a thiol group, and a sulfonyl group.
[9] A substrate with a transparent coating, on which a transparent coating is formed, the transparent coating comprising the microring-shaped inorganic oxide particles of [1] to [4] and a matrix component, A substrate with a transparent coating, characterized in that the content of the microring-like inorganic oxide particles is in the range of 0.01 to 80% by mass as a solid content.
[10] The substrate with a transparent coating according to [9], wherein the thickness (Th) of the transparent coating is in the range of 50 nm to 20 μm.
[11] The film thickness (Th) of the transparent coating is in the range of 50 nm to 20 μm, the average outer diameter (D O ) is in the range of 10 nm to 20 μm, and the average outer diameter (D O ) and film thickness (Th ) And (D O ) / (Th) in the range of 0.3 to 1.0, [9] to [10] a substrate with a transparent coating.
[12] The substrate with a transparent coating according to [9] to [11], wherein the matrix component is an organic resin matrix component.
[13] The organic resin-based matrix component has at least one ultraviolet curable functional group selected from (meth) acrylic acids, γ-glycyloxys, urethanes, and vinyls. A substrate with a transparent coating.
[14] A coating solution for forming a transparent film, comprising the microring-shaped inorganic oxide particles of [1] to [4], a matrix-forming component, and an organic solvent.
[15] The coating liquid for forming a transparent film according to [14], wherein the matrix forming component is an organic resin matrix forming component.
[16] The organic resin-based matrix-forming component has at least one UV-curable functional group selected from (meth) acrylic acids, γ-glycyloxys, urethanes, and vinyls [14] to [15] A coating solution for forming a transparent film.
本発明によれば、無機酸化物粒子が内部に貫通孔を有しているためにマトリックス成分が貫通孔に浸入して透明被膜が形成され、応力が加わった場合にも粒子とマトリックスの間で剥離が生じたりボイドが発生することがなく、このため耐擦傷性、膜強度、基材との密着性等の向上に好適に用いることのできるマイクロリング状無機酸化物粒子、該粒子を用いた透明被膜付基材および透明被膜形成用塗布液を提供することができる。 According to the present invention, since the inorganic oxide particles have through-holes therein, the matrix component penetrates into the through-holes to form a transparent film, and even when stress is applied, between the particles and the matrix. The microring-shaped inorganic oxide particles that can be suitably used for improving the scratch resistance, film strength, adhesion to the substrate, and the like are used without the occurrence of peeling or voids. A substrate with a transparent coating and a coating solution for forming a transparent coating can be provided.
以下、先ず、マイクロリング状無機酸化物粒子について説明する。
[マイクロリング状無機酸化物粒子]
本発明に係るマイクロリング状無機酸化物粒子は、平均外径(DO)が10nm〜20μmの範囲にあり、貫通孔の平均径(DI)が1nm〜12μmの範囲にあり、リング幅(WR)と平均外径(DO)との比(WR)/(DO)が0.2〜0.45の範囲にあることを特徴としている。本発明に係るマイクロリング状無機酸化物粒子は貫通孔を有している。
Hereinafter, first, the microring-shaped inorganic oxide particles will be described.
[Microring-like inorganic oxide particles]
The microring-shaped inorganic oxide particles according to the present invention have an average outer diameter (D O ) in the range of 10 nm to 20 μm, an average diameter (D I ) of the through holes in the range of 1 nm to 12 μm, and a ring width ( The ratio (W R ) / (D O ) between W R ) and the average outer diameter (D O ) is in the range of 0.2 to 0.45. The microring-shaped inorganic oxide particles according to the present invention have through holes.
図1に、本発明に係るマイクロリング状無機酸化物粒子の平面モデル図を示す。
図1中、DOは外径を表し、DIは貫通孔の径を表し、WRはリング幅を表す。
マイクロリングを構成する無機酸化物としては、マイクロリング状無機酸化物粒子が得られれば特に制限はないが、シリカ、アルミナ、チタニア、ジルコニア、シリカ・アルミナ、シリカ・ジルコニア、シリカ・ボリア等の酸化物、複合酸化物等が挙げられる。
In FIG. 1, the plane model figure of the micro ring-shaped inorganic oxide particle which concerns on this invention is shown.
In FIG. 1, D O represents the outer diameter, D I represents the diameter of the through hole, and W R represents the ring width.
The inorganic oxide constituting the microring is not particularly limited as long as microring-like inorganic oxide particles are obtained, but oxidation of silica, alumina, titania, zirconia, silica-alumina, silica-zirconia, silica-boria, etc. And composite oxides.
本発明では、シリカまたはシリカとシリカ以外の酸化物とからなる複合酸化物が好ましい。複合酸化物としてはシリカ・アルミナ、シリカ・ジルコニア、シリカ・ボリア等が挙げられる。複合酸化物の場合、シリカの含有量が50質量%以上のものが好ましい。 In the present invention, silica or a composite oxide composed of silica and an oxide other than silica is preferable. Examples of the composite oxide include silica / alumina, silica / zirconia, and silica / boria. In the case of the composite oxide, the silica content is preferably 50% by mass or more.
このようなシリカ、あるいはシリカを主成分とする複合酸化物(以下、シリカ系無機酸化物ということがある。)以外の酸化物、複合酸化物では、必ずしも所望のマイクロリング状無機酸化物粒子を得ることができないこともある。 Such oxides or composite oxides other than silica or composite oxides containing silica as a main component (hereinafter sometimes referred to as silica-based inorganic oxides) do not necessarily contain desired microring-shaped inorganic oxide particles. Sometimes you can't get it.
マイクロリング状粒子は、貫通孔が少なくとも1個以上で構成する粒子であってもよい。さらに、1次粒子がリング状であってもよく、また2次粒子(すなわち複数の粒子の集合体)がリング状を形成していてもよい。このような本発明に係るマイクロリング状粒子の電子顕微鏡写真を図2、3および4に示す。図2、3は実施例1、図4は実施例2で得られたマイクロリング状粒子の電子顕微鏡写真(SEM)である。 The micro ring-shaped particle may be a particle having at least one through hole. Further, the primary particles may be ring-shaped, and the secondary particles (that is, an aggregate of a plurality of particles) may form a ring shape. Electron micrographs of such microring-like particles according to the present invention are shown in FIGS. 2 and 3 are Example 1 and FIG. 4 are electron micrographs (SEM) of the microring-shaped particles obtained in Example 2. FIG.
1次粒子からリング状粒子を構成する場合、その粒子径は、10〜500nm、さらには10〜300nmの範囲にあることが望ましい。2次粒子からリング状粒子を構成する場合、2次粒子を構成する1次粒子の粒子径は、通常3〜100nm、さらには5〜50nmの範囲にあることが望ましい。 In the case where ring-shaped particles are formed from primary particles, the particle diameter is preferably in the range of 10 to 500 nm, more preferably 10 to 300 nm. In the case of forming ring-shaped particles from secondary particles, the particle diameter of the primary particles constituting the secondary particles is preferably 3 to 100 nm, more preferably 5 to 50 nm.
本発明に係るマイクロリング状無機酸化物粒子の平均外径(DO)は10nm〜20μmの範囲にあり、さらには20nm〜20μmの範囲にあることが好ましい。平均外径が前記範囲の下限未満のものは、得ること自体が困難であり、また貫通孔を設けることも難しくなる。平均外径の上限は特に制限されるものではないが、前記範囲の上限を越えると、透明被膜形成用塗布液に用いた場合に容易に沈降したり分離する場合があり、得られる透明被膜の透明性やヘーズ、膜強度、耐擦傷性、基材との密着性が不充分となる場合がある。但し、用途によっては、上記上限を超えたものでも使用可能である。 The average outer diameter (D O ) of the microring-shaped inorganic oxide particles according to the present invention is in the range of 10 nm to 20 μm, and more preferably in the range of 20 nm to 20 μm. When the average outer diameter is less than the lower limit of the above range, it is difficult to obtain, and it is difficult to provide a through hole. The upper limit of the average outer diameter is not particularly limited, but if it exceeds the upper limit of the above range, it may easily settle or separate when used in a coating liquid for forming a transparent film. Transparency, haze, film strength, scratch resistance, and adhesion to the substrate may be insufficient. However, depending on the application, even those exceeding the upper limit can be used.
貫通孔の平均径(DI)は、外径にもよるが、1nm〜12μm、さらには2nm〜10μmの範囲にあることが好ましい。また、リング幅(WR)と平均外径(DO)との比(WR)/(DO)が0.2〜0.45、さらには0.25〜0.4の範囲にあることが好ましい。 Although the average diameter (D I ) of the through holes depends on the outer diameter, it is preferably in the range of 1 nm to 12 μm, more preferably 2 nm to 10 μm. Further, the ratio (W R ) / (D O ) between the ring width (W R ) and the average outer diameter (D O ) is in the range of 0.2 to 0.45, more preferably 0.25 to 0.4. It is preferable.
貫通孔を前記範囲の下限未満にすること自体が困難であり、また平板状の粒子と何ら代わることが無く、発明の耐擦傷性、膜強度、基材との密着性等を向上させる効果が得られない場合がある。貫通孔が大きすぎると、外径にもよるが、リング形状の効果が乏しく、粒子の強度が低くなり、充分な膜強度、耐擦傷性等が得られない場合がある。(WR)/(DO)が小さすぎると、粒子径の割にリング幅が狭いので粒子強度が低く、透明被膜に用いても充分な膜強度、耐擦傷性等が得られない場合がある。(WR)/(DO)が大きすぎると、平均外径の大きさによっては貫通孔が小さすぎてしまい、貫通孔を設ける効果が発現できない場合もあり、透明被膜に応力を加えた場合にボイドが生成する場合がある。 It is difficult to make the through-hole less than the lower limit of the above-mentioned range, and there is no replacement for the tabular grains, and the effect of improving the scratch resistance, film strength, adhesion to the substrate, etc. of the invention is achieved. It may not be obtained. If the through-hole is too large, depending on the outer diameter, the effect of the ring shape is poor, the strength of the particles is lowered, and sufficient film strength, scratch resistance, etc. may not be obtained. If (W R ) / (D O ) is too small, the ring width is narrow relative to the particle diameter, so the particle strength is low, and even when used for a transparent coating, sufficient film strength, scratch resistance, etc. may not be obtained. is there. When (W R ) / (D O ) is too large, the through hole may be too small depending on the size of the average outer diameter, and the effect of providing the through hole may not be manifested. When stress is applied to the transparent coating In some cases, voids are generated.
また前記した平均外径(DO)、貫通孔の平均径(DI)およびリング幅(WR)は、粒子の電子顕微鏡写真を撮影し、100個の粒子について平均外径(DO)、貫通孔の平均径(DI)およびリング幅(WR)測定し、その平均値として得られる。 The average outer diameter (D O ), the average diameter of the through holes (D I ), and the ring width (W R ) were obtained by taking an electron micrograph of the particles, and the average outer diameter (D O ) for 100 particles. The average diameter (D I ) and ring width (W R ) of through-holes are measured and obtained as the average value.
表面処理
本発明に係るマイクロリング状無機酸化物粒子は、必要に応じて有機ケイ素化合物等で処理されていてもよい。
Surface Treatment The microring-shaped inorganic oxide particles according to the present invention may be treated with an organosilicon compound or the like as necessary.
有機ケイ素化合物で表面処理されていると、マトリックス中に均一に分散し、マトリックスが貫通孔に浸入した透明被膜を形成することができ、ボイドの生成が抑制され、膜強度、耐擦傷性等に優れた透明被膜を得ることができる。さらには、マトリックス成分と基材調製時に共に重合反応する官能基を有する有機ケイ素化合物で表面処理を行うことで、形成された塗膜の膜強度、耐擦傷性、密着性の増加することが期待される。
有機ケイ素化合物としては、下記式(1)で表されるものが好ましい。
Rn-SiX4-n (1)
When the surface is treated with an organosilicon compound, a transparent coating can be formed in which the matrix is uniformly dispersed in the matrix and the matrix penetrates into the through-holes, and the formation of voids is suppressed, and the film strength, scratch resistance, etc. are improved. An excellent transparent film can be obtained. Furthermore, it is expected that the film strength, scratch resistance, and adhesion of the formed coating film will be increased by performing surface treatment with an organosilicon compound having a functional group that undergoes a polymerization reaction during matrix preparation and substrate preparation. Is done.
As the organosilicon compound, those represented by the following formula (1) are preferable.
R n -SiX 4-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、水素を示す。nは0〜3の整数であり、好ましくは1〜3の整数である。 However, in formula, R is a C1-C10 unsubstituted or substituted hydrocarbon group, Comprising: You may mutually be same or different. X: An alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, or hydrogen. n is an integer of 0 to 3, preferably an integer of 1 to 3.
かかる有機ケイ素化合物は、少なくも1個の炭化水素基を有するため、特に互いに混合しにくい疎水性マトリックス成分との親和性が高く、マトリックス中に金属酸化物粒子を偏在させることなく分散させることができ、基材との密着性、耐擦傷性等が向上したハードコート膜付基材を得ることができる。 Since such an organosilicon compound has at least one hydrocarbon group, it has a particularly high affinity with hydrophobic matrix components that are difficult to mix with each other, and the metal oxide particles can be dispersed without being unevenly distributed in the matrix. In addition, a base material with a hard coat film having improved adhesion to the base material, scratch resistance and the like can be obtained.
前記Rが、ハロゲン置換されていてもよいアルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、アミノ基、アミド基、アルコキシ基、エポキシ基、カルボキシル基、ケトン基、エーテル基、アリール基、ヘテロアリール基、ホスフェート基、ハロゲン基、チオール基、スルホニル基から選ばれる少なくとも1種以上の有機官能基を含むことが好ましい。このような有機官能基を有することで、特にマトリックス成分として有機官能基を有するものと組合わせたときに、耐擦傷性、膜強度、密着性等に優れ、また応力がかかってもボイドを生じにくく、このため被膜付基材の透明性、ヘーズが悪化しない。また、このように組合わせることで、非常に少量であっても本発明のマイクロリング状粒子を使用する効果を高く発現される。 R may be halogen-substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, amino group, amide group, alkoxy group, epoxy group, carboxyl group, ketone group, ether group, aryl It preferably contains at least one organic functional group selected from a group, a heteroaryl group, a phosphate group, a halogen group, a thiol group, and a sulfonyl group. By having such an organic functional group, particularly when combined with an organic functional group as a matrix component, it has excellent scratch resistance, film strength, adhesion, etc., and even when stress is applied, voids are generated. Therefore, the transparency and haze of the coated substrate are not deteriorated. Moreover, by combining in this way, the effect of using the micro-ring-like particles of the present invention is highly expressed even in a very small amount.
このような式(1)で表される有機ケイ素化合物としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシシラン、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、N−β(アミノエチル)γ-アミノプロピルメチルジメトキシシラン、N−β(アミノエチル)γ-アミノプロピルトリメトキシシラン、N-フェニル-γ-アミノ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が挙げられる。 Examples of the organosilicon compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltrimethylsilane. Ethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyl Trimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycid Xymethyltrioxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xylpropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acryl Rooxymethyltrioxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meta ) Acryloxypropyltrimethoxysilane, γ- (meth) acrylooxypropi Rutriethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane Hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, Trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-a Roh trimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, trimethylsilanol, methyl trichlorosilane and the like.
これらの有機ケイ素化合物は、マトリックス成分との反応性を鑑み、適宜選択される。
有機ケイ素化合物による処理方法は、従来公知の方法を採用することができ、例えば、マイクロリング状無機酸化物粒子のアルコール分散液に有機ケイ素化合物を必要量加え、これに水を加え、必要に応じて加水分解用触媒として酸またはアルカリを加えて有機ケイ素化合物を加水分解することによって表面処理することができる。
These organosilicon compounds are appropriately selected in view of the reactivity with the matrix component.
Conventionally known methods can be used as the treatment method with the organosilicon compound. For example, a necessary amount of the organosilicon compound is added to the alcohol dispersion of the microring-shaped inorganic oxide particles, and water is added thereto. The surface treatment can be performed by adding an acid or alkali as a hydrolysis catalyst to hydrolyze the organosilicon compound.
有機ケイ素化合物の使用量はマイクロリング状無機酸化物粒子の大きさにもよるが、Rn-SiO(4-n)/2としてマイクロリング状無機酸化物粒子の概ね2〜50質量%、さらには5〜20質量%の範囲にあることが好ましい。 Although the amount of the organosilicon compound used depends on the size of the microring-shaped inorganic oxide particles, it is generally 2 to 50% by mass of the microring-shaped inorganic oxide particles as R n —SiO 2 (4-n) / 2. Is preferably in the range of 5 to 20% by mass.
マイクロリング状無機酸化物粒子の製造方法
このようなマイクロリング状無機酸化物粒子は、上記した粒子径(平均外径)、貫通孔等を有する粒子が得られれば特に制限はないが、本発明のマイクロリング状無機酸化物粒子の製造方法としては、以下の方法が好ましい。
Method for producing microring-shaped inorganic oxide particles Such microring-shaped inorganic oxide particles are not particularly limited as long as particles having the above-described particle diameter (average outer diameter), through-holes, and the like are obtained. As a method for producing the microring-shaped inorganic oxide particles, the following method is preferable.
第1の製造方法
先ず、平均粒子径が概ね3〜100nmの従来公知の前記無機酸化物ゾルを噴霧乾燥して、少なくとも表面に窪み(凹部)を有する粒子を調製する。噴霧乾燥方法としては、例えば、本願出願人の出願による特開昭61−174103号公報に開示した方法に準拠して製造することができる。
First Production Method First, the conventionally known inorganic oxide sol having an average particle diameter of approximately 3 to 100 nm is spray-dried to prepare particles having at least a depression (concave portion) on the surface. As a spray-drying method, it can manufacture based on the method disclosed by Unexamined-Japanese-Patent No. 61-174103 by the application of this applicant, for example.
この時、噴霧乾燥雰囲気の温度は、噴霧する無機酸化物ゾルの濃度によっても異なるが、概ね20〜150℃、好ましくは30〜120℃の範囲にあることが好ましい。
噴霧乾燥雰囲気の温度が20℃未満の場合は所望の貫通孔または凹部ができない場合があり、150℃を越えるとリングが薄くなりすぎたり、破壊した破片状(お椀状)の粒子となる場合がある。
At this time, the temperature of the spray-drying atmosphere varies depending on the concentration of the inorganic oxide sol to be sprayed, but is generally in the range of 20 to 150 ° C., preferably 30 to 120 ° C.
If the temperature of the spray-drying atmosphere is less than 20 ° C, the desired through hole or recess may not be formed. If the temperature exceeds 150 ° C, the ring may become too thin, or broken crushed particles may be formed. is there.
また、無機酸化物ゾルの濃度は、無機酸化物ゾルの種類、粒子の大きさによっても異なるが0.1〜50質量%、さらには1〜20質量%の範囲にあることが好ましい。
無機酸化物ゾルの濃度が低過ぎても、高すぎても噴霧乾燥で貫通孔または凹部を有する粒子が得られず、単なる微粒子が得られる場合がある。
Moreover, although the density | concentration of inorganic oxide sol changes also with the kind of inorganic oxide sol and the magnitude | size of particle | grains, it is preferable that it exists in the range of 0.1-50 mass%, Furthermore, 1-20 mass%.
Even if the concentration of the inorganic oxide sol is too low or too high, particles having through holes or recesses cannot be obtained by spray drying, and simple particles may be obtained.
また、必要に応じて噴霧乾燥雰囲気の湿度を調節することができる。この時の湿度は、乾燥速度を補助的に調節し、所望の貫通孔を生成させるためで、湿度は概ね3〜13vol%、好ましくは5〜9vol%の気流中に噴霧して乾燥する。 Moreover, the humidity of the spray drying atmosphere can be adjusted as needed. The humidity at this time is for adjusting the drying speed to produce a desired through-hole, and the humidity is generally sprayed in an air flow of 3 to 13 vol%, preferably 5 to 9 vol%, and dried.
なお、噴霧方法は特に制限はないが、アトマイザー法、ノズル法等従来公知の方法を採用することができる。
ついで、得られた粒子を酸または塩基で処理する。酸としては、粒子を構成する酸化物の種類によっても異なるが、塩酸、硝酸、硫酸、フッ酸、有機酸等が挙げられ、塩基としてNaOH、KOH、アンモニア、第4級アンモニウムハイドロオキサイド等が挙げられる。
The spraying method is not particularly limited, and conventionally known methods such as an atomizer method and a nozzle method can be employed.
The resulting particles are then treated with acid or base. Examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, organic acid and the like, and examples of the base include NaOH, KOH, ammonia, quaternary ammonium hydroxide, etc. It is done.
酸または塩基で処理すると、凹部が浸食されて貫通孔が形成され、さらに貫通孔の大きさ、リング幅等を前記所望の大きさに調整することができる。
上記した第1の製造方法で得られるマイクロリング状無機酸化物粒子の大きさは、平均粒子径が概ね0.5〜20μmである。
When treated with an acid or a base, the recesses are eroded to form through holes, and the size of the through holes, the ring width, etc. can be adjusted to the desired size.
The average size of the microring-shaped inorganic oxide particles obtained by the first production method described above is approximately 0.5 to 20 μm.
第2の製造方法
第2の製造方法は、例えば、本願出願人の出願による特開2001−233611号公報、特開2004−203683号公報等に開示した中空シリカ系微粒子の製造方法に準拠して製造することができる。
Second Manufacturing Method The second manufacturing method is based on, for example, the manufacturing method of hollow silica-based fine particles disclosed in Japanese Patent Application Laid-Open No. 2001-233611, Japanese Patent Application Laid-Open No. 2004-203683, etc. filed by the applicant of the present application. Can be manufactured.
具体的には、シリカとシリカ以外の無機酸化物とからなる複合酸化物微粒子を核として使用する。このとき、必要に応じて10nm以下のシリカ被覆層(1)を形成してもよい。
そして、かかる核粒子からシリカ以外の無機酸化物を酸にて除去する。
Specifically, composite oxide fine particles composed of silica and an inorganic oxide other than silica are used as nuclei. At this time, a silica coating layer (1) of 10 nm or less may be formed as necessary.
Then, inorganic oxides other than silica are removed from the core particles with an acid.
酸でシリカ以外の無機酸化物を除去すると、スポンジのようなスカスカした粒子となり、これが前駆体となる。この前駆体に、さらに必要に応じてシリカ被覆層(2)を形成してもよい。 When an inorganic oxide other than silica is removed with an acid, it becomes a squirted particle such as a sponge, which becomes a precursor. If necessary, a silica coating layer (2) may be formed on this precursor.
得られたリング状粒子の前駆体を酸または塩基で処理するか、水熱処理することによって得ることができる。
上記において、シリカ以外の無機酸化物を酸にて除去した段階で表面に凹部を有する粒子が得られ、ついで酸または塩基で処理するか、水熱処理することによって貫通孔を有するマイクロリング状無機酸化物粒子が得られる。なお、このような処理することなく、単にシリカ被覆層を形成しただけでは、中空粒子となる。
The obtained ring-shaped particle precursor can be obtained by treating with an acid or base, or hydrothermally treating.
In the above, particles having concaves on the surface are obtained at the stage where inorganic oxides other than silica are removed with an acid, and then microring-like inorganic oxidation having through holes by treatment with acid or base or hydrothermal treatment Product particles are obtained. In addition, it will become a hollow particle only by forming a silica coating layer, without performing such a process.
酸(無機酸化物を溶解するものおよび、後段の処理に使用されるもの)およびアルカリとし種類としては、特に制限されないが、前記第1の製造方法で例示したものと同じものが挙げられる。 Although it does not restrict | limit especially as an acid (what melt | dissolves an inorganic oxide, and what is used for a process of a back | latter stage) and an alkali, The same thing as what was illustrated by the said 1st manufacturing method is mentioned.
この方法で得られるマイクロリング状無機酸化物粒子の大きさ(粒子外径)は、平均粒子径が概ね10〜500nm(0.5μm)である。
なお、以上のようにして貫通孔形成の処理を行う前の粒子は凡球状粒子であり、貫通孔形成後のリング粒子の厚みは平均外径(DO)以下となる。
As for the size (particle outer diameter) of the microring-shaped inorganic oxide particles obtained by this method, the average particle diameter is approximately 10 to 500 nm (0.5 μm).
In addition, the particles before the through-hole formation treatment as described above are approximately spherical particles, and the thickness of the ring particles after the through-hole formation is equal to or less than the average outer diameter (D O ).
こうして調製したマイクロリング状無機酸化物粒子を必要に応じて、前記したような有機ケイ素化合物で表面処理してもよい。
つぎに、本発明に係る透明被膜付基材について説明する。
The microring-shaped inorganic oxide particles thus prepared may be surface-treated with an organosilicon compound as described above, if necessary.
Below, the base material with a transparent film which concerns on this invention is demonstrated.
[透明被膜付基材]
本発明に係る透明被膜付基材は、基材上に透明被膜が形成された透明被膜付基材であって、該透明被膜が前記したマイクロリング状無機酸化物粒子とマトリックス成分とからなり、透明被膜中のマイクロリング状無機酸化物粒子の含有量が0.01〜80質量%の範囲にあ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 is a substrate with a transparent coating in which a transparent coating is formed on the substrate, and the transparent coating comprises the above-described microring-shaped inorganic oxide particles and a matrix component, The content of the microring-shaped inorganic oxide particles in the transparent film is in the range of 0.01 to 80% by mass.
基材
本発明に用いる基材としては、従来公知のものを特に制限なく使用することが可能であり、ガラス、ポリカーボネート(PC)、アクリル系樹脂、ポリエチレンテレフタレート(PET)、トリアセチルセルロース(TAC)、シクロポリオレフィン、ノルボルネン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が挙げられる。中でも樹脂系基材を好適に用いることができる。また、このような基材上に、他の被膜が形成された被膜付基材を用いこともできる。他の被膜としては従来公知のプライマー膜、ハードコート膜、高屈折率膜、導電性膜等が挙げられる。
Substrate As the substrate used in the present invention, conventionally known ones can be used without particular limitation, and glass, polycarbonate (PC), acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC) And plastic sheets such as cyclopolyolefin and norbornene, plastic films, and plastic panels. Among these, a resin base material can be preferably used. Moreover, the base material with a film in which another film was formed on such a base material can also be used. Examples of other coatings include conventionally known primer films, hard coat films, high refractive index films, and conductive films.
マイクロリング状無機酸化物粒子
マイクロリング状無機酸化物粒子としては前記のマイクロリング状無機酸化物粒子が用いられる。
Microring-shaped inorganic oxide particles The above-mentioned microring-shaped inorganic oxide particles are used as the microring-shaped inorganic oxide particles.
透明被膜中のマイクロリング状無機酸化物粒子の含有量が固形分として0.01〜80質量%、さらには0.05〜75質量%の範囲にあることが好ましい。
透明被膜中のマイクロリング状無機酸化物粒子の含有量が少ないと、耐擦傷性、膜強度等が不充分となる場合があり、多すぎてもマトリックス成分が少なく、基材との密着性、透明性、ヘーズ、耐擦傷性等が不充分となる場合がある。
The content of the microring-shaped inorganic oxide particles in the transparent film is preferably in the range of 0.01 to 80% by mass, more preferably 0.05 to 75% by mass as the solid content.
If the content of the microring-like inorganic oxide particles in the transparent film is small, scratch resistance, film strength, etc. may be insufficient, and if it is too much, there are few matrix components, adhesion to the substrate, Transparency, haze, scratch resistance, etc. may be insufficient.
本発明では、目的に応じて、前記マイクロリング状無機酸化物粒子以外に、従来公知の粒子を混合して用いることができる。例えば、低屈折率無機酸化物粒子、高屈折率無機酸化物粒子、導電性無機酸化物粒子等を使用することができる。 In the present invention, conventionally known particles can be mixed and used in addition to the microring-shaped inorganic oxide particles according to the purpose. For example, low refractive index inorganic oxide particles, high refractive index inorganic oxide particles, conductive inorganic oxide particles, and the like can be used.
マトリックス成分
マトリックス成分としては、有機樹脂系マトリックス成分が好適に用いられる。
有機樹脂系マトリックス成分として、具体的には塗料用樹脂として公知の紫外線硬化性樹脂、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(メタ)アクリル酸系樹脂、γ‐グリシルオキシ系樹脂、ウレタン系樹脂、ビニル系樹脂をはじめとする紫外線硬化性樹脂、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。
As the matrix component , an organic resin matrix component is preferably used.
As the organic resin-based matrix component, specifically, any of UV curable resins, thermosetting resins, thermoplastic resins, and the like known as coating resins can be employed. For example, conventionally used (meth) acrylic acid resins, γ-glycyloxy resins, urethane resins, vinyl resins and other UV curable resins, polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins , Thermoplastic resins such as acrylic resin, vinyl chloride resin, fluororesin, vinyl acetate resin, silicone rubber, urethane resin, melamine resin, silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated Examples thereof include thermosetting resins such as polyester resins and thermosetting acrylic resins. Further, it may be a copolymer or modified body of two or more of these resins.
これらの樹脂は、エマルジョン樹脂、水溶性樹脂、親水性樹脂であってもよい。さらに、熱硬化性樹脂、あるいは紫外線等電子線硬化型のものであってもよく、熱硬化性樹脂の場合、硬化触媒が含まれていてもよい。 These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, it may be a thermosetting resin or an electron beam curable type such as an ultraviolet ray, and in the case of a thermosetting resin, a curing catalyst may be included.
透明被膜中のマトリックス成分の含有量は固形分として20〜99.99質量%、さらには25〜99.95質量%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、基材との密着性、透明性、ヘーズ、耐擦傷性等が不充分となる場合がある。マトリックス成分の含有量が多すぎても、却って粒子の量が少なくなり耐擦傷性、膜強度等が不充分となる場合がある。しかしながら、マトリックス成分と基材調製時に重合反応する官能基を有する有機ケイ素化合物で表面処理を行った粒子を用いた場合、含有量が少なくても形成された塗膜は高い膜強度、耐擦傷性、密着性が増加する。 The content of the matrix component in the transparent coating is preferably in the range of 20 to 99.99% by mass, more preferably 25 to 99.95% by mass as the solid content. If the content of the matrix component is small, adhesion to the substrate, transparency, haze, scratch resistance, etc. may be insufficient. Even if the content of the matrix component is too large, the amount of particles may be reduced and the scratch resistance, film strength, etc. may be insufficient. However, when using particles that have been surface-treated with an organosilicon compound that has a functional group that undergoes a polymerization reaction during matrix preparation and base material preparation, the coating film formed has a high film strength and scratch resistance even if the content is small. , Adhesion increases.
本発明に係る透明被膜の膜厚(Th)は、使用するリング状粒子の大きさにもよるが、50nm〜20μm、さらには100nm〜20μmの範囲にあることが好ましい。但し、膜厚はリング状粒子の大きさを越えることはない。 The film thickness (Th) of the transparent coating according to the present invention is preferably in the range of 50 nm to 20 μm, more preferably 100 nm to 20 μm, although it depends on the size of the ring-shaped particles used. However, the film thickness does not exceed the size of the ring-shaped particles.
透明被膜の膜厚が薄過ぎると、耐擦傷性、膜強度が不充分となる場合がある。膜厚が厚すぎると、膜の厚さが不均一になったり、透明被膜にクラックやボイドを生じたり、このため膜強度が不充分となったり、プラスチック等の基材ではカーリング(湾曲あるいは反り)を生じる場合がある。 If the film thickness of the transparent coating is too thin, the scratch resistance and film strength may be insufficient. If the film thickness is too thick, the film thickness will be uneven, cracks and voids will occur in the transparent film, resulting in insufficient film strength, and curling (curving or warping in plastics and other substrates). ) May occur.
本発明では、透明被膜の膜厚(Th)が50nm〜20μmの範囲にある場合、マイクロリング状無機酸化物粒子の平均外径(DO)が10nm〜20μmの範囲にあり、平均外径(DO)と膜厚(Th)との比(DO)/(Th)が0.3〜1.0、好ましくは0.5〜0.9の範囲にある透明被膜とすることが好ましい。 In the present invention, when the film thickness (Th) of the transparent coating is in the range of 50 nm to 20 μm, the average outer diameter (D O ) of the microring-shaped inorganic oxide particles is in the range of 10 nm to 20 μm, and the average outer diameter ( A transparent film having a ratio (D O ) / (Th) of D O ) to film thickness (Th) in the range of 0.3 to 1.0, preferably 0.5 to 0.9 is preferable.
前記(DO)/(Th)が小さいと、基材との密着性を向上させる効果、硬度、耐擦傷性を向上させる効果等が不充分となり、前記(DO)/(Th)が大きくすると透明被膜表面に凹凸が形成される場合があり、耐擦傷性、鉛筆硬度等が低下する場合がある。(DO)/(Th)が前記範囲にあれば、より基材との密着性、硬度、耐擦傷性等に優れた透明被膜付基材を得ることができる。つぎに、本発明に係る透明被膜形成用塗布液について説明する。 If the (D O ) / (Th) is small, the effect of improving the adhesion to the substrate, the effect of improving the hardness, the scratch resistance and the like are insufficient, and the (D O ) / (Th) is large. Then, irregularities may be formed on the surface of the transparent coating, and scratch resistance, pencil hardness, etc. may be reduced. If (D O ) / (Th) is within the above range, a substrate with a transparent coating that is more excellent in adhesion to the substrate, hardness, scratch resistance and the like can be obtained. 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、前記マイクロリング状無機酸化物粒子とマトリックス形成成分と有機溶媒とからなることを特徴としている。
マイクロリング状無機酸化物粒子
マイクロリング状無機酸化物粒子としては前記したマイクロリング状無機酸化物粒子が用いられる。
[Transparent coating solution]
The coating liquid for forming a transparent film according to the present invention is characterized by comprising the microring-shaped inorganic oxide particles, a matrix-forming component, and an organic solvent.
Microring-shaped inorganic oxide particles The microring-shaped inorganic oxide particles described above are used as the microring-shaped inorganic oxide particles.
マトリックス形成成分
マトリックス形成成分としては、前記した有機樹脂系マトリックス形成成分が好適に用いられる。なお、熱硬化型、電子線硬化型などの硬化性樹脂の場合は、マトリックス形成成分は、反応前のモノマーであり、マトリックス成分は重合・反応したポリマーである。
Matrix-forming component As the matrix-forming component, the aforementioned organic resin-based matrix-forming component is preferably used. In the case of a curable resin such as a thermosetting type or an electron beam curable type, the matrix forming component is a monomer before the reaction, and the matrix component is a polymer obtained by polymerization and reaction.
有機溶媒
本発明に用いる有機溶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前記したマイクロリング状無機酸化物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。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、酢酸エチル、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、エチレングリコールイソプロピルエーテル、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、プロピレングリコールモノエ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、ブチルメチルケトン、シクロヘキサノン、メチルシクロヘキサノン、ジプロピルケトン、メチルペンチルケトン、ジイソブチルケトン、イソホロン、アセチルアセトン、アセト酢酸エステルなどのケトン類、トルエン、キシレン等が挙げられる。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。
Organic solvent The organic solvent 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 microring-shaped inorganic oxide particles described above. A conventionally known solvent can be used. 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 and butyl acetate; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Ethers such as monoethyl ether; acetone, methyl Ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, acetylacetone, ketones such as acetoacetate, toluene, xylene and the like. These may be used alone or in combination of two or more.
重合開始剤
本発明では、重合開始剤が含まれていてもよい。重合開始剤としては、公知のものを特に制限なく使用することが可能であり、例えば、ビス(2、4、6−トリメチルベンゾイル)フェニルフォスフィンオキサイド、ビス(2、6−ジメトキシベンゾイル)2、4、4−トリメチル-ペンチルフォスフィンオキサイド、2−ヒドロキシメチル-2-メチルフェニル-プロパン-1-ケトン、2、2-ジメトキシ-1、2-ジフェニルエタン-1-オン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン等が挙げられる。
Polymerization initiator In the present invention, a polymerization initiator may be contained. As the polymerization initiator, known ones can be used without particular limitation. For example, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2, 4,4-trimethyl-pentylphosphine oxide, 2-hydroxymethyl-2-methylphenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and the like.
塗布液組成
透明被膜形成用塗布液中のマトリックス形成成分とマイクロリング状無機酸化物粒子との合計濃度は特に制限されないが、固形分として1〜60質量%、さらには2〜50質量%の範囲にあることが好ましい。
The total concentration of the matrix-forming component and the microring-shaped inorganic oxide particles in the coating liquid composition transparent coating film-forming coating liquid is not particularly limited, but is in the range of 1 to 60 mass%, more preferably 2 to 50 mass% as the solid content. It is preferable that it exists in.
前記合計濃度が少なすぎると、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、経済性において不利である。
前記合計濃度が高すぎると、得られる透明被膜の厚さが不均一になる場合がある。
If the total concentration is too small, a predetermined film thickness may not be obtained by a single application, and if application and drying are repeated, adhesion and the like are insufficient, and this is disadvantageous in terms of economy.
When the said total density | concentration is too high, the thickness of the transparent film obtained may become non-uniform | heterogenous.
透明被膜形成用塗布液中のマイクロリング状無機酸化物粒子の濃度は、得られる透明被膜中のマイクロリング状無機酸化物粒子の含有量が前記したように固形分として0.01〜80質量%、さらには0.05〜75質量%の範囲となるように用いる。 The concentration of the microring-shaped inorganic oxide particles in the coating liquid for forming a transparent film is 0.01 to 80% by mass as the solid content of the microring-shaped inorganic oxide particles in the obtained transparent film as described above. Further, it is used so as to be in the range of 0.05 to 75% by mass.
また、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、得られる透明被膜中のマトリックス成分の含有量が前記したように固形分として20〜99.99質量%、さらには25〜99.95質量%の範囲となるように用いる。 The concentration of the matrix-forming component in the coating solution for forming a transparent film is 20 to 99.99% by mass as the solid content of the matrix component in the obtained transparent film as described above, and further 25 to 99.99%. It uses so that it may become the range of 95 mass%.
さらに具体的には、透明被膜形成用塗布液中のマイクロリング状無機酸化物粒子の濃度は、固形分として0.05〜48質量%、さらには0.1〜30質量%の範囲にあることが好ましい。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、固形分として0.2〜57質量%、さらには0.5〜54質量%の範囲にあることが好ましい。 More specifically, the concentration of the microring-shaped inorganic oxide particles in the coating liquid for forming a transparent film is in the range of 0.05 to 48% by mass, further 0.1 to 30% by mass as the solid content. Is preferred. The concentration of the matrix-forming component in the coating solution for forming a transparent film is preferably in the range of 0.2 to 57% by mass, more preferably 0.5 to 54% by mass as the solid content.
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。
得られた透明被膜の膜厚は、50nm〜20μmの範囲にあることが好ましい。
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.
The film thickness of the obtained transparent coating is preferably in the range of 50 nm to 20 μm.
[実施例]
以下、本発明を実施例により説明するが、本発明はこれら実施例に限定されるものではない。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[実施例1]
マイクロリング状無機酸化物粒子(1)の調製
シリカゾル(日揮触媒化成(株)製:CataloidTM SI−30、平均粒子径12nm、SiO2濃度30質量%)を噴霧乾燥装置の対向式2流体ノズルに供給し、処理液量120L/Hr、ノズル圧力0.40MPa、乾燥雰囲気温度50℃、湿度7.2VOl%、の条件下に噴霧乾燥して、表面に凹部を有する無機酸化物粒子を調製した。
[Example 1]
Preparation of micro ring-shaped inorganic oxide particles (1) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid ™ SI-30, average particle size 12 nm, SiO 2 concentration 30% by mass) opposed two-fluid nozzle of spray dryer And spray-dried under the conditions of a treatment liquid amount of 120 L / Hr, a nozzle pressure of 0.40 MPa, a drying atmosphere temperature of 50 ° C., and a humidity of 7.2% by volume to prepare inorganic oxide particles having concave portions on the surface. .
ついで、濃度25質量%のテトラエチルアンモニウムハイドロオキサイド水溶液10gに、表面に凹部を有する無機酸化物粒子1gを添加し、25℃で12時間撹拌した後、濾過し、充分に洗浄し、ついで120℃で10時間乾燥してマイクロリング状無機酸化物粒子(1)を調製した。得られたマイクロリング状無機酸化物粒子(1)について、走査型電子顕微鏡写真(SEM)を撮影し、平均外径(DO)、貫通孔の平均径(DI)を測定し、結果を表1に示す。また、かかるマイクロリング状無機酸化物粒子のSEM写真および一部を拡大したものを図2および3に示す。 Next, 1 g of inorganic oxide particles having concave portions on the surface was added to 10 g of an aqueous tetraethylammonium hydroxide solution having a concentration of 25% by mass, stirred for 12 hours at 25 ° C., filtered, washed thoroughly, and then washed at 120 ° C. Micro ring-shaped inorganic oxide particles (1) were prepared by drying for 10 hours. Scanning electron micrographs (SEM) of the obtained microring-shaped inorganic oxide particles (1) were taken, and the average outer diameter (D O ) and the average diameter of the through holes (D I ) were measured. Table 1 shows. Moreover, the SEM photograph of this micro ring-shaped inorganic oxide particle and what expanded a part are shown in FIG.
[実施例2]
マイクロリング状無機酸化物粒子(2)の調製
シリカゾル(日揮触媒化成(株)製:CataloidTM SI−550、平均粒子径5nm、SiO2濃度20質量%)100gに純水3900gを加えて98℃に加温し、この温度を保持しながら、SiO2として濃度1.5質量%の珪酸ナトリウム水溶液13345gとAl2O3としての濃度0.5質量%のアルミン酸ナトリウム水溶液13345gを添加して、SiO2・Al2O3粒子分散液(平均粒子径35nm)を得た。このときの反応液のpHは12.0であった。
[Example 2]
Preparation of micro ring-shaped inorganic oxide particles (2) 3900 g of pure water was added to 100 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid ™ SI-550, average particle size 5 nm, SiO 2 concentration 20% by mass) and 98 ° C. While maintaining this temperature, 13345 g of a sodium silicate aqueous solution having a concentration of 1.5% by mass as SiO 2 and 13345 g of a sodium aluminate aqueous solution having a concentration of 0.5% by mass as Al 2 O 3 were added, A SiO 2 .Al 2 O 3 particle dispersion (average particle size 35 nm) was obtained. The pH of the reaction solution at this time was 12.0.
ついで、SiO2として濃度1.5質量%の珪酸ナトリウム水溶液109830gとAl2O3としての濃度0.5質量%のアルミン酸ナトリウム水溶液36610gを添加して複合酸化物微粒子(2)(平均粒子径60nm)の分散液を得た。このときの反応液のpHは12.0であった。 Subsequently, 109830 g of a sodium silicate aqueous solution with a concentration of 1.5% by mass as SiO 2 and 36610 g of a sodium aluminate aqueous solution with a concentration of 0.5% by mass as Al 2 O 3 were added to form composite oxide fine particles (2) (average particle size) 60 nm) dispersion was obtained. The pH of the reaction solution at this time was 12.0.
ついで、限外濾過膜で洗浄して固形分濃度13質量%になった複合酸化物微粒子(2)の分散液500gに純水1125gを加え、さらに濃塩酸(濃度35.5質量%)を滴下してpH1.0とし、脱アルミニウム処理を行った。次いで、pH3の塩酸水溶液10Lと純水5Lを加えながら限外濾過膜で溶解したアルミニウム塩を分離・洗浄して固形分濃度20質量%のシリカ系中空微粒子の水分散液を得た。 Next, 1125 g of pure water was added to 500 g of the dispersion of the composite oxide fine particles (2) which had been washed with an ultrafiltration membrane to a solid content concentration of 13% by mass, and concentrated hydrochloric acid (concentration 35.5% by mass) was added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Subsequently, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated and washed to obtain an aqueous dispersion of silica-based hollow fine particles having a solid content concentration of 20% by mass.
ついで、シリカ系中空微粒子の水分散液150gと、純水500g、エタノール1750gおよび濃度28質量%のアンモニア水626gとの混合液を35℃に加温した後、エチルシリケート(SiO2濃度28質量%)47gを添加してシリカ被覆層を形成し、純水5Lを加えながら限外濾過膜で洗浄して固形分濃度20質量%のシリカ被覆層を形成したシリカ系中空微粒子の水分散液を得た。 Next, a mixed liquid of 150 g of silica-based hollow fine particle aqueous dispersion, 500 g of pure water, 1750 g of ethanol, and 626 g of ammonia water having a concentration of 28% by mass was heated to 35 ° C., and then ethyl silicate (SiO 2 concentration 28% by mass). ) 47 g was added to form a silica coating layer and washed with an ultrafiltration membrane while adding 5 L of pure water to obtain an aqueous dispersion of silica-based hollow fine particles having a silica coating layer with a solid content concentration of 20% by mass. It was.
つぎに、シリカ被覆層を形成したシリカ系中空微粒子分散液にアンモニア水を添加して分散液のpHを10.5に調整し、ついで200℃にて11時間熟成した後、常温に冷却した。ついで、水酸化ナトリウムを添加してpHを12に調整し、80℃で12時間撹拌した後、充分に洗浄し、固形分濃度20質量%のマイクロリング状無機酸化物粒子(2)の水分散液を得た。 Next, ammonia water was added to the silica-based hollow fine particle dispersion with the silica coating layer formed thereon to adjust the pH of the dispersion to 10.5, and then aged at 200 ° C. for 11 hours, and then cooled to room temperature. Next, sodium hydroxide is added to adjust the pH to 12, and the mixture is stirred for 12 hours at 80 ° C., and then sufficiently washed, and the water dispersion of microring-shaped inorganic oxide particles (2) having a solid content concentration of 20% by mass is obtained. A liquid was obtained.
得られたマイクロリング状無機酸化物粒子(2)について、走査型電子顕微鏡写真(SEM)を撮影し、平均外径(DO)、貫通孔の平均径(DI)を測定し、結果を表1に示す。また、SEM写真を図4に示す。 Scanning electron micrographs (SEM) of the obtained microring-shaped inorganic oxide particles (2) were taken, and the average outer diameter (D O ) and the average diameter of the through holes (D I ) were measured. Table 1 shows. An SEM photograph is shown in FIG.
[実施例3]
有機ケイ素化合物処理したマイクロリング状無機酸化物粒子(3)の調製
実施例1で調製したマイクロリング状無機酸化物粒子(固形分濃度10質量%)200gと純水400g、エタノール400gおよび濃度28質量%のアンモニア水0.68gを加えた後、メタクリル酸系有機ケイ素化合物 (3-メタクリロキシプロピルトリメトキシシラン、信越化学(株)製: KBM―503)30gを添加して液温を50℃に加温して、シリカ被覆層を形成し、エタノール5Lを加えながら限外濾過膜で洗浄して固形分濃度20質量%のシリカ被覆層を形成したマイクロリング状無機酸化物粒子(3)のエタノール分散液を得た。
[Example 3]
Preparation of microring-shaped inorganic oxide particles (3) treated with an organosilicon compound 200 g of microring-shaped inorganic oxide particles (solid content concentration 10% by mass) prepared in Example 1, 400 g of pure water, 400 g of ethanol, and a concentration of 28 masses. After adding 0.68 g of aqueous ammonia, 30 g of methacrylic acid organic silicon compound (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added to bring the liquid temperature to 50 ° C. Heating to form a silica coating layer, washing with an ultrafiltration membrane while adding 5 L of ethanol to form a microring-like inorganic oxide particle (3) ethanol having a silica coating layer with a solid content concentration of 20% by mass A dispersion was obtained.
透明被膜形成用塗布液(1)の調製
実施例1で調製したマイクロリング状無機酸化物粒子(1)をエタノールに分散させた固形分濃度20質量%のマイクロリング状無機酸化物粒子(1)分散液7.5gとアクリル樹脂(DIC(株)製: UNIDICTM 17−824−9 固形分濃度77質量%)17.53gおよびイソプロパノールとエチレングリコールモノブチルエーテルの1/1(重量比)混合溶媒25.0gとを充分に混合して透明被膜形成用塗布液(1)を調製した。
Preparation of coating liquid for forming transparent film (1) Microring-shaped inorganic oxide particles (1) having a solid content concentration of 20% by mass, in which microring-shaped inorganic oxide particles (1) prepared in Example 1 are dispersed in ethanol 7.5 g of dispersion and acrylic resin (made by DIC Corporation: UNIDIC ™ 17-824-9 solid content concentration 77 mass%) 17.53 g and 1/1 (weight ratio) mixed solvent 25 of isopropanol and ethylene glycol monobutyl ether A coating solution (1) for forming a transparent film was prepared by sufficiently mixing 0.0 g.
透明被膜付基材(F-1)の製造
透明被膜形成用塗布液(1)をPETフィルム(東洋紡(株)製:コスモシャインA−4300、厚さ:188μm、屈折率1.65、基材透過率90.0%、ヘーズ0.6%))にバーコーター法(バー#20)で塗布し、80℃で2分間乾燥した後、高圧水銀灯(120W/cm)を搭載した紫外線照射装置(日本電池(株)製UV照射装置: CS30L21−3)で600mJ/cm2照射して硬化させ、透明被膜付基材(F-1)を調製した。このときの透明被膜の厚さは8μmであった。
Production of substrate (F-1) with a transparent coating A coating solution (1) for forming a transparent coating was prepared by using a PET film (Toyobo Co., Ltd .: Cosmo Shine A-4300, thickness: 188 μm, refractive index 1.65, substrate (Transparency 90.0%, haze 0.6%)) by a bar coater method (bar # 20), dried at 80 ° C. for 2 minutes, and then an ultraviolet irradiation device (120 W / cm) equipped with a high-pressure mercury lamp (120 W / cm) A UV irradiation device manufactured by Nippon Battery Co., Ltd .: CS30L21-3) was irradiated and cured by 600 mJ / cm 2 to prepare a substrate with transparent coating (F-1). The thickness of the transparent film at this time was 8 μm.
得られた透明被膜の全光線透過率およびヘーズをヘーズメーター(日本電色工業(株)製)により測定し、結果を表2に示す。さらに、鉛筆硬度、可撓性、耐擦傷性および密着性を以下の方法および評価基準で評価し、結果を表2に示す。 The total light transmittance and haze of the transparent film thus obtained were measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.), and the results are shown in Table 2. Furthermore, pencil hardness, flexibility, scratch resistance and adhesion were evaluated by the following methods and evaluation criteria, and the results are shown in Table 2.
鉛筆硬度の測定
JIS−K−5400に準じて鉛筆硬度試験器により測定した。
耐擦傷性の測定
#0000スチールウールを用い、荷重500g/cm2で50回摺動し、膜の表面を目視観察し、以下の基準で評価し、結果を表に示す。
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 pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.
Measurement of scratch resistance Using # 0000 steel wool, sliding 50 times at a load of 500 g / cm 2 , visually observing the surface of the film, evaluating according to the following criteria, and the results are shown in the table.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
There are many scratches on the streak: △
The surface has been cut entirely: ×
密着性
透明被膜付基材(F-1)の表面にナイフで縦横1mmの間隔で11本の平行な傷を付け100個の升目を作り、これにセロハンテープ(登録商標)を接着し、ついで、セロハンテープ(登録商標)を剥離したときに被膜が剥離せず残存している升目の数を、以下の4段階に分類することによって密着性を評価した。結果を表2に示す。
残存升目の数100個 : ◎
残存升目の数93〜97個: ○
残存升目の数85〜92個: △
残存升目の数84個以下 : ×
Adhesive transparent film-coated substrate (F-1) surface is made with 11 parallel scratches with a knife at intervals of 1 mm in length and width to make 100 squares, and cellophane tape (registered trademark) is adhered to it, then Adhesiveness was evaluated by classifying the number of squares remaining after the cellophane tape (registered trademark) was peeled off into the following four stages. The results are shown in Table 2.
Number of remaining squares: ◎
93-97 remaining squares: ○
Number of remaining squares: 85-92: △
Number of remaining squares: 84 or less: ×
可撓性(ボイド)
透明被膜付基材(F-1)の幅1cm、長さ5cmの切片を作成し、切片の一端を固定し、他端を上下5cmの幅で湾曲させる操作を20回繰り返した後、目視観察し、以下の基準で評価した。
透明被膜は元のまま透明性を維持していた : ◎
透明被膜の透明性が僅かに低下していた : ○
透明被膜に白化が認められた : △
透明被膜にボイドの生成による白化が認められた : ×
Flexibility (void)
After making a section of transparent substrate (F-1) 1cm wide and 5cm long, fixing one end of the section and bending the other end up and down 5cm wide, repeat the observation 20 times, then visually observe And evaluated according to the following criteria.
The transparent film maintained its original transparency: ◎
The transparency of the transparent coating was slightly reduced: ○
Whitening was observed in the transparent film: △
Whitening due to void formation was observed in the transparent film: ×
[実施例5]
透明被膜形成用塗布液(2)の調製
実施例1において、マイクロリング状無機酸化物粒子(1)分散液3.75gとアクリル樹脂(DIC(株)製: UNIDICTM 17−824−9 固形分濃度(質量)77%)18.51gおよびイソプロパノールとエチレングリコールモノブチルエーテルの1/1(重量比)混合溶媒27.66gとを充分に混合して透明被膜形成用塗布液(2)を調製した。
[Example 5]
Preparation of coating liquid for forming transparent film (2) In Example 1, 3.75 g of the microring-shaped inorganic oxide particle (1) dispersion and acrylic resin (made by DIC Corporation: UNIDIC ™ 17-824-9 solid content) Concentration (mass) 77%) 18.51 g and 27.66 g of a 1/1 (weight ratio) mixed solvent of isopropanol and ethylene glycol monobutyl ether were sufficiently mixed to prepare a coating solution (2) for forming a transparent film.
透明被膜付基材(F-2)の製造
実施例4において、透明被膜形成用塗布液(2)を用いた以外は同様にして透明被膜付基材(F-2)を製造した。得られた透明被膜付基材(F-2)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (F-2) A substrate with transparent film (F-2) was produced in the same manner as in Example 4 except that the coating liquid for forming a transparent film (2) was used. For the obtained substrate with transparent coating (F-2), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent coating were evaluated. Show.
[実施例6]
透明被膜形成用塗布液(3)の調製
実施例1において、マイクロリング状無機酸化物粒子(1)分散液15.0gとアクリル樹脂(DIC(株)製: UNIDICTM 17−824−9 固形分濃度(質量)77%)15.58gおよびイソプロパノールとエチレングリコールモノブチルエーテルの1/1(重量比)混合溶媒19.42gとを充分に混合して透明被膜形成用塗布液(3)を調製した。
[Example 6]
Preparation of coating liquid for forming transparent film (3) In Example 1, 15.0 g of microring-shaped inorganic oxide particles (1) dispersion and acrylic resin (made by DIC Corporation: UNIDIC ™ 17-824-9 solid content) Concentration (mass) 77%) 15.58 g and 19.42 g of a mixed solvent of 1/1 (weight ratio) of isopropanol and ethylene glycol monobutyl ether were sufficiently mixed to prepare a coating solution (3) for forming a transparent film.
透明被膜付基材(F-3)の製造
実施例4において、透明被膜形成用塗布液(3)を用いた以外は同様にして透明被膜付基材(F-3)を製造した。得られた透明被膜付基材(F-3)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (F-3) A substrate with transparent film (F-3) was produced in the same manner as in Example 4 except that the coating liquid for forming a transparent film (3) was used. For the obtained substrate with transparent coating (F-3), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent coating were evaluated. Show.
[実施例7]
透明被膜形成用塗布液(4)の調製
実施例2で調製した固形分濃度20質量%のマイクロリング状無機酸化物粒子(2)の水分散液を限外濾過膜を用いて溶媒をエタノールに置換した固形分濃度20質量%のマイクロリング状無機酸化物粒子(2)アルコール分散液を調製した。
[Example 7]
Preparation of coating liquid for forming transparent film (4 ) The aqueous dispersion of microring-like inorganic oxide particles (2) having a solid content of 20% by mass prepared in Example 2 was used as the solvent in ethanol using an ultrafiltration membrane. A substituted microring-like inorganic oxide particle (2) alcohol dispersion having a solid content concentration of 20% by mass was prepared.
ついで、固形分濃度20質量%のマイクロリング状無機酸化物粒子(2)アルコール分散液100gにアクリル酸系有機ケイ素化合物 (3-アクリロキシプロピルトリメトキシシラン、信越化学(株)製:KBM-5103)3gを添加し、50℃で加熱処理を行い、再び限外濾過膜を用いて溶媒をエタノールに置換した固形分濃度20質量%の表面処理したマイクロリング状無機酸化物粒子(2)アルコール分散液を調製した。 Next, microring-shaped inorganic oxide particles having a solid content of 20% by mass (2) An acrylic acid-based organosilicon compound (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103) was added to 100 g of the alcohol dispersion. ) Add 3g, heat-treat at 50 ° C, and again use ultrafiltration membrane to replace the solvent with ethanol. Surface-treated microring-like inorganic oxide particles with a solid content of 20% by mass (2) Alcohol dispersion A liquid was prepared.
ついで、表面処理したマイクロリング状無機酸化物粒子(2)アルコール分散液75gとアクリル樹脂(DIC(株)製: UNIDICTM 17−824−9 固形分濃度77質量%)19.48gおよびイソプロパノールとエチレングリコールモノブチルエーテルの1/1(重量比)混合溶媒5.52gとを充分に混合して透明被膜形成用塗布液(4)を調製した。 Next, surface-treated microring-like inorganic oxide particles (2) Alcohol dispersion (75 g) and acrylic resin (manufactured by DIC Corporation: UNIDIC ™ 17-824-9, solid content concentration 77 mass%) 19.48 g and isopropanol and ethylene A coating liquid (4) for forming a transparent film was prepared by sufficiently mixing with 1/15 (weight ratio) mixed solvent of glycol monobutyl ether and 5.52 g.
透明被膜付基材(F-4)の製造
透明被膜形成用塗布液(4)をPETフィルム(東洋紡(製):コスモシャインA−4300、厚さ:188μm、屈折率1.65、基材透過率90.0%、ヘーズ0.6%))にバーコーター法(バー#20)で塗布し、80℃で2分間乾燥した後、高圧水銀灯(120W/cm)を搭載した紫外線照射装置(日本電池製UV照射装置: CS30L21−3)で600mJ/cm2照射して硬化させ、透明被膜付基材(F-4)を調製した。このときの透明被膜の厚さは7μmであった。得られた透明被膜付基材(F-4)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent coating (F-4) Coating solution (4) for forming a transparent coating was prepared by using a PET film (Toyobo Co., Ltd .: Cosmo Shine A-4300, thickness: 188 μm, refractive index 1.65, substrate transmission). (Approx. 90.0%, haze 0.6%)) by a bar coater method (bar # 20), dried at 80 ° C. for 2 minutes and then equipped with a high pressure mercury lamp (120 W / cm) (Japan) Battery UV irradiation apparatus: CS30L21-3) was cured by irradiation with 600 mJ / cm 2 to prepare a substrate with transparent coating (F-4). The thickness of the transparent film at this time was 7 μm. For the obtained substrate with transparent film (F-4), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film were evaluated, and the results are shown in Table 2. Show.
[実施例8]
透明被膜形成用塗布液(5)の調製
実施例7において、表面処理したマイクロリング状無機酸化物粒子(2)アルコール分散液50gとアクリル樹脂(DIC(株)製: UNIDICTM 17−824−9 固形分濃度77質量%)29.87gおよびイソプロパノールとエチレングリコールモノブチルエーテルの1/1(重量比)混合溶媒30.13gとを充分に混合して透明被膜形成用塗布液(5)を調製した。
[Example 8]
Preparation of coating liquid for forming transparent film (5) In Example 7, 50 g of surface-treated microring-shaped inorganic oxide particles (2) Alcohol dispersion liquid and acrylic resin (made by DIC Corporation: UNIDIC ™ 17-824-9) A coating solution (5) for forming a transparent film was prepared by sufficiently mixing 29.87 g (solid content concentration: 77% by mass) and 30.13 g of a mixed solvent of isopropanol and ethylene glycol monobutyl ether in 1/1 (weight ratio).
透明被膜付基材(F-5)の製造
実施例7において、透明被膜形成用塗布液(5)を用いた以外は同様にして透明被膜付基材(F-5)を製造した。得られた透明被膜付基材(F-5)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (F-5) A substrate with transparent film (F-5) was produced in the same manner as in Example 7 except that the coating liquid for forming a transparent film (5) was used. For the obtained substrate with transparent coating (F-5), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent coating were evaluated. Show.
[実施例9]
透明被膜形成用塗布液(6)の調製
実施例7において、表面処理したマイクロリング状無機酸化物粒子(2) アルコール分散液85gとアクリル樹脂(DIC(株)製 UNIDICTM 17−824−9 固形分濃度77質量%)14.68gおよびイソプロパノールとエチレングリコールモノブチルエーテルの1/1(重量比)混合溶媒1.39gとを充分に混合して透明被膜形成用塗布液(6)を調製した。
[Example 9]
Preparation of coating liquid for forming transparent film (6) In Example 7, surface-treated microring-like inorganic oxide particles (2) 85 g of an alcohol dispersion and acrylic resin (Unidic ™ 17-824-9 manufactured by DIC Corporation) A coating solution (6) for forming a transparent film was prepared by sufficiently mixing 14.68 g of a partial concentration of 77% by mass) and 1.39 g of a mixed solvent of 1/1 (weight ratio) of isopropanol and ethylene glycol monobutyl ether.
透明被膜付基材(F-6)の製造
実施例7において、透明被膜形成用塗布液(6)を用いた以外は同様にして透明被膜付基材(F-6)を製造した。得られた透明被膜付基材(F-6)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (F-6) A substrate with transparent film (F-6) was produced in the same manner as in Example 7 except that the coating liquid for forming a transparent film (6) was used. For the obtained substrate with transparent film (F-6), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film were evaluated. Show.
[実施例10]
透明被膜形成用塗布液(7)の調製
実施例3において、有機ケイ素化合物処理したマイクロリング状無機酸化物粒子(3)分散液3.75gとアクリル樹脂(共栄社化学(株)製: LIGHT−ACRYLATETM DPE−6A)12.83gとアクリル樹脂(共栄社化学(株)製: LIGHT−ACRYLATETM 1.6HX−A)1.42g、およびイソプロパノールとプロピレングリコールモノメチルエーテルの1/1(重量比)混合溶媒33.75gと光重合開始剤(CIBA・JAPAN KK製:IRGACURETM 184)0.86gを充分に混合して透明被膜形成用塗布液(7)を調製した。
[Example 10]
Preparation of coating liquid for forming transparent film (7) In Example 3, 3.75 g of microring-shaped inorganic oxide particles (3) dispersion treated with an organosilicon compound and an acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: LIGHT-ACRYLATE) TM DPE-6A) 12.83 g and acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: LIGHT-ACRYLATE TM 1.6HX-A) 1.42 g, and 1/1 (weight ratio) mixed solvent of isopropanol and propylene glycol monomethyl ether 33.75 g and 0.86 g of a photopolymerization initiator (CIBA / JAPAN KK: IRGACURE ™ 184) were sufficiently mixed to prepare a coating solution (7) for forming a transparent film.
透明被膜付基材(F-7)の製造
実施例7において、透明被膜形成用塗布液(7)を用いた以外は同様にして透明被膜付基材(F-7)を製造した。得られた透明被膜付基材(F-7)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (F-7) A substrate with transparent film (F-7) was produced in the same manner as in Example 7 except that the coating liquid for forming a transparent film (7) was used. For the obtained substrate with transparent coating (F-7), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent coating were evaluated. Show.
[実施例11]
透明被膜形成用塗布液(8)の調製
実施例3において、有機ケイ素化合物処理したマイクロリング状無機酸化物粒子(3)分散液7.5gとアクリル樹脂(共栄社化学(株)製: LIGHT−ACRYLATETM DPE−6A)12.15gとアクリル樹脂(共栄社化学(株)製: LIGHT−ACRYLATETM 1.6HX−A)1.35g、およびイソプロパノールとプロピレングリコールモノメチルエーテル14.5gおよびイソプロパノールとn−ブタノールの1/1(重量比)混合溶媒29.0gと光重合開始剤(CIBA・JAPAN KK製:IRGACURETM 184)0.81gを充分に混合して透明被膜形成用塗布液(8)を調製した。
[Example 11]
Preparation of coating liquid for forming transparent film (8) In Example 3, 7.5 g of microring-shaped inorganic oxide particles (3) dispersion treated with an organosilicon compound and acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: LIGHT-ACRYLATE) TM DPE-6A) 12.15 g, acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: LIGHT-ACRYLATE TM 1.6HX-A) 1.35 g, and isopropanol and propylene glycol monomethyl ether 14.5 g and isopropanol and n-butanol A coating solution (8) for forming a transparent film was prepared by sufficiently mixing 29.0 g of a 1/1 (weight ratio) mixed solvent and 0.81 g of a photopolymerization initiator (CIBA • JAPAN KK: IRGACURE ™ 184).
透明被膜付基材(F-8)の製造
実施例7において、透明被膜形成用塗布液(8)を用いた以外は同様にして透明被膜付基材(F-8)を製造した。得られた透明被膜付基材(F-8)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (F-8) A substrate with transparent film (F-8) was produced in the same manner as in Example 7 except that the coating liquid for forming a transparent film (8) was used. For the obtained substrate with transparent film (F-8), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film were evaluated. Show.
[実施例12]
透明被膜形成用塗布液(9)の調製
実施例3において、有機ケイ素化合物処理したマイクロリング状無機酸化物粒子(3)分散液0.08gとアクリル樹脂(共栄社化学(株)製: LIGHT−ACRYLATETM DPE−6A)13.49gとアクリル樹脂(共栄社化学(株)製: LIGHT−ACRYLATETM 1.6HX−A)1.50g、およびイソプロパノールとプロピレングリコールモノメチルエーテルの1/1(重量比)混合溶媒34.93gと光重合開始剤(CIBA・JAPAN KK製:IRGACURETM 184)0.90gを充分に混合して透明被膜形成用塗布液(9)を調製した。
[Example 12]
Preparation of coating liquid for forming transparent film (9) In Example 3, 0.08 g of microring-shaped inorganic oxide particles (3) dispersion treated with an organosilicon compound and acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: LIGHT-ACRYLATE) TM DPE-6A) 13.49 g and acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: LIGHT-ACRYLATE TM 1.6HX-A) 1.50 g, and 1/1 (weight ratio) mixed solvent of isopropanol and propylene glycol monomethyl ether 34.93 g and 0.90 g of a photopolymerization initiator (CIBA JAPAN KK: IRGACURE ™ 184) were sufficiently mixed to prepare a coating solution (9) for forming a transparent film.
透明被膜付基材(F-9)の製造
実施例7において、透明被膜形成用塗布液(9)を用いた以外は同様にして透明被膜付基材(F-9)を製造した。得られた透明被膜付基材(F-9)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (F-9) A substrate with transparent film (F-9) was produced in the same manner as in Example 7 except that the coating liquid for forming a transparent film (9) was used. For the obtained substrate with transparent film (F-9), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film were evaluated. Show.
[実施例13]
透明被膜形成用塗布液(10)の調製
実施例3において、有機ケイ素化合物処理したマイクロリング状無機酸化物粒子(3)分散液0.75gとアクリル樹脂(共栄社化学(株)製: LIGHT−ACRYLATETM DPE−6A)13.37gとアクリル樹脂(共栄社化学(株)製: LIGHT−ACRYLATETM 1.6HX−A)1.48g、およびイソプロパノールとプロピレングリコールモノメチルエーテルの1/1(重量比)混合溶媒34.4gと光重合開始剤(CIBA・JAPAN KK製:IRGACURETM 184)0.89gを充分に混合して透明被膜形成用塗布液(10)を調製した。
[Example 13]
Preparation of coating liquid for forming transparent film (10) In Example 3, 0.75 g of microring-shaped inorganic oxide particles (3) dispersion treated with an organosilicon compound and acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: LIGHT-ACRYLATE) TM DPE-6A) 13.37 g and acrylic resin (manufactured by Kyoeisha Chemical Co., Ltd .: LIGHT-ACRYLATE TM 1.6HX-A) 1.48 g, and 1/1 (weight ratio) mixed solvent of isopropanol and propylene glycol monomethyl ether 34.4 g and 0.89 g of a photopolymerization initiator (CIBA / JAPAN KK: IRGACURE ™ 184) were sufficiently mixed to prepare a coating solution (10) for forming a transparent film.
透明被膜付基材(F-10)の製造
実施例7において、透明被膜形成用塗布液(10)を用いた以外は同様にして透明被膜付基材(F-10)を製造した。得られた透明被膜付基材(F-10)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (F-10) A substrate with transparent film (F-10) was produced in the same manner as in Example 7 except that the coating liquid for forming a transparent film (10) was used. For the obtained substrate with transparent coating (F-10), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent coating were evaluated. Show.
[比較例1]
無機酸化物粒子(R1)の調製
シリカゾル(日揮触媒化成(株)製:CataloidTM S-20L、平均粒子径15nm、SiO2濃度20質量%)を噴霧乾燥装置の対向式2流体ノズルに供給し、処理液量20L/Hr、ノズル圧力0.38MPa、乾燥雰囲気温度120℃、湿度7.2VOl%、の条件下に噴霧乾燥して、無機酸化物粒子(R1)を調製した。得られた無機酸化物粒子(R1)には貫通孔はなく、平均粒径は5μmであった。
[Comparative Example 1]
Preparation of inorganic oxide particles (R1) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid ™ S-20L, average particle size 15 nm, SiO 2 concentration 20% by mass) is supplied to the opposed two-fluid nozzle of the spray dryer. Inorganic oxide particles (R1) were prepared by spray drying under the conditions of a treatment liquid amount of 20 L / Hr, a nozzle pressure of 0.38 MPa, a drying atmosphere temperature of 120 ° C., and a humidity of 7.2 VOL%. The obtained inorganic oxide particles (R1) had no through holes and had an average particle size of 5 μm.
[比較例2]
無機酸化物粒子(R2)の調製
シリカ・アルミナゾル(日揮触媒化成(株)製: Fine CataloidTM USBB−120、平均粒子径25nm、SiO2・Al2O3濃度20質量%、固形分中Al2O3含有量27質量%)100gに純水3900gを加えて98℃に加温し、この温度を保持しながら、SiO2として濃度1.5質量%の珪酸ナトリウム水溶液1750gとAl2O3としての濃度0.5質量%のアルミン酸ナトリウム水溶液1750gを添加して、SiO2・Al2O3粒子分散液(平均粒子径35nm)を得た。このときのMOX/SiO2モル比=0.2、であった。また、このときの反応液のpHは12.0であった。
[Comparative Example 2]
Preparation of inorganic oxide particles (R2) Silica-alumina sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Fine Catalyst ™ USBB-120, average particle size 25 nm, SiO 2 · Al 2 O 3 concentration 20 mass%, Al 2 in solid content 3900 g of pure water was added to 100 g of O 3 content (27 mass%) and heated to 98 ° C. While maintaining this temperature, 1750 g of an aqueous sodium silicate solution having a concentration of 1.5 mass% as SiO 2 and Al 2 O 3 17.5 g of a sodium aluminate aqueous solution having a concentration of 0.5% by mass was added to obtain a SiO 2 .Al 2 O 3 particle dispersion (average particle size 35 nm). The MO X / SiO 2 molar ratio at this time was 0.2. Further, the pH of the reaction solution at this time was 12.0.
ついで、SiO2として濃度1.5質量%の珪酸ナトリウム水溶液6,300gとAl2O3としての濃度0.5質量%のアルミン酸ナトリウム水溶液2,100gを添加して複合酸化物微粒子(2)(平均粒子径50nm)の分散液を得た。 Next, 6,300 g of a sodium silicate aqueous solution having a concentration of 1.5% by mass as SiO 2 and 2,100 g of a sodium aluminate aqueous solution having a concentration of 0.5% by mass as Al 2 O 3 were added to form composite oxide fine particles (2). A dispersion having an average particle diameter of 50 nm was obtained.
ついで、限外濾過膜で洗浄して固形分濃度13質量%になった複合酸化物微粒子(2)の分散液500gに純水1,125gを加え、さらに濃塩酸(濃度35.5質量%)を滴下してpH1.0とし、脱アルミニウム処理を行った。次いで、pH3の塩酸水溶液10Lと純水5Lを加えながら限外濾過膜で溶解したアルミニウム塩を分離・洗浄して固形分濃度20質量%のシリカ系中空微粒子の水分散液を得た。 Next, 1,125 g of pure water was added to 500 g of the dispersion of the composite oxide fine particles (2) having a solid concentration of 13% by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (concentration 35.5% by mass). Was dropped to pH 1.0, and dealumination was performed. Subsequently, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated and washed to obtain an aqueous dispersion of silica-based hollow fine particles having a solid content concentration of 20% by mass.
ついで、シリカ系中空微粒子の水分散液150gと、純水500g、エタノール1,750gおよび濃度28質量%のアンモニア水626gとの混合液を35℃に加温した後、エチルシリケート(SiO2濃度28質量%)140gを添加してシリカ被覆層を形成し、純水5Lを加えながら限外濾過膜で洗浄して固形分濃度20質量%のシリカ被覆層を形成したシリカ系中空微粒子の水分散液を得た。 Next, a mixed liquid of 150 g of silica-based hollow fine particle water dispersion, 500 g of pure water, 1,750 g of ethanol and 626 g of ammonia water having a concentration of 28% by mass was heated to 35 ° C., and then ethyl silicate (SiO 2 concentration 28 (Mass%) 140 g was added to form a silica coating layer, washed with an ultrafiltration membrane while adding 5 L of pure water to form a silica coating layer having a solid content concentration of 20 mass%. Got.
つぎに、シリカ被覆層を形成したシリカ系中空微粒子分散液にアンモニア水を添加して分散液のpHを10.5に調整し、ついで200℃にて11時間熟成した後、常温に冷却し、陽イオン交換樹脂(三菱化学(株)製:DIAIONTM SK1B)400gを用いて3時間イオン交換し、ついで、陰イオン交換樹脂(三菱化学(株)製:DIAIONTMSA20A)200gを用いて3時間イオン交換し、さらに陽イオン交換樹脂(三菱化学(株)製:DIAIONTM SK1B)200gを用い、80℃で3時間イオン交換して洗浄を行い、固形分濃度20質量%の無機酸化物粒子(R2)の水分散液を得た。得られた無機酸化物粒子(R2)には貫通孔はなく、平均粒径は60nmであった。 Next, ammonia water is added to the silica-based hollow fine particle dispersion with the silica coating layer formed therein to adjust the pH of the dispersion to 10.5, then aging at 200 ° C. for 11 hours, and then cooled to room temperature. Ion exchange using 400 g of cation exchange resin (Mitsubishi Chemical Corporation: DIAION ™ SK1B), followed by 3 hours using 200 g of anion exchange resin (Mitsubishi Chemical Corporation: DIAION ™ SA20A) Ion exchange was performed, and 200 g of cation exchange resin (Made by Mitsubishi Chemical Corporation: DIAION ™ SK1B) was used for ion exchange at 80 ° C. for 3 hours for washing, and inorganic oxide particles having a solid content concentration of 20% by mass ( An aqueous dispersion of R2) was obtained. The obtained inorganic oxide particles (R2) had no through holes and an average particle size of 60 nm.
[比較例3]
透明被膜形成用塗布液(R1)の調製
実施例4において、マイクロリング状無機酸化物粒子(1)の代わりに無機酸化物粒子(R1)を用いた以外は同様にして透明被膜形成用塗布液(R1)を調製した。
[Comparative Example 3]
Preparation of coating liquid for forming transparent film (R1) In Example 4, the coating liquid for forming transparent film was the same except that inorganic oxide particles (R1) were used instead of microring-shaped inorganic oxide particles (1). (R1) was prepared.
透明被膜付基材(RF-1)の製造
実施例4において、透明被膜形成用塗布液(R1)を用いた以外は同様にして透明被膜付基材(RF-1)を製造した。得られた透明被膜付基材(RF-1)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (RF-1) A substrate with transparent film (RF-1) was produced in the same manner as in Example 4 except that the coating liquid for transparent film formation (R1) was used. For the obtained substrate with transparent coating (RF-1), the thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent coating were evaluated. Show.
[比較例4]
透明被膜形成用塗布液(R2)の調製
実施例7において、マイクロリング状無機酸化物粒子(2)の代わりに比較例2で調製した無機酸化物粒子(R2)用いた以外は同様にして表面処理した無機酸化物粒子(R2) アルコール分散液を調製し、ついで、透明被膜形成用塗布液(R2)を調製した。
[Comparative Example 4]
Preparation of coating liquid for forming transparent film (R2) In Example 7, the surface was the same except that inorganic oxide particles (R2) prepared in Comparative Example 2 were used instead of microring-shaped inorganic oxide particles (2). Treated inorganic oxide particles (R2) An alcohol dispersion was prepared, and then a coating liquid (R2) for forming a transparent film was prepared.
透明被膜付基材(RF-2)の製造
実施例7において、透明被膜形成用塗布液(R2)を用いた以外は同様にして透明被膜付基材(RF-2)を製造した。得られた透明被膜付基材(RF-2)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (RF-2) A substrate with transparent film (RF-2) was produced in the same manner as in Example 7 except that the coating liquid for transparent film formation (R2) was used. For the obtained substrate with transparent film (RF-2), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film were evaluated. Show.
[比較例5]
透明被膜形成用塗布液(R3)の調製
実施例7において、マイクロリング状無機酸化物粒子(2)の代わりにシリカゾル(日揮触媒化成(株)製:CataloidTM SI−45P、平均粒子径45nm、SiO2濃度30質量%)を用いた以外は同様にして表面処理した無機酸化物粒子(R3) アルコール分散液を調製し、ついで、透明被膜形成用塗布液(R3)を調製した。
[Comparative Example 5]
Preparation of coating liquid for forming transparent film (R3) In Example 7, instead of the microring-shaped inorganic oxide particles (2), silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid ™ SI-45P, average particle size 45 nm, An inorganic oxide particle (R3) alcohol dispersion that was surface-treated in the same manner except that the SiO 2 concentration was 30% by mass) was prepared, and then a coating liquid for forming a transparent film (R3) was prepared.
透明被膜付基材(RF-3)の製造
実施例7において、透明被膜形成用塗布液(R3)を用いた以外は同様にして透明被膜付基材(RF-3)を製造した。得られた透明被膜付基材(RF-3)について、透明被膜の膜厚、全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表2に示す。
Production of substrate with transparent film (RF-3) A substrate with transparent film (RF-3) was produced in the same manner as in Example 7 except that the coating liquid for transparent film formation (R3) was used. With respect to the obtained substrate with transparent film (RF-3), the film thickness, total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film were evaluated. Show.
Claims (16)
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:0〜3の整数) The microring-like inorganic oxide particles according to claim 1 or 2, which are surface-treated 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 0 to 3)
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:0〜3の整数) The method for producing microring-like inorganic oxide particles according to claim 5 or 6, wherein the obtained microring-like inorganic oxide particles are surface-treated 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 0 to 3)
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JP2012106893A (en) * | 2010-11-18 | 2012-06-07 | Jgc Catalysts & Chemicals Ltd | Micro ring-like inorganic oxide particle in which fibrous bacterial cellulose penetrates through hole |
KR20180049907A (en) * | 2016-11-04 | 2018-05-14 | 전자부품연구원 | Hollow sphere structured metal oxide particle and preparing method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2011046122A1 (en) * | 2009-10-13 | 2011-04-21 | 曙ブレーキ工業株式会社 | Bead-like hollow particles, method for producing same, and friction material using the bead-like hollow particles |
JP2011102226A (en) * | 2009-10-13 | 2011-05-26 | Akebono Brake Ind Co Ltd | Bead-like hollow particle and method for producing same, and friction material using the bead-like hollow particle |
JP2012106893A (en) * | 2010-11-18 | 2012-06-07 | Jgc Catalysts & Chemicals Ltd | Micro ring-like inorganic oxide particle in which fibrous bacterial cellulose penetrates through hole |
KR20180049907A (en) * | 2016-11-04 | 2018-05-14 | 전자부품연구원 | Hollow sphere structured metal oxide particle and preparing method thereof |
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