JP2006263929A - Transparent barrier sheet - Google Patents
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- JP2006263929A JP2006263929A JP2005081021A JP2005081021A JP2006263929A JP 2006263929 A JP2006263929 A JP 2006263929A JP 2005081021 A JP2005081021 A JP 2005081021A JP 2005081021 A JP2005081021 A JP 2005081021A JP 2006263929 A JP2006263929 A JP 2006263929A
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- 230000004888 barrier function Effects 0.000 title claims abstract description 135
- 239000011521 glass Substances 0.000 claims abstract description 79
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003822 epoxy resin Substances 0.000 claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 24
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 230000009477 glass transition Effects 0.000 claims abstract description 12
- 125000002091 cationic group Chemical group 0.000 claims abstract description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 5
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 59
- 239000000758 substrate Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 21
- 239000012044 organic layer Substances 0.000 claims description 20
- 238000004544 sputter deposition Methods 0.000 claims description 19
- 239000004033 plastic Substances 0.000 claims description 18
- 239000004744 fabric Substances 0.000 claims description 17
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 14
- 239000011342 resin composition Substances 0.000 claims description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 13
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 13
- 239000011368 organic material Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 9
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000001588 bifunctional effect Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 238000002834 transmittance Methods 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 238000001771 vacuum deposition Methods 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 239000011243 crosslinked material Substances 0.000 abstract 1
- -1 aromatic sulfonium salts Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 6
- 125000003566 oxetanyl group Chemical group 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 0 *(C1CC2OC2CC1)C1CC(C2)OC2C1 Chemical compound *(C1CC2OC2CC1)C1CC(C2)OC2C1 0.000 description 1
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- IBPADELTPKRSCQ-UHFFFAOYSA-N 9h-fluoren-1-yl prop-2-enoate Chemical compound C1C2=CC=CC=C2C2=C1C(OC(=O)C=C)=CC=C2 IBPADELTPKRSCQ-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PRWNDQXXTXXMMW-UHFFFAOYSA-N butan-1-ol;prop-2-enoic acid Chemical compound CCCCO.OC(=O)C=C PRWNDQXXTXXMMW-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
本発明は、線膨張係数が小さく、耐熱性、透明性、ガス・水蒸気バリア性に優れた吸湿寸法変化の少ない透明バリア性シートに関するものである。 The present invention relates to a transparent barrier sheet having a small coefficient of linear expansion, excellent heat resistance, transparency, and gas / water vapor barrier properties, and having little moisture absorption dimensional change.
一般に、液晶表示素子や有機ＥＬ表示素子用の表示素子基板(特にアクティブマトリックスタイプ)、カラーフィルター基板、太陽電池用基板等としては、ガラス板が広く用いられている。しかしながらガラス板は、割れ易い、曲げられない、比重が大きく軽量化に不向きなどの理由から、近年、その代替としてプラスチック素材が検討されている。
表示素子用プラスチック基板に用いられる樹脂は例えば特許文献１には脂環式エポキシ樹脂、酸無水物系硬化剤、アルコール、硬化触媒からなる組成物、特許文献２には脂環式エポキシ樹脂、アルコールで部分エステル化した酸無水物系硬化剤、硬化触媒からなる樹脂組成物が、特許文献３には脂環式エポキシ樹脂、カルボン酸を有する酸無水物系硬化剤、硬化触媒からなる樹脂組成物が示されている。しかしながら、これら従来のガラス代替用プラスチック材料は、ガラス板に比べ線膨張係数が大きく、特に、アクティブマトリックス表示素子基板に用いるとその製造工程において反りやアルミ配線の断線などの問題が生じ、これら用途への使用は困難である。さらに、従来のガラス代替用プラスチック材料は、ガス・水蒸気バリア性に関しても、ガラス板にくらべ劣っている。したがって、表示素子基板、特にアクティブマトリックス表示素子用基板に要求される、透明性や耐熱性、ガス・水蒸気バリア性等を満足しつつ線膨張係数の小さなプラスチック素材が求められている。
In general, glass plates are widely used as display element substrates (particularly active matrix type) for liquid crystal display elements and organic EL display elements, color filter substrates, solar cell substrates, and the like. However, in recent years, plastic materials have been studied as an alternative to glass plates because they are easily broken, cannot be bent, have a large specific gravity, and are not suitable for weight reduction.
Resin used for the plastic substrate for display elements is, for example, a composition comprising an alicyclic epoxy resin, an acid anhydride curing agent, alcohol and a curing catalyst in Patent Document 1, and an alicyclic epoxy resin and alcohol in Patent Document 2. A resin composition comprising an acid anhydride-based curing agent partially esterified with a curing catalyst and a curing catalyst, Patent Document 3 discloses a resin composition comprising an alicyclic epoxy resin, an acid anhydride-based curing agent having a carboxylic acid, and a curing catalyst. It is shown. However, these conventional plastic materials for glass substitutes have a larger coefficient of linear expansion than glass plates, and particularly when used for active matrix display element substrates, problems such as warping and disconnection of aluminum wiring occur in the manufacturing process. It is difficult to use. Furthermore, conventional plastic materials for glass substitutes are inferior to glass plates in terms of gas / water vapor barrier properties. Therefore, there is a demand for a plastic material having a small linear expansion coefficient while satisfying the transparency, heat resistance, gas / water vapor barrier properties, and the like required for display element substrates, particularly active matrix display element substrates.
このような問題を解決するため、特許文献４や特許文献５には、無機酸化物が分散された粒子分散系樹脂シートが、特許文献６にはフィラー分散系樹脂シートが、更に特許文献７にはエポキシ樹脂とガラス繊維製布状体からなる樹脂シートが示されている。これら樹脂シートは、従来の樹脂シートに比較して線膨張係数は低いが、これらの材料をガラス基板に代えてアクティブマトリックス表示素子基板などに用いると耐熱性が不十分であった。 In order to solve such problems, Patent Document 4 and Patent Document 5 include a particle-dispersed resin sheet in which an inorganic oxide is dispersed, Patent Document 6 includes a filler-dispersed resin sheet, and Patent Document 7 further discloses. Shows a resin sheet made of an epoxy resin and a glass fiber cloth. These resin sheets have a lower coefficient of linear expansion than conventional resin sheets, but their heat resistance is insufficient when these materials are used for active matrix display element substrates or the like instead of glass substrates.
本発明の目的は、線膨張係数が小さく、透明性、耐熱性、ガス・水蒸気バリア性に優れ、ガラスに代替可能な透明バリア性シートを提供することにある。本発明の透明バリア性シートは、アクティブマトリックスタイプを含む液晶表示素子用基板、有機ＥＬ表示素子基板、カラーフィルター用基板、タッチパネル用基板、電子ペーパー用基板、太陽電池基板などの光学シート、透明板、光学レンズ、光学素子、光導波路、ＬＥＤ封止材等に好適に用いられる。 An object of the present invention is to provide a transparent barrier sheet having a small linear expansion coefficient, excellent transparency, heat resistance, and gas / water vapor barrier properties, which can be substituted for glass. The transparent barrier sheet of the present invention includes an active matrix type liquid crystal display element substrate, an organic EL display element substrate, a color filter substrate, a touch panel substrate, an electronic paper substrate, a solar cell substrate, and other optical sheets, a transparent plate , Optical lenses, optical elements, optical waveguides, LED sealing materials and the like.
本発明は、
（１）吸水率が３％以下でガラス転移温度が２３０℃以上の透明樹脂（ａ）とガラスフィラー（ｂ）とから構成される透明複合シート上に、透明でガス・水蒸気バリア性を有する無機化合物から成るバリア層を形成した透明バリア性シート、
（２）透明樹脂（ａ）が下記化学式（１）で示される脂環式エポキシ樹脂を構成成分として含む組成物の架橋体である（１）記載の透明バリア性シート、
（３）透明樹脂（ａ）が下記化学式（２）で示される水添ビフェニル型脂環式エポキシ樹脂を構成成分として含む組成物の架橋体である（１）記載の透明バリア性シート、
（５）前記透明樹脂（ａ）の屈折率と前記ガラスフィラー（ｂ）の屈折率との差が０．０１以下である（１）〜（４）何れか記載の透明バリア性シート、
（６）前記ガラスフィラー（ｂ）の屈折率が１．４５〜１．５５である（１）〜（５）何れか記載の透明バリア性シート、
（７）前記ガラスフィラー（ｂ）がガラス繊維布である（１）〜（６）何れか記載の透明バリア性シート、
（８）前記バリア層が透明複合シートの両面に形成された（１）〜（７）何れか記載の透明バリア性シート、
（９）前記バリア層と透明複合シートの間に有機物層を有する（１）〜（８）何れか記載の透明バリア性シート、
（１０）前記バリア層の上に更に有機物層を形成した（１）〜（９）何れか記載の透明バリア性シート、
（１１）前記バリア層上の有機物層の上に、更に透明でガス・水蒸気バリア性を有する無機化合物から成るバリア層を形成した（１０）記載の透明バリア性シート、
（１２）前記有機物層が、吸水率が３％以下でガラス転移温度が２３０℃以上の透明樹脂（ａ）を主成分とする有機物である（９）〜（１１）何れか記載の透明バリア性シート、
（１３）前記有機物層が２官能以上のアクリロイル基を有する１種類以上のモノマーを主成分とする樹脂組成物、又は２官能以上のアクリロイル基を有する１種類以上のモノマーと単官能以上のアクリロイル基を有する１種類以上のモノマーとの混合物を主成分とする樹脂組成物を、架橋させて得られるものである（９）〜（１１）何れか記載の透明バリア性シート、
（１４）前記アクリロイル基を有するモノマーが、ノルボルネン骨格を有するモノマー、フルオレン骨格を有するモノマー、臭素化ビスフェノールA型エポキシアクリレート及びイソシアヌール酸ＥＯ変性トリアクリレートから選ばれる少なくとも一つのモノマーを含むものである（１３）記載の透明バリア性シート、
（１５）バリア層が少なくとも珪素を主成分とする化合物から成る（１）〜（１４）何れか記載の透明バリア性シート、
（１６）バリア層が少なくとも珪素酸化物または珪素窒化物もしくは珪素酸化窒化物を主成分とする化合物から成る（１）〜（１５）何れか記載の透明バリア性シート、
（１７）バリア層の厚さが２０〜５００ｎｍである（１）〜（１６）何れか記載の透明バリア性シート、
（１８）バリア層が真空蒸着方式、又はＳｉターゲットを用いたスパッタリング方式により形成される（１）〜（１７）何れか記載の透明バリア性シート、
（１９）厚さが５０〜２０００μｍである（１）〜（１８）何れか記載の透明バリア性シート、
（２０）波長５５０ｎｍでの光線透過率が８０％以上である（１）〜（１９）何れか記載の透明バリア性シート、
（２１）透明バリア性シートが、光学シート、表示素子用プラスチック基板、又はアクティブマトリックス表示素子用基板である（１）〜（２０）何れか記載の透明バリア性シート、
である。
The present invention
(1) On a transparent composite sheet composed of a transparent resin (a) having a water absorption of 3% or less and a glass transition temperature of 230 ° C. or more and a glass filler (b), it is transparent and has an inorganic gas / water vapor barrier property. A transparent barrier sheet having a barrier layer made of a compound,
(2) The transparent barrier sheet according to (1), wherein the transparent resin (a) is a crosslinked product of a composition containing an alicyclic epoxy resin represented by the following chemical formula (1) as a constituent component,
(3) The transparent barrier sheet according to (1), wherein the transparent resin (a) is a crosslinked product of a composition containing a hydrogenated biphenyl type alicyclic epoxy resin represented by the following chemical formula (2) as a constituent component,
(5) The transparent barrier sheet according to any one of (1) to (4), wherein the difference between the refractive index of the transparent resin (a) and the refractive index of the glass filler (b) is 0.01 or less.
(6) The transparent barrier sheet according to any one of (1) to (5), wherein the glass filler (b) has a refractive index of 1.45 to 1.55.
(7) The transparent barrier sheet according to any one of (1) to (6), wherein the glass filler (b) is a glass fiber cloth,
(8) The transparent barrier sheet according to any one of (1) to (7), wherein the barrier layer is formed on both surfaces of the transparent composite sheet,
(9) The transparent barrier sheet according to any one of (1) to (8), having an organic layer between the barrier layer and the transparent composite sheet,
(10) The transparent barrier sheet according to any one of (1) to (9), wherein an organic layer is further formed on the barrier layer,
(11) The transparent barrier sheet according to (10), wherein a barrier layer made of an inorganic compound having a gas / water vapor barrier property is further formed on the organic layer on the barrier layer,
(12) The transparent barrier property according to any one of (9) to (11), wherein the organic material layer is an organic material mainly composed of a transparent resin (a) having a water absorption rate of 3% or less and a glass transition temperature of 230 ° C. or more. Sheet,
(13) The organic material layer is a resin composition mainly composed of one or more monomers having a bifunctional or higher acryloyl group, or one or more monomers having a bifunctional or higher acryloyl group and a monofunctional or higher acryloyl group. The transparent barrier sheet according to any one of (9) to (11), which is obtained by crosslinking a resin composition mainly composed of a mixture with one or more types of monomers having
(14) The monomer having an acryloyl group includes at least one monomer selected from a monomer having a norbornene skeleton, a monomer having a fluorene skeleton, a brominated bisphenol A type epoxy acrylate, and an isocyanuric acid EO-modified triacrylate (13 ) Transparent barrier sheet according to
(15) The transparent barrier sheet according to any one of (1) to (14), wherein the barrier layer comprises a compound containing at least silicon as a main component,
(16) The transparent barrier sheet according to any one of (1) to (15), wherein the barrier layer comprises at least silicon oxide, silicon nitride, or a compound mainly composed of silicon oxynitride,
(17) The transparent barrier sheet according to any one of (1) to (16), wherein the thickness of the barrier layer is 20 to 500 nm,
(18) The transparent barrier sheet according to any one of (1) to (17), wherein the barrier layer is formed by a vacuum deposition method or a sputtering method using a Si target.
(19) The transparent barrier sheet according to any one of (1) to (18), wherein the thickness is 50 to 2000 μm,
(20) The transparent barrier sheet according to any one of (1) to (19), wherein the light transmittance at a wavelength of 550 nm is 80% or more,
(21) The transparent barrier sheet according to any one of (1) to (20), wherein the transparent barrier sheet is an optical sheet, a plastic substrate for a display element, or a substrate for an active matrix display element,
It is.
本発明の透明バリア性シートは、低線膨張係数で、透明性や耐熱性、ガス・水蒸気バリア性に優れ、透明板、光学レンズ、液晶表示素子用プラスチック基板、カラーフィルター用基板、有機ＥＬ表示素子用プラスチック基板、電子ペーパー用基板、太陽電池基板、タッチパネル、導光板、光学素子、光導波路、ＬＥＤ封止材等に好適に利用できる。 The transparent barrier sheet of the present invention has a low linear expansion coefficient, excellent transparency, heat resistance, and gas / water vapor barrier properties. Transparent plate, optical lens, liquid crystal display plastic substrate, color filter substrate, organic EL display It can be suitably used for a plastic substrate for elements, a substrate for electronic paper, a solar cell substrate, a touch panel, a light guide plate, an optical element, an optical waveguide, an LED sealing material, and the like.
本発明に用いられる透明樹脂（ａ）は、一般式（１）で示される脂環式エポキシ樹脂または一般式（２）で示される水添ビフェニル型脂環式エポキシ樹脂を構成成分として含むことを特徴とする。 The transparent resin (a) used in the present invention contains an alicyclic epoxy resin represented by the general formula (1) or a hydrogenated biphenyl alicyclic epoxy resin represented by the general formula (2) as a constituent component. Features.
一般式（１）で示される脂環式エポキシ樹脂または一般式（２）で示される水添ビフェニル型脂環式エポキシ樹脂を用いることにより、極めて優れた耐熱性と良好な透明性を両立することができる。具体的には、熱カチオン系硬化触媒で一般式（１）で示される脂環式エポキシ樹脂または一般式（２）で示される水添ビフェニル型脂環式エポキシ樹脂を硬化した場合には、耐熱性(ガラス転移温度)が２００℃以上で透明な硬化物を得ることができる。特に一般式（１）でＸが−Ｃ(ＣＨ3)2−である２，２−ビス（３’，４’−エポキシシクロヘキシル）プロパンを用いた場合にはガラス転移温度が２５０℃以上、一般式（２）で示される水添ビフェニル型脂環式エポキシ樹脂を用いた場合には耐熱性(ガラス転移温度)が３００℃以上となり、特に好ましい。
耐熱性(ガラス転移温度)が２３０℃未満であると透明複合シート、透明バリア性シートとして使用する際、高温プロセスにおいて、高温での透明複合シート、透明バリア性シートの強度や弾性率か不十分で透明複合シート、透明バリア性シートが変形するおそれがある。
By using the alicyclic epoxy resin represented by the general formula (1) or the hydrogenated biphenyl alicyclic epoxy resin represented by the general formula (2), both excellent heat resistance and good transparency can be achieved. Can do. Specifically, when the alicyclic epoxy resin represented by the general formula (1) or the hydrogenated biphenyl alicyclic epoxy resin represented by the general formula (2) is cured with a thermal cationic curing catalyst, A transparent cured product having a property (glass transition temperature) of 200 ° C. or higher can be obtained. In particular, when 2,2-bis (3 ′, 4′-epoxycyclohexyl) propane having the general formula (1) where X is —C (CH 3 ) 2 — is used, the glass transition temperature is 250 ° C. or higher. When the hydrogenated biphenyl type alicyclic epoxy resin represented by the formula (2) is used, the heat resistance (glass transition temperature) is 300 ° C. or more, which is particularly preferable.
When the heat resistance (glass transition temperature) is less than 230 ° C, the strength and elastic modulus of the transparent composite sheet and the transparent barrier sheet at high temperature are insufficient in the high temperature process when used as a transparent composite sheet and a transparent barrier sheet. The transparent composite sheet and the transparent barrier sheet may be deformed.
本発明に使用する透明樹脂（ａ）は、ガラスフィラー（ｂ）との屈折率を合わせる目的で一般式（１）で示される脂環式エポキシ樹脂または一般式（２）で示される水添ビフェニル型脂環式エポキシ樹脂と屈折率の異なる成分を併用することが好ましい。屈折率の異なる成分としては、併用することでガラスフィラー（ｂ）と屈折率を合わせる事ができ、透明な複合体を得ることができる成分であれば特に制限されないが、エポキシ基を有する化合物やオキセタニル基を有する化合物が、一般式（１）で示される脂環式エポキシ樹脂または一般式（２）で示される水添ビフェニル型脂環式エポキシ樹脂と共架橋するので好ましい。 The transparent resin (a) used in the present invention is an alicyclic epoxy resin represented by the general formula (1) or a hydrogenated biphenyl represented by the general formula (2) for the purpose of matching the refractive index with the glass filler (b). It is preferable to use a component having a refractive index different from that of the type alicyclic epoxy resin. The component having a different refractive index is not particularly limited as long as it is a component that can be combined with the glass filler (b) and have a refractive index, and can obtain a transparent composite. A compound having an oxetanyl group is preferable because it co-crosslinks with the alicyclic epoxy resin represented by the general formula (1) or the hydrogenated biphenyl alicyclic epoxy resin represented by the general formula (2).
ガラスフィラー（ｂ）として、ＮＥガラスを用いる場合には、一般式（１）で示される脂環式エポキシ樹脂または一般式（２）で示される水添ビフェニル型脂環式エポキシ樹脂よりも屈折率の低い樹脂を併用することが好ましい。一般式（１）で示される脂環式エポキシ樹脂または一般式（２）で示される水添ビフェニル型脂環式エポキシ樹脂よりも屈折率の低い成分としては、各種のエポキシ基を有する化合物やオキセタニル基を有する化合物を用いることができるが、耐熱性が優れていることからオキセタニル基を有するシルセスキオキサン（ｃ）が特に好ましい。オキセタニル基を有するシルセスキオキサン（ｃ）を併用することで、優れた耐熱性を維持したまま、ガラスフィラー（ｂ）と屈折率を合わせる事ができる。 When NE glass is used as the glass filler (b), the refractive index is higher than that of the alicyclic epoxy resin represented by the general formula (1) or the hydrogenated biphenyl alicyclic epoxy resin represented by the general formula (2). It is preferable to use a low-resin together. As a component having a lower refractive index than the alicyclic epoxy resin represented by the general formula (1) or the hydrogenated biphenyl alicyclic epoxy resin represented by the general formula (2), compounds having various epoxy groups and oxetanyl Although a compound having a group can be used, silsesquioxane (c) having an oxetanyl group is particularly preferable because of excellent heat resistance. By using together the silsesquioxane (c) which has an oxetanyl group, a refractive index can be match | combined with a glass filler (b), maintaining the outstanding heat resistance.
本発明で用いられる透明樹脂（ａ）は、耐熱性が高い硬化物が得られることからカチオン系硬化触媒（ｄ）で硬化することが好ましい。カチオン系硬化触媒（ｄ）としては、加熱によりカチオン重合を開始させる物質を放出する開始剤や活性エネルギー線によってカチオン重合を開始させる物質を放出させる開始剤などがあげられるが、耐熱性が高い硬化物が得られることから加熱によりカチオン重合を開始する物質を放出する開始剤、すなわち熱カチオン系硬化触媒が特に好ましい。 The transparent resin (a) used in the present invention is preferably cured with a cationic curing catalyst (d) because a cured product having high heat resistance is obtained. Examples of the cationic curing catalyst (d) include an initiator that releases a substance that initiates cationic polymerization by heating and an initiator that releases a substance that initiates cationic polymerization by active energy rays. In particular, an initiator that releases a substance that initiates cationic polymerization upon heating, that is, a thermal cationic curing catalyst, is preferable because a product is obtained.
好ましい熱カチオン硬化触媒としては、芳香族スルホニウム塩、芳香族ヨードニウム塩、アルミニウムキレートなどがある。具体的な例としては、芳香族スルホニウム塩としては三新化学工業製のＳＩ−６０Ｌ、ＳＩ−８０Ｌ、ＳＩ−１００Ｌ、旭電化工業製のＳＰ−６６やＳＰ−７７などがあり、アルミニウムキレートとしては、ダイセル化学工業製ＤＡＩＣＡＴ ＥＸ−１などがあげられる。 Preferred thermal cation curing catalysts include aromatic sulfonium salts, aromatic iodonium salts, aluminum chelates and the like. Specific examples include aromatic sulfonium salts such as SI-60L, SI-80L, SI-100L manufactured by Sanshin Chemical Industry, SP-66 and SP-77 manufactured by Asahi Denka Kogyo Co., Ltd. Is Daicel Chemical Industries' DAICAT EX-1.
また、前記透明樹脂(ａ)を用いることで透明複合シートの吸水率を低く押さえることができる。吸水率が大きいと、後の基板形成時、さらにその後の基板使用時に吸水に起因する基板の変形が生じる。基板の変形を抑えるには透明樹脂(ａ)の吸水率は３％以下であることが必要である。 Moreover, the water absorption rate of the transparent composite sheet can be kept low by using the transparent resin (a). When the water absorption rate is large, the substrate is deformed due to water absorption when the substrate is formed later and when the substrate is used thereafter. In order to suppress the deformation of the substrate, the water absorption of the transparent resin (a) needs to be 3% or less.
本発明の透明樹脂(ａ)の屈折率とガラスフィラー(ｂ)の屈折率との差は、優れた透明性を維持するため０.０１以下であることが好ましく、０.００５以下がより好ましい。屈折率差が０.０１より大きい場合には、得られるプラスチック基板の透明性が劣る傾向がある。 The difference between the refractive index of the transparent resin (a) of the present invention and the refractive index of the glass filler (b) is preferably 0.01 or less, more preferably 0.005 or less in order to maintain excellent transparency. . When the refractive index difference is larger than 0.01, the resulting plastic substrate tends to be inferior in transparency.
本発明で用いるガラスフィラー(ｂ)の屈折率は、優れた透明性の複合体を得るため１.４５〜１.５５であるのが好ましい。特にガラスフィラーの屈折率が１.５０〜１.５４の場合には、ガラスのアッベ数に近い透明樹脂が選択できるので特に好ましい。透明樹脂とガラスとのアッベ数が近いと広い波長領域で屈折率が一致し、広範囲で高い光線透過率が得られる。 The refractive index of the glass filler (b) used in the present invention is preferably 1.45 to 1.55 in order to obtain an excellent transparent composite. In particular, when the refractive index of the glass filler is 1.50 to 1.54, a transparent resin close to the glass Abbe number can be selected, which is particularly preferable. When the Abbe number between the transparent resin and the glass is close, the refractive indexes coincide in a wide wavelength region, and a high light transmittance can be obtained in a wide range.
本発明で用いるガラスフィラー(ｂ)としては、ガラス繊維、ガラスクロスやガラス不織布などのガラス繊維布、ガラスビーズ、ガラスフレーク、ガラスパウダー、ミルドガラスなどがあげられ、中でも線膨張係数の低減効果が高いことから、ガラス繊維、ガラスクロス、ガラス不織布が好ましく、ガラスクロスが最も好ましい。 Examples of the glass filler (b) used in the present invention include glass fiber cloths such as glass fiber, glass cloth and glass nonwoven fabric, glass beads, glass flakes, glass powder, and milled glass. Since it is high, glass fiber, glass cloth and glass nonwoven fabric are preferable, and glass cloth is most preferable.
ガラスの種類としては、Ｅガラス、Ｃガラス、Ａガラス、Ｓガラス、Ｄガラス、ＮＥガラス、Ｔガラス、クオーツ、低誘電率ガラス、高誘電率ガラスなどが挙げられ、中でもアルカリ金属などのイオン性不純物がすくなく入手の容易なＥガラス、Ｓガラス、Ｔガラス、ＮＥガラスが好ましい。 Examples of the glass include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, quartz, low dielectric constant glass, and high dielectric constant glass. E glass, S glass, T glass, and NE glass, which have few impurities and are easily available, are preferred.
ガラスフィラー(ｂ)の配合量は１〜９０重量％が好ましく、より好ましくは１０〜８０重量％、さらに好ましくは３０〜７０重量％である。ガラスフィラーの配合量がこの範囲であれば成形が容易で、複合化による線膨張の低下の効果が認められる。 The blending amount of the glass filler (b) is preferably 1 to 90% by weight, more preferably 10 to 80% by weight, and still more preferably 30 to 70% by weight. If the blending amount of the glass filler is within this range, molding is easy and the effect of lowering linear expansion due to compounding is recognized.
本発明の透明複合体組成物においては、ガラスフィラーと樹脂とが密着しているほど、表示素子用プラスチック基板など複合体組成物の透明性がよくなるため、ガラスフィラー表面をシランカップリング剤などの公知の表面処理剤で処理するのが好ましい。好ましいシランカップリング剤しては、カチオン硬化触媒で樹脂とともに反応することからエポキシシランやオキセタニルシランなどがあげられる。 In the transparent composite composition of the present invention, as the glass filler and the resin are in close contact with each other, the transparency of the composite composition such as a plastic substrate for a display element is improved. It is preferable to treat with a known surface treating agent. Preferable silane coupling agents include epoxy silane and oxetanyl silane because they react with a resin with a cationic curing catalyst.
本発明の透明バリア性シートの透明複合シート部分には、必要に応じて、透明性、耐溶剤性、耐熱性等の特性を損なわない範囲で、熱可塑性又は熱硬化性のオリゴマーやポリマーを併用してよい。これら熱可塑性または熱硬化性のオリゴマーやポリマーを併用する場合は、全体の屈折率がガラスフィラーの屈折率に合うように組成比を調整する必要がある。また、本発明の透明複合シート中には、必要に応じて、透明性、耐溶剤性、耐熱性等の特性を損なわない範囲で、少量の酸化防止剤、紫外線吸収剤、染顔料、他の無機フィラー等の充填剤等を含んでいても良い。 In the transparent composite sheet portion of the transparent barrier sheet of the present invention, if necessary, a thermoplastic or thermosetting oligomer or polymer is used in combination as long as the properties such as transparency, solvent resistance and heat resistance are not impaired. You can do it. When these thermoplastic or thermosetting oligomers or polymers are used in combination, it is necessary to adjust the composition ratio so that the overall refractive index matches the refractive index of the glass filler. In the transparent composite sheet of the present invention, if necessary, a small amount of antioxidant, ultraviolet absorber, dye / pigment, and the like, as long as the properties such as transparency, solvent resistance and heat resistance are not impaired. It may contain a filler such as an inorganic filler.
透明複合シートの成形方法に制限はなく、例えば、未硬化の樹脂組成物とガラスフィラーとを直接混合し、必要な型に注型したのち架橋させてシートなどとする方法、未硬化の樹脂組成物を溶剤に溶解しガラスフィラーを分散させキャストした後、架橋させてシートなどとする方法、未硬化の樹脂組成物をガラスクロスやガラス不織布に含浸させたのち架橋させてシートなどとする方法等々が挙げられる。 There is no limitation on the molding method of the transparent composite sheet, for example, a method in which an uncured resin composition and a glass filler are directly mixed, cast into a required mold and then cross-linked into a sheet, an uncured resin composition A method in which a product is dissolved in a solvent and a glass filler is dispersed and cast, followed by crosslinking to form a sheet, a method in which an uncured resin composition is impregnated into glass cloth or a glass nonwoven fabric, and then crosslinked to form a sheet, etc. Is mentioned.
本発明の透明バリア性シートのバリア層は真空プロセスにより形成される無機物から成ることが好ましい。透明でガス・水蒸気バリア性をもつ無機物なら特に制限は無いが例えば、Ｓｉ、Ａｌ、Ｉｎ、Ｓｎ、Ｚｎ、Ｔｉ、Ｃｕ、Ｃｅ、Ｍｇ、Ｌａ、Ｃｒ、Ｃａ、Ｚｒ、Ｔａ等の１種以上を含む酸化物もしくは窒化物もしくは酸化窒化物、もしくはハロゲン化物などを用いることができる。なかでもＳｉの酸化物、窒化物、酸化窒化物はガス・水蒸気バリア性能および加工コストの面から好適な材料である。 The barrier layer of the transparent barrier sheet of the present invention is preferably made of an inorganic material formed by a vacuum process. There are no particular restrictions as long as it is transparent and has a gas / water vapor barrier property. For example, one or more of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Mg, La, Cr, Ca, Zr, Ta, etc. An oxide, a nitride, an oxynitride, a halide, or the like containing can be used. Of these, Si oxides, nitrides, and oxynitrides are suitable materials in terms of gas / water vapor barrier performance and processing cost.
バリア層の厚さは２０〜５００ｎｍが好ましく、５０〜２００ｎｍであればさらに好ましい。バリア層の厚さが２０ｎｍ未満だとガス・水蒸気の透過を防ぐに十分ではなく、バリア層が５００ｎｍよりも厚くなると、曲げに弱いバリア層となり、クラックなどの層破壊を生じて、バリア性能の劣化を招きやすくなる。 The thickness of the barrier layer is preferably 20 to 500 nm, and more preferably 50 to 200 nm. If the thickness of the barrier layer is less than 20 nm, it is not sufficient to prevent the permeation of gas and water vapor. If the barrier layer is thicker than 500 nm, it becomes a barrier layer that is weak against bending, causing layer breakdown such as cracks, It tends to cause deterioration.
バリア層の形成には真空プロセスであれば特に制限は無い。真空プロセスとは、バリア層の形成を大気圧よりも小さな圧力雰囲気下で施すプロセスである。例えば、真空蒸着法やスパッタリング法、ＣＶＤ法などを選ぶことができる。真空蒸着法には抵抗加熱方式、電子ビーム方式など様々な方式があるがバリア層を形成できるものであればとくに制限は無い。スパッタリング法にもＲＦスパッタリング方式、ＤＣスパッタリング方式、パルス成分や波動成分を重畳するＤＣスパッタ方式など様々な方式があるがバリア層を形成できるものであればとくに制限は無い。コストの面から真空蒸着方式、ＤＣスパッタ方式が好適である。ＤＣスパッタを選ぶ場合は、プロセス安定性の高い、パルス成分や波動成分を重畳するＤＣスパッタ方式が好ましい。 The formation of the barrier layer is not particularly limited as long as it is a vacuum process. The vacuum process is a process in which the barrier layer is formed in an atmosphere having a pressure smaller than atmospheric pressure. For example, a vacuum deposition method, a sputtering method, a CVD method, or the like can be selected. There are various methods such as a resistance heating method and an electron beam method in the vacuum evaporation method, but there is no particular limitation as long as a barrier layer can be formed. There are various sputtering methods such as an RF sputtering method, a DC sputtering method, and a DC sputtering method in which a pulse component and a wave component are superimposed, but there is no particular limitation as long as a barrier layer can be formed. From the viewpoint of cost, a vacuum deposition method and a DC sputtering method are preferable. When DC sputtering is selected, a DC sputtering method in which a pulse component and a wave component are superimposed with high process stability is preferable.
本発明の透明バリア性シートを表示素子用プラスチック基板とする場合、平滑牲を向上させるために透明バリア性シートの透明複合シート部分の片面もしくは両面に有機物層を設けても良い。かかる有機物は優れた透明性、耐熱性、耐薬品性を有していることが好ましく、具体的には多官能アクリレートやエポキシ樹脂などが好ましい。 When the transparent barrier sheet of the present invention is used as a plastic substrate for a display element, an organic layer may be provided on one or both sides of the transparent composite sheet portion of the transparent barrier sheet in order to improve smoothness. Such organic materials preferably have excellent transparency, heat resistance, and chemical resistance, and specifically, polyfunctional acrylates and epoxy resins are preferable.
該有機物層の有機物としては、例えば、エポキシアクリレート、ウレタンアクリレート、イソシアヌール酸ＥＯ変性アクリレート、ペンタエリスリトールアクリレート、トリメチロールプロパンアクリレート、エチレングリコールアクリレート、ポリエステルアクリレート、環状エーテル型アクリレート、ノルボルネンアクリレート等のアクリロイル基を有するモノマーを主成分とする樹脂組成物を好適に用いる事ができるが、特に限定はしない。また、２官能以上のアクリロイル基を有するモノマーを主成分とすることが好ましい。これらの２官能以上のアクリロイル基を有するモノマーは２種類以上を混合して用いても、また１官能のアクリレートを混合して用いても良く、１官能のアクリレートを混合する方法は硬化収縮を小さく抑える点でより好ましい。また、特に架橋度が高く、ガラス転移温度が２００℃以上である、イソシアヌール酸ＥＯ変性トリアクリレートを主成分とすることも好ましい。また、シリコン系、フッ素系のレベリング材、シリコン系、チタネート系、メルカプト系のシランカップリング材等を添加しても良い。 Examples of the organic substance in the organic layer include acryloyl groups such as epoxy acrylate, urethane acrylate, isocyanuric acid EO-modified acrylate, pentaerythritol acrylate, trimethylolpropane acrylate, ethylene glycol acrylate, polyester acrylate, cyclic ether acrylate, norbornene acrylate, and the like. Although the resin composition which has as a main component the monomer which has can be used suitably, it does not specifically limit. Moreover, it is preferable that the monomer which has bifunctional or more acryloyl group is made into a main component. These monomers having a bifunctional or higher acryloyl group may be used as a mixture of two or more types, or may be used as a mixture of monofunctional acrylates. The method of mixing monofunctional acrylates reduces cure shrinkage. It is more preferable in terms of suppression. In addition, it is also preferable that the main component is an isocyanuric acid EO-modified triacrylate having a particularly high degree of crosslinking and a glass transition temperature of 200 ° C. or higher. Further, a silicon-based or fluorine-based leveling material, a silicon-based, titanate-based, or mercapto-based silane coupling material may be added.
有機物層の厚みは０.０１〜５０μｍが好ましく、０.５〜３０μｍがより好ましい。厚みが０．０１μｍ未満の場合は、有機物層の成膜方法にも依存するが面内の膜厚が不均一になるため、平滑化の効果が乏しくなり、厚みが５０μｍを超えると透明バリア性シートのフレキシブル性が低下する。 The thickness of the organic layer is preferably from 0.01 to 50 μm, more preferably from 0.5 to 30 μm. When the thickness is less than 0.01 μm, the in-plane film thickness becomes non-uniform depending on the method of forming the organic layer, but the smoothing effect becomes poor. When the thickness exceeds 50 μm, the transparent barrier property The flexibility of the sheet is reduced.
本発明の透明バリア性シートのバリア層の上の片面もしくは両面に有機物層を設けても良い。バリア層は傷つきやすく、取り扱い時に入った傷などでバリア性能が劣化する場合があるが、バリア層の上に有機物層を設けてバリア層を保護することでバリア層が傷つきバリア性能が劣化するのを防ぐことができる。かかる有機物としては本発明の透明樹脂（ａ）、もしくは前記のバリア層と透明複合シートの間の有機物層と同じ有機物が適用できる。 An organic layer may be provided on one or both sides of the barrier layer of the transparent barrier sheet of the present invention. The barrier layer is easily damaged, and the barrier performance may be deteriorated due to scratches entered during handling. However, by protecting the barrier layer by providing an organic layer on the barrier layer, the barrier layer is damaged and the barrier performance is deteriorated. Can be prevented. As the organic substance, the transparent resin (a) of the present invention or the same organic substance as the organic substance layer between the barrier layer and the transparent composite sheet can be applied.
また、この有機物層の上にさらにバリア層を形成する場合には有機物層によりバリア層どうしの密着性の向上や表面の平滑性の向上が期待できる。また、かかる有機物層の有機物にバリア性能のより良い有機物を使うことで透明バリア性シートのバリア性能を向上することができる。 When a barrier layer is further formed on the organic material layer, the organic material layer can be expected to improve the adhesion between the barrier layers and the surface smoothness. Moreover, the barrier performance of a transparent barrier sheet | seat can be improved by using organic substance with better barrier performance for the organic substance of this organic substance layer.
バリア性能を向上させるに好ましく用いる樹脂としては、ＪＩＳ Ｋ ７１２９のＢ法による水蒸気透過度測定において、アクリロイル基の反応率を３０％以上として２００μｍ厚に硬化させた時の水蒸気透過度が３０ｇ／ｍ２／ｄａｙより小さいアクリロイル基を有するモノマーを主成分とする樹脂組成物であれば特に制限はないが、臭素化ビスフェノールＡ型エポキシアクリレート等のエポキシアクリレート、ウレタンアクリレート、イソシアヌール酸ＥＯ変性アクリレート、トリメチロールプロパンアクリレート、ポリエステルアクリレート、環状エーテル型アクリレート、ノルボルネンアクリレート、ジシクロペンタジエニルアクリレート等のシクロオレフィン型アクリレート、シクロオレフィン型エポキシアクリレート、フルオレン型アクリレート、フルオレン型エポキシアクリレート等を用いることができる。特にこれらのうち、２官能以上のアクリロイル基を有するモノマーを主成分とすることが好ましく、中でもイソシアヌール酸ＥＯ変性アクリレート、ノルボルネンジアクリレート、ジシクロペンタジエニルジアクリレート、臭素化ビスフェノールＡ型エポキシジアクリレート、フルオレン型ジアクリレート、フルオレン型エポキシジアクリレートの内、一種類以上を主成分とすることが有機物層の水蒸気透過度を低く抑える点でより好ましい。これらの２官能以上のアクリロイル基を有するモノマーは単独で用いても２種類以上を混合して用いても良い。また、それ自体で樹脂としては比較的バリア性能の高いＰＶＡ系やＥＶＡ系、ポリ塩化ビニリデン、もしくはこれらの樹脂の複数を混用することもできる。また、シリコン系、フッ素系のレベリング材、シリコン系、チタネート系、メルカプト系のシランカップリング材等を添加しても良い。 As a resin preferably used for improving the barrier performance, the water vapor transmission rate when cured to 200 μm thickness with a reaction rate of acryloyl group of 30% or more in the water vapor transmission rate measurement by B method of JIS K 7129 is 30 g / m. The resin composition is not particularly limited as long as it is a resin composition mainly composed of a monomer having an acryloyl group smaller than 2 / day. However, epoxy acrylate such as brominated bisphenol A type epoxy acrylate, urethane acrylate, isocyanuric acid EO-modified acrylate, Cycloolefin type acrylate such as methylolpropane acrylate, polyester acrylate, cyclic ether type acrylate, norbornene acrylate, dicyclopentadienyl acrylate, cycloolefin type epoxy acrylate, fluorene Acrylate, and fluorene epoxy acrylate. In particular, it is preferable to use a monomer having a bifunctional or higher acryloyl group as a main component. Among them, isocyanuric acid EO-modified acrylate, norbornene diacrylate, dicyclopentadienyl diacrylate, brominated bisphenol A type epoxy diester. Of the acrylate, fluorene type diacrylate, and fluorene type epoxy diacrylate, it is more preferable that one or more kinds thereof are the main component from the viewpoint of keeping the water vapor permeability of the organic layer low. These monomers having a bifunctional or higher functional acryloyl group may be used alone or in admixture of two or more. Further, as the resin itself, PVA type, EVA type, polyvinylidene chloride having a relatively high barrier performance, or a plurality of these resins can be used in combination. Further, a silicon-based or fluorine-based leveling material, a silicon-based, titanate-based, or mercapto-based silane coupling material may be added.
有機物層の厚みは０.０１〜５０μｍが好ましく、０.５〜３０μｍがより好ましい。厚みが０．０１μｍ未満の場合は、有機物層の成膜方法にも依存するが面内の膜厚が不均一になるため、平滑化の効果が乏しくなり、厚みが５０μｍを超えると透明バリア性シートのフレキシブル性が低下する。 The thickness of the organic layer is preferably from 0.01 to 50 μm, more preferably from 0.5 to 30 μm. When the thickness is less than 0.01 μm, the in-plane film thickness becomes non-uniform depending on the method of forming the organic layer, but the smoothing effect becomes poor. When the thickness exceeds 50 μm, the transparent barrier property The flexibility of the sheet is reduced.
本発明の透明バリア性シートを、液晶表示素子用プラスチック基板、カラーフィルター用基板、有機ＥＬ表示素子用プラスチック基板、電子ペーパー用基板、太陽電池基板、タッチパネル等の光学用途として用いる場合、基板の厚さは好ましくは５０〜２０００μｍであり、より好ましくは５０〜１０００μｍである。基板の厚さがこの範囲にあると平坦性に優れ、ガラス基板と比較して基板の軽量化を図ることができる。 When the transparent barrier sheet of the present invention is used for optical applications such as a liquid crystal display element plastic substrate, a color filter substrate, an organic EL display element plastic substrate, an electronic paper substrate, a solar cell substrate, and a touch panel, the thickness of the substrate The thickness is preferably 50 to 2000 μm, more preferably 50 to 1000 μm. When the thickness of the substrate is within this range, the flatness is excellent, and the weight of the substrate can be reduced as compared with the glass substrate.
この透明バリア性シートを前記光学用途として用いる場合、３０〜１５０℃における平均線膨張係数が４０ｐｐｍ以下であることが好ましく、より好ましくは３０ｐｐｍ以下、最も好ましくは２０ｐｐｍ以下である。例えば、この透明バリア性シートをアクティブマトリックス表示素子基板に用いた場合、この上限値を越えると、その製造工程において反りやアルミ配線の断線などの問題が生じる恐れがある。 When this transparent barrier sheet is used as the optical application, the average linear expansion coefficient at 30 to 150 ° C. is preferably 40 ppm or less, more preferably 30 ppm or less, and most preferably 20 ppm or less. For example, when this transparent barrier sheet is used for an active matrix display element substrate, if this upper limit is exceeded, problems such as warpage and disconnection of aluminum wiring may occur in the manufacturing process.
本発明の透明バリア性シートを表示基板用プラスチック基板として用いる場合、波長５５０ｎｍにおける光線透過率８０％以上が必要であり、さらに好ましくは８５％以上であり、最も好ましくは８８％以上である。波長５５０ｎｍにおける光線透過率が下限値未満では表示性能が充分でない。 When the transparent barrier sheet of the present invention is used as a plastic substrate for a display substrate, the light transmittance at a wavelength of 550 nm is required to be 80% or more, more preferably 85% or more, and most preferably 88% or more. If the light transmittance at a wavelength of 550 nm is less than the lower limit, the display performance is not sufficient.
本発明の透明バリア性シートを前記表示基板用プラスチック基板として用いる場合はＪＩＳ Ｋ ７１２９のＢ法による水蒸気透過度測定において１ｇ／ｍ２／ｄａｙ以下であることが好ましく、より好ましくは０．１ｇ／ｍ２／ｄａｙ以下である。例えば、この透明バリア性シートをアクティブマトリックス表示素子基板に用いた場合、この上限値を越えると、その製造工程において吸湿による反りや寸法変化が生じたり、表示素子内部にガスや水分が浸入してくるなどの不具合を生じる。 When the transparent barrier sheet of the present invention is used as the display substrate plastic substrate, it is preferably 1 g / m 2 / day or less, more preferably 0.1 g / m 2 in water vapor permeability measurement by JIS K 7129 method B. m 2 / day or less. For example, when this transparent barrier sheet is used for an active matrix display element substrate, if this upper limit is exceeded, warpage or dimensional change due to moisture absorption may occur in the manufacturing process, or gas or moisture may enter the display element. This causes problems such as coming.
以下、本発明の内容を実施例により詳細に説明するが、本発明は、その要旨を越えない限り以下の例に限定されるものではない。
(実施例１)
Ｓガラス系ガラスクロス(厚さ１００μｍ、屈折率１.５２８、ユニチカクロス製、＃２１１７タイプ)を焼きだしし、有機物を除去した後、グリシドキシプロピルトリメトキシシラン(エポキシシラン)で処理した。このガラスクロスに、水添ビフェニル型脂環式エポキシ樹脂（ダイセル化学工業製、Ｅ−ＢＰ）９４重量部、オキセタニル基を有するシルキセスキオキサン(東亞合成製、ＯＸ−ＳＱ)４重量部、芳香族スルホニウム系熱カチオン触媒（三新化学製、ＳＩ−１００Ｌ）１重量部を溶融混合した樹脂（硬化後の樹脂の屈折率１．５３０）を含浸し、脱泡した。このガラスクロスを離型処理したガラス板に挟み込んで、オーブン中、８０℃にて２時間加熱後、さらに２００℃にて２時間加熱して、厚さ０.１ｍｍの透明複合シートを得た。こうして得られた透明複合シートをＤＣスパッタ装置にセットし１０−４Ｐａの真空雰囲気下に置いた状態でアルゴンガスを０．１Ｐａ、窒素ガスを０．０７Ｐａ、酸素ガスを０．０５Ｐａ導入した。ここで透明複合シートと対向するように設置されたＳｉターゲット上に電界をかけてプラズマを生じさせ、スパッタリングを開始した。ここではパルス成分を重畳するＤＣスパッタ方式を用いた。透明複合シート上に１２０ｎｍのＳｉＯＮ層を堆積させたところでスパッタプロセスを終了し透明複合シートをスパッタ装置から取り出した。さらに、いまＳｉＯＮ層を堆積した面とは反対側の面にも、前記方法にてＳｉＯＮ層を堆積させて透明バリア性シートを得た。
Hereinafter, the contents of the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
(Example 1)
S glass-based glass cloth (thickness: 100 μm, refractive index: 1.528, manufactured by Unitika cloth, # 2117 type) was baked to remove organic substances, and then treated with glycidoxypropyltrimethoxysilane (epoxysilane). In this glass cloth, 94 parts by weight of hydrogenated biphenyl type alicyclic epoxy resin (manufactured by Daicel Chemical Industries, E-BP), 4 parts by weight of silxesquioxane having an oxetanyl group (manufactured by Toagosei Co., Ltd., OX-SQ), aromatic A resin obtained by melt-mixing 1 part by weight of a group sulfonium-based thermal cation catalyst (manufactured by Sanshin Chemical Co., Ltd., SI-100L) (refractive index of cured resin 1.530) was defoamed. The glass cloth was sandwiched between release-molded glass plates, heated in an oven at 80 ° C. for 2 hours, and further heated at 200 ° C. for 2 hours to obtain a transparent composite sheet having a thickness of 0.1 mm. The transparent composite sheet thus obtained was set in a DC sputtering apparatus and placed in a vacuum atmosphere of 10 −4 Pa, and argon gas was introduced at 0.1 Pa, nitrogen gas at 0.07 Pa, and oxygen gas at 0.05 Pa. Here, an electric field was applied to the Si target placed so as to face the transparent composite sheet to generate plasma, and sputtering was started. Here, a DC sputtering method in which a pulse component is superimposed is used. When a 120 nm SiON layer was deposited on the transparent composite sheet, the sputtering process was terminated and the transparent composite sheet was taken out from the sputtering apparatus. Further, the SiON layer was deposited on the surface opposite to the surface on which the SiON layer was deposited, to obtain a transparent barrier sheet.
（実施例２）
ＮＥガラス系ガラスクロス(厚さ１００μｍ、屈折率１.５１０、日東紡製)を焼きだしして有機物を除去した後、グリシドキシプロピルトリメトキシシラン(エポキシシラン)で処理した。このガラスクロスに水添ビフェニル型脂環式エポキシ樹脂（ダイセル化学工業製、Ｅ−ＢＰ）７５重量部、オキセタニル基を有するシルキセスキオキサン(東亞合成製、ＯＸ−ＳＱ)２５重量部、芳香族スルホニウム系熱カチオン触媒（三新化学製、ＳＩ−１００Ｌ）１重量部を溶融混合した樹脂（硬化後の樹脂の屈折率１．５１０）を含浸し、脱泡した。溶融混合した樹脂を含浸し、脱泡した。樹脂を含浸したこのガラスクロスを離型処理したガラス板に挟み込んで、オーブン中、実施例１と同条件にて加熱処理を行い、厚さ０.１ｍｍの透明複合シートを得た。さらに、実施例１と同じ方法で透明複合シートの両面にＳｉＯＮ層を堆積させて透明バリア性シートを得た。
(Example 2)
NE glass-based glass cloth (thickness: 100 μm, refractive index: 1.510, manufactured by Nittobo) was baked to remove organic substances, and then treated with glycidoxypropyltrimethoxysilane (epoxysilane). On this glass cloth, 75 parts by weight of hydrogenated biphenyl type alicyclic epoxy resin (manufactured by Daicel Chemical Industries, E-BP), 25 parts by weight of silxesquioxane having an oxetanyl group (manufactured by Toagosei Co., Ltd., OX-SQ), aromatic A resin (refractive index of the cured resin 1.510) obtained by melting and mixing 1 part by weight of a sulfonium-based thermal cation catalyst (manufactured by Sanshin Chemical Co., Ltd., SI-100L) was impregnated and defoamed. The melt-mixed resin was impregnated and degassed. The glass cloth impregnated with the resin was sandwiched between the release-treated glass plates and heat-treated in the oven under the same conditions as in Example 1 to obtain a transparent composite sheet having a thickness of 0.1 mm. Further, SiON layers were deposited on both surfaces of the transparent composite sheet by the same method as in Example 1 to obtain a transparent barrier sheet.
（実施例３）
ＮＥガラス系ガラスクロス(厚さ１００μｍ、屈折率１.５１０、日東紡製)を焼きだしして有機物を除去した後、グリシドキシプロピルトリメトキシシラン(エポキシシラン)で処理した。このガラスクロスに２，２−ビス（３’，４’−エポキシシクロヘキシル）プロパン（ダイセル化学工業製、Ｅ−ＤＯＡ）１００重量部、芳香族スルホニウム系熱カチオン触媒（三新化学製、ＳＩ−１００Ｌ）１重量部を溶融混合した樹脂（硬化後の樹脂の屈折率１．５１２）を含浸し、脱泡した。溶融混合した樹脂を含浸し、脱泡した。樹脂を含浸したこのガラスクロスを離型処理したガラス板に挟み込んで、オーブン中、８０℃にて２時間加熱後、さらに２５０℃にて２時間加熱して、厚さ０.１ｍｍの透明複合シートを得た。さらに、実施例１と同じ方法で透明複合シートの両面にＳｉＯＮ層を堆積させて透明バリア性シートを得た。
(Example 3)
NE glass-based glass cloth (thickness: 100 μm, refractive index: 1.510, manufactured by Nittobo) was baked to remove organic substances, and then treated with glycidoxypropyltrimethoxysilane (epoxysilane). 2,2-bis (3 ′, 4′-epoxycyclohexyl) propane (Daicel Chemical Industries, E-DOA) 100 parts by weight on this glass cloth, aromatic sulfonium-based thermal cation catalyst (manufactured by Sanshin Chemical, SI-100L) ) 1 part by weight of a resin melted and mixed (refractive index of cured resin 1.512) was impregnated and defoamed. The melt-mixed resin was impregnated and degassed. This glass cloth impregnated with resin is sandwiched between release-treated glass plates, heated in an oven at 80 ° C. for 2 hours, and further heated at 250 ° C. for 2 hours to form a transparent composite sheet having a thickness of 0.1 mm Got. Further, SiON layers were deposited on both surfaces of the transparent composite sheet by the same method as in Example 1 to obtain a transparent barrier sheet.
（実施例４）
平均粒子径３．２μｍのＮＥガラスパウダー(屈折率１.５１０、日東紡製)を焼きだしして有機物を除去した後、グリシドキシプロピルトリメトキシシラン(エポキシシラン)で処理した。このガラスパウダー１００重量部に２，２−ビス（３’，４’−エポキシシクロヘキシル）プロパン（ダイセル化学工業製、Ｅ−ＤＯＡ）１００重量部、芳香族スルホニウム系熱カチオン触媒（三新化学製、ＳＩ−１００Ｌ）１重量部を溶融混合した樹脂（硬化後の樹脂の屈折率１．５１２）に分散し、脱泡した。これを厚さ８０μｍのアルミ箔をスペーサーとしてガラス板に挟み込んで、オーブン中、８０℃にて２時間加熱後、さらに２５０℃にて２時間加熱して、厚さ０.１ｍｍの透明複合シートを得た。こうして得られた透明複合シートの片面に有機物層としてイソシアヌール酸ＥＯ変性トリアクリレート（東亞合成製 Ｍ−３１５）３０重量部、エポキシアクリレート（昭和高分子社製 ＶＲ−６０ＬＡＶ）４．５重量部、ウレタンアクリレート（大日本インキ社製 ユニディック１７−８０６）３重量部、光開始剤（チバガイギー社製 ＩＲＧ−９０７）１．５重量部、メチルセロソルブアセテート（沸点＝１４５℃）１２重量部、酢酸ブチル（沸点＝１２６℃）４０重量部，ブチルセロソルブ（沸点＝１７０℃）７．０重量部にて撹拌、溶解してＲＣ＝３６ｗｔ％の均一な溶液としたものをバーコーターにて塗布し、加熱乾燥機中９０℃で２分間続いて１２０℃で３分間加熱して溶媒を除去した。乾燥後の樹脂組成物に、高圧水銀灯にて350ｍＪ／cm2の紫外線を照射させ有機物層を透明複合シート上に作製した。これと反対側の面にも前記と同様に有機物層を設けた。さらに、実施例１と同じ方法で透明複合シートの両面の有機物層上にＳｉＯＮ層を堆積させた。さらにこの透明複合シートの片面のＳｉＯＮ層上に有機物層としてイソシアヌール酸ＥＯ変性トリアクリレート（東亞合成製 Ｍ−３１５）３０重量部、エポキシアクリレート（昭和高分子社製 ＶＲ−６０ＬＡＶ）４．５重量部、ウレタンアクリレート（大日本インキ社製 ユニディック１７−８０６）３重量部、光開始剤（チバガイギー社製 ＩＲＧ−９０７）１．５重量部、メチルセロソルブアセテート（沸点＝１４５℃）１２重量部、酢酸ブチル（沸点＝１２６℃）４０重量部，ブチルセロソルブ（沸点＝１７０℃）７．０重量部にて撹拌、溶解してＲＣ＝３６ｗｔ％の均一な溶液としたものをバーコーターにて塗布し、加熱乾燥機中９０℃で２分間続いて１２０℃で３分間加熱して溶媒を除去した。乾燥後の樹脂組成物に、高圧水銀灯にて350ｍＪ／cm2の紫外線を照射させ有機物層を作製した。作成した有機物層上に実施例１と同じ方法でＳｉＯＮ層を堆積させて透明バリア性シートを得た。
Example 4
NE glass powder having an average particle diameter of 3.2 μm (refractive index: 1.510, manufactured by Nittobo) was baked to remove organic substances, and then treated with glycidoxypropyltrimethoxysilane (epoxysilane). 100 parts by weight of this glass powder, 100 parts by weight of 2,2-bis (3 ′, 4′-epoxycyclohexyl) propane (manufactured by Daicel Chemical Industries, E-DOA), aromatic sulfonium-based thermal cation catalyst (manufactured by Sanshin Chemical) (SI-100L) 1 part by weight was dispersed in a melt-mixed resin (refractive index of cured resin 1.512) and defoamed. This is sandwiched between glass plates with an aluminum foil having a thickness of 80 μm as a spacer, heated in an oven at 80 ° C. for 2 hours, and further heated at 250 ° C. for 2 hours to obtain a transparent composite sheet having a thickness of 0.1 mm. Obtained. 30 parts by weight of an isocyanuric acid EO-modified triacrylate (Moto 315 manufactured by Toagosei Co., Ltd.), 4.5 parts by weight of an epoxy acrylate (VR-60LAV manufactured by Showa Polymer Co., Ltd.) as an organic layer on one side of the transparent composite sheet thus obtained. 3 parts by weight of urethane acrylate (Dai Nippon Ink Co., Ltd. Unidic 17-806), 1.5 parts by weight of photoinitiator (IRG-907 manufactured by Ciba Geigy), 12 parts by weight of methyl cellosolve acetate (boiling point = 145 ° C.), butyl acetate (Boiling point = 126 ° C.) 40 parts by weight, Butyl cellosolve (boiling point = 170 ° C.) 7.0 parts by weight Stirred and dissolved to obtain a uniform solution with RC = 36 wt% was applied with a bar coater and dried by heating. The solvent was removed by heating in the machine at 90 ° C. for 2 minutes and then at 120 ° C. for 3 minutes. The dried resin composition was irradiated with ultraviolet rays of 350 mJ / cm 2 with a high-pressure mercury lamp to produce an organic layer on the transparent composite sheet. An organic layer was provided on the opposite surface as described above. Further, SiON layers were deposited on the organic material layers on both sides of the transparent composite sheet in the same manner as in Example 1. Further, 30 parts by weight of isocyanuric acid EO-modified triacrylate (M-315, manufactured by Toagosei Co., Ltd.) and epoxy acrylate (VR-60LAV, manufactured by Showa Polymer Co., Ltd.) as an organic layer on the SiON layer on one side of the transparent composite sheet. Parts, 3 parts by weight of urethane acrylate (Dai Nippon Ink Co., Ltd. Unidic 17-806), 1.5 parts by weight of photoinitiator (IRG-907 manufactured by Ciba Geigy), 12 parts by weight of methyl cellosolve acetate (boiling point = 145 ° C.), Stirring and dissolving in 40 parts by weight of butyl acetate (boiling point = 126 ° C) and 7.0 parts by weight of butyl cellosolve (boiling point = 170 ° C) and applying a uniform solution of RC = 36 wt% with a bar coater, The solvent was removed by heating at 90 ° C. for 2 minutes followed by heating at 120 ° C. for 3 minutes in a heat dryer. The dried resin composition was irradiated with ultraviolet rays of 350 mJ / cm 2 with a high-pressure mercury lamp to produce an organic layer. A SiON layer was deposited on the prepared organic layer by the same method as in Example 1 to obtain a transparent barrier sheet.
（比較例１）
ビスフェノールＡ型エポキシ樹脂樹脂（ＪＥＲ（株）製、エピコート８２８）１００重量部、メチルヘキサヒドロフタル酸（新日本理化株式会社製、ＭＨ−７００）７８重量部、テトラフェニルホスホニウムブロマイド（北興化学工業製、ＴＰＰ−ＰＢ）１重量部を溶融混合し１００℃／２ｈ、２００℃／２ｈ硬化し厚さ３００μｍのシートを得た。こうして得られたシートをバッチ式ＤＣスパッタ装置にセットし１０−４Ｐａの真空雰囲気下に置いた状態でアルゴンガスを０．１Ｐａ、窒素ガスを０．０７Ｐａ、酸素ガスを０．０５Ｐａ導入した。ここでシートと対向するように設置されたＳｉターゲット上に電界をかけてプラズマを生じさせ、スパッタリングを開始した。ここではパルス成分を重畳するＤＣスパッタ方式を用いた。透明複合シート上に１２０ｎｍのＳｉＯＮ層を堆積させたところでスパッタプロセスを終了しシートをスパッタ装置から取り出した。さらに、いまＳｉＯＮ層を堆積した面とは反対側の面にも、前記方法にてＳｉＯＮ層を堆積させてシートを得た。
(Comparative Example 1)
100 parts by weight of bisphenol A type epoxy resin (manufactured by JER Corporation, Epicoat 828), 78 parts by weight of methylhexahydrophthalic acid (manufactured by Shin Nippon Rika Co., Ltd., MH-700), tetraphenylphosphonium bromide (manufactured by Hokuko Chemical Industries) , TPP-PB) 1 part by weight was melt-mixed and cured at 100 ° C./2 h and 200 ° C./2 h to obtain a sheet having a thickness of 300 μm. The sheet thus obtained was set in a batch type DC sputtering apparatus and placed in a vacuum atmosphere of 10 −4 Pa, and argon gas 0.1 Pa, nitrogen gas 0.07 Pa, and oxygen gas 0.05 Pa were introduced. Here, plasma was generated by applying an electric field on the Si target placed so as to face the sheet, and sputtering was started. Here, a DC sputtering method in which a pulse component is superimposed is used. When a 120 nm SiON layer was deposited on the transparent composite sheet, the sputtering process was terminated and the sheet was taken out of the sputtering apparatus. Further, the sheet was obtained by depositing the SiON layer on the surface opposite to the surface on which the SiON layer was deposited by the above method.
（比較例２）
脂環式エポキシ樹脂（ダイセル化学工業製、ＣＥＬ‐２０２１Ｐ）１００重量部、メチルヘキサヒドロフタル酸（新日本理化株式会社製、ＭＨ−７００）１１４重量部、テトラフェニルホスホニウムブロマイド（北興化学工業製、ＴＰＰ−ＰＢ）１重量部を溶融混合し１００℃／２ｈ、２００℃／２ｈ硬化し厚さ３００μｍのシートを得た。
(Comparative Example 2)
100 parts by weight of an alicyclic epoxy resin (manufactured by Daicel Chemical Industries, CEL-2021P), 114 parts by weight of methylhexahydrophthalic acid (manufactured by Shin Nippon Rika Co., Ltd., MH-700), tetraphenylphosphonium bromide (manufactured by Hokuko Chemical Industries, 1 part by weight of TPP-PB) was melt mixed and cured at 100 ° C./2 h and 200 ° C./2 h to obtain a sheet having a thickness of 300 μm.
以上のようにして作製した光学シートについて、下記に示す評価方法により、各種特性を測定した。
実施例、比較例の配合及び結果を表１、表２にそれぞれ示す。
ａ)平均線膨張係数
作成した透明バリア性シートについて、セイコー電子(株)製ＴＭＡ／ＳＳ１２０Ｃ型熱応力歪測定装置を用いて、窒素雰囲気下、１分間に５℃の割合で温度を３０℃から１５０℃まで上昇させた後、一旦０℃まで冷却し、再び１分間に５℃の割合で温度を上昇させて３０℃〜１５０℃の時の値を測定して求めた。荷重を５ｇにし、引張モードで測定を行った。
ｂ）耐熱性（ガラス転移温度）
透明複合シート作成に使用した透明樹脂について、セイコー電子（株）製ＤＭＳ―２１０型粘弾性測定装置で測定し、１Ｈｚでのｔａｎδの最大値をガラス転移温度とした。
ｃ）光線透過率
作成した透明バリア性シートについて、分光光度計Ｕ３２００（島津製作所製）で４００ｎｍ及び５５０ｎｍの光線透過率を測定した。
ｄ）水蒸気透過度
作成した透明バリア性シートについて、ＪＩＳ Ｋ ７１２９Ｂ法４０℃９０％にて水蒸気透過度を測定した。
ｅ）吸水率
透明複合シート作成に使用した透明樹脂について、１５０℃で２時間乾燥後に９０℃の温水中に５時間浸した処理を行い、温水処理前後の重量を測定することで吸水率を求めた。
About the optical sheet produced as mentioned above, various characteristics were measured by the evaluation method shown below.
The formulations and results of Examples and Comparative Examples are shown in Tables 1 and 2, respectively.
a) Average linear expansion coefficient About the prepared transparent barrier sheet | seat, using a TMA / SS120C type | mold thermal stress-strain measuring apparatus by Seiko Electronics Co., Ltd., the temperature was changed from 30 ° C at a rate of 5 ° C per minute in a nitrogen atmosphere. After raising the temperature to 150 ° C., the temperature was once cooled to 0 ° C., and the temperature was raised again at a rate of 5 ° C. per minute, and the value at 30 ° C. to 150 ° C. was measured and determined. The load was 5 g and the measurement was performed in the tensile mode.
b) Heat resistance (glass transition temperature)
The transparent resin used for the preparation of the transparent composite sheet was measured with a DMS-210 type viscoelasticity measuring device manufactured by Seiko Electronics Co., Ltd., and the maximum value of tan δ at 1 Hz was defined as the glass transition temperature.
c) Light transmittance About the created transparent barrier sheet | seat, the light transmittance of 400 nm and 550 nm was measured with the spectrophotometer U3200 (made by Shimadzu Corporation).
d) Water vapor transmission rate The water vapor transmission rate of the transparent barrier sheet thus prepared was measured at JIS K 7129B method 40 ° C 90%.
e) Water absorption rate The transparent resin used for the preparation of the transparent composite sheet was dried at 150 ° C for 2 hours and then immersed in 90 ° C warm water for 5 hours, and the water absorption rate was obtained by measuring the weight before and after the hot water treatment. It was.
本発明の透明バリア性シートは、例えば、透明板、光学レンズ、液晶表示素子用プラスチック基板、カラーフィルター用基板、有機ＥＬ表示素子用プラスチック基板、太陽電池基板、タッチパネル、導光板、光学素子、光導波路、ＬＥＤ封止材等に好適に利用できる。 The transparent barrier sheet of the present invention is, for example, a transparent plate, an optical lens, a liquid crystal display element plastic substrate, a color filter substrate, an organic EL display element plastic substrate, a solar cell substrate, a touch panel, a light guide plate, an optical element, and a light guide. It can utilize suitably for a waveguide, LED sealing material, etc.
Claims (21)
The transparent barrier sheet according to any one of claims 1 to 20, wherein the transparent barrier sheet is an optical sheet, a plastic substrate for a display element, or a substrate for an active matrix display element.
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