CN116547594A - 夹层玻璃 - Google Patents
夹层玻璃 Download PDFInfo
- Publication number
- CN116547594A CN116547594A CN202180057802.4A CN202180057802A CN116547594A CN 116547594 A CN116547594 A CN 116547594A CN 202180057802 A CN202180057802 A CN 202180057802A CN 116547594 A CN116547594 A CN 116547594A
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- CN
- China
- Prior art keywords
- liquid crystal
- laminated glass
- protective film
- glass
- layer
- 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.)
- Pending
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 6
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- 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 claims description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
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- 238000000576 coating method Methods 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
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- 239000005341 toughened glass Substances 0.000 description 6
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- JMKNNRIUBHHHNA-UHFFFAOYSA-N 6-methylheptyl 2-[4-[4,6-bis[2-hydroxy-4-[1-(6-methylheptoxy)-1-oxopropan-2-yl]oxyphenyl]-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]propanoate Chemical compound CC(C)CCCCCOC(=O)C(C)Oc1ccc(c(O)c1)-c1nc(nc(n1)-c1ccc(OC(C)C(=O)OCCCCCC(C)C)cc1O)-c1ccc(OC(C)C(=O)OCCCCCC(C)C)cc1O JMKNNRIUBHHHNA-UHFFFAOYSA-N 0.000 description 3
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
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- 229910052724 xenon Inorganic materials 0.000 description 3
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- GEVOVACRJRUQOB-UHFFFAOYSA-N 1,2-dibutyl-4-(4,7-dihydroxy-1,3-benzodithiol-2-ylidene)pyrazolidine-3,5-dione Chemical compound C1=CC(=C2C(=C1O)SC(=C1C(=O)N(N(C1=O)CCCC)CCCC)S2)O GEVOVACRJRUQOB-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical group C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
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- VPXSRGLTQINCRV-UHFFFAOYSA-N dicesium;dioxido(dioxo)tungsten Chemical compound [Cs+].[Cs+].[O-][W]([O-])(=O)=O VPXSRGLTQINCRV-UHFFFAOYSA-N 0.000 description 2
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- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 2
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- GOZHNJTXLALKRL-UHFFFAOYSA-N (5-benzoyl-2,4-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(O)=C(C(=O)C=2C=CC=CC=2)C=C1C(=O)C1=CC=CC=C1 GOZHNJTXLALKRL-UHFFFAOYSA-N 0.000 description 1
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- CKMGULKXPQZAHN-UHFFFAOYSA-N 2-(4,7-dihydroxy-1,3-benzodithiol-2-ylidene)-4,4-dimethyl-3-oxopentanenitrile Chemical compound OC1=CC=C(O)C2=C1SC(=C(C#N)C(=O)C(C)(C)C)S2 CKMGULKXPQZAHN-UHFFFAOYSA-N 0.000 description 1
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- DOZGRCMRCPSZHG-UHFFFAOYSA-N 2-(4-benzoyl-3-hydroxyphenoxy)ethyl 2-methylprop-2-enoate Chemical compound OC1=CC(OCCOC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 DOZGRCMRCPSZHG-UHFFFAOYSA-N 0.000 description 1
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 1
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
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- NTONJNKQQYVVCF-UHFFFAOYSA-N [3-(4-benzoyl-3-hydroxyphenoxy)-3-hydroxypropyl] 2-methylprop-2-enoate Chemical compound OC1=CC(OC(O)CCOC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 NTONJNKQQYVVCF-UHFFFAOYSA-N 0.000 description 1
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- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical class C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- G02F1/133331—Cover glasses
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- B32B17/10082—Properties of the bulk of a glass sheet
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Abstract
本发明能抑制调光元件受损。夹层玻璃(10)具备:一对玻璃板(11)、(12),和设置在一对玻璃板(11)、(12)之间并具有液晶层(153)、基材(151)、形成于基材(151)的一个表面(151S1)上的导电膜(152)、以及形成于基材(151)的另一个表面(151S2)上的保护膜(154)的调光元件(15)。液晶层具有选自宾主效应型液晶、TN型液晶、PC型液晶、STN型液晶、ECB型液晶、OCB型液晶、IPS型液晶和VA型液晶中的至少1种。保护膜(154)的耐磨耗性比基材(151)更高。
Description
技术领域
本发明涉及夹层玻璃。
背景技术
已知例如专利文献1所示那样的将调光元件封入中间层而成的夹层玻璃。这样的调光元件中,用于向功能层通电的导电膜形成于基材上。
专利文献1:日本专利特开2018-141891号公报
发明内容
发明所要解决的技术问题
这种调光元件组装到夹层玻璃时其外表面可能会受损,可能会造成外观上的问题。因此,需要抑制调光元件受损。
本发明基于上述技术问题而完成,其目的在于,提供一种能够抑制调光元件受损的夹层玻璃。
解决技术问题所采用的技术方案
为了解决上述问题并达成目的,本公开的夹层玻璃具备:一对玻璃板,和设置于所述一对玻璃板之间并具有液晶层、基材、形成于所述基材的一个表面上的导电膜、以及形成于所述基材的另一个表面上的保护膜的调光元件,所述液晶层具有选自宾主效应型液晶、TN型液晶、PC型液晶、STN型液晶、ECB型液晶、OCB型液晶、IPS型液晶和VA型液晶中的至少1种,所述保护膜的耐磨耗性比所述基材更高。
发明效果
根据本发明,能够抑制调光元件受损。
附图说明
图1所示为本实施方式的夹层玻璃的示意图。
图2所示为本实施方式的夹层玻璃的示意性剖视图。
图3所示为本实施方式的另一示例的夹层玻璃的示意性剖视图。
具体实施方式
以下参照附图对本发明的优选实施方式进行详细说明。本发明并不受该实施方式所限定,而且,在实施方式有多个的情况下,其还包括各实施方式组合而构成的实施方式。此外,数值包含四舍五入的范围。
(夹层玻璃)
图1所示为本实施方式的夹层玻璃的示意图。图1所示的本实施方式的夹层玻璃10为车辆用夹层玻璃。夹层玻璃10例如可以适用于车辆用天窗、后窗、后侧窗、后三角窗、附加窗(エクストラウインドウ)、前窗等。另外,附加窗是指为了提升车辆驾驶员的后方识别性而安装在车辆后侧的窗玻璃。本文的车辆典型地是指机动车,但是认为应指包括电车、船舶、飞机等在内的具有窗玻璃的移动物体。但夹层玻璃10的用途并不限于车辆。
图1示意性地示出将夹层玻璃10安装在车辆上时从车厢外识别车厢内的情形。图1示出夹层玻璃10为平板形状,但并不限于此,也可以是在长边方向和短边方向上弯曲的形状。此外,夹层玻璃10可以是仅在长边方向上弯曲的形状或仅在短边方向上弯曲的形状。
此外,图1中夹层玻璃10的平面形状为矩形,但是夹层玻璃10的平面形状并不限于矩形,也可以是包括梯形或三角形等在内的任意形状。此处的平面形状是指从夹层玻璃10的车内侧面的法线方向观察夹层玻璃10的规定区域时的形状。此外,下文中的俯视是指朝向图2所示的方向Z(即从夹层玻璃10的车内侧面的法线方向)观察夹层玻璃10的规定区域。另外,方向Z可以说是相对于玻璃板11的玻璃板12侧,在夹层玻璃10为弯曲形状的情况下,其也可以说是相对于凹面侧的凸面侧。
图2所示为本实施方式的夹层玻璃的示意性剖视图。图2所示为沿图1的A-A线的剖视图。如图2所示,夹层玻璃10具备:玻璃板11、12,中间层13,遮蔽层14和调光元件15。若将从车内侧向车外侧的方向设为方向Z,则夹层玻璃10中,沿着方向Z,遮蔽层14、玻璃板11、中间层13和调光元件15、遮蔽层14、玻璃板12依次层叠。方向Z也可以说是层叠方向。另外,遮蔽层14可以根据需要设置。
夹层玻璃10的总厚度T0优选2.8mm以上10mm以下。若夹层玻璃10的总厚度T0在2.8mm以上,则可以确保足够的刚性。此外,若夹层玻璃10的总厚度T0在10mm以下,则能够在获得足够透射率的同时降低雾度。另外,本文中的总厚度以及下文所述的厚度都是指Z方向上的长度。
在夹层玻璃10的至少1条边处,玻璃板11和玻璃板12的板偏差优选1.5mm以下,更优选1mm以下。此处,玻璃板11和玻璃板12的板偏差是指俯视下玻璃板11的端部(周缘部)11T和玻璃板12的端部(周缘部)12T的偏差量。在夹层玻璃10的至少1条边处,若玻璃板11和玻璃板12的板偏差在1.5mm以下,则在不损害外观得得方面是有利的,而若上述板偏差在1.0mm以下,则在不损害外观的方面更加有利。
(玻璃板)
玻璃板11与玻璃板12是相互相向的一对玻璃板。中间层13和调光元件15位于玻璃板11与玻璃板12之间。玻璃板11与玻璃板12以夹持着中间层13和调光元件15的状态固定。
玻璃板11为将夹层玻璃10安装在车辆上时成为车内侧的车内侧玻璃板。玻璃板12为将夹层玻璃10安装在车辆上时成为车外侧的车外侧玻璃板。玻璃板11、12可以具有规定的曲率。
玻璃板11和12可以是无机玻璃也可以是有机玻璃。作为无机玻璃,例如可以采用钠钙玻璃、铝硅酸盐玻璃、硼硅酸盐玻璃、无碱玻璃、石英玻璃等,没有特别限定。位于夹层玻璃10的车外侧的玻璃板12从耐受损性的观点考虑优选无机玻璃,从成形性的观点考虑优选钠钙玻璃。在玻璃板11和12为钠钙玻璃的情况下,可以适宜地使用透明玻璃、含有规定量以上的铁成分的绿色玻璃和UV截止绿色玻璃、隐私玻璃。
无机玻璃可以是未强化玻璃、强化玻璃中的任一种。未强化玻璃是将熔融玻璃成形为板状并退火而成的玻璃。强化玻璃是在未强化玻璃的表面形成压缩应力层而成的玻璃。
强化玻璃可以是例如风冷强化玻璃等物理强化玻璃、化学强化玻璃中的任一种。在其为物理强化玻璃的情况下,可以通过例如在弯曲成形过程中将均匀加热后的玻璃板从软化点附近的温度急冷等退火以外的操作,利用玻璃表面与玻璃内部间的温度差在玻璃表面产生压缩应力层,从而将玻璃表面强化。
在其为化学强化玻璃的情况下,可以通过例如在弯曲成形后利用离子交换法等使玻璃表面产生压缩应力,从而将玻璃表面强化。此外,也可以使用吸收紫外线或红外线的玻璃,进一步优选透明的玻璃,但是也可以使用以不损害到透明性的程度着色过的玻璃板。
而作为有机玻璃的材料,可列举聚碳酸酯、例如聚甲基丙烯酸甲酯等丙烯酸类树脂、聚氯乙烯、聚苯乙烯等透明树脂。
玻璃板11和12的形状并不特别限定为矩形,也可以是加工成各种形状和曲率的形状。玻璃板11和12的弯曲成形可以使用重力成形、加压成形、辊成形等。对于玻璃板11和12的成形法也没有特别限定,但是例如在无机玻璃的情况下,优选由浮法等成形的玻璃板。
玻璃板12的厚度T1没有特别限定,一般在0.1mm以上10mm以下的范围内,可以根据适用夹层玻璃10的车辆种类或部位等进行适当选择。若玻璃板12的厚度T1在0.3mm以上,则其适宜保持耐冲击性并且耐飞石性能等强度变得足够因而优选,更优选0.5mm以上,进一步优选0.7mm以上,特别优选1.1mm以上,最优选1.6mm以上。
若玻璃板12的厚度T1在3mm以下,则夹层玻璃10的质量不会过大,从车辆油耗的观点考虑是优选的,更优选2.6mm以下,进一步优选2.2mm以下,特别优选2.1mm以下。另外,本文中的厚度T1优选为玻璃板12的最薄部的厚度。
玻璃板12优选用于车辆而具备足够的耐冲击性。此处的耐冲击性可以采用UN R43中的耐冲击性试验来进行评价。耐冲击性试验为研究例如像机动车用夹层玻璃那样的安全玻璃对于小而硬的飞来物的冲击是否具有必需的粘接性或强度的试验。具体而言,该试验的进行方式为,将夹层玻璃(安全玻璃)保持在规定温度下后,将其以位于车外侧的玻璃面朝上的方式放置于支持框上,从规定高度使钢球自然掉落。
玻璃板11的厚度T2可以说与玻璃板12的厚度T1相同。玻璃板12也可以具有与玻璃板11不同的组成和/或与玻璃板11不同的厚度。例如,玻璃板11可以比玻璃板12更薄。
在玻璃板11的厚度T2在1mm以下的情况下,从强度的观点考虑,玻璃板11优选化学强化玻璃。
玻璃板11和12的至少一方的与中间层13相反侧的面可以设置有拒水、具有紫外线或红外线截止功能的被膜、具有低反射特性、低放射特性或防污性的被膜或具有防结露特性的被膜。此外,玻璃板11和12的至少一方的与中间膜13相接的一侧也可以设置有紫外线或红外线截止、低放射特性、可见光吸收或着色等被膜。此外,玻璃板11的车内侧面上可以形成有低放射涂层。
即,玻璃板11和12的至少一方可以具有拒水层、紫外线遮断层、红外线反射层、低反射率层、低放射率层、防结露层、可见光吸收层、着色层中的任一种以上。另外,这些层可以具有玻璃板11和12、中间层13、和调光元件15的后述基材151中的至少一者。
玻璃板11和12可以是平板形状也可以是弯曲形状。在玻璃板11和12是弯曲形状的无机玻璃的情况下,玻璃板11和12可以在通过浮法成形后、介由中间层13粘接前进行弯曲成形。弯曲成形通过加热使玻璃软化来进行。弯曲成形时玻璃的加热温度为约550℃以上700℃以下。
(中间层)
中间层13是将玻璃板11和玻璃板12接合的膜。中间层13例如具有与玻璃板11接合的中间层131、与玻璃板12接合的中间层132、和位于中间层131与中间层132之间并包围调光元件15外周的画框状的中间层133。但是,中间层13也可以不具有中间层133。在不具有中间层133的情况下,夹层玻璃10制造工序中的压接时,由中间层131和中间层132中的至少1者包围调光元件15外周。
另外,本实施方式中,中间层13中的中间层131、132、133各自独立而在夹层玻璃10制造时接合,但并不限于此,例如在将流动性高的材料注入玻璃板11、12之间以形成中间层13的情况下等,中间层13也可以是一体的。
作为中间层13,常用热塑性树脂,可列举增塑性聚乙烯醇缩醛类树脂、增塑性聚氯乙烯类树脂、饱和聚酯类树脂、增塑性饱和聚酯类树脂、聚氨酯类树脂、增塑性聚氨酯类树脂、乙烯-乙酸乙烯酯共聚物类树脂、乙烯-丙烯酸乙酯共聚物类树脂、环烯烃聚合物树脂、离聚物树脂等以往用于该种用途的热塑性树脂。此外,也可以适宜地使用日本专利第6065221号中记载的含有改性嵌段共聚物氢化物的树脂组合物。
作为中间层13的材料,其中,从透明性、耐候性、强度、粘接力、耐贯穿性、冲击能量吸收性、耐湿性、隔热性以及隔音性等各项性能的平衡优异的观点考虑,适宜使用增塑性聚乙烯醇缩醛类树脂。此类热塑性树脂可以单独使用,也可以2种以上并用。上述增塑性聚乙烯醇缩醛类树脂中的“增塑性”表示可以通过添加增塑剂来增塑的含义。对于其它增塑性树脂也表示相同含义。
但是,在中间层13中封入调光元件15的情况下,可能会根据封入物的种类而因特定增塑剂导致劣化,在该情况下,优选使用实质上不含该增塑剂的树脂。即,有时优选中间层13不含增塑剂。作为不含增塑剂的树脂,可例举乙烯-乙酸乙烯酯共聚物类树脂等。
作为上述聚乙烯醇缩醛类树脂,可列举通过使聚乙烯醇(以下根据需要也称为“PVA”)与甲醛反应而得的聚乙烯醇缩甲醛树脂、使PVA与乙醛反应而得的狭义的聚乙烯醇缩乙醛类树脂、使PVA和正丁醛反应而得的聚乙烯醇缩丁醛树脂(以下根据需要也称为“PVB”)等,其中,从透明性、耐候性、强度、粘接力、耐贯穿性、冲击能量吸收性、耐湿性、隔热性以及隔音性等各项性能的平衡优异的观点考虑,特别适宜使用PVB。此类聚乙烯醇缩醛类树脂可以单独使用,也可以2种以上并用。
作为中间层13,可以使用也称为光学透明树脂(OCR)的固化型透明树脂或也称为光学透明粘合片(OCA)的透明粘合片。通过使用固化型透明树脂或透明粘合片,能够在常温下制备层叠体因而更为理想。作为固化型透明树脂或透明粘合片,使用丙烯酸类树脂、有机硅类树脂、聚氨酯丙烯酸酯类树脂、环氧类树脂等。另外,此类固化型透明树脂或透明粘合片可以单独使用,也可以2种以上并用。
中间层13的25℃下剪切模量优选在1.0×103Pa以上且100.0×106Pa以下,优选在1.0×103Pa以上且2.0×106Pa以下。若25℃下剪切模量在上述范围内,则能够在常温下制备层叠体、夹层玻璃的制造变得容易因而理想。另外,本说明书中的剪切模量可以通过将样品在频率1Hz的条件下通过剪切法、例如通过安东帕公司(アントンパール社)制的MCR301进行动态粘弹性试验来测定。
此外,在中间层13使用像OCR那样的固化物质的情况下,固化后的25℃下剪切模量优选1.0×103Pa以上且2.0×106Pa以下。而在中间层13由多种材料形成的情况下,呈现出最大剪切模量的材料优选满足上述关系。
但是,形成中间层13的材料并不限于热塑性树脂,也可以包含红外线吸收剂、紫外线吸收剂、发光剂等功能性粒子,还可以具有被称之为遮光带的着色部。
中间膜13的厚度在最薄部优选0.3mm以上。若中间膜13的最薄部的厚度为0.3mm以上,则作为夹层玻璃10所必需的耐冲击性足够。中间膜13的厚度在最薄部优选3mm以下。若中间膜13的厚度的最大值为3mm以下,则夹层玻璃10的质量不会过大。中间膜13的厚度最大值更优选2.8mm以下,进一步优选2.6mm以下。
另外,中间层13的厚度是指除去调光元件15的厚度的仅中间层13的厚度。因此,中间层13的厚度是指从中间层131的玻璃板11侧表面到中间层132的玻璃板12侧表面的厚度T3中除去调光元件15的厚度T4后的长度。
此外,中间层13的最厚部是指例如未夹入调光元件15的部分(俯视下与调光元件15不重叠的部分),因此中间层13的最厚部的厚度由于不存在调光元件15而也可以说是厚度T3。而中间层13的最薄部是指例如夹入调光元件15的部分(俯视下与调光元件15重叠的部分),因此中间层13的最薄部的厚度也可以说是从厚度T3中减去调光元件15的厚度T4后的值。
另外,中间层13也可以具有4层以上的层。例如,由4层以上的层形成中间层13,通过增塑剂的调整等使得除两侧层以外的若干层的剪切弹性模量小于两侧层的剪切弹性模量,能够提高夹层玻璃10的隔音性。该情况下,两侧层的剪切弹性模量可以相同也可以不同。
此外,理想的是中间层13中所含的中间层131、132和133全部由相同材料形成,但是中间层131、132和133的一部分或全部也可以由不同材料形成。
例如,可以是中间层133的剪切弹性模量小于中间层131、132的剪切弹性模量的材料。在中间层133的剪切弹性模量小于中间层131、132的剪切弹性模量的情况下,夹层玻璃10的隔音性能够得以提升。
另外,在中间层131的剪切弹性模量小于中间层132、133的剪切弹性模量的情况下,夹层玻璃10的遮音性也能得以提升。此外,在中间层132的剪切弹性模量小于中间层131、133的剪切弹性模量的情况下,夹层玻璃10的遮音性仍能得以提升。但是,从与玻璃板11及12的粘接性、或在夹层玻璃10中掺入的功能材料等的观点考虑,理想的是中间层13膜厚的50%以上使用上述树脂材料。
制造中间层13时,例如适当选择形成中间层23的上述树脂材料、使用挤出机以加热熔融状态进行挤出成形。挤出机的挤出速度等挤出条件设定为使其均匀的条件。然后,使挤出成形而得的树脂膜匹配夹层玻璃10的设计,例如根据需要进行拉伸以使上边和下边具有曲率,藉此完成中间层13。
(遮蔽层)
遮蔽层14是不透明的层,例如可以沿着夹层玻璃10的周缘部设置成带状。遮蔽层14例如为不透明的(例如黑色的)着色陶瓷层。遮蔽层14可以是具有遮光性的着色中间膜、着色膜、着色中间膜与着色陶瓷层的组合。着色膜可以与红外线反射膜等一体化。着色中间膜或着色膜可以在厚度方向上整体着色,也可以仅在表面上着色。
通过在夹层玻璃10中存在不透明的遮蔽层14,能够抑制将夹层玻璃10的周缘部保持在车身上的聚氨酯等树脂因紫外线而导致的劣化。此外,可以隐藏与调光元件15电连接的电极或电极伸出配线,使得从车外侧和车内侧中的至少一方不易识别其存在。
遮蔽层14例如可以通过利用丝网印刷等将包含含有黑色颜料的熔融性玻璃料的陶瓷色浆涂布在玻璃板上并烧成来形成,但并不限于此。遮蔽层14例如也可以通过利用丝网印刷等将含有黑色或深色颜料的有机油墨涂布在玻璃板上并使其干燥来形成。
在图2的示例中,遮蔽层14设置于玻璃板11的车内侧面的周缘部和玻璃板12的车内侧面的周缘部。但并不限于此,遮蔽层14也可以设置于玻璃板11的车内侧面的周缘部和玻璃板12的车内侧面的周缘部中的至少一方。另外,一般而言,相较于位于车内侧的玻璃板,位于车外侧的玻璃板更容易受损,因此遮蔽层14通常不设置于玻璃板12的车外侧面。
(调光元件)
调光元件15是能够切换夹层玻璃10的光的透射率的元件。调光元件15根据需要可以配置在夹层玻璃10的几乎整面,也可以仅配置在一部分。调光元件15的平面形状例如为比夹层玻璃10的平面形状更小的矩形。但是,调光元件15的平面形状也可以不是矩形。在图1的示例中,调光元件15的周缘部位于与遮蔽层14在俯视下不重叠的位置。
如图2所示,调光元件15具备作为第1保护膜的保护膜154A、作为第1基材的基材151A、作为第1导电膜的导电膜152A、液晶层153、作为第2导电膜的导电膜152B、作为第2基材的基材151B、以及作为第2保护膜的保护膜154B,其被封入中间层13中。即,调光元件15的周围被中间层13包围。调光元件15中,沿着方向Z,保护膜154A、基材151A、导电膜152A、液晶层153、导电膜152B、基材151B、保护膜154B依次层叠。
以下,在不区分基材151A与基材151B的情况下记为基材151,在不区分导电膜152A与导电膜152B的情况下记为导电膜152,而在不区分保护膜154A与保护膜154B的情况下记为保护膜154。
调光元件15例如为膜状。调光元件15的厚度T4例如在0.05mm以上0.5mm以下,优选0.1mm以上0.4mm以下。
(基材)
基材151A、151B是支承导电膜152A、152B并夹持液晶层153的一对基板。基材151A位于比液晶层153更靠近玻璃板11侧(车内侧)处,而基材151B位于比液晶层153更靠近玻璃板12侧(车外侧)处。
基材151优选由25℃下拉伸模量比中间层13更高的构件构成,从耐冲击性的观点考虑,优选25℃下拉伸模量在1000MPa以上。本实施方式中,由于基材151的25℃下拉伸模量比中间层13更高,因此其耐冲击性也比中间层13更高。另外,本实施方式中,基材151A和基材151B中的至少一方可以由25℃下拉伸模量比中间层13更高的构件构成。拉伸模量可以使用动态粘弹性测定装置(例如IT计测控制株式会社(アイティー計測制御社)制的itk DVA-225)进行测定。
将基材151的25℃下拉伸模量设为Es,将中间层13的25℃下拉伸模量设为Ei时,优选为3<(Es/Ei)/1000<1400,更优选为10<(Es/Ei)/1000<800,进一步优选为20<(Es/Ei)/1000<400。Es/Ei在该数值范围内,则可以由基材151适宜地提升耐冲击性。
此外,在中间层13为OCR的情况下,OCR的模量低、容易变形,无法直接测定25℃下拉伸模量E,因此将使用泊松比ν而由其与25℃下剪切模量G的关系式G=E/2(1+ν)的值换算得到的E值作为25℃下拉伸模量。
此外,基材151对波长590nm的光的面内相位差优选在0nm以上300nm以下,更优选在0nm以上100nm以下,进一步优选在0nm以上50nm以下。面内相位差在该范围内,则可以适宜地进行调光。另外,面内相位差可以通过相位差测定装置(例如王子计测机器株式会社(王子計測機器(株))制的在线相位差计KOBRA-WI)进行测定。
基材151优选透明树脂层。基材151例如优选含有选自聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚酰胺、聚醚、聚砜、聚醚砜、聚碳酸酯、聚苯乙烯、环状聚烯烃、聚芳酯、聚醚酰亚胺、聚醚醚酮、聚酰亚胺、芳族聚酰胺、聚对苯二甲酸丁二醇酯、三乙酰基纤维素、聚氨酯和环烯烃聚合物中的1种以上。
另外,基材151A和基材151B可由例如与上述所示的材料相同的材料构成,但并不限于此,也可以由其他材料构成。
基材151的厚度T5例如在5μm以上500μm以下,优选在10μm以上200μm以下,更优选在50μm以上150μm以下。厚度T5为5μm以上则能有利地抑制夹层玻璃10的耐冲击性下降,为500μm以下则夹层玻璃10的厚度不会过大。
另外,基材151A和基材151B为相同厚度T5,但是厚度也可以不同。
此外,基材151的厚度T5相对于厚度T3优选2.5%以上50%以下,更优选3%以上40%以下,进一步优选4%以上18%以下。厚度T5相对于厚度T3在2.5%以上则能够适宜地提升耐冲击性,在50%以下则能够抑制中间层13的厚度相对变得过小。
在图2的示例中,基材151的周缘部151T相对于液晶层153的周缘部153T在放射方向(Z方向)上处于相同位置,但并不限于此,例如也可以比液晶层153的周缘部153T在放射方向上更延伸至外侧。另外,液晶层153的周缘部153T是指包围后述的调光部153A外周的封止件153B的放射方向外侧的端部(外周面)。
(导电膜)
导电膜152A形成于基材151A的液晶层153侧表面151S1上,其与液晶层153的玻璃板11侧的面相接。导电膜152B形成于基材151B的液晶层153侧的表面151S1上,其与液晶层153的玻璃板12侧的面相接。即,导电膜152A和152B是夹持液晶层153的一对导电膜。
作为导电膜152,例如可以使用透明导电性氧化物(TCO:transparent conductiveoxide)。作为TCO,可例举掺锡氧化铟(ITO:tin-doped indium oxide)、掺铝氧化锌(AZO:aluminum doped zinc oxide)、掺铟氧化镉等,但并不限于此。
作为导电膜152,可以有利地使用聚(3,4-乙烯二氧噻吩)(PEDOT)或聚(4,4-二辛基环戊二噻吩)等透明导电性聚合物。此外,作为导电膜152,也可以有利地使用金属层和电介质层的层叠膜、银纳米线、银或铜的金属网等。
导电膜152例如可以使用溅射法、真空蒸镀法、离子电镀法等物理蒸镀法(PVD:Physical Vapor Deposition)形成。导电膜152也可以使用化学蒸镀法(CVD:ChemicalVapor Deposition)及湿式涂布法形成。
另外,本实施方式中,导电膜152形成于基材151的整面,但并不限于此,也可以仅形成于基材151的一部分区域。此外,导电膜152直接形成于基材151上,但并不限于此,也可以在基材151与导电膜152之间还形成有其他层。
(液晶层)
作为调光层的液晶层153位于形成有导电膜152A的基材151A与形成有导电膜152B的基材151B之间。液晶层153具备进行调光的调光部153A、和将调光部153A的外侧封住的封止件153B。本实施方式中,液晶层153为宾主效应型的液晶层。宾主效应型的液晶层153中,例如作为主体的向列型液晶中溶解作为客体的二色性色素而成的液晶组合物包含在调光部153A中。二色性色素例如具有1根光吸收轴,其仅吸收在光吸收轴方向上振动的光,因而根据电场所致的液晶运动,使得二色性色素的取向发生变化,从而能够控制光吸收轴的朝向,使光的透射状态发生变化而调光。
但是,调光元件15并不限于具有宾主效应型的液晶层153。例如,调光元件15作为调光层也可以具有例如选自悬浊粒子装置(SPD:Suspended Particle Device)、宾主效应型液晶、光致变色元件、电致变色元件、电动力元件、高分子分散型液晶、高分子网络液晶、有机EL(Electro-Luminescence)元件和无机EL元件中的任1种以上。例如在调光层不含液晶等而不需要封止件153B的情况下,也可以不设置封止件153B。该情况下,调光部153A外侧的端部为调光层的周缘部。
换而言之,调光元件15可以具有选自由相互相向配置的形成有导电膜152A的基材151A,形成有导电膜152B的基材151B,以及配置于相向的导电膜152A和导电膜152B之间的选自悬浊粒子装置、宾主效应型液晶、光致变色元件、电致变色元件和电动力元件中的任1种以上构成的调光层。
作为悬浊粒子装置,可以使用以导电膜涂布于内侧而得的2块基材夹持含有能够通过施加电压而取向的悬浊粒子的聚合物层而构成的通常的SPD膜。通过开启电源开关而在透明导电膜间施加电压以使聚合物层中的悬浊粒子取向,这种SPD膜处于可见光透射率高、透明性高的状态。在电源开关关闭的状态下,聚合物层中的悬浊粒子不取向而处于可见光透射率低、透明性低的状态。
作为SPD膜,例如可以使用LCF-1103DHA(商品名,日立化成株式会社(日立化成社)制)等市售品。另外,由于这种市售品是以规定的大小提供的,因此将其切割成希望的大小来使用。另外,作为SPD膜的厚度,没有特别限定,但是从操作性和获得容易性的观点考虑,优选0.1mm以上0.4mm以下。
另外,作为调光部153A,例如可以使用选自宾主效应型液晶、TN(扭曲向列)型液晶、PC(相变)型液晶、STN(超级扭曲向列)型液晶、ECB(电控双折射)型液晶、OCB(光学补偿弯曲)型液晶、IPS(平面转换)型液晶、VA(垂直取向)型液晶、FFS(边缘场开关)型液晶、FPA(电场感应光反应取向)型液晶、电致变色元件、电动力元件、有机EL(电致发光)元件、无机EL元件中的至少1种。上述元件中,优选使用选自宾主效应型液晶、TN型液晶、PC型液晶、STN型液晶、ECB型液晶、OCB型液晶、IPS型液晶和VA型液晶中的至少1种。
(保护膜)
保护膜154形成于基材151的与形成有导电膜152的表面151S1相反侧的表面151S2上。换而言之,基材151在液晶层153侧的表面151S1上形成有导电膜152,而在与液晶层153相反侧的表面151S2上形成有保护膜154。进一步说,如图2所示,基材151A在表面151S1上形成有导电膜152A,而在表面151S2上形成有保护膜154A。基材151B则在表面151S1上形成有导电膜152B,而在表面151S2上形成有保护膜154B。
保护膜154是耐磨耗性比基材151更高的硬涂层。例如,保护膜154优选在JISR3212所述的耐磨耗性试验中进行100次试验后的雾度变化相较于基材151在JIS R3212所述的耐磨耗性试验中进行100次试验后的雾度变化更小。JIS R3212所述的耐磨耗性试验例如可以以具有保护膜154的基材151和不具有保护膜154的基材151分别作为受试体来实施。此外,保护膜154在JIS R3212所述的耐磨耗性试验中进行100次试验后的雾度变化优选在0%以上20%以下,更优选在0%以上15%以下,进一步优选在0%以上10%以下。保护膜154的耐磨耗性在该范围内,则能够适宜地抑制调光元件15受损。另外,例如,作为保护膜154,使用含有30质量%以上的官能团数为2个以上的化合物的固化膜,可以使保护膜154的耐磨耗性适宜地在上述范围内。此外,保护膜154的耐磨耗性相对于基材151的耐磨耗性的比率优选50%以下,更优选40%以下,进一步优选30%以下。此处,保护膜154的耐磨耗性相对于基材151的耐磨耗性的比率是指,例如保护膜154在JIS R3212所述的耐磨耗性试验中进行100次试验后的雾度变化量相对于基材151在JIS R3212所述的耐磨耗性试验中进行100次试验后的雾度变化量。耐磨耗性的比率在该范围内,则能够因基材151而持有柔软性以抑制调光元件15变形,同时由保护膜154来抑制调光元件15受损。
保护膜154的波长550nm的光的透射率优选在60%以上100%以下,优选在70%以上100%以下,进一步优选在80%以上100%以下。透射率在该范围内,则能够适宜地透射可见光,适宜地发挥出调光元件的效果。该透射率由保护膜154形成前后的透射率之差求得。
保护膜154的厚度T6优选0.1μm以上20μm以下,更优选0.2μm以上15μm以下,进一步优选0.3μm以上10μm以下。保护膜154的厚度在该范围内,则能够在抑制调光元件15整体厚度的同时适宜地由保护膜154来抑制调光元件15受损。此外,保护膜154的厚度优选比基材151更薄。保护膜154的厚度T6相对于基材151的厚度T5优选0.1%以上50%以下,更优选0.1%以上20%以下,进一步优选0.1%以上15%以下。保护膜154和基材151的厚度比率在该范围内,能够由基材151而持有耐冲击性以抑制调光元件15变形,同时由保护膜154来抑制调光元件15受损。
另外,保护膜154A和保护膜154B为相同厚度T6,但是厚度也可以不同。
保护膜154优选含有选自例如分子中具有2个以上聚合性官能团的聚合固化性化合物的固化体(透明被覆膜)和硅类醇盐化合物的固化体(透明被覆膜)中的1种以上。分子中具有2个以上聚合性官能团的聚合固化性化合物例如在涂布于基材151后通过热或紫外线等活性能量射线固化而成为固化体。而硅类醇盐化合物例如在涂布于基材151后通过热固化而成为固化体。另外,保护膜154A和保护膜154B由例如与上述所示的材料相同的材料构成,但并不限于此,也可以由相互不同的材料构成。
保护膜154中上述固化体的含量优选在50质量%以上100质量%以下,更优选在70质量%以上98质量%以下。若在上述范围内,则可以达到更高的耐磨耗性。
下面对用作保护膜154的分子中具有2个以上聚合性官能团的聚合固化性化合物进行更详细的说明。分子中具有2个以上聚合性官能团的聚合固化性化合物也可以称为活性能量射线固化性组合物中的多官能性化合物。此处的聚合固化性化合物、即活性能量射线固化性组合物中的多官能性化合物具有2个以上活性能量射线固化性的聚合性官能团。作为该多官能性化合物中的活性能量射线固化性的聚合性官能团,优选丙烯酰基、甲基丙烯酰基、乙烯基、烯丙基等α,β-不饱和基或具有该基的基团,更优选丙烯酰基或甲基丙烯酰基。即,作为多官能性化合物,优选具有2个以上选自丙烯酰基和甲基丙烯酰基的1种以上聚合性官能团的化合物。进而,其中更优选容易因紫外线而聚合的丙烯酰基。另外,该多官能性化合物可以是1分子中具有合计2个以上的2种以上聚合性官能团的化合物,也可以是具有合计2个以上的相同聚合性官能团的化合物。多官能性化合物1分子中聚合性官能团的数量为2个以上,其上限没有特别限定。通常2~50个是适宜的,特别优选2~30个。
作为多官能性化合物的优选化合物为具有2个以上(甲基)丙烯酰基的化合物。其中,优选具有2个以上(甲基)丙烯酰氧基的化合物、即多元醇等具有2个以上羟基的化合物与(甲基)丙烯酸的聚酯。该聚酯例如优选六丙烯酸二季戊四醇酯、二(三羟甲基)丙烷四丙烯酸酯、(三/四)丙烯酸季戊四醇酯、三羟甲基丙烷三丙烯酸酯。这些化合物可以单独使用,也可以2种以上并用。
活性能量射线固化性组合物中,作为多官能性化合物可以包含2种以上的多官能性化合物。此外,除多官能性化合物以外,还可以包含具有1个能够因活性能量射线而聚合的聚合性官能团的单官能性化合物。作为该单官能性化合物,优选具有(甲基)丙烯酰基的化合物,特别优选具有丙烯酰基的化合物。
作为多官能性化合物,也可以是还具有除聚合性官能团以外的各种官能团或键的化合物。例如,其可以还具有羟基、羧基、卤素原子、氨基甲酸酯键、醚键、酯键、硫醚键、酰胺键等。特别优选具有氨基甲酸酯键的含(甲基)丙烯酰基化合物(即丙烯酸氨基甲酸酯)和不具有氨基甲酸酯键的(甲基)丙烯酸酯化合物。
作为多官能性化合物,在其为丙烯酸氨基甲酸酯的情况下,优选为:
·作为季戊四醇或作为其多聚体的聚季戊四醇和聚异氰酸酯和羟烷基(甲基)丙烯酸酯的反应产物的丙烯酸氨基甲酸酯,或
·作为季戊四醇或聚季戊四醇的含羟基聚(甲基)丙烯酸酯和聚异氰酸酯的反应产物的丙烯酸氨基甲酸酯,其为具有3官能团以上(优选4~20官能团)的化合物。
作为不具有氨基甲酸酯键的多官能性化合物,优选季戊四醇类聚(甲基)丙烯酸酯或异氰脲酸酯类聚(甲基)丙烯酸酯。
季戊四醇类聚(甲基)丙烯酸酯是指季戊四醇或聚季戊四醇与(甲基)丙烯酸的聚酯(优选4~20官能者)。
异氰脲酸酯类聚(甲基)丙烯酸酯是指三(羟烷基)异氰脲酸酯或其1摩尔中加成1~6摩尔己内酯或烯化氧而得到的加成物与(甲基)丙烯酸的聚酯(2~3官能者)。优选将这些优选的多官能性化合物与其他2官能团以上的多官能性化合物(特别是多元醇的聚(甲基)丙烯酸酯)并用。
活性能量射线固化性组合物还可以包含能够提高露出层的表面硬度的有效量的平均粒径200nm以下的胶态二氧化硅。胶态二氧化硅的平均粒径优选1~100nm,特别优选1~50nm。此外,从提升胶态二氧化硅的分散稳定性和胶态二氧化硅与多官能性化合物的密合性的方面考虑,胶态二氧化硅优选为经下述表面修饰过的胶态二氧化硅。另外,平均粒径可以作为电子显微镜观察下能够确认的各个粒径的平均值算出。
作为用于活性能量射线固化性组合物的光聚合引发剂,可以使用公知、周知的那些。特别优选容易获得的市售品。作为光聚合引发剂,例如有芳基酮类光聚合引发剂(例如苯乙酮类、二苯酮类、烷氨基二苯酮类、苯偶酰类、苯偶姻类、苯偶姻醚类、苯偶酰二甲基缩酮类、苯甲酰苯甲酸酯类、α-酰基肟酯类等)、含硫类光聚合引发剂(例如硫醚类、噻吨酮类等)、酰基氧化膦类、其他的光聚合引发剂。光聚合引发剂可以2种以上并用。此外,光聚合引发剂可以与胺类等光敏化剂组合使用。
活性能量射线固化性组合物中的光聚合引发剂的量相对于固化性成分(多官能性化合物和单官能性化合物的合计)100重量份优选0.01~20重量份,特别优选0.1~10重量份。
活性能量射线固化性组合物除上述基本成分以外还可以包含溶剂或各种配合剂。溶剂优选作为必要成分,例如在多官能性化合物不是粘度特别低的液体的情况下使用溶剂。
作为使上述这种组合物固化的活性能量射线,特别优选紫外线。但并不限于紫外线,也可以使用电子射线或其他活性能量射线。作为紫外线源,可以使用氙灯、脉冲氙灯、低压汞灯、高压汞灯、超高压汞灯、金属卤化物灯、碳弧灯、钨灯等。
作为保护膜154使用的硅类醇盐化合物优选含有有机聚硅氧烷的固化物作为主成分,而作为形成该固化物的聚有机硅氧烷,只要是固化性聚有机硅氧烷即可,可以没有特别限制地使用。
有机聚硅氧烷由称为M单元、D单元、T单元、Q单元的含硅键单元构成。其中,固化性有机聚硅氧烷有:主要由T单元或Q单元构成的低聚物状的聚合物、仅由T单元构成的聚合物、仅由Q单元构成的聚合物、由T单元和Q单元构成的聚合物。此外,这些聚合物有时还包含少量的M单元或D单元。
固化性有机聚硅氧烷中,T单元为具有1个硅原子并具有与该硅原子键合的1个氢原子或1价有机基团、以及3个与其他硅原子键合的氧原子(或能够与其他硅原子键合的官能团)的单元。M单元为具有1个硅原子并具有与该硅原子键合的3个氢原子或1价有机基团、以及1个与其他硅原子键合的氧原子(或能够与其他硅原子键合的官能团)的单元。D单元为具有1个硅原子并具有与该硅原子键合的2个氢原子或1价有机基团、以及2个与其他硅原子键合的氧原子(或能够与其他硅原子键合的官能团)的单元。Q单元为具有1个硅原子并具有4个与其他硅原子键合的氧原子(或能够与其他硅原子键合的官能团)的单元。
在这些固化性有机聚硅氧烷中,优选使用以T单元为主要含硅键单元构成的固化性有机聚硅氧烷。以下,只要没有特别提及,则将固化性有机聚硅氧烷简单称为有机聚硅氧烷。此处,本说明书中以T单元作为主要构成单元的有机聚硅氧烷(以下根据需要称为“有机聚硅氧烷(T)”)是指T单元数相对于M单元、D单元、T单元和Q单元的合计数的比例为50~100%的有机聚硅氧烷,但是本实施方式中更优选的是使用该T单元数的比例为70~100%的有机聚硅氧烷,特别优选的是使用该T单元数的比例为90~100%的有机聚硅氧烷。此外,作为除T单元以外少量包含的其他单元,优选D单元和Q单元,特别优选Q单元。
即,本实施方式中,这些固化性有机聚硅氧烷中,特别优选使用仅由T单元和Q单元构成且其个数比例为T:Q=90~100:10~0的有机聚硅氧烷。
本实施方式所使用的有机聚硅氧烷(T)可以通过上述T单体等部分水解缩合而得到。通常,该反应通过将T单体等和水在溶剂中加热来进行。反应体系内优选存在催化剂。可调节单体的种类、水量、加热温度、催化剂的种类或量、反应时间等反应条件来制造目标有机聚硅氧烷。此外,根据情况下,也可以将市售的有机聚硅氧烷直接用作目标有机聚硅氧烷,或者使用市售的有机聚硅氧烷来制造目标有机聚硅氧烷。
例如在中间层13的材料为固化型透明树脂(OCR)的情况下,优选基材151的材料为聚碳酸酯且保护膜154的材料为分子中具有2个以上聚合性官能团的聚合固化性化合物的固化体,更优选保护膜154包含含有水解性甲硅烷基的化合物。籍此,特别是在宾主效应型的调光元件15中,其能够因中间层13而持有柔软性以抑制调光元件15变形,同时由基材151或保护膜154而与中间层13的适配性良好,并且适宜地赋予耐冲击性和耐受损性。
保护膜154例如可以将分子中具有2个以上丙烯酰基等聚合性官能团的聚合固化性化合物涂布于基材上并通过热或紫外线等活性能量射线固化而形成。
保护膜154如上所述形成于基材151的与液晶层153相反侧的表面151S2上,也可以说形成于Z方向上调光元件15的最外表面。但是,保护膜154也可以形成在基材151的液晶层153侧表面151S2上、更具体是在基材151与导电膜152之间。此外,保护膜154形成于基材151的整面,但并不限于此,也可以仅形成于基材151的一部分区域。此外,本实施方式中,保护膜154直接形成于基材151上,但并不限于此,也可以在基材151与保护膜154之间还形成有其他层。
(紫外线吸收层)
如上构成的调光元件15优选包含吸收紫外线的紫外线吸收层。调光元件15包含紫外线吸收层能够抑制紫外线向车内侧透射。液晶层153会因紫外线而发生劣化,因此紫外线吸收层优选形成于比液晶层153更靠近车外侧处。
此处,如图2所示,将从车外侧的玻璃板12的外侧入射到夹层玻璃10内的紫外线设为紫外线UVa,将在夹层玻璃10内行进而入射到液晶层153的紫外线设为UVb。而且,以紫外线UVb的强度相对于紫外线UVa的强度为夹层玻璃10(车外侧)的紫外线透射率。紫外线UVb可以说是透过夹层玻璃10中比液晶层153更靠近车外侧的部分的紫外线UVa,而紫外线透射率可以说是夹层玻璃10中比液晶层153更靠近车外侧的部分的紫外线的透射率。紫外线透射率可以按照ISO9050:2003算出。如此定义的夹层玻璃10的波长380nm的紫外线透射率优选0%以上20%以下,更优选0%以上15%以下,进一步优选0%以上10%以下。此外,为了保护液晶层153,除了波长380nm以外,将波长400nm截止也是重要的。因此,夹层玻璃10的波长400nm的紫外线透射率优选0%以上20%以下,更优选0%以上15%以下,进一步优选0%以上10%以下。
本实施方式的示例中,保护膜154优选具有紫外线吸收功能。保护膜154通过在母材中包含紫外线吸收剂而起到作为紫外线吸收层的功能。此处的母材是指上述保护膜154的材料,作为紫外线吸收剂,可以使用公知、周知的那些,多种紫外线吸收剂可以并用。例如,作为紫外线吸收剂,可列举2-羟基-4-(2-甲基丙烯酰氧基乙氧基)二苯甲酮、2-羟基-4-(4-甲基丙烯酰氧基丁氧基)二苯甲酮、2,2’-二羟基-4-(2-甲基丙烯酰氧基乙氧基)二苯甲酮、2,4-二羟基-4’-(2-甲基丙烯酰氧基乙氧基)二苯甲酮、2,2’,4-三羟基-4’-(2-甲基丙烯酰氧基乙氧基)二苯甲酮、2-羟基-4-(3-甲基丙烯酰氧基氧基-2-羟基丙氧基)二苯甲酮、2-羟基-4-(3-甲基丙烯酰氧基氧基-1-羟基丙氧基)二苯甲酮、2-(2-羟基-5-甲基丙烯酰氧基氧基苯基)-2H-苯并***、2-(2-羟基-3-叔丁基-5-甲基丙烯酰氧基氧基甲基苯基)-2H-苯并***、2-[2-羟基-5-(2-甲基丙烯酰氧基氧基乙基)苯基]-2H-苯并***、2-[2-羟基-3-叔丁基-5-(2-甲基丙烯酰氧基氧基乙基)苯基]-5-氯-2H-苯并***、2-[2-羟基-3-甲基-5-(8-甲基丙烯酰氧基氧基辛基)苯基]-2H-苯并***、2-[4-(4,6-二联苯基-4-基-[1,3,5]三嗪-2-基)-3-羟基-苯氧基]-丙酸-6-甲基-庚酯、2-[4-(4,6-二{2-羟基-4-[1-(6-甲基-庚基氧基羰基)-乙氧基]-苯基}-[1,3,5]三嗪-2-基)-3-羟基-苯氧基]-丙酸-6-甲基-庚酯、2-(4,6-二(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-羟基苯基与环氧乙烷的反应产物、2,4-二[2-羟基-4-丁氧基苯基]-6-(2,4-二丁氧基苯基)-1,3,5-三嗪、2-(2,4-二羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪与(2-乙基己基)-环氧丙烯酸酯的反应产物、4,6-二苯甲酰间苯二酚等。
上述苯并二硫醇类化合物可例举2-(4,7-二羟基-1,3-苯并二硫醇-2-亚基)-4,4-二甲基-3-氧戊腈、2-氰基-2-(4,7-二羟基-1,3-苯并二硫醇-2-亚基)-2-乙基己基乙酸酯、2-(4,7-二羟基-1,3-苯并二硫醇-2-亚基)丙二腈、1,2-二丁基-4-(4,7-二羟基-1,3-苯并二硫醇-2-亚基)-3,5-吡唑烷二酮、4-(4,7-二羟基-1,3-苯并二硫醇-2-亚基)-3-(1,1-二甲基酯)-5(4H)-异噁唑啉酮、4-(4,7-二羟基-1,3-苯并二硫醇-2-亚基)-1,2-二苯基-3,5-吡唑烷二酮、2-(4,7-二羟基-5-甲基-1,3-苯并二硫醇-2-亚基)丙二腈、2,2'-(4,8-二羟基苯并[1,2-d:4,5-d']双[1,3]二硫醇-2,6-二亚基)双[4,4-二甲基-3-氧戊腈]、2,2'-(4,8-二羟基苯并[1,2-d:4,5-d']双[1,3]二硫醇-2,6-二亚基)双[2-氰基-1,1'-双(2-乙基己基)乙酸酯]、4,4'-(4,8-二羟基苯并[1,2-d:4,5-d']双[1,3]二硫醇-2,6-二亚基)双[2,4-二氢-5-甲基-2-苯基-3H-吡唑-3-酮]等。另外,在该情况下,可以是保护膜154A、154B两者均为紫外线吸收层,也可以是车内侧的保护膜154A不是紫外线吸收层而仅车外侧的保护膜154B为紫外线吸收层。
另外,紫外线吸收层不限于由保护膜154来实现,例如也可以在保护膜154之外形成紫外线吸收层。图3所示为本实施方式的另一示例的夹层玻璃的示意性剖视图。图3所示为另外形成紫外线吸收层的示例。如图3所示,在另外形成紫外线吸收层155的情况下,仍然优选保护膜154形成在Z方向上调光元件15的最外表面上,因此紫外线吸收层155在Z方向上形成于保护膜154与液晶层153之间。图3的示例中,紫外线吸收层155形成于基材151与保护膜154之间,但并不限于此,例如也可以形成于基材151与导电膜152之间。此外,图3的示例中,基材151A与保护膜154A之间形成有紫外线吸收层155A,而基材151B与保护膜154B之间形成有紫外线吸收层155B。但是,也可以不形成车内侧的紫外线吸收层155A而仅形成车外侧的紫外线吸收层155B。此外,紫外线吸收层155的材料可以是任意的,但是与例如保护膜154为紫外线吸收层的情况相同,其可以是母材包含紫外线吸收剂而成者。
此外,紫外线吸收层也可以由基材151或中间层13来实现。该情况下,基材151或中间层13通过在母材中包含紫外线吸收剂而起到作为紫外线吸收层的功能。此处的母材是指上述基材151或中间层13的材料。
考虑到与固化型透明树脂或透明粘合片的相溶性优异,紫外线吸收剂优选苯并***类化合物和二苯甲酮类化合物,进一步优选苯并***类化合物。作为苯并***类化合物,可以使用市售的苯并***类化合物。作为市售的苯并***类化合物,可例举巴斯夫公司(BASF社)制的Tinuvin384-2、Tinuvin326、Tinuvin970,这些物质与固化型透明树脂的相溶性优异。另外,例如即使是与规定的固化型透明树脂基质相溶性低的紫外线吸收剂,也可以通过改性并键合对固化型透明树脂基质相溶性高的部分来提升紫外线吸收剂的相溶性,从而可以使用大范围的紫外线吸收剂。即,例如可以对有机硅类固化型透明树脂合适地使用经有机硅改性的紫外线吸收剂。
(红外线吸收层)
调光元件15优选包含吸收红外线的红外线吸收层。调光元件15包含红外线吸收层能够抑制红外线向车内侧透射,能够抑制车内的温度上升。液晶层153可能会因红外线所产生的光和热而发生劣化,因此红外线吸收层优选形成于比液晶层153更靠近车外侧处。
此处,如图2所示,将从车外侧玻璃板12入射到夹层玻璃10内的红外线设为入射红外线IRa,将从玻璃板12入射而在夹层玻璃10内行进而入射到液晶层153的红外线设为红外线IRb。而且,以红外线IRb的强度相对于红外线IRa的强度为夹层玻璃10的红外线透射率。红外线IRb可以说是透过夹层玻璃10中比液晶层153更靠近车外侧的部分的入射红外线IRa,而此处的红外线透射率可以说是夹层玻璃10中比液晶层153更靠近车外侧的部分的红外线的透射率。红外线透射率可以按照ISO9050:2003算出。如此定义的夹层玻璃10的红外线透射率在红外线的波长1000nm的情况下优选0%以上60%以下,更优选0%以上50%以下,进一步优选0%以上40%以下。地表面的太阳光强度中,可见光较强,红外线区域中波长越长则强度越弱,因此波长1000nm下的透射率降低对能量降低的效果较高。
本实施方式的示例中,保护膜154优选为红外线吸收层。保护膜154例如通过在母材中包含能够吸收红外线的红外线吸收剂而起到作为红外线吸收层的功能。此处的母材是指上述保护膜154的材料,作为红外线吸收剂,可例举ITO(锡氧化铟)微粒、ATO(锑氧化锡)微粒、LaB6(六硼化镧)、CWO(铯氧化钨)微粒。另外,在该情况下,可以是保护膜154A、154B两者均为红外线吸收层,也可以是车内侧的保护膜154A不是红外线吸收层而仅车外侧的保护膜154B为红外线吸收层。另外,在保护膜154的母材包含紫外线吸收剂和红外线吸收剂的情况下,保护膜154起到紫外线和红外线吸收层的功能。此外,保护膜154例如可以作为2层以上的结构具有紫外线吸收层和红外线吸收层。
另外,红外线吸收层不限于由保护膜154来实现,例如也可以在保护膜154之外形成红外线吸收层。该情况下,优选在图3所示的紫外线吸收层155的位置处形成红外线吸收层。此外,在形成紫外线吸收层和红外线吸收层两者的情况下,可以让紫外线吸收层155兼具红外线吸收层的功能,也可以分别形成紫外线吸收层155和红外线吸收层。
此外,红外线吸收层也可以由基材151或中间层13来实现。该情况下,基材151或中间层13通过在母材包含红外线吸收层而起到作为红外线吸收层的功能。此处的母材是指上述基材151或中间层13的材料。
此外,红外线吸收层可以包含在玻璃板12中,可以使用玻璃板12表面实施过红外线截止处理的玻璃,也可以在玻璃板12上贴合红外线截止膜来使用。
(夹层玻璃的制造方法)
接着,就以上说明的夹层玻璃10的制造方法进行说明。在制造夹层玻璃10的情况下,制造调光元件15。制造调光元件15时,先准备基材151,在基材151的一个表面151S1上形成导电膜152。然后,在基材151的另一个表面151S2上形成保护膜154。导电膜152与保护膜154的形成顺序任意。可以在导电膜152的表面上形成取向层或绝缘层。随后,与一对基材151的导电膜152侧表面相向地在一对基材151之间形成液晶层153。籍此,制成最外表面形成有保护膜154的调光元件15。但是,调光元件15的制造方法并不限于此,例如也可以在之后形成保护膜154。即,可以在形成有导电膜152的一对基材151之间形成液晶层153后在基材151的外表面上形成保护膜154。
制成调光元件15后,将中间层13和调光元件15夹在玻璃板11与玻璃板12之间而制成层叠体。调光元件15的外表面受保护膜154保护,因此该工艺中调光元件15的受损得到抑制。制成层叠体后,例如将该层叠体放入橡胶袋中,在-100kPa以上-65kPa以下的真空中于约50℃以上110℃以下温度下进行预压接。考虑到调光元件15的性质,适当选择预压接的加热条件、温度条件、真空条件和层叠方法,使其在层叠中不发生劣化。
进一步,例如通过在80℃以上150℃以下、压力为0.6以上1.3MPa以下的条件下用高压釜进行加热加压的压接处理,可以获得耐久性更优异的夹层玻璃10。但是,根据情况,考虑到工序的简化以及夹层玻璃10中封入的材料的特性,有时也不使用该加热加压工序。
在制备层叠体的工序中,在使用透明粘合片(OCA)作为中间层13的情况下,可以在玻璃板12上介由成为中间层13的一部分的中间层132来粘接调光元件15而制成第1层叠体,而在第1层叠体的调光元件15侧介由成为中间层13的一部分的中间层131粘接玻璃板11而制成层叠体。该情况下,中间层13可以使用粘接膜,预压接工序可以使用辊式贴合机代替橡胶袋来进行。
温度条件、真空条件可以考虑中间层13、调光元件15的性质适当选择,使其在层叠中不发生劣化。特别是,通过在常温下粘接,制造变得容易,因此是理想的。此外,也可以追加位于中间层131与中间层132之间并包围调光元件15外周的画框状的中间层133。
此外,在制备层叠体的工序中,在使用固化型透明树脂(OCR)作为中间层13的情况下,例如在玻璃板12与玻璃板11之间的空间中***调光元件15,将玻璃板12与玻璃板11之间的空间内的调光元件15的位置固定。然后,用胶带等将玻璃板12与玻璃板11之间的空间的周围封住,将该空间与外部分开。随后,向该空间中注入固化型透明树脂,用固化型透明树脂充满该空间。再通过使该固化型透明树脂固化而形成中间层13。固化型透明树脂的固化方法是任意的,可例举反应固化、热固化、光固化、湿气固化等。
另外,在夹层玻璃10为弯曲形状的情况下,玻璃板11和玻璃板12可以通过以往已知的弯曲方法来进行弯曲成形。例如,可以将玻璃板11和玻璃板12重叠并载置于环状模具上,加热至软化点以上,通过其自重进行弯曲成形。此外,可以在玻璃板11和玻璃板12经加热的状态下,将其分别或重叠进行加压成形。
另外,以上的夹层玻璃10的制造工序是一个示例,例如也可以用冷弯法的方法制造夹层玻璃10。
(本实施方式的效果)
如上说明的那样,本实施方式的夹层玻璃10具备一对玻璃板、和设置于一对玻璃板之间的调光元件15。调光元件15具有宾主效应型的液晶层153、基材151、形成于基材151的一个表面151S1上的导电膜152、以及形成于基材151的另一个表面151S2上的保护膜154。保护膜154的耐磨耗性比基材151更高。这里,调光元件在组装于夹层玻璃时(换而言之,搭载到夹层玻璃内时)等若外表面受损,则调光功能可能无法适宜地发挥。与此相对,本实施方式的夹层玻璃10在基材151的表面151S2上形成有硬度比基材151更高的保护膜154。因此,本实施方式的夹层玻璃10能够抑制调光元件15受损,使其适宜地发挥调光功能。特别是在宾主效应型的调光元件15上设置保护膜154能够抑制受损、适宜地抑制外观缺点。
此外,优选的是,夹着液晶层153设置一对导电膜152,基材151包含一个表面151S1上形成有一个导电膜152的第1基材(基材151A)、一个表面151S1上形成有另一个导电膜152的第2基材(基材151B),保护膜154包含形成于第1基材(基材151A)的另一个表面151S2上的第1保护膜(保护膜154A)、和形成于第2基材(基材151B)的另一个表面151S2上的第2保护膜(保护膜154B)。本实施方式的夹层玻璃10能够抑制调光元件15受损,使其适宜地发挥调光功能。此外,通过在调光元件15的基材表面上具有保护膜154,能够在基材上不需要另外粘贴和剥离保护膜的情况下继续抑制调光元件15受损的发生。特别是,在液晶层153包含宾主效应型液晶、TN型液晶、PC型液晶、STN型液晶、ECB型液晶、OCB型液晶、IPS型液晶、VA型液晶这种流动性高的液体的情况下,调光元件15的基材与液晶层153容易剥离。因此,不需要粘贴和剥离保护膜这一点有助于进一步适宜地发挥调光功能。
保护膜154优选在JIS R3212所述的耐磨耗性试验中进行100次试验后的雾度变化在0%以上20%以下。本实施方式的夹层玻璃10通过保护膜154的耐磨耗性在该范围内,能够抑制调光元件15受损,使其适宜地发挥调光功能。
保护膜154优选含有选自分子中具有2个以上聚合性官能团的聚合固化性化合物的固化体(透明被覆膜)和硅类醇盐化合物的固化体(透明被覆膜)中的1种以上。本实施方式的夹层玻璃10通过使用这样的保护膜154,能够抑制调光元件15受损,使其适宜地发挥调光功能。
基材151优选含有选自聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚酰胺、聚醚、聚砜、聚醚砜、聚碳酸酯、聚苯乙烯、环状聚烯烃、聚芳酯、聚醚酰亚胺、聚醚醚酮、聚酰亚胺、芳族聚酰胺、聚对苯二甲酸丁二醇酯、三乙酰基纤维素、聚氨酯和环烯烃聚合物中的1种以上。本实施方式的夹层玻璃10能够由保护膜154来抑制调光元件15受损,同时由基材151来提升耐冲击性。特别是对于宾主效应型的调光元件15,能够适宜地抑制色差。
调光元件15优选包含吸收紫外线的紫外线吸收层。本实施方式的夹层玻璃10通过具有紫外线吸收层,能够适宜地抑制紫外线透射。
此外,优选保护膜154为紫外线吸收层。本实施方式的夹层玻璃10通过以保护膜154作为紫外线吸收层,能够抑制调光元件15受损并适宜地抑制紫外线透射,同时抑制膜厚不变得过厚。
此外,优选从一块玻璃板12入射到夹层玻璃10而入射到液晶层153的波长380nm的紫外线(紫外线UVb)的强度相对于入射到一块玻璃板12的紫外线(紫外线UVa)的强度为0%以上20%以下。紫外线透射率在该范围内,特别能够适宜地抑制UVA(紫外线A波)透射。
调光元件15优选包含吸收红外线的红外线吸收层。本实施方式的夹层玻璃10通过具有红外线吸收层,能够适宜地抑制红外线透射。
此外,优选保护膜154为红外线吸收层。本实施方式的夹层玻璃10通过以保护膜154作为红外线吸收层,能够抑制调光元件15受损并适宜地抑制红外线透射,同时抑制膜厚不变得过厚。
此外,优选从一块玻璃板12入射到夹层玻璃10而入射到液晶层153的波长1000nm的红外线(红外线IRb)的强度相对于入射到一块玻璃板12的红外线(入射红外线IRa)的强度为0%以上60%以下。红外线透射率在该范围内,能够适宜地抑制红外线透射。
此外,一对玻璃板11、12之间设置有中间层13,调光元件15设置在中间层13内。本实施方式的夹层玻璃10通过在中间层13内设置调光元件15,能够抑制调光元件15变形。
此外,中间层13优选含有选自增塑性聚乙烯醇缩醛类树脂、增塑性聚氯乙烯类树脂、饱和聚酯类树脂、增塑性饱和聚酯类树脂、聚氨酯类树脂、增塑性聚氨酯类树脂、乙烯-乙酸乙烯酯共聚物类树脂、乙烯-丙烯酸乙酯共聚物类树脂、环烯烃聚合物树脂和离聚物树脂中的1种以上。使用这种中间层13,能够抑制液晶层153的膜厚偏差所导致的色差。进一步,对于这种中间层13,设置本实施方式的基材151对耐冲击性下降特别有效。
作为中间层13,可以使用固化型透明树脂(OCR)、透明粘合片(OCA)中的至少1种。通过使用固化型透明树脂或透明粘合片,能够在常温下制备层叠体,因此是理想的。作为固化型透明树脂或透明粘合片,使用丙烯酸类、有机硅类、聚氨酯丙烯酸酯类、环氧类等。
中间层13优选在测定频率1Hz下的动态粘弹性测定中的25℃下剪切模量在1.0×103Pa以上且2.0×1056Pa以下。通过使用这种中间层13,能够在常温下制备层叠体,因此是理想的。
此外,本实施方式的夹层玻璃10优选为车辆用玻璃。本实施方式的夹层玻璃10能够抑制调光元件15受损,因此对车辆用玻璃特别有效。
(实施例)
下面就实施例进行说明。表1为对实施例进行说明的表。但是,本发明并不限定于这些实施例。
[表1]
(例1)
例1中,准备第1玻璃板、第1中间层、调光元件、第2中间层、第2玻璃板从车外侧向车内侧依次层叠而成的夹层玻璃。例1中,作为第1玻璃板和第2玻璃板,分别使用AGC株式会社(AGC社)制的VFL2.0(厚度:2mm),作为第1中间层,使用帕纳科公司(パナック)制的丙烯酸类OCA PD-S1(厚度:25μm),作为第2中间层,使用迈图高新材料公司(モメンティブ社)制的2液固化型有机硅OCR(商品名:SN1001)。此外,例1中,作为调光元件,使用第1保护膜、第1基材、宾主效应型的调光部、第2基材、第2保护膜从车外侧向车内侧依次层叠而成者。例1中,作为第1基材和第2基材,分别使用AGC聚碳酸酯株式会社(AGCポリカーボネート社)制的聚碳酸酯(商品名:CARBOGLASS C110C)的厚度100μm的材料,作为第1、第2保护膜,分别使用横浜橡胶株式会社(横浜ゴム社)的硬质涂布液HR350形成5μm的厚度。另外,HR350含有六丙烯酸二季戊四醇酯。例1中,未形成紫外线吸收层和红外线吸收层。
(例2)
例2中,除了将第1保护膜作为紫外线吸收层这一点以外,以与例1相同的方法制造了夹层玻璃。例2中,向母材HR350中添加相对于第1保护膜整体为5质量%的紫外线吸收剂2-[4-(4,6-二{2-羟基-4-[1-(6-甲基-庚基氧基羰基)-乙氧基]-苯基}-[1,3,5]三嗪-2-基)-3-羟基-苯氧基]-丙酸-6-甲基-庚酯,从而生成作为紫外线吸收层的第1保护膜。
(例3)
例3中,除了以东洋纺株式会社(東洋紡社)制的聚对苯二甲酸乙二醇酯(商品名:COSMOSHINE A4360)的厚度100μm的材料作为第1基材和第2基材这一点以外,以与例2相同的方法制造了夹层玻璃。
(例4)
例4中,除了将第1保护膜作为红外线吸收层这一点以外,以与例2相同的方法制造了夹层玻璃。即,例4中,第1保护膜兼具紫外线吸收层的功能和红外线吸收层的功能。例4中,向母材HR350中添加相对于第1保护膜整体为5质量%的紫外线吸收剂2-[4-(4,6-二{2-羟基-4-[1-(6-甲基-庚基氧基羰基)-乙氧基]-苯基}-[1,3,5]三嗪-2-基)-3-羟基-苯氧基]-丙酸-6-甲基-庚酯,并添加相对于第1保护膜整体为5质量%的作为红外线吸收剂的ITO分散液(三菱综合材料株式会社(三菱マテリアル)制的PI-6T),从而生成第1保护膜。
(例5)
例5中,除了将第1中间层作为紫外线吸收层这一点以外,以与例1相同的方法制造了夹层玻璃。例5中,向母材2液固化型有机硅树脂添加相对于第1中间层整体为1质量%的紫外线吸收剂C7-C9-烷基-3-[3-(2H-苯并***-2-基)-5-(1,1-二甲基乙基)-4-羟基苯基]丙醚,从而生成作为紫外线吸收层的第1中间层。
(例6)
例6中,使用迈图高新材料公司制的2液固化型有机硅OCR(商品名:SN1001)作为第1中间层,使用帕纳科公司制的丙烯酸类OCA PD-S1作为第2中间层。然后,除了将第1中间层作为紫外线吸收层这一点以外,以与例1相同的方法制造了夹层玻璃。作为紫外线吸收剂,使用1,2-二丁基-4-(4,7-二羟基-1,3-苯并二硫醇-2-亚基)-3,5-吡唑烷二酮加入环氧改性有机硅(信越化学株式会社(信越化学社)制的“KF-105”)和胺催化剂在80℃下加热搅拌进行有机硅改性而成的化合物。通过添加相对于第1中间层整体为1质量%的经有机硅改性的紫外线吸收剂,生成作为紫外线吸收层的第1中间层。即,第1中间层为溶解有经有机硅改性的紫外线吸收剂的有机硅类OCR。
(例7)
例7中,除了未设置第1保护膜和第2保护膜这一点以外,以与例1相同的方法制造了夹层玻璃。
(评价)
对例1到例7的夹层玻璃分别进行了操作损伤的评价和耐候性的评价。
操作损伤的评价中,进行了JIS R3212所述的耐磨耗性试验。将100次试验后雾度变化在20%以下的记为圆(〇),将超过20%的记为叉(×),以圆(〇)为合格。如表1所示,作为实施例的例1~例6中,操作损伤的评价均为合格,而未设置保护膜的作为比较例的例7中,操作损伤的评价为不合格。
耐候性的评价为可选评价,使用氙灯耐候测试仪在黑色面板温度83℃下以照射量150W暴露1500小时后,测定深色状态下的可见光透射率(Tv)。将试验前后可见光透射率的变化量的绝对值在1.5%以下的记为双重圆(◎),将2.0%以下的记为圆(〇),将5.0%以下的记为三角(△)。如表1所示可知,设置紫外线吸收层或红外线吸收层能够提升耐候性因而更优选。
以上对本发明的实施方式进行了说明,但是该实施方式的内容并不限定实施方式。此外,前述构成要素中包含本领域技术人员容易想到的那些、实质上相同的那些、即所谓等同范围中的那些。再者,前述构成要素可以适当组合。进而,在不脱离前述实施方式要旨的范围内,可以进行构成要素的各种省略、置换或变更。
符号说明
10 夹层玻璃
11、12 玻璃板
13 中间层
14 遮蔽层
15 调光元件
151、151A、151B基材
152、152A、152B导电膜
153液晶层
154、154A、154B保护膜
另外,这里引用2020年08月07日提出申请的日本专利申请2020-135139号的说明书、权利要求书、摘要和附图的全部内容作为本发明的说明书的揭示。
Claims (17)
1.一种夹层玻璃,其具备:
一对玻璃板,和
设置于所述一对玻璃板之间并具有液晶层、基材、形成于所述基材的一个表面上的导电膜、以及形成于所述基材的另一个表面上的保护膜的调光元件,其中,
所述液晶层具有选自宾主效应型液晶、TN型液晶、PC型液晶、STN型液晶、ECB型液晶、OCB型液晶、IPS型液晶和VA型液晶中的至少1种,
所述保护膜的耐磨耗性比所述基材更高。
2.如权利要求1所述的夹层玻璃,其中,所述液晶层为宾主效应型液晶。
3.如权利要求1或权利要求2所述的夹层玻璃,其中,
所述导电膜包含夹持所述液晶层的第1导电膜和第2导电膜,
所述基材包含一个表面上形成有所述第1导电膜的第1基材、和一个表面上形成有所述第2导电膜的第2基材,
所述保护膜包含形成于所述第1基材的另一个表面上的第1保护膜、和形成于所述第2基材的另一个表面上的第2保护膜。
4.如权利要求1~权利要求3中任一项所述的夹层玻璃,其中,所述保护膜在JIS R3212所述的耐磨耗性试验中进行100次试验后的雾度变化在0%以上20%以下。
5.如权利要求1~权利要求4中任一项所述的夹层玻璃,其中,所述保护膜含有选自分子中具有2个以上聚合性官能团的聚合固化性化合物的固化体和硅类醇盐化合物的固化体中的1种以上。
6.如权利要求1~权利要求5中任一项所述的夹层玻璃,其中,所述基材含有选自聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚酰胺、聚醚、聚砜、聚醚砜、聚碳酸酯、聚苯乙烯、环状聚烯烃、聚芳酯、聚醚酰亚胺、聚醚醚酮、聚酰亚胺、芳族聚酰胺、聚对苯二甲酸丁二醇酯、三乙酰基纤维素、聚氨酯和环烯烃聚合物中的1种以上。
7.如权利要求1~权利要求6中任一项所述的夹层玻璃,其中,所述调光元件包含紫外线吸收层。
8.如权利要求7所述的夹层玻璃,其中,所述保护膜为所述紫外线吸收层。
9.如权利要求7或权利要求8所述的夹层玻璃,其中,相对于从所述一对玻璃板中的一块玻璃板的外侧入射到所述夹层玻璃内的波长380nm的紫外线的强度,在所述夹层玻璃内行进而入射到所述液晶层的所述紫外线的强度在0%以上20%以下。
10.如权利要求1~权利要求9中任一项所述的夹层玻璃,其中,所述调光元件包含红外线吸收层。
11.如权利要求10所述的夹层玻璃,其中,所述保护膜为所述红外线吸收层。
12.如权利要求10或权利要求11所述的夹层玻璃,其中,相对于从所述一对玻璃板中的一块玻璃板的外侧入射到所述夹层玻璃内的波长1000nm的所述红外线的强度,在所述夹层玻璃内行进而入射到所述液晶层的红外线的强度在0%以上60%以下。
13.如权利要求1~权利要求12中任一项所述的夹层玻璃,其中,所述一对玻璃板之间设置有中间层,所述调光元件设置于所述中间层内。
14.如权利要求13所述的夹层玻璃,其中,所述中间层含有选自增塑性聚乙烯醇缩醛类树脂、增塑性聚氯乙烯类树脂、饱和聚酯类树脂、增塑性饱和聚酯类树脂、聚氨酯类树脂、增塑性聚氨酯类树脂、乙烯-乙酸乙烯酯共聚物类树脂、乙烯-丙烯酸乙酯共聚物类树脂、环烯烃聚合物树脂和离聚物树脂中的1种以上。
15.如权利要求13或权利要求14所述的夹层玻璃,其中,所述中间层包含透明粘合片和固化型透明树脂中的至少1种。
16.如权利要求13~权利要求15中任一项所述的夹层玻璃,其中,所述中间层在测定频率1Hz下的动态粘弹性测定中的25℃下剪切模量在1.0×103Pa以上且100.0×106Pa以下。
17.如权利要求1~权利要求16中任一项所述的夹层玻璃,其为车辆用玻璃。
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