JP2012006002A - Base material with transparent film, and coating liquid for forming transparent film - Google Patents
Base material with transparent film, and coating liquid for forming transparent film Download PDFInfo
- Publication number
- JP2012006002A JP2012006002A JP2010146928A JP2010146928A JP2012006002A JP 2012006002 A JP2012006002 A JP 2012006002A JP 2010146928 A JP2010146928 A JP 2010146928A JP 2010146928 A JP2010146928 A JP 2010146928A JP 2012006002 A JP2012006002 A JP 2012006002A
- Authority
- JP
- Japan
- Prior art keywords
- group
- inorganic oxide
- transparent film
- microring
- oxide particles
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000000576 coating method Methods 0.000 title claims description 143
- 239000011248 coating agent Substances 0.000 title claims description 141
- 239000007788 liquid Substances 0.000 title claims description 47
- 239000002245 particle Substances 0.000 claims abstract description 187
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 132
- 239000011159 matrix material Substances 0.000 claims abstract description 68
- 239000007787 solid Substances 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 96
- 239000000758 substrate Substances 0.000 claims description 81
- 239000000377 silicon dioxide Substances 0.000 claims description 46
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000005372 silanol group Chemical group 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000000468 ketone group Chemical group 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims 2
- 239000011800 void material Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- 239000006185 dispersion Substances 0.000 description 44
- 239000000243 solution Substances 0.000 description 32
- 238000004519 manufacturing process Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 19
- 229910004298 SiO 2 Inorganic materials 0.000 description 18
- 239000002585 base Substances 0.000 description 18
- 239000010419 fine particle Substances 0.000 description 17
- -1 polyethylene terephthalate Polymers 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 238000002834 transmittance Methods 0.000 description 14
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 13
- 229920002050 silicone resin Polymers 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- 239000002131 composite material Substances 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 9
- 238000000108 ultra-filtration Methods 0.000 description 9
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 8
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 4
- 229920002284 Cellulose triacetate Polymers 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 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 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-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
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
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- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 2
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- YUTHQCGFZNYPIG-UHFFFAOYSA-N 1-[2-(2-methylprop-2-enoyloxy)ethyl]cyclohexane-1,2-dicarboxylic acid Chemical compound CC(=C)C(=O)OCCC1(C(O)=O)CCCCC1C(O)=O YUTHQCGFZNYPIG-UHFFFAOYSA-N 0.000 description 1
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- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
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- 229940126062 Compound A Drugs 0.000 description 1
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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を用いた透明被膜付基材および透明被膜形成用塗布液とに関する。 The present invention relates to a substrate with a transparent coating using a microring-shaped inorganic oxide particle having a through-hole inside and a coating solution for forming a transparent coating.
さらに詳しくは、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透明被膜付基材および透明被膜形成用塗布液とに関する。 More specifically, 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, the particles and the matrix are separated. The present invention relates to a substrate with a transparent coating and a coating solution for forming a transparent coating that can be suitably used for improving scratch resistance, film strength, adhesion to a substrate, and the like.
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]基材と、該基材表面に形成された透明被膜を有する透明被膜付基材であって、該透明
被膜がマイクロリング状無機酸化物粒子と有機無機ハイブリッドマトリックス成分とを含み、かつ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％の範囲にある透明被膜付基材。
[2]前記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、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[1]の透明被膜付基材。
[3]前記マイクロリング状無機酸化物粒子を構成する無機酸化物が、シリカ系無機酸化物
である[1]または[2]の透明被膜付基材。
[4]前記マイクロリング状無機酸化物粒子が下記式(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]〜[3]の透明被膜付基材。
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）
[5]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、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[4]の透明被膜付基材。
[6]前記透明被膜の膜厚（Ｔh）が５０ｎｍ〜２０μｍの範囲にある[1]〜[5]の透明被膜付基材。
[7]前記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の範囲にある[1]〜[6]の透明被膜付基材。
[8]前記有機無機ハイブリッドマトリックス成分が、下記式(2)で表される有機珪素化合物の加水分解重縮合物を含む[1]〜[7]の透明被膜付基材。
Ｒn-ＳiＸ4-n （２）
（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、シラノール基、ハロゲン、水素から選ばれる少なくとも１種であり、ｎは１〜３の整数を示す）
[9]前記有機無機ハイブリッドマトリックス成分が、さらに下記式(3)で表される有機珪素化合物の加水分解重縮合物を含む[8]の透明被膜付基材。
ＳiＸ4 （３）
（但し、式中、Ｘは炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素から選ばれる少なくとも１種である）
[10]マイクロリング状無機酸化物粒子と有機無機ハイブリッドマトリックス形成成分と有機溶媒とを含む透明被膜形成用塗布液。
[11]前記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、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[10]の透明被
膜形成用塗布液。
[12]前記マイクロリング状無機酸化物粒子を構成する無機酸化物が、シリカ系無機酸化物である[10]または[11]の透明被膜形成用塗布液。
[13]前記マイクロリング状無機酸化物粒子が下記式(1)で表される有機ケイ素化合物で表
面処理されている[10]〜[12]の透明被膜形成用塗布液。
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は炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素から選ばれる少なくとも１種を示し、ｎは０〜３の整数を示す）
[14]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、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[13]の透明被膜形成用塗布液。
[15]前記有機無機ハイブリッドマトリックス形成成分が、下記式(2)で表される有機珪素
化合物の加水分解物を含む[10]〜[14]の透明被膜形成用塗布液。
Ｒn-ＳiＸ4-n （２）
（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は炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素から選ばれる少なくとも１種を示す。ｎは１〜３の整数を示す）
[16]前記有機無機ハイブリッドマトリックス成分が、さらに下記式(3)で表される有機珪
素化合物の加水分解物を含む[15]の透明被膜形成用塗布液。
ＳiＸ4 （３）
（但し、式中、Ｘは炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素から選ばれる少なくとも１種を示す）
[17]前記マイクロリング状無機酸化物粒子の濃度が固形分として０．０００１〜４８質量％の範囲にあり、有機無機ハイブリッドマトリックス形成成分の濃度が固形分として０．２〜５７質量％の範囲にあり、全固形分濃度が１〜６０質量％の範囲にある[10]〜[16]の透明被膜形成用塗布液。
The requirements of the present invention are as follows.
[1] A substrate with a transparent coating having a substrate and a transparent coating formed on the surface of the substrate, the transparent coating comprising microring-shaped inorganic oxide particles and an organic-inorganic hybrid matrix component, and A substrate with a transparent coating, wherein the content of microring-shaped inorganic oxide particles in the transparent coating is in the range of 0.01 to 80% by mass as a solid content.
[2] The average diameter (D O ) of the microring-shaped inorganic oxide particles is in the range of 10 nm to 20 μm, the average diameter of the through holes (D I ) is in the range of 1 nm to 12 μm, and the ring width (W The substrate with a transparent coating according to [1], wherein the ratio (W R ) / (D O ) of R 1 ) to the average outer diameter (D O ) is in the range of 0.2 to 0.45.
[3] The transparent film-coated substrate according to [1] or [2], wherein the inorganic oxide constituting the microring-shaped inorganic oxide particles is a silica-based inorganic oxide.
[4] The substrate with a transparent coating according to [1] to [3], wherein the 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)
[5] R may be halogen-substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, amino group, amide group, epoxy group, carboxyl group, ketone group, ether group, aryl [4] The substrate with a transparent coating, comprising at least one organic functional group selected from a group, heteroaryl group, phosphate group, halogen group, thiol group, and sulfonyl group.
[6] The substrate with a transparent film according to [1] to [5], wherein the film thickness (T h ) of the transparent film is in the range of 50 nm to 20 μm.
[7] 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 ratio of the average outer diameter (D O ) to the film thickness (T h ) (D O ) / [1] to [6] A substrate with a transparent coating, wherein (T h ) is in the range of 0.3 to 1.0.
[8] The substrate with a transparent coating according to [1] to [7], wherein the organic-inorganic hybrid matrix component contains a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (2).
R n -SiX 4-n (2)
(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 or a silanol group) , Halogen or hydrogen, and n represents an integer of 1 to 3)
[9] The substrate with a transparent coating according to [8], wherein the organic-inorganic hybrid matrix component further contains a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (3).
SiX 4 (3)
(In the formula, X is at least one selected from an alkoxy group having 1 to 4 carbon atoms, a silanol group, halogen, and hydrogen)
[10] A coating solution for forming a transparent film, comprising microring-shaped inorganic oxide particles, an organic-inorganic hybrid matrix-forming component, and an organic solvent.
[11] The average outer diameter (D O ) of the microring-shaped inorganic oxide particles is in the range of 10 nm to 20 μm, the average diameter of the through holes (D I ) is in the range of 1 nm to 12 μm, and the ring width (W The coating solution for forming a transparent film according to [10], wherein the ratio (W R ) / (D O ) of R ) to the average outer diameter (D O ) is in the range of 0.2 to 0.45.
[12] The coating solution for forming a transparent film according to [10] or [11], wherein the inorganic oxide constituting the microring-shaped inorganic oxide particles is a silica-based inorganic oxide.
[13] The coating liquid for forming a transparent film according to [10] to [12], wherein the 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. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, At least one selected from halogen and hydrogen, and n represents an integer of 0 to 3)
[14] R is an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, amino group, amide group, epoxy group, carboxyl group, ketone group, ether group, aryl [13] The coating solution for forming a transparent film, comprising 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.
[15] The coating liquid for forming a transparent film according to [10] to [14], wherein the organic-inorganic hybrid matrix forming component contains a hydrolyzate of an organic silicon compound represented by the following formula (2).
R n -SiX 4-n (2)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms or a silanol group. And at least one selected from halogen and hydrogen, n represents an integer of 1 to 3)
[16] The coating liquid for forming a transparent film according to [15], wherein the organic-inorganic hybrid matrix component further contains a hydrolyzate of an organic silicon compound represented by the following formula (3).
SiX 4 (3)
(Wherein, X represents at least one selected from an alkoxy group having 1 to 4 carbon atoms, a silanol group, halogen, and hydrogen)
[17] The concentration of the microring-shaped inorganic oxide particles is in the range of 0.0001 to 48% by mass as the solid content, and the concentration of the organic-inorganic hybrid matrix forming component is in the range of 0.2 to 57% by mass as the solid content. The coating solution for forming a transparent film according to [10] to [16], wherein the total solid content concentration is in the range of 1 to 60% by mass.
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有機無機ハイブリッドマトリックス形成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 organic-inorganic hybrid matrix-forming component penetrates into the through-holes to form a transparent film, and even when stress is applied. Uses microring-shaped inorganic oxide particles that can be suitably used for improving scratch resistance, film strength, adhesion to a substrate, etc., without causing separation or voids between matrices. The substrate with a transparent coating and the coating solution for forming a transparent coating can be provided.
有機無機ハイブリットマトリックスを併用することで、有機無機ハイブリッドマトリックス併用することで、耐熱性に優れ、硬度にも優れた透明被膜を得ることができる。 By using the organic / inorganic hybrid matrix in combination, a transparent coating having excellent heat resistance and hardness can be obtained by using the organic / inorganic hybrid matrix together.
以下、先ず、本発明に係る透明被膜付基材について説明する。
透明被膜付基材
本発明に係る透明被膜付基材は、基材と、該基材表面に形成された透明被膜を有する透明被膜付基材であって、該透明被膜がマイクロリング状無機酸化物粒子と有機無機ハイブリッドマトリックス成分とを含み、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している。
Hereinafter, first, the substrate with a transparent coating according to the present invention will be described.
A substrate with a transparent coating The substrate with a transparent coating according to the present invention is a substrate with a transparent coating having a substrate and a transparent coating formed on the surface of the substrate, and the transparent coating is a microring-shaped inorganic oxide It is characterized in that the content of the microring-like inorganic oxide particles in the transparent coating is in the range of 0.01 to 80% by mass as a solid content.
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
本発明に用いるマイクロリング状無機酸化物粒子は、平均外径（ＤO）が１０ｎｍ〜２
０μｍ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。
Microring- shaped inorganic oxide particles The microring-shaped inorganic oxide particles used in the present invention have an average outer diameter (D O ) of 10 nm to 2 nm.
In the range of 0 .mu.m, the range the average diameter (D I) of 1nm~12μm the through hole, the ratio of the ring width (W R) and the average outer diameter (D O) (W R) / (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。 In FIG. 1, the plane model figure of the micro ring-shaped inorganic oxide particle which concerns on this invention is shown.
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。 In FIG. 1, D O represents the outer diameter, D I represents the diameter of the through hole, and WR represents the ring width.
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。
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シリカ系複合酸化物が好ましい。
シリカ系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。シリカ系複合酸化物の場合、シリカの含有量が５０質量％以上のものが好ましい。
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.
In the present invention, silica-based composite oxide composed of silica or silica and an oxide other than silica is preferable.
Examples of the silica-based composite oxide include silica / alumina, silica / zirconia, and silica / boria. In the case of a silica-based 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シリカ系無機酸化物以外の酸化物、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。 With such an oxide or composite oxide other than silica or a silica-based inorganic oxide containing silica as a main component, desired microring-shaped inorganic oxide particles may not always be obtained.
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は後述する実施例１、図４は実施例７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 described later, and FIG. 4 is an electron micrograph (SEM) of the microring-shaped particles obtained in Example 7.
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 of forming ring-shaped particles 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 in the range of usually 3 to 100 nm, more preferably 5 to 50 nm.
本発明に用いるマイクロリング状無機酸化物粒子の平均外径（ＤO）は１０ｎｍ〜２０
μｍ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 used in the present invention is 10 nm to 20
It is in the range of 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〜１
０μｍ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。
The average diameter (D I ) of the through holes depends on the outer diameter, but is 1 nm to 12 μm, more preferably 2 nm to 1
It is preferably in the range of 0 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、本発明の耐擦傷性、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 tabular grains, and the effect of improving the scratch resistance, film strength, adhesion to the substrate, etc. of the present invention 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. (W R )
If (/ D O ) is too small, the ring width is narrow relative to the particle diameter, so the particle strength is low, and sufficient film strength, scratch resistance, etc. may not be obtained even when used for a transparent coating. 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、マトリックス形成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。 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, by performing surface treatment with an organosilicon compound having a functional group that undergoes a polymerization reaction at the time of preparing the matrix forming component and the base material, the film strength, scratch resistance, and adhesion of the formed coating film may be increased. Be expected.
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。 As the organosilicon compound, those represented by the following formula (1) are preferable.
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、水素から選ばれる少なくとも１種を示す。ｎは０〜３の整数であり、好ましくは１〜３の整数である。
R n -SiX 4-n (1 )
However, in formula, R is a C1-C10 unsubstituted or substituted hydrocarbon group, Comprising: You may mutually be same or different. X: At least one selected from an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, and 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が高く発現される。 R is an optionally 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-shaped 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) acrylooxyethyltriethoxysilane, γ- (meth) acrylooxypropyltrimethoxysilane,
γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane,
Butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3 -Ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-amino Propylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Emissions, .gamma.-mercaptopropyltrimethoxysilane,
Examples include trimethylsilanol and methyltrichlorosilane.
これらの有機ケイ素化合物は、後述するマトリックス成分との反応性に鑑み、適宜選択される。 These organosilicon compounds are appropriately selected in view of reactivity with a matrix component described later.
このような有機ケイ素化合物で表面処理されていると、後述する有機無機ハイブリッドマトリックス成分との親和性が高く、マイクロリング状粒子のリング部分のマトリックスとの接着性を高め、その結果、硬度に優れた透明被膜を得ることができる。 When surface-treated with such an organosilicon compound, the affinity with the organic / inorganic hybrid matrix component described later is high, and the adhesion to the matrix of the ring portion of the micro-ring-like particles is enhanced, resulting in excellent hardness. A transparent film can be obtained.
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。
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、本発明に用いる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。
(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。
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 manufacturing method of the micro ring-shaped inorganic oxide particles used for the following, the following method is preferable.
(First manufacturing 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。 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.
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、破壊した破片状の粒子となる場合がある。 When the temperature of the spray-drying atmosphere is less than 20 ° C., a desired through-hole or recess may not be formed, and when it exceeds 150 ° C., the ring may become too thin or may be broken pieces.
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。 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%.
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。 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。 The spraying method is not particularly limited, and conventionally known methods such as an atomizer method and a nozzle method can be employed.
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 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。 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.
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。
(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。
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.
(Second manufacturing method)
The second production method can be produced in accordance with, for example, the production method of hollow silica-based fine particles disclosed in Japanese Patent Application Laid-Open Nos. 2001-233611 and 2004-203683 filed by the applicant of the present application. .
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。 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.
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。 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、表面に凹部を有する多孔質粒子となり、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 inorganic oxides other than silica are removed with an acid, porous particles having concave portions on the surface are formed, and this 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。 The obtained ring-shaped particle precursor can be obtained by treating with an acid or base, or hydrothermally treating.
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。 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）およびアルカリの種類としては、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。 The acid (dissolving the inorganic oxide and the one used for the subsequent treatment) and the kind of alkali are not particularly limited, but the same as those exemplified in the first production method can be 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。 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).
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。 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。 The microring-shaped inorganic oxide particles thus prepared may be surface-treated with an organosilicon compound as described above, if necessary.
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は固形分として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。 The content of the microring-shaped inorganic oxide particles in the transparent coating is preferably in the range of 0.01 to 80% by mass, more preferably 0.05 to 75% by mass as the solid content.
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。 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.
有機無機ハイブリッドマトリックス成分
本発明に用いる有機無機ハイブリッドマトリックス成分としては有機珪素化合物が用いられる。なかでも、下記式(2)で表される加水分解性有機珪素化合物の加水分解重縮合物
であることが好ましい。
Ｒn-ＳiＸ4-n （２）
（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、シラノール基、ハロゲン、水素から選ばれる少なくとも１種であり、ｎは１〜３の整数を示す）
このような有機珪素化合物としては前記した式(2)で表される有機珪素化合物のｎ＝１
，２，３の有機珪素化合物が挙げられる。
Organic-inorganic hybrid matrix component An organic silicon compound is used as the organic-inorganic hybrid matrix component used in the present invention. Among these, a hydrolysis polycondensate of a hydrolyzable organosilicon compound represented by the following formula (2) is preferable.
R n -SiX 4-n (2)
(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 or a silanol group) , Halogen or hydrogen, and n represents an integer of 1 to 3)
As such an organosilicon compound, n = 1 of the organosilicon compound represented by the above formula (2)
, A few organosilicon compounds.
本発明では、前記有機無機ハイブリッドマトリックス成分が、さらに下記式(3)で表さ
れる有機珪素化合物の加水分解重縮合物を含んでいてもよい。
ＳiＸ4 （３）
（但し、式中、Ｘ：炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素から選ばれる少なくとも１種）
具体的には、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、テトラブトキシシランなどの加水分解重縮合物が挙げられる。
In the present invention, the organic-inorganic hybrid matrix component may further contain a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (3).
SiX 4 (3)
(Wherein, X: at least one selected from an alkoxy group having 1 to 4 carbon atoms, a silanol group, halogen, and hydrogen)
Specific examples include hydrolytic polycondensates such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
このような有機珪素化合物の加水分解重縮合物の含有量は有機無機ハイブリッドマトリックス成分中に固形分として１〜５０質量％、さらには２〜３０質量％の範囲にあることが好ましい。 The content of such a hydrolyzed polycondensate of an organosilicon compound is preferably in the range of 1 to 50% by mass, more preferably 2 to 30% by mass as a solid content in the organic-inorganic hybrid matrix component.
本発明では、有機無機ハイブリッドマトリックス成分として、さらに下記式(4)で表さ
れる２官能シリコン樹脂を用いることができる。
In the present invention, a bifunctional silicone resin represented by the following formula (4) can be used as the organic / inorganic hybrid matrix component.
（但し、Ｒ1〜Ｒ5は置換、非置換の炭素数１〜６のアルキル基、Ｘ1、Ｘ2はアクリル基、メタクリル基、グリシジル基、を表し、同じであってもよく、異なっていてもよい。ｎは１〜１０の正数を示す）
具体的には、ジアクリレート変成ポリシロキサン、ジメタクリル変成ポリシロキサン、ジグリシジル変成ポリシロキサン、ジポリエステル変性ポリシロキサン、ジポリエーテル変性ポリシロキサン等、およびこれらの混合物が挙げられる。このとき、２官能シリコン樹脂はモノマーを用いることが好ましい。
このような２官能シリコン樹脂を用いると、撥水性、撥油性、耐指紋付着性、耐薬品性等に優れ、１官能シリコン樹脂の脱離（以下、ブリードアウトということがある）を抑制することができ、撥水性、撥油性、耐指紋付着性、耐薬品性を長期に維持することができる。
(However, R 1 to R 5 represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X 1 and X 2 represent an acryl group, a methacryl group, and a glycidyl group, and may be the same or different. (N represents a positive number of 1 to 10)
Specific examples include diacrylate-modified polysiloxane, dimethacryl-modified polysiloxane, diglycidyl-modified polysiloxane, dipolyester-modified polysiloxane, dipolyether-modified polysiloxane, and the like. At this time, it is preferable to use a monomer for the bifunctional silicone resin.
Use of such a bifunctional silicone resin is excellent in water repellency, oil repellency, fingerprint resistance, chemical resistance, etc., and suppresses detachment of monofunctional silicone resin (hereinafter sometimes referred to as bleed out). It is possible to maintain water repellency, oil repellency, fingerprint resistance, and chemical resistance for a long time.
このような２官能シリコン樹脂の含有量は有機無機ハイブリッドマトリックス成分中に固形分として０．１〜１０質量％、さらには０．５〜８質量％の範囲にあることが好ましい。 The content of such a bifunctional silicon resin is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 8% by mass as a solid content in the organic-inorganic hybrid matrix component.
さらに、本発明では、有機無機ハイブリッドマトリックス成分として下記式(5)で表さ
れる１官能シリコン樹脂を用いることができる。
Furthermore, in the present invention, a monofunctional silicon resin represented by the following formula (5) can be used as the organic-inorganic hybrid matrix component.
（但し、Ｒ1〜Ｒ5は置換、非置換の炭素数１〜３のアルキル基、Ｘはアクリル基、メタクリル基、グリシジル基、を表す。ｎは１〜２０の正数を示す）
具体的には、アクリル変性ポリシロキサン、メタクリル変性ポリシロキサン、ポリエーテル変性ポリシロキサン、グリシジル変成ポリシロキサン、ポリエステル変性ポリシロキサン、ポリエーテル変性ポリシロキサン等およびこれらの混合物が挙げられる。例えば、片末端（メタ）アクリルシリコン、片末端グリシジルシリコンオイル等が挙げられる。また、アクリル系シリコン樹脂モノマーまたはそのポリマー（シリコンオイル）、エポキシ系シリコン樹脂モノマーまたはそのポリマー（シリコンオイル）も好適である。このとき、１官能シリコン樹脂としてはモノマーを用いることが好ましい。
(However, R 1 to R 5 represents a substituted, unsubstituted alkyl group having 1 to 3 carbon atoms, X is an acrylic group, a methacrylic group, a positive number of .n 1 to 20 representing the glycidyl group)
Specific examples include acrylic-modified polysiloxane, methacryl-modified polysiloxane, polyether-modified polysiloxane, glycidyl-modified polysiloxane, polyester-modified polysiloxane, polyether-modified polysiloxane, and the like. For example, one terminal (meth) acrylic silicon, one terminal glycidyl silicone oil, etc. are mentioned. An acrylic silicone resin monomer or a polymer thereof (silicon oil) and an epoxy silicone resin monomer or a polymer thereof (silicon oil) are also suitable. At this time, it is preferable to use a monomer as the monofunctional silicone resin.
このような１官能シリコン樹脂を用いると、撥水性、撥油性、耐指紋付着性、耐薬品性等に優れた透明被膜を得ることができる。また、１官能シリコン樹脂を前記２官能シリコン樹脂と併用すると１官能シリコン樹脂の脱離を抑制することができ、撥水性、撥油性、耐指紋付着性、耐薬品性を長期に維持することができる。 When such a monofunctional silicon resin is used, a transparent film excellent in water repellency, oil repellency, fingerprint resistance, chemical resistance and the like can be obtained. Further, when the monofunctional silicone resin is used in combination with the bifunctional silicone resin, the detachment of the monofunctional silicone resin can be suppressed, and water repellency, oil repellency, fingerprint resistance, and chemical resistance can be maintained for a long time. it can.
このような１官能シリコン樹脂の含有量は有機無機ハイブリッドマトリックス成分中に固形分として０．１〜１０質量％、さらには０．５〜８質量％の範囲にあることが好ましい。 The content of such monofunctional silicone resin is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 8% by mass as a solid content in the organic-inorganic hybrid matrix component.
透明被膜中の有機無機ハイブリッド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。有機無機ハイブリッド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。有機無機ハイブリッド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、有機無機ハイブリッド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 organic-inorganic hybrid matrix component in the transparent film 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 organic / inorganic hybrid matrix component is small, adhesion to the substrate, transparency, haze, scratch resistance, etc. may be insufficient. Even if the content of the organic-inorganic hybrid matrix component is too large, the amount of particles may be decreased, and the scratch resistance, film strength, and the like may be insufficient. However, when using particles that have been surface-treated with an organic silicon compound having a functional group that undergoes a polymerization reaction during the preparation of the organic / inorganic hybrid matrix component and the base material, the formed coating film has high film strength, even if the content is small. Increases scratch resistance and adhesion.
このような有機無機ハイブリッドマトリックスを使用することで、硬度、耐熱性に優れた透明被膜を得ることができる。 By using such an organic-inorganic hybrid matrix, a transparent film having excellent hardness and heat resistance can be obtained.
かかる有機無機ハイブリッドマトリックスを使用することで、有機樹脂マトリックスと比べて耐熱性、硬度等は優た被膜を形成できる。 By using such an organic-inorganic hybrid matrix, it is possible to form a film having excellent heat resistance, hardness and the like as compared with the organic resin matrix.
本発明では、有機無機ハイブリッドマトリックス成分に加えてＯＨ基を有する有機樹脂を使用することができる。ＯＨ基を有する有機樹脂としては、２-ヒドロキシエチルアク
リレート、２-ヒドロキシプロピルアクリレート、２-ヒドロキシブチルアクリレート、２-ヒドロキシエチルメタクリレート、２-ヒドロキシプロピルメタクリレート、メタクリル酸、２−メタクリロイロキシエチルコハク酸、２−メタクリロイロキシエチルヘキサヒドロフタル酸、２−メタクリロイロキシエチルアシッドホスフェート、グリセリンジメタクリレート、２-ヒドロキシ−３−アクリロイロキシプロピルメタクリレート等が挙げられ
る。このようなＯＨ基を有する有機樹脂を有機無機ハイブリッドマトリックス成分と混合して使用すると基材の種類によっても異なるが、密着性に優れた透明被膜を得ることができる。基材によっては密着性が不良になる場合があり、たとえば、基材がＴＡＣの場合、２-ヒドロキシエチルアクリレートの（少量の）使用によって密着性を向上させることが
可能となる。かかる有機樹脂を使用する場合、必要に応じて触媒を含んでいてもよい。
In the present invention, an organic resin having an OH group can be used in addition to the organic / inorganic hybrid matrix component. Examples of the organic resin having an OH group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid, and 2-methacryloyloxyethyl succinic acid. 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl acid phosphate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and the like. When such an organic resin having an OH group is mixed with an organic-inorganic hybrid matrix component and used, a transparent film excellent in adhesion can be obtained, although it varies depending on the type of substrate. Depending on the substrate, the adhesion may be poor. For example, when the substrate is TAC, the adhesion can be improved by using (a small amount) of 2-hydroxyethyl acrylate. When such an organic resin is used, a catalyst may be included as necessary.
マトリックス成分中のＯＨ基を有する有機樹脂の含有量は１〜２０質量％、さらには２〜１５質量％の範囲にあることが好ましい。 The content of the organic resin having an OH group in the matrix component is preferably 1 to 20% by mass, more preferably 2 to 15% by mass.
マトリックス成分中のＯＨ基を有する有機樹脂の含有量が１質量％未満の場合は、密着性を向上させる効果が不充分となる場合があり、２０質量％を越えると、さらに密着性が向上することもなく、硬度が低下したり、耐熱性が不充分となる場合がある。 When the content of the organic resin having an OH group in the matrix component is less than 1% by mass, the effect of improving the adhesion may be insufficient, and when it exceeds 20% by mass, the adhesion is further improved. In some cases, the hardness may decrease or the heat resistance may be insufficient.
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 (T h ) of the transparent coating according to the present invention depends on the size of the ring-shaped particles used,
It is preferably in the range of 50 nm to 20 μm, more preferably 100 nm to 20 μm. 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、１次粒
子からリング状粒子を構成し、その粒子径（平均外径（ＤO））が、１０〜５００ｎｍに
ある場合、平均外径（ＤO）と膜厚（Ｔh）との比（ＤO）／（Ｔh）が０．０５〜１．０、好ましくは０．１〜０．９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 (T h ) of the transparent coating is in the range of 50 nm to 20 μm, the primary particles constitute ring-shaped particles, and the particle diameter (average outer diameter (D O )) is 10 to 10. when in 500 nm, the ratio of the average outer diameter and (D O) and the thickness (T h) (D O) / (T h) is 0.05 to 1.0, preferably from 0.1 to 0.9 It is preferable to use a transparent film in the range.
マイクロリング状無機酸化物粒子が二次粒子から形成される場合、粒子径（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。 If micro-ring inorganic oxide particles are formed from the secondary particles, the particle diameter ratio (average outer diameter (D O)) and thickness (T h) (D O) / (T h) 0. It is preferable to use a transparent film in the range of 3-1.0, preferably 0.5-0.9.
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。
If the (D O ) / (T h ) is small, the effect of improving adhesion to the substrate, the effect of improving hardness, scratch resistance, etc. are insufficient, and the (D O ) / (T h ) If the thickness is increased, irregularities may be formed on the surface of the transparent coating, and the scratch resistance, pencil hardness, etc. may be reduced. (D O )
When / (T h ) is in 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.
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。
[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有機無機ハイブリッド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。
Next, the coating liquid for forming a transparent film according to the present invention will be described.
[Transparent coating solution]
The coating liquid for forming a transparent film according to the present invention is characterized by comprising the above-mentioned microring-shaped inorganic oxide particles, an organic / inorganic hybrid 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.
有機無機ハイブリッドマトリックス形成成分
有機無機ハイブリッドマトリックス形成成分としては、前記式(2)で表される有機珪素
化合物の加水分解物であることが好ましい。
Organic / Inorganic Hybrid Matrix Forming Component The organic / inorganic hybrid matrix forming component is preferably a hydrolyzate of the organosilicon compound represented by the formula (2).
このような有機珪素化合物としては前記した有機珪素化合物が挙げられる。 Examples of such an organosilicon compound include the aforementioned organosilicon compounds.
さらに、本発明では、前記有機無機ハイブリッドマトリックス形成成分が、さらに前記式(3)で表される有機珪素化合物の加水分解物を含んでいてもよい。 Further, in the present invention, the organic-inorganic hybrid matrix-forming component may further contain a hydrolyzate of the organosilicon compound represented by the formula (3).
このような有機珪素化合物の加水分解物の含有量は、得られる透明被膜中の有機無機ハイブリッドマトリックス成分中に固形分として１〜５０質量％、さらには２〜３０質量％の範囲にあることが好ましい。 The content of the hydrolyzate of such an organosilicon compound is in the range of 1 to 50% by mass, further 2 to 30% by mass as a solid content in the organic-inorganic hybrid matrix component in the transparent film to be obtained. preferable.
さらに、本発明では、前記した１官能シリコン樹脂、２官能シリコン樹脂を混合して用いることができる。さらにまた、前記したＯＨ基を有する有機樹脂マトリックス形成成分を使用することができる。 Furthermore, in the present invention, the above-described monofunctional silicone resin and bifunctional silicone resin can be mixed and used. Furthermore, the organic resin matrix-forming component having the OH group described above can be used.
有機溶媒
本発明に用いる有機溶媒としては前記有機無機ハイブリッドマトリックス形成成分を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モノプロピルエーテル、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 disperse the organic-inorganic hybrid matrix-forming component and uniformly disperse the above-described microring-shaped inorganic oxide particles, and a conventionally known solvent is used. Can do. 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 monopropyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ester Ethers such as ter; acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, ketones such as isophorone, acetylacetone, acetoacetate, toluene, xylene, etc. Is mentioned. These may be used alone or in combination of two or more.
塗布液組成
透明被膜形成用塗布液中の有機無機ハイブリッド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。
Although the total concentration of the organic-inorganic hybrid matrix-forming component of the coating solution composition transparent film-forming coating liquid and the micro ring inorganic oxide particles is not particularly limited, 1 to 60 wt% as a solid content, further 2 to 50 weight % Is preferable.
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。 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.
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。 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有機無機ハイブリッドマトリックス形成成分の濃度は、得られる透明被膜中の有機無機ハイブリッド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。 Further, the concentration of the organic-inorganic hybrid matrix forming component in the coating liquid for forming a transparent film is such that the content of the organic-inorganic hybrid matrix component in the obtained transparent film is 20 to 99.99% by mass as the solid content as described above. Furthermore, it uses so that it may become the range of 25-99.95 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０．０００１〜４８質量％、さらには０．０００５〜３０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有機無機ハイブリッド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 solution for forming a transparent film is in the range of 0.0001 to 48% by mass, further 0.0005 to 30% by mass as the solid content. Is preferred. The concentration of the organic-inorganic hybrid 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。 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.
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 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１
２ｎｍ、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０．４５ＭＰａ、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 1
2 nm, SiO 2 concentration of 30% by mass) is supplied to the opposed two-fluid nozzle of the spray drying apparatus, and the processing liquid amount is 120 L / Hr, the nozzle pressure is 0.45 MPa, the drying atmosphere temperature is 50 ° C., and the humidity is 7.2 VOL%. The inorganic oxide particles having a concave portion on the surface were prepared by spray drying below.
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。 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.
ついで、マイクロリング状無機酸化物粒子(1)４００ｇをメタノール１６００ｇに分散
させ、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)メタノール分散液を
調製した。
Next, 400 g of the microring-shaped inorganic oxide particles (1) were dispersed in 1600 g of methanol to prepare a microring-shaped inorganic oxide particle (1) methanol dispersion having a solid content concentration of 20% by mass.
マイクロリング状無機酸化物粒子(1)メタノール分散液２０００ｇに表面処理剤として
γ-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−５１０３
、ＳｉＯ2成分８１．２質量％）４０ｇとメタノール２０００ｇ、濃度２８質量％のアン
モニア水を０．１５ｇ入れ５０℃で１８時間攪拌して表面処理を行った。このあと、エタノールに溶媒置換して固形分濃度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(1) エタノール分散液を調製した。
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。
Microring-shaped inorganic oxide particles (1) 2000 g of methanol dispersion as a surface treating agent, γ-acrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103)
The surface treatment was performed by adding 40 g of SiO 2 component (81.2% by mass), 2,000 g of methanol and 0.15 g of ammonia water having a concentration of 28% by mass and stirring at 50 ° C. for 18 hours. Thereafter, the solvent was replaced with ethanol, and the surface-treated microring-like inorganic oxide particles (1) ethanol dispersion liquid having a solid content concentration of 20% by mass was prepared.
About the obtained micro ring-shaped inorganic oxide particle (1), a scanning electron micrograph (SEM
), The average outer diameter (D O ) and the average diameter of the through holes (D I ) were measured, and the results are shown in Table 1.
有機無機ハイブリッドマトリックス形成成分(1)の調製
有機珪素化合物としてメチルトリメトキシシラン（信越化学（株）製：ＫＢＭ-１３）
を４５４．５ｇ、エタノール１８５．５ｇ、純水３６０．０ｇの混合溶液を濃硝酸でｐＨ１．０に調整した後、５０℃で２時間加水分解させた。その後、濃度１質量％のアンモニア水を添加し、ｐＨを７．０に調整した後、さらに５０℃で２時間撹拌した。次にロータリーエバポレーターで、水、アルコールを留去し、エチレングリコールモノプロピルエーテルと溶媒置換し、固形分濃度が２０質量％のエチレングリコールモノプロピルエーテル溶媒に分散した有機無機ハイブリッドマトリックス形成成分(1)を調製した。
Preparation of organic-inorganic hybrid matrix forming component (1) Methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-13) as an organosilicon compound
A mixed solution of 454.5 g, 185.5 g of ethanol and 360.0 g of pure water was adjusted to pH 1.0 with concentrated nitric acid and then hydrolyzed at 50 ° C. for 2 hours. Thereafter, ammonia water having a concentration of 1% by mass was added to adjust the pH to 7.0, followed by further stirring at 50 ° C. for 2 hours. Next, an organic-inorganic hybrid matrix forming component (1) in which water and alcohol are distilled off with a rotary evaporator, the solvent is replaced with ethylene glycol monopropyl ether, and the solid content concentration is dispersed in an ethylene glycol monopropyl ether solvent having a solid content of 20% by mass. Was prepared.
透明被膜形成用塗布液(1)の調製
固形分濃度２０重量％のマイクロリング状無機酸化物粒子(1) エタノール分散液７．５ｇと有機無機ハイブリッドマトリックス形成成分(1)３３０．７５ｇと、２-ヒドロキシエチルアクリレート（共栄社化学製：ライトエステルＨＯＡ）７．３５ｇと光重合開始剤1-ヒドロキシシクロヘキシルフェニルケトン（チバ・ジャパン（株）製イルガキュア１８４）３．０ｇと、イソプロパノールとエチレングリコールモノプロピルエーテルの１／１（重量比）混合溶媒１５４．４ｇ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 having a solid concentration of 20% by weight (1) 7.5 g of ethanol dispersion, 330.75 g of organic / inorganic hybrid matrix forming component (1), 2 -7.35 g of hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light ester HOA), 3.0 g of photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Japan Co., Ltd.), isopropanol and ethylene glycol monopropyl ether A coating solution (1) for forming a transparent film was prepared by thoroughly mixing 154.4 g of a 1/1 (weight ratio) mixed solvent.
透明被膜付基材(F-1)の製造
透明被膜形成用塗布液(1)をＴＡＣフィルム（パナック（株）製：ＦＴ−ＰＢ８０ＵＬ
−Ｍ、厚さ：８０μｍ、屈折率１．４９、基材透過率９３．０％、ヘーズ０．２％）にバーコーター法（バー＃２０）で塗布し、１００℃で５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： ＣＳ３０Ｌ
２１−３）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４μｍであった。
Manufacture of substrate (F-1) with transparent coating TAC film (manufactured by Panac Corporation: FT-PB80UL)
-M, thickness: 80 μm, refractive index 1.49, substrate transmittance 93.0%, haze 0.2%) by bar coater method (bar # 20) and dried at 100 ° C. for 5 minutes , UV irradiation device equipped with high pressure mercury lamp (120W / cm) (Japan Battery Co., Ltd. UV irradiation device: CS30L)
21-3) was cured by irradiation with 600 mJ / cm 2 to prepare a substrate with a transparent coating (F-1). At this time, the thickness of the transparent film was 4 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、結果を表に示す。
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。
The total light transmittance and haze of the transparent coating obtained were measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.), and the results are shown in the table. Furthermore, pencil hardness, flexibility, scratch resistance and adhesion are evaluated by the following methods and evaluation criteria, and the results are shown in the table.
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.
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 ： ×
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１
００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。結果を表に示す。
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
There are many scratches on the streak: △
The surface has been cut entirely: ×
11 parallel scratches were made on the surface of the substrate with adhesive transparent coating (F-1) with a 1mm vertical and horizontal interval with a knife.
00 cells were made, cellophane tape (registered trademark) was adhered to this, and then the cellophane tape (registered trademark) was peeled off, and the number of cells remaining without peeling off was determined by the following four steps. The adhesion was evaluated by classifying into The results are shown in the table.
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 ： ×
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。
Number of remaining squares: ◎
93-97 remaining squares: ○
Number of remaining squares: 85-92: △
Number of remaining squares: 84 or less: ×
Flexibility (void)
Create a 1cm wide and 5cm long section of the substrate with transparent coating (F-1), fix one end of the section,
The operation of bending the other end with a width of 5 cm up and down was repeated 20 times, then visually observed and evaluated according to the following criteria.
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 ： ×
[実施例２]
透明被膜形成用塗布液(2)の調製
実施例１と同様にして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(1) エタノール分散液３．０ｇと有機無機ハイブリッドマトリックス形成成分(1)５３
７．３ｇ、２-ヒドロキシエチルアクリレート（共栄社化学製：ライトエステルＨＯＡ）
１１．９４ｇと光重合開始剤1-ヒドロキシシクロヘキシルフェニルケトン（チバ・ジャパン（株）製イルガキュア１８４）４．８ｇと、イソプロパノールとエチレングリコールモノプロピルエーテルの１／１（重量比）混合溶媒２４７．７６ｇ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。
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: ×
[Example 2]
Preparation of coating liquid for forming transparent film (2) Microring-shaped inorganic oxide particles having a solid content of 20% by mass prepared in the same manner as in Example 1 (1) 3.0 g of ethanol dispersion and organic-inorganic hybrid matrix forming component (1) 53
7.3 g, 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light ester HOA)
11.94 g, 4.8 g of photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Japan Co., Ltd.), and 1/1 (weight ratio) mixed solvent of isopropanol and ethylene glycol monopropyl ether 247.76 g And a coating solution (2) for forming a transparent film was prepared.
透明被膜付基材(F-2)の製造
実施例１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)を調製した。このときの透明被膜の厚さは４μｍであった。
Production of substrate with transparent coating (F-2) A substrate with transparent coating (F-2) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (2) was used. At this time, the thickness of the transparent film was 4 μm.
得られた透明被膜の全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表に示す。 The total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film thus obtained were evaluated, and the results are shown in the table.
[実施例３]
透明被膜形成用塗布液(3)の調製
実施例１と同様にして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(1) エタノール分散液３７．５ｇと有機無機ハイブリッドマトリックス形成成分(1)３
０３．７５ｇ、２-ヒドロキシエチルアクリレート（共栄社化学製：ライトエステルＨＯ
Ａ）６．７５ｇと光重合開始剤1-ヒドロキシシクロヘキシルフェニルケトン（チバ・ジャパン（株）製イルガキュア１８４）２．７ｇと、イソプロパノールとエチレングリコールモノプロピルエーテルの１／１（重量比）混合溶媒１５２．０ｇ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 3]
Preparation of coating liquid for forming transparent film (3) Microring-shaped inorganic oxide particles having a solid content of 20% by mass prepared in the same manner as in Example 1 (1) 37.5 g of ethanol dispersion and organic-inorganic hybrid matrix forming component (1) 3
03.75 g, 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical: Light Ester HO
A) 6.75 g, 2.7 g of photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Japan Co., Ltd.), and 1/1 (weight ratio) mixed solvent 152 of isopropanol and ethylene glycol monopropyl ether 0.0 g was mixed well 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１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)を調製した。このときの透明被膜の厚さは４μｍであった。
Production of substrate with transparent film (F-3) A substrate with transparent film (F-3) was prepared in the same manner as in Production Example 1 except that the coating liquid for forming a transparent film (3) was used. At this time, the thickness of the transparent film was 4 μm.
得られた透明被膜の全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表に示す。 The total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film thus obtained were evaluated, and the results are shown in the table.
[実施例４]
透明被膜形成用塗布液(4)の調製
実施例１と同様にして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(1) エタノール分散液０．７５ｇと有機無機ハイブリッドマトリックス形成成分(1)１
３４９．３３ｇ、２-ヒドロキシエチルアクリレート（共栄社化学製：ライトエステルＨ
ＯＡ）２９．９８ｇと光重合開始剤1-ヒドロキシシクロヘキシルフェニルケトン（チバ・ジャパン（株）製イルガキュア１８４）１２．０ｇと、イソプロパノールとエチレングリコールモノプロピルエーテルの１／１（重量比）混合溶媒６１９．９４ｇ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。
[Example 4]
Preparation of coating liquid for forming transparent film (4) Microring-shaped inorganic oxide particles having a solid content of 20% by mass prepared in the same manner as in Example 1 (1) 0.75 g of ethanol dispersion and organic / inorganic hybrid matrix forming component (1) 1
349.33 g, 2-hydroxyethyl acrylate (Kyoeisha Chemical: Light Ester H
(OA) 29.98 g, 12.0 g of photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Japan Co., Ltd.), 1/1 (weight ratio) mixed solvent 619 of isopropanol and ethylene glycol monopropyl ether A coating solution (4) for forming a transparent film was prepared by sufficiently mixing .94 g.
透明被膜付基材(F-4)の製造
実施例１において、透明被膜形成用塗布液(4)を用いた以外は同様にして透明被膜付基
材(F-4)を調製した。このときの透明被膜の厚さは４μｍであった。
Production of substrate with transparent film (F-4) A substrate with transparent film (F-4) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (4) was used. At this time, the thickness of the transparent film was 4 μm.
得られた透明被膜の全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表に示す。 The total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film thus obtained were evaluated, and the results are shown in the table.
[実施例５]
マイクロリング状無機酸化物粒子(2)の調製
実施例１と同様にして調製したマイクロリング状無機酸化物粒子(1)２００ｇをエタノ
ール８００ｇに分散させ、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)
エタノール分散液を調製した。なお、表面処理は行なっていない。
[Example 5]
Micro ring inorganic oxide particles (2) Micro ring inorganic oxide particles were prepared in the same manner as in Preparation Example 1 of (1) 200 g was dispersed in ethanol 800g of micro ring inorganic solid concentration of 20 wt% Oxide particles (2)
An ethanol dispersion was prepared. The surface treatment is not performed.
透明被膜形成用塗布液(5)の調製
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) エタノール分散液７．５ｇと有機無機ハイブリッドマトリックス形成成分(1) ３３０．７５ｇ、２-ヒドロキシエ
チルアクリレート（共栄社化学製：ライトエステルＨＯＡ）７．３５ｇと光重合開始剤1-ヒドロキシシクロヘキシルフェニルケトン（チバ・ジャパン（株）製イルガキュア１８４）３．０ｇと、イソプロパノールとエチレングリコールモノプロピルエーテルの１／１（重量比）混合溶媒１５４．４ｇ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
。
Preparation of coating liquid for forming transparent film (5 ) Microring-shaped inorganic oxide particles having a solid content concentration of 20% by mass (2) 7.5 g of ethanol dispersion and 330.75 g of organic-inorganic hybrid matrix forming component (2) 7.35 g of hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light ester HOA), 3.0 g of photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Japan Co., Ltd.), isopropanol and ethylene glycol monopropyl ether A coating solution (5) for forming a transparent film was prepared by thoroughly mixing 154.4 g of a 1/1 (weight ratio) mixed solvent.
透明被膜付基材(F-5)の製造
実施例１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)を調製した。このときの透明被膜の厚さは４μｍであった。
Production of substrate with transparent coating (F-5) A substrate with transparent coating (F-5) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (5) was used. At this time, the thickness of the transparent film was 4 μm.
得られた透明被膜の全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表に示す。 The total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film thus obtained were evaluated, and the results are shown in the table.
[実施例６]
有機無機ハイブリッドマトリックス形成成分(2)の調製
有機珪素化合物としてメチルトリメトキシシラン（信越化学（株）製：ＫＢＭ-１３）
を４０９．１ｇ、正珪酸エチル（多摩化学製：エチルシリケート２８）を６９．４ｇ、エタノール１８５．５ｇ、純水３６０．０ｇの混合溶液を濃硝酸でｐＨ１．０に調整した後、５０℃で２時間加水分解させた。その後、濃度１質量％のアンモニア水を添加し、ｐＨを７．０に調整した後、さらに５０℃で２時間撹拌した。次にロータリーエバポレーターで、水、アルコールを留去し、エチレングリコールモノプロピルエーテルと溶媒置換し、固形分濃度が２０質量％のエチレングリコールモノプロピルエーテル溶媒に分散した有機無機ハイブリッドマトリックス形成成分(2)を調製した。
[Example 6]
Preparation of organic / inorganic hybrid matrix-forming component (2) Methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-13) as an organosilicon compound
Was adjusted to pH 1.0 with concentrated nitric acid at a temperature of 50 ° C after adjusting a mixed solution of 69.1 g of normal ethyl silicate (produced by Tama Chemicals: ethyl silicate 28), 185.5 g of ethanol and 360.0 g of pure water. Hydrolyzed for 2 hours. Thereafter, ammonia water having a concentration of 1% by mass was added to adjust the pH to 7.0, followed by further stirring at 50 ° C. for 2 hours. Next, water and alcohol are distilled off with a rotary evaporator, and the solvent is replaced with ethylene glycol monopropyl ether, and the organic-inorganic hybrid matrix forming component (2) dispersed in an ethylene glycol monopropyl ether solvent having a solid content concentration of 20% by mass. Was prepared.
透明被膜形成用塗布液(6)の調製
実施例１と同様にして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(1) エタノール分散液７．５ｇと有機無機ハイブリッドマトリックス形成成分(2) ３３０．７５ｇ、２-ヒドロキシエチルアクリレート（共栄社化学製：ライトエステルＨＯＡ
）７．３５ｇと光重合開始剤1-ヒドロキシシクロヘキシルフェニルケトン（チバ・ジャパン（株）製イルガキュア１８４）３．０ｇと、イソプロパノールとエチレングリコールモノプロピルエーテルの１／１（重量比）混合溶媒１５４．４ｇ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。
Preparation of coating liquid for forming transparent film (6) Microring-shaped inorganic oxide particles having a solid content of 20% by mass prepared in the same manner as in Example 1 (1) 7.5 g of ethanol dispersion and organic-inorganic hybrid matrix forming component (2) 330.75 g, 2-hydroxyethyl acrylate (Kyoeisha Chemical: Light Ester HOA
7.35 g, 3.0 g of photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Japan Co., Ltd.), 1/1 (weight ratio) mixed solvent of isopropanol and ethylene glycol monopropyl ether 154. 4 g was mixed well to prepare a coating solution (6) for forming a transparent film.
透明被膜付基材(F-6)の製造
実施例１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)を調製した。このときの透明被膜の厚さは４μｍであった。
Production of substrate with transparent film (F-6) A substrate with transparent film (F-6) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (6) was used. At this time, the thickness of the transparent film was 4 μm.
得られた透明被膜の全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表に示す。 The total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film thus obtained were evaluated, and the results are shown in the table.
[実施例７]
マイクロリング状無機酸化物粒子(3)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 7]
Preparation of micro ring-shaped inorganic oxide particles (3 ) 100 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid ™ SI-550, average particle diameter 5 nm, SiO 2 concentration 20 mass%) was added 3900 g of pure water to 98 ° C. Warm,
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, and SiO 2 · Al 2 An 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(3)（平均粒子径６０ｎｍ）の分散液を得た。このときの反応液のｐＨは１
２．０であった。
Next, 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 (3) (average particle size 60 nm) dispersion was obtained. The pH of the reaction solution at this time is 1
2.0.
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(3)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 (3) 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 further 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 an aqueous dispersion of silica-based hollow fine particles, 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、ついで、限外濾過膜でエタノールに溶媒置換して固形分濃度２０質量％のマイクロリング状無機酸化物粒子(3)のエタノール（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 was added to adjust the pH to 12, and the mixture was stirred for 12 hours at 80 ° C., then washed thoroughly, and then the solvent was replaced with ethanol by an ultrafiltration membrane to obtain a solid content concentration of 20% by mass. An ethanol (water) dispersion of microring-shaped inorganic oxide particles (3) was obtained.
得られたマイクロリング状無機酸化物粒子(3)について、走査型電子顕微鏡写真（ＳＥ
Ｍ）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。
About the obtained microring-shaped inorganic oxide particles (3), a scanning electron micrograph (SE
M) was photographed, the average outer diameter (D O ) and the average diameter (D I ) of the through holes were measured, and the results are shown in Table 1.
透明被膜形成用塗布液(7)の調製
固形分濃度２０質量％のマイクロリング状無機酸化物粒子(3) エタノール分散液７．５ｇと有機無機ハイブリッドマトリックス形成成分(1) ３３０．７５ｇ、２-ヒドロキシエ
チルアクリレート（共栄社化学製：ライトエステルＨＯＡ）７．３５ｇと光重合開始剤1-ヒドロキシシクロヘキシルフェニルケトン（チバ・ジャパン（株）製イルガキュア１８４）３．０ｇと、イソプロパノールとエチレングリコールモノプロピルエーテルの１／１（重量比）混合溶媒１５４．４ｇとを充分に混合して透明被膜形成用塗布液(7)を調製した
。
Preparation of coating liquid for forming transparent film (7 ) Microring-shaped inorganic oxide particles having a solid content of 20% by mass (3) 7.5 g of ethanol dispersion and 330.75 g of organic / inorganic hybrid matrix forming component (2) 7.35 g of hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light ester HOA), 3.0 g of photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Japan Co., Ltd.), isopropanol and ethylene glycol monopropyl ether A coating solution (7) for forming a transparent film was prepared by thoroughly mixing 154.4 g of a 1/1 (weight ratio) mixed solvent.
透明被膜付基材(F-7)の製造
実施例１において、透明被膜形成用塗布液(7)を用い、バーコーター法（バー＃３）で
塗布した以外は同様にして透明被膜付基材(F-7)を調製した。このときの透明被膜の厚さ
は０．６μｍであった。
Production of substrate with transparent coating (F-7) Substrate with transparent coating in the same manner as in Example 1 except that the coating solution for forming a transparent coating (7) was applied by the bar coater method (bar # 3). (F-7) was prepared. At this time, the thickness of the transparent film was 0.6 μm.
得られた透明被膜の全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性
を評価し、結果を表に示す。
The total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film thus obtained were evaluated, and the results are shown in the table.
[実施例８]
マイクロリング状無機酸化物粒子(4)の調製
実施例７と同様にして固形分濃度２０質量％のマイクロリング状無機酸化物粒子(3)の
エタノール（水）分散液を得た。
[Example 8]
Preparation of microring-shaped inorganic oxide particles (4) In the same manner as in Example 7, an ethanol (water) dispersion of microring-shaped inorganic oxide particles (3) having a solid content concentration of 20% by mass was obtained.
ついで、限外濾過膜でメタノールに溶媒置換し、濃縮して固形分濃度２０質量％のマイクロリング状無機酸化物粒子(3)メタノール分散液を調製した。 Subsequently, the solvent was replaced with methanol by an ultrafiltration membrane, followed by concentration to prepare a microring-shaped inorganic oxide particle (3) methanol dispersion having a solid content concentration of 20% by mass.
マイクロリング状無機酸化物粒子(3)メタノール分散液２０００ｇに表面処理剤として
γ-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−５１０３
、ＳｉＯ2成分８１．２質量％）４０ｇとメタノール２０００ｇ、濃度２８質量％のアン
モニア水を０．１５ｇ入れ５０℃で１８時間攪拌して表面処理を行った。このあと、エタノールに溶媒置換して固形分濃度１０質量％の表面処理したマイクロリング状無機酸化物粒子(4) エタノール分散液を調製した。
Microring-like inorganic oxide particles (3) γ-acrylooxypropyltrimethoxysilane (made by Shin-Etsu Chemical Co., Ltd .: KBM-5103) as a surface treatment agent on 2000 g of methanol dispersion
The surface treatment was performed by adding 40 g of SiO 2 component (81.2% by mass), 2,000 g of methanol and 0.15 g of ammonia water having a concentration of 28% by mass and stirring at 50 ° C. for 18 hours. Thereafter, the solvent was replaced with ethanol to prepare a microring-like inorganic oxide particle (4) ethanol dispersion liquid having a surface treatment with a solid content concentration of 10% by mass.
得られたマイクロリング状無機酸化物粒子(4)について、走査型電子顕微鏡写真（ＳＥ
Ｍ）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。
About the obtained microring-shaped inorganic oxide particles (4), a scanning electron micrograph (SE
M) was photographed, the average outer diameter (D O ) and the average diameter (D I ) of the through holes were measured, and the results are shown in Table 1.
透明被膜形成用塗布液(8)の調製
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(4)エタノール
分散液７．５ｇと、実施例６と同様にして調製した有機無機ハイブリッドマトリックス形成成分(2) ３３０．７５ｇ、２-ヒドロキシエチルアクリレート（共栄社化学製：ライト
エステルＨＯＡ）７．３５ｇと光重合開始剤1-ヒドロキシシクロヘキシルフェニルケトン（チバ・ジャパン（株）製イルガキュア１８４）３．０ｇと、イソプロパノールとエチレングリコールモノプロピルエーテルの１／１（重量比）混合溶媒１５４．４ｇとを充分に混合して透明被膜形成用塗布液(8)を調製した。
Preparation of coating liquid (8) for forming transparent film Surface-treated microring-like inorganic oxide particles (4) with a solid content concentration of 20% by mass (4) Ethanol dispersion liquid prepared in the same manner as in Example 6 Hybrid matrix forming component (2) 330.75 g, 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light ester HOA) 7.35 g and photoinitiator 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Japan Co., Ltd.) 3.0 g and 154.4 g of a 1/1 (weight ratio) mixed solvent of isopropanol and ethylene glycol monopropyl ether were sufficiently mixed to prepare a coating solution (8) for forming a transparent film.
透明被膜付基材(F-8)の製造
実施例１において、透明被膜形成用塗布液(8)を用い、バーコーター法（バー＃３）で
塗布した以外は同様にして透明被膜付基材(F-8)を調製した。このときの透明被膜の厚さ
は０．６μｍであった。
Production of substrate with transparent coating (F-8) Substrate with transparent coating in the same manner as in Example 1 except that the coating solution for forming a transparent coating (8) was applied by the bar coater method (bar # 3). (F-8) was prepared. At this time, the thickness of the transparent film was 0.6 μm.
得られた透明被膜の全光線透過率、ヘーズ、鉛筆硬度、可撓性、耐擦傷性および密着性を評価し、結果を表に示す。 The total light transmittance, haze, pencil hardness, flexibility, scratch resistance and adhesion of the transparent film thus obtained were evaluated, and the results are shown in the table.
[実施例９]
透明被膜付基材(F-9)の製造
実施例１と同様にして調製した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、１００℃で５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-9)を調製した。このときの透明被膜の厚さは４μｍであった。
[実施例１０]
透明被膜付基材(F-10)の製造
実施例８と同様にして調製した透明被膜形成用塗布液(8)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、１００℃で
５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-10)を調製した。このときの透明被膜の厚さは４μｍであった。
[Example 9]
Production of substrate with transparent coating (F-9) A coating solution (1) for forming a transparent coating prepared in the same manner as in Example 1 was obtained by applying a PET film (Toyobo (
Co., Ltd .: Cosmo Shine A-4300, thickness: 188 μm, refractive index 1.65, base material transmittance 90.0%, haze 0.6%)) applied by the bar coater method (bar # 20), After drying at 100 ° C. for 5 minutes, it is cured by irradiation with 600 mJ / cm 2 with an ultraviolet irradiation device (Nihon Battery Co., Ltd. UV irradiation device: CS30L21-3) equipped with a high-pressure mercury lamp (120 W / cm).
A substrate with a transparent coating (F-9) was prepared. At this time, the thickness of the transparent film was 4 μm.
[Example 10]
Production of substrate with transparent coating (F-10) A coating solution for forming a transparent coating (8) prepared in the same manner as in Example 8 was prepared by applying PET film (Toyobo (
Co., Ltd .: Cosmo Shine A-4300, thickness: 188 μm, refractive index 1.65, base material transmittance 90.0%, haze 0.6%)) applied by the bar coater method (bar # 20), After drying at 100 ° C. for 5 minutes, it is cured by irradiation with 600 mJ / cm 2 with an ultraviolet irradiation device (Nihon Battery Co., Ltd. UV irradiation device: CS30L21-3) equipped with a high-pressure mercury lamp (120 W / cm).
A substrate with a transparent coating (F-10) was prepared. At this time, the thickness of the transparent film was 4 μm.
[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０．４０ＭＰａ、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４μｍ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 0.40 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 an average particle size of 4 μm.
ついで、無機酸化物粒子(R1)４００ｇをメタノール１６００ｇに分散させ、固形分濃度２０質量％の無機酸化物粒子(R1)メタノール分散液を調製した。 Next, 400 g of inorganic oxide particles (R1) were dispersed in 1600 g of methanol to prepare an inorganic oxide particle (R1) methanol dispersion having a solid content concentration of 20% by mass.
無機酸化物粒子(R1)メタノール分散液２０００ｇに表面処理剤としてγ-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−５１０３、ＳｉＯ2成分８
１．２質量％）４０ｇとメタノール２０００ｇ、濃度２８質量％のアンモニア水を０．１５ｇ入れ５０℃で１８時間攪拌して表面処理を行った。このあと、エタノールに溶媒置換して固形分濃度１０質量％の表面処理した無機酸化物粒子(R1) エタノール分散液を調製
した。
Γ-acrylooxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-5103, SiO 2 component 8) as a surface treatment agent in 2000 g of inorganic oxide particles (R1) in methanol dispersion
1.2 mass%) 40 g, methanol 2000 g, and 0.15 g of ammonia water having a concentration of 28 mass% were added and stirred at 50 ° C. for 18 hours for surface treatment. Thereafter, the solvent was replaced with ethanol, and a surface-treated inorganic oxide particle (R1) ethanol dispersion having a solid content concentration of 10% by mass was prepared.
透明被膜形成用塗布液(R1)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)の代わりに表面処理した無機
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。
Preparation of coating liquid for forming transparent film (R1) In Example 1, transparent film was formed in the same manner except that the surface-treated inorganic oxide particles (R1) were used instead of the microring-shaped inorganic oxide particles (1). A coating solution (R1) was prepared.
透明被膜付基材(RF-1)の製造
実施例１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 1 except that the coating liquid for transparent film formation (R1) was used. For the obtained substrate with transparent film (RF-1), 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 the table. .
[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 ＵＳ
ＢＢ−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Ａl2Ｏ3／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 ™ US)
BB-120, average particle diameter 25 nm, SiO 2 · Al 2 O 3 concentration 20% by mass, solid content Al 2 O 3 content 27% by mass) 100 g of pure water 3900 g was added and heated to 98 ° C. While maintaining the temperature, 1750 g of a sodium silicate aqueous solution having a concentration of 1.5% by mass as SiO 2 and 1750 g of a sodium aluminate aqueous solution having a concentration of 0.5% by mass as Al 2 O 3 were added, and SiO 2 · Al 2 O A three- particle dispersion (average particle size 35 nm) was obtained. The Al 2 O 3 / 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。
Subsequently, a mixed liquid of 150 g of an aqueous dispersion of silica-based hollow fine particles, 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 was performed for 3 hours using 400 g of a cation exchange resin (Mitsubishi Chemical Corporation: DIAIONTM SK1B), and then ion exchange was performed for 3 hours using 200 g of an anion exchange resin (Mitsubishi Chemical Corporation: DIAIONTM SA20A). Further, 200 g of a cation exchange resin (Mitsubishi Chemical Co., Ltd .: DIAION ™ SK1B) was used for ion exchange at 80 ° C. for 3 hours for washing, and water of inorganic oxide particles (R2) having a solid content concentration of 20% by mass was obtained. A dispersion was obtained. The obtained inorganic oxide particles (R2) had no through holes and an average particle size of 60 nm.
ついで、無機酸化物粒子(R2)水分散液を限外濾過膜にてメタノールに溶媒置換し、固形分濃度２０質量％の無機酸化物粒子(R2)メタノール分散液を調製した。 Subsequently, the inorganic oxide particle (R2) aqueous dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to prepare an inorganic oxide particle (R2) methanol dispersion having a solid concentration of 20% by mass.
無機酸化物粒子(R2)メタノール分散液２０００ｇに表面処理剤としてγ-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−５１０３、ＳｉＯ2成分８
１．２質量％）４０ｇとメタノール２０００ｇ、濃度２８質量％のアンモニア水を０．１５ｇ入れ５０℃で１８時間攪拌して表面処理を行った。このあと、エタノールに溶媒置換して固形分濃度１０質量％の表面処理した無機酸化物粒子(R2) エタノール分散液を調製
した。
Γ-acrylooxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .: KBM-5103, SiO 2 component 8) as a surface treatment agent in 2000 g of inorganic oxide particle (R2) methanol dispersion
1.2 mass%) 40 g, methanol 2000 g, and 0.15 g of ammonia water having a concentration of 28 mass% were added and stirred at 50 ° C. for 18 hours for surface treatment. Thereafter, the solvent was replaced with ethanol to prepare a surface-treated inorganic oxide particle (R2) ethanol dispersion having a solid content concentration of 10% by mass.
透明被膜形成用塗布液(R2)の調製
実施例８において、マイクロリング状無機酸化物粒子(4) エタノール分散液の代わりに表面処理した無機酸化物粒子(R2) エタノール分散液を用いた以外は同様にして透明被膜形
成用塗布液(R2)を調製した。
Preparation of coating liquid for forming transparent film (R2) In Example 8, instead of microring-shaped inorganic oxide particles (4) ethanol dispersion, surface-treated inorganic oxide particles (R2) ethanol dispersion was used. A coating solution (R2) for forming a transparent film was prepared in the same manner except that it was used.
透明被膜付基材(RF-2)の製造
実施例８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 8, 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, and the results are shown in the table. .
[比較例３]
透明被膜形成用塗布液(R3)の調製
実施例８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 3]
Preparation of coating liquid for forming transparent film (R3) In Example 8, instead of microring-shaped inorganic oxide particles (2), silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid ™ SI-45P, average particle diameter 45 nm, SiO An inorganic oxide particle (R3) alcohol dispersion liquid surface-treated in the same manner except that 2 concentration (30% by mass) was used was prepared, and then a coating liquid (R3) for forming a transparent film was prepared.
透明被膜付基材(RF-3)の製造
実施例８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 8 except that the coating liquid for transparent film formation (R3) was used. For 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, and the results are shown in the table. .
Claims (17)
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す
る請求項１に記載の透明被膜付基材。 The average outer diameter (D O ) of the microring-shaped inorganic oxide particles 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, and the ring width (W R ) 2. The substrate with a transparent coating according to claim 1, wherein the ratio (W R ) / (D O ) with respect to the average outer diameter (D O ) is in the range of 0.2 to 0.45.
処理されていることを特徴とする請求項１〜３のいずれかに記載の透明被膜付基材。
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 substrate with a transparent coating according to any one of claims 1 to 3, wherein the 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)
項１〜５のいずれかに記載の透明被膜付基材。 The substrate with a transparent coating according to any one of claims 1 to 5, wherein a film thickness (T h ) of the transparent coating is in a range of 50 nm to 20 µm.
にあり、平均外径（ＤO）と膜厚（Ｔh）との比（ＤO）／（Ｔh）が０．３〜１．０の範囲にあることを特徴とする請求項１〜６のいずれかに記載の透明被膜付基材。 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 ratio of the average outer diameter (D O ) to the film thickness (T h ) (D O ) / (T h ) Is in the range of 0.3 to 1.0, the substrate with a transparent coating according to any one of claims 1 to 6.
の加水分解重縮合物を含むことを特徴とする請求項１〜７のいずれかに記載の透明被膜付基材。
Ｒn-ＳiＸ4-n （２）
（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、シラノール基、ハロゲン、水素から選ばれる少なくとも１種であり、ｎは１〜３の整数を示す） The substrate with a transparent coating according to any one of claims 1 to 7, wherein the organic-inorganic hybrid matrix component contains a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (2).
R n -SiX 4-n (2)
(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 or a silanol group) , Halogen or hydrogen, and n represents an integer of 1 to 3)
化合物の加水分解重縮合物を含むことを特徴とする請求項８に記載の透明被膜付基材。
ＳiＸ4 （３）
（但し、式中、Ｘは炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素から選ばれる少なくとも１種である） The substrate with a transparent film according to claim 8, wherein the organic-inorganic hybrid matrix component further contains a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (3).
SiX 4 (3)
(In the formula, X is at least one selected from an alkoxy group having 1 to 4 carbon atoms, a silanol group, halogen, and hydrogen)
溶媒とを含むことを特徴とする透明被膜形成用塗布液。 A coating liquid for forming a transparent film, comprising microring-shaped inorganic oxide particles, an organic-inorganic hybrid matrix-forming component, and an organic solvent.
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す
る請求項１０に記載の透明被膜形成用塗布液。 The average outer diameter (D O ) of the microring-shaped inorganic oxide particles 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, and the ring width (W R ) The coating liquid for forming a transparent film according to claim 10, wherein the ratio (W R ) / (D O ) to the average outer diameter (D O ) is in the range of 0.2 to 0.45.
処理されていることを特徴とする請求項１０〜１２のいずれかに記載の透明被膜形成用塗布液。
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は炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素から選ばれる少なくとも１種を示し、ｎは０〜３の整数を示す） The coating liquid for forming a transparent film according to any one of claims 10 to 12, wherein the 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. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, At least one selected from halogen and hydrogen, and n represents an integer of 0 to 3)
合物の加水分解物を含むことを特徴とする請求項１０〜１４のいずれかに記載の透明被膜形成用塗布液。
Ｒn-ＳiＸ4-n （２）
（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は炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素から選ばれる少なくとも１種を示す。ｎは１〜３の整数を示す） The coating liquid for forming a transparent film according to any one of claims 10 to 14, wherein the organic-inorganic hybrid matrix-forming component contains a hydrolyzate of an organosilicon compound represented by the following formula (2).
R n -SiX 4-n (2)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms or a silanol group. And at least one selected from halogen and hydrogen, n represents an integer of 1 to 3)
化合物の加水分解物を含むことを特徴とする請求項１５に記載の透明被膜形成用塗布液。ＳiＸ4 （３）
（但し、式中、Ｘは炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素から選ばれる少なくとも１種を示す） The coating liquid for forming a transparent film according to claim 15, wherein the organic-inorganic hybrid matrix component further contains a hydrolyzate of an organosilicon compound represented by the following formula (3). SiX 4 (3)
(Wherein, X represents at least one selected from an alkoxy group having 1 to 4 carbon atoms, a silanol group, halogen, and hydrogen)
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| JP2018115318A (en) * | 2017-01-18 | 2018-07-26 | 三洋化成工業株式会社 | Active energy ray-curable resin composition |
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| JP2009035594A (en) * | 2007-07-31 | 2009-02-19 | Jgc Catalysts & Chemicals Ltd | Base material with transparent coating, and coating material for forming transparent coating |
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