CN1046893C - 路面标记材料 - Google Patents
路面标记材料 Download PDFInfo
- Publication number
- CN1046893C CN1046893C CN91101859A CN91101859A CN1046893C CN 1046893 C CN1046893 C CN 1046893C CN 91101859 A CN91101859 A CN 91101859A CN 91101859 A CN91101859 A CN 91101859A CN 1046893 C CN1046893 C CN 1046893C
- Authority
- CN
- China
- Prior art keywords
- top layer
- making material
- pavement making
- pavement
- polyurethane
- 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.)
- Expired - Lifetime
Links
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- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 15
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 4
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- -1 4,4 '-methylene Chemical group 0.000 description 3
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- 239000004606 Fillers/Extenders Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
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- TWDJIKFUVRYBJF-UHFFFAOYSA-N Cyanthoate Chemical compound CCOP(=O)(OCC)SCC(=O)NC(C)(C)C#N TWDJIKFUVRYBJF-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
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- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
- E01F9/00—Arrangement of road signs or traffic signals; Arrangements for enforcing caution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
- E01F9/00—Arrangement of road signs or traffic signals; Arrangements for enforcing caution
- E01F9/50—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users
- E01F9/506—Road surface markings; Kerbs or road edgings, specially adapted for alerting road users characterised by the road surface marking material, e.g. comprising additives for improving friction or reflectivity; Methods of forming, installing or applying markings in, on or to road surfaces
- E01F9/512—Preformed road surface markings, e.g. of sheet material; Methods of applying preformed markings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2375/00—Polyureas; Polyurethanes
-
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
- Y10T428/24298—Noncircular aperture [e.g., slit, diamond, rectangular, etc.]
- Y10T428/24314—Slit or elongated
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- Y10T428/24372—Particulate matter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Road Signs Or Road Markings (AREA)
- Road Paving Structures (AREA)
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
一种路面标记材料包括一种能与不规则路面整合的基底。一种耐久、耐磨，聚合物顶层与所述基底的一面粘合。顶层在0℃到45℃温度下能经受脆性断裂使得基底与不规则表面整合时，顶层则较易形成断裂以释放在顶层形成的张力，而由断裂限定的顶层裂区仍与基底粘合且服从其整合性。在顶层嵌入了许多突出于顶层表面的微粒。在优选实施例中，顶层的杨氏模量大约为50,000Psi到300,000Psi，断裂伸度大约为4%到35%。
Description
本发明涉及一种改进的路面标记材料，这种材料可粘附在公路上作交通控制标记等用。
用作交通控制标记的预制的路面标记材料有广泛的用途，例如矩距离车道条纹线、停止线、十字路口的人行横道标记等。预制的路面标记材料一般包括一条连续的、覆盖在柔性基片上的耐磨的顶层。使用压敏胶或接触性胶粘剂将这样的材料施加在基片上。
例如，美国专利第4,020,211号公开的一种预制的标记复合材料包括一条连续的、粘在柔性基片上的聚氨酯顶层。这种标记材料具有很高的杨氏模量，大大高于300,000Psi(磅/英吋2)因此，这种材料非常硬且不易适形，因而由于与路面的不良粘合而使得整个复合材料往往会从不规则路面上脱开。
在受让人同案未决申请，申请日为1989年6月26日，美国序号为第07/372,183(它是现已撤卷的1986年5月29日申请的美国序号为06/866,570案的接续申请)中描述了一种适形性较好的预制的标记材料，它包括一种粘在柔性基片上的弹性较好且连续的聚氨酯耐磨层。在美国专利第4,248,932号；4,117,192号；3,935,365号；和欧洲专利申请第0,162,229号中也描述了类似的材料。由于这种聚氨酯耐磨层具有较低的模量，这些材料与不规则路面的初始适形性较好。虽然这种标记材料与路面粘合和适形时，聚氨酯耐磨层的弹性性能在顶层产生弹性拉应力，但时间一长，这种应力会使粘合剂失效。到那时，标记材料会从路面脱开。
本受让人的未决申请(1988年6月9日提出的美国申请第07/204,349号)描述了一种路面标记材料，它包括覆盖在一面具有突出点的柔性基片上的聚氨酯颗粒粘合剂。这种颗粒粘合剂覆盖了部分选择的突出点。公开的一种颗粒粘合剂是一种聚氨酯脲，它包括大约两当量的双(异氢酸4环己酶)(H12MDI)和大约一当量的聚己酸内酯三醇，这种聚己酸内酯三醇的分子量约为540，羟基数约为310。
本发明提供了一种改进的路面标记材料，它包括能与不规则路面整合、且不产生导致粘合剂失效的弹性应力的耐磨顶层。最佳的路面标记材料在保留铺底的适形层的柔性之同时，其顶层还具有坚韧、耐磨、坚硬等卓越的耐用特性。因为这些特性，本发明的路面标记材料能容易和持久地铺在粗糙或不规则的路面上。
本发明的优点在于应用了一种包括能与不规则路面适形的基片的路面标记材料，在基片的一面粘上耐久、耐磨、聚合物的顶层。在0℃到45℃的温度下，这种顶层能够经受脆性断裂使得在基片与不规则路面适形时，顶层可较易裂开以释放积聚在顶层的应力，同时，由断裂限定的顶层区仍与衬片粘合且与其形状相一致。在顶层嵌入了一些突出于顶层表面的微粒。在优选的实施方案中，顶层的特征为，其杨氏模量约为50,000Psi到300,000Psi，断裂百分伸长率约为4％到35％。
根据本发明的路面标记材料比弹性更好、能抗裂的顶层的路面标记材料的适形性要好。实验表明，优选的路面标记材料比先前已知的材料与不规则路面的粘合要耐久得多。在测定在公路面上保持性的性能试验中，性能最接近的先前已知材料比本发明材料大约要差两倍。此外，在同一的性能试验中，发现本发明材料的持久反射率和白度均和先前已知材料一样好，并且比大部分已知材料的性能更好。
优选的材料还显示卓越的耐久性，在使用503型标准磨蚀试验机和(Abrasion Tester)(由Taber Abraser,Teledyne Tabor,North Tonawonda,New York，制造)的试验中，试验机装有H-22磨擦轮和一公斤的负荷，优选的材料经1000转后的重量损耗大约为0.05克到0.30克。
图1为本发明的优选的路面标记材料的侧截面。
图2为图1所示材料与不规则路粘合的截面图，其中在顶层有断裂形成。
图3为本发明另一实施方案的透视图，其中顶层上的许多切口为断裂处。
图4为一透视图，其中图3所示的路面标记材料已被弯曲。
现在参看图1，它图示了根据本发明的路面标记材料10的一种优选实施方案。该路面标记材料10包括一个能与不规则路面16适形的柔性基片12。基片12最好基本上是平的，没有突出物。例如，合适的基片可以是此处引为参考文献的美国专利第4,117,192号或第4,490,432号所说的减小弹性的基片。这种减小弹性的基片包括未硫化的弹性体前体、增充树脂诸如氯化石蜡、填料、以及用纺粘的聚烯烃或聚酯制成的非织造织物。
基片12一般约为20密耳到50密耳厚以提供所期望的适形性和强度。基片12最好为35密耳厚。低于约20密耳时，基片12不能对路面标记材料10提供足够的强度或作为其支承物。高于约50密耳时，标记材料10可能高于路面14太多而使得铲雪机可能损坏或使标记材料10移位，而且如果太高的话，还得考虑成本。
可在基片12中随意地加入颜料进行着色。二氧化钛给基片12着上白色。另一种有用的颜料是铬酸铅，它给基片12着以黄色。还可以在基片12中加入颗粒填料，一般用量很大，以减少成本和改进性能，如强化，增充，表面硬度，以及耐磨性。
将耐久、耐磨、聚合物的顶层18粘合到基片12的一面上。顶层18能在0℃到45℃，最好在0℃到35℃的温度下进行脆性断裂。最好如图2所示，顶层18易于在路面16的粗糙或不规则处形成断裂20。顶层18是在顶层与不规则路面的适形性超出顶层断裂伸长率时形成断裂20的。但是，在铺底面为平滑处顶层18一般不形成断裂。
路面标记材料10比具有更好弹性、能抗裂的顶层的路面标记材料的适形性要好。当弹性更好的顶层变形以与粗糙或不规则路面适形时，在顶层产生弹性应力。这种应力会以与用来将路面标记材料保持在路面上的粘合剂相反方向回拉路面标记材料。久而久之，这些应力将引起粘合剂失效，届时，路面标记材料开始从路面脱开。
但是，在本发明中，顶层18没有积聚这种弹性应力的能量。相反，在顶层18与路面14适形时，通过形成断裂20消耗了这种能量。因此，使引起路面标记材料10从路面14脱开的弹性应力减小或根除。所以，本发明材料与粗糙或不规则路面的粘合更长久。断裂后，顶层18仍然是一耐久的耐磨层。
在顶层中断裂20是宏观裂缝，而不是微观裂缝。由脆性断裂形成的宏观裂缝一般能穿过整个顶层18，因而能有效地释放在顶层18中形成的应力，裂缝之间相距为1mm到50mm。宏观裂缝比微观裂缝对路面标记材料的白度的危害性要小。微观裂缝只在顶层18的表面形成，因而不能有效地释放在顶层18中形成的应力。另外一个区别是，微观裂缝之间只相距为10到100微米。
顶层18的杨氏模量优选为50,000 Psi(350MPa)到300,000Psi (2100MPa)，最好是50,000 Psi(350MPa)到250,000Psi (1750MPa)。如果模量太低的话，那么顶层18不具备足够的耐磨性能，如果模量太高的话，那么顶层18不具备充分的适形性。顶层18的断裂伸长率较好为4％到35％，更好为4％到20％，最好为4％到10％。
在测试聚氨酯的拉伸性能时，可采用如下测试步骤：将聚氨酯流延在涂布纸衬上，然后放在温度为120℃到135℃的炉中处理10到15分钟。冷却后，从纸衬上取出聚氨酯并把它切成0.5英吋(1.3厘米)×6英吋(15.2厘米)的条。这些聚氨酯条在72°F(22.2℃)和50％的相对湿度下预调理48小时。然后把它们固定在英斯特朗多能试验仪(Instron公司，Canton麻萨诸塞州)的相隔为4英时(10.2厘米)的夹头上。然后以每分钟10英时(25.4厘米/分钟)的速率把夹头拉开直至样品断开。将进行这种分离所需的力绘制成曲线并记录下来。断裂伸长率是通过伸长的英时数/4英吋乘100％而测出的。弹性模量(杨氏模量)是使样品产生1％应变所需的力除以样品的截面积来确定的。
再参看图1，顶层18的合适聚合物材料包括聚氨酯、环氧树脂、聚酰胺，聚脲，以及聚酯。这些材料的混合物也适合于本发明。合适的聚合物既可以是热塑性聚合物也可以是热固性聚合物。顶层18优选由聚氨酯组成。聚氨酯的一般特征为：它与基本上嵌入顶层的微粒26和28的粘合性非常好。优选的聚氨酯是脂族聚氨酯。与基片12紧密粘合的脂族聚氨酯粘性强，并且耐环境的天候老化。
适用于本发明的聚氨酯的例子是由多羟基化合物组分和聚异氰酸酯衍生的，其中聚异氰酸酯的NCO基与多羟基化合物组分的OH基的当量比约为0.5到1.5，优选为约1.05，多羟基化合物组分可以是任何低分子量多羟基化合物和/或聚合多羟基化合物的混合物，只要产生出的聚氨酯在0℃到45℃度下能脆性断裂就行。
优选的是，多羟基化合物组分包含一种或多种多羟基化合物，它们的平均分子量约为300到660，平均羟基当量约为100到220，且每个多羟基化合物分子平均有3个或更多个的羟基。更优选的是，多羟基化合物组分由约一当量的、其羟基当量约为100的聚己酸内酯三醇和0到0.33当量的，其羟基当量约为300的聚己酸内酯三醇组成。
聚异氰酸酯最好的是脂族化合物，因为在室外天候老化的条件下，这样的化合物比芳族化合物裉色性弱。具有芳环的聚异氰酸酯也有用，所说的芳环不直接连到异氰酸酯基上，而是连到无氢的碳原子上。在美国专利第4,377,530号和第4,379,767号中公开了这类化合物。
有用的聚异氰酸酯包括异佛尔酮二异氰酸盐；4,4＇-亚甲基一双一环已基二异氰酸酯；四亚甲基二异氰酸酯；1,3及1,4环己基二异氰酸酯；1,6六亚甲基二异氰酸酯，1,6六亚甲基二异氰酸酯的加合物。四甲基亚二甲苯基二异氰酸酯异构体；或由多元醇和双官能脂族异氰酸酯衍生的异氰酸酯封端聚合物。
在一种特别优选的聚氨酯中，多羟基化合物组分包含约100份重量的其分子量约为300的聚己酸内酯三醇，例如可在UnionCarbide公司买到的Tone 0 301。多羟基化合物组分还可包含约为0到100份重量的、优选为10到25份重量。更优选为约19份重量，其分子量约为960的聚己酸内酯三醇，如可在Union Carbide公司买到的Tone 0310。低分子量的三醇赋予聚氨酯以刚性，而高分子量的三醇用来降低聚氨酯的模量。但是，如果用了太多的高分子量的三醇的话，则聚氨酯不够耐磨。另外，如果用了太多的高分子量的三醇的话，则聚氨酯将丧失所需要的断裂特性。
特别优选的聚氨酯还可包括大约190到230份重量、更优选为/约210份重量的1,6六亚甲基二异氰酸酯的缩二脲加合物，如可从美国贝叶(Bayer)公司Mobay化学部买到的聚氨基甲酸酯类粘合剂N-100。就特别优选的聚氨酯来说，聚异氰酸酯的NCO基与多羟基化合物组分的OH基的当量比约为1.05。
象现有的路面标记材料一样，顶层18还可包含各种无机添加剂，例如，惰性填料、增充剂、和颜料。各种无机添加剂可用诸如硅烷的偶联剂处理以强化与聚氨酯类聚合物的结合。惰性填料包括矾土；硅酸镁；氧化镁；碳酸钙；偏硅酸钙；非晶形或结晶硅石；氧化锌；铬酸铅；和氧化锆。
在顶层18中还可包含足够量的颜料或其它着色剂为特殊用途的标记材料着色。例如，当用作路面标记材料时，氧化钛是一种理想的颜料和填料，它为基本上嵌入顶层18的反光珠26提供白色和温反射背景。而铬酸铅一般呈黄色。
顶层18至少为约4-30密耳厚。优选的是，顶层18约为12-16密耳厚，最优选为约13密耳厚。如果顶层18不够厚的话，则顶层18不能牢固地粘合基本上嵌入顶层的微粒。如果顶层18太厚的话，则整个结构太硬而不能达到理想的适形性，而且如果顶层18太厚的话，还得考虑成本。
顶层18最好是支化的，交联的聚合物网络。交联有助于所期望的断裂特性，而且还可以认为交联有助于基材标记材料10的耐磨性。我们还发现如果聚合顶层18高度交联的话，则顶层具有较好的抗裉色性，而裉色是由于车辆轮胎经过标记、或油污、尘垢接触基材标记材料10所引起的。
顶层18一般是通过将液体配料直接涂在基片12上形成的。但是，顶层18也可独自形成，然后经一个层压工序粘合到基片12上，例如在顶层18和基片12之间施一层胶(图1和图2中未示出)。
在顶层18嵌入许多微粒26和28，它们突出于顶层表面。微粒26和28包括反光珠26和防滑微料28。通过浮色涂敷法(floodcoating process)将微粒26和28施加到仍为液体的顶层18中，在顶层18上就密积了微粒26和28。另一种方法是，经顶层18上撒或喷射微粒26和28，这可以避免微粒密积。喷撒处理的特殊优点是：使微粒用量最少；微粒间垢物减少，优化了反光性。
在微粒26和28嵌入顶层后，顶层断裂所需的断裂应力明显涉于没有这种微粒时所需的断裂应力。先前已知材料一般由合成橡胶材料制成，意在防裂。与先前已知材料不同，本发明并不想防止顶层断裂的自然趋势，而是利用这种趋势从中受益。
本发明适用的反光珠包括折射率约为1.5到1.9的玻璃珠。折射率接近1.5的玻璃珠比较便宜且较能防划防刻。但是折射率大约为1.7到1.9的玻璃珠能更有效地反光。
在美国专利第4,564,556号和第4,758,469号中介绍优选的反光珠26，这里引用此两篇文献作参考。所介绍的优选成反光珠是固体、透明、非玻态的陶瓷小球。这种球至少有一个由金属氧化物组成的晶相。这种反光珠也可能具有一个非晶相，如非晶形硅石相。“非玻态的”意指反光珠不是由原材料配料在高温下液化或溶化得到的。这种反光珠的防刻划性能极好，制造出的反光珠折射率可约为1.4到2.6。
在英国移动式防滑试验中，采用防滑微粒28的标记材料具有至少50BPN的残余防滑性。在采用英国(Crawthorne,Berkshire)公路研究实验室制造的移动式防滑测试仪测量时，采用BPN单位，意指British Portable Number(英式可移动数)。合适的防滑微粒包括白色氧化铝微粒。我们发现细小的氧化铝微粒和较大的氧化铝微粒的掺合物可提供合格的、长久的防滑性。在本受让人未决申请(申请日为1988年9月7日美国序号07/241,318)中描述了一种优选的防滑微粒，这里引用该文献作参考。这种防滑微粒是一种烧制陶瓷的陶瓷小球，它包含矿物粒子、矾土和粘合剂。这种防滑小球极其耐用，使路面标记材料具有优秀的防滑特性。
可用偶联剂对微粒26和28进行处理以增强微粒26和28与顶层18之间的粘合性。另一种方法是，顶层18可包含这样的偶联剂使得在微粒26和28嵌入顶层18时偶联剂能与微粒26和28相互作用。这些偶联剂通常包含与微粒26和28缔合的无机部分和与顶层18的有机成分相缔合并起反应的有机部分。优选的偶联剂是硅烷化合剂，如氨基硅烷化合物。
在固化处理期间，影响优选的路面标记材料性能的一个因素是顶层18的粘度。上述特别优选的聚氨酯的粘度随着顶层18的加热固化具有下降的倾向。如果在这个低粘度阶段向顶层18加入微粒26和28，则微粒26和28可能沉到顶层18的底部，从而降低了微粒26和28的效果。为了解决这一问题，最好在向顶层18掺加微粒26和28之前预先固化顶层18以增加顶层18的粘度。为此，在约150℃的温度下对聚氨酯顶层18加热足够长的时间以改进顶层18的粘度使得微粒26和28沉到约离顶层顶部有半个微粒直径的距离处。
在基片12的底面可附有一粘合层30用于粘合衬底14。另一种方法是，首先在衬底14上刷上粘合剂层30，然后把基质标记材料10粘到粘合层30上。最佳粘合剂为压敏胶，也可用接触性粘合剂。
图3和图4图示了本发明的另一种实施方案。图3示出了由粘在基片12上的顶层18组成的路面标记材料。在此实施方案中，顶层18的断裂是由顶层上许多刻划的切口32组成。在路面标记材料用于路面之前，就在顶层18上刻好了切口32。切口32有利于顶层与不规则路面的适形，同时能释放顶层被弯曲时所形成的应力。图4示出了图3中路面标记材料，它已被弯曲以便使它与不规则路面相适形。
参见下列各实施例以进一步介绍本发明。
实施例1
已备好具有优选的聚氨酯顶层的路面标记材料，顶层包含以下成份：
成份 重量份
Tone 0301一分子量为303的聚己酸内酯 100
三醇，可在Union Carbide公司获得
Tone 0310一分子量为966的聚己酸内酯 10
三醇，可在Union Carbide公司获得
二氧化钛颜料 64.5
聚氨基甲酸酯类粘合剂N-100
-1,6六亚甲基二异氰酸酯的编 205
二脲加合物，可在美国贝叶公司
Mobay化学部获得
使用在康涅狄格州New Haven地区的C。Cowles andCompany公司制造的高速、低切力的Cowles Dissolver混合设备充分混合上述前三种成份。然后把所得混合物和聚氨基甲酸酯类粘合剂N-100一起涂布在35密耳厚、高度充填的、压延的柔性丙烯腈聚-丁二烯橡胶衬底上，达18密耳厚。在150℃的温度下对涂层固化3分钟后，往涂层表面喷撒玻璃珠(直径为600微米，折射率为1.5，已经过从Union Carbide公司购得的A1100，即3-氨丙基三乙氧基硅烷处理)和防滑微粒(#30氧化铝砂，已经过从Union Carbide公司购得的Al100，即3-氨丙基三乙氧基硅烷处理)。在163℃下经2分钟完成固化。1987年9月23日用接触性粘合剂将所得的路面标记材料。样品A，铺在一个高ADT十字路口。“高ADT十字路口”是指每天每个车道平均有8,000到10,000辆车通过的十字路口。在1.5个月，4个月和一年后作了定期检查，在同一十字路口还铺上了其它路面标记材料的比较样品，并在同一时间进行检查。比较样品如下：
一比较样品1:Catatile路面标记材料，可在意大利米兰
Roline 55,Nirosa的美国批发公司Cataphote Corporation获得。
一比较样品2:Stamark 5760路面标记材料。可在St.Paul,Minnesota的Minnesota矿产制造公司获得。
通过测量反射性保持率，白度和公路保持率来测定样品的性能。反射性保持率用Ecolux反射光测量仪测量，单位是MCD，意为每勒每m2的毫堪数；白度用美能达比色计测量，单位是Capy。公路保持率的单位是产品损耗率，现场性能结果摘要如下：
初值 1.5个月 4个月 一年
样品A
反射性(MCD) 100％ 57％ 15％ 20％
白度(Capy) 85 65 60 52
％产品磨耗 0 0 0 3.7比较样品1反射性(MCD) 100％ 27％ 7％ 11％白度(Capy) 86 - - 49％产品磨耗 0 0 0.2 6.5比较样品2反射性(MCD) 100％ 19％ 13％ 30％白度(Capy) 82 53 54 50％产品磨耗 0 0 0 17.5
*产品磨耗，没有发现粘性受损。
从此结果可看出，本发明获得了较好的反射保持率，白度和产品保持率。
1.5个月后：本发明的样品A的反射率为57％，而性能最接近的比较样品的反射率只有27％。样品A的白度也比比较样品2好。此时，比较样品1未测量白度，所有样品都未发现有可测量的产品磨耗。
4个月后，样品A的反射性仍比其它样品好。此时，所有样品都未发现有明显的产品磨耗。
一年后：本发明使产品损耗大大降低。本发明样品A的产品磨耗只有3.7％，而性能最接近的比较样品的产品损耗为6.5％，样品A的白度也比其它样品好。但此时，比较样品2的反射性最好。
一年后对所有样品进行了检查，发现本发明材料在路面不平处有断裂，因而释放了施加于聚氨酯顶层的拉应力。另外，用电子显微镜扫描后发现本发明顶层的微粒保持性也比其它样品好。在一年后的测试中还发现本发明顶层没有磨穿，而比较样品1和比较样品2的顶层已经磨穿，暴露出下面的基底。
比较例1：
美国专利第4,020,211(Eigenmann)第5栏第16-27行公开了一种聚氨酯样品。用所公开的成份做一膜片并测试其张力性能，发现膜片的杨氏模量比本发明优选的聚氨酯的杨氏模量要高(362,000PSI,+/-32,000)，其断裂伸长率比本发明优选的聚氨酯的断裂伸长率要低(2.0％,+/-0.6％)。因此，由于杨氏模量高，断裂伸长率低之故，这种聚氨酯会过度破裂，过量堆积尘土，且会裉色。
对研究了这份说明书或根据这里所公开的发明进行了实践的同行专家来说，本发明的其它实施方案是显而易见的。在不违背权利要求书所指出的本发明的范围和精神的情况下，同行专家可以进行各种改进和变化。
Claims (12)
1．一种路面标记材料，包括：
(a)一层能与不规则路面适形的柔性基片；
(b)一层与所述基片粘合的耐久、耐磨的聚合物顶层；
(c)嵌入在顶层中且突出于顶层表面的许多微粒；
其特征在于其中顶层在0℃到45℃的温度下能进行脆性断裂，使其在基底与不规则表面适形时较易形成断裂以释放在顶层中积聚的应力，裂纹限定的顶层裂区仍然与衬片粘合并与其形状相一致。
2．根据权利要求1的路面标记材料，其中柔性基片基本平滑，而且基本上无突出物。
3．根据权利要求1的路面标记材料，其中顶层的杨氏模量为50,000psi(350Mpa)到300,000psi(2100Mpa)，断裂伸长率为4％到35％。
4．根据权利要求3的路面标记材料，其中顶层的杨氏模量为50,000psi(350Mpa)到250,000psi(1750Mpa)。
5．根据权利要求3的路面标记材料，其中顶层的断裂伸长率为4％到20％。
6．根据权利要求5的路面标记材料，其中顶层的断裂伸长率为4％到10％。
7．根据权利要求1的路面标记材料，其中在顶层上形成许多断裂。
8．根据权利要求1的路面标记材料，其中顶层包含选自聚氨酯、环氧树脂、聚酰胺、聚脲、聚酯、以及它们的混合物的聚合物。
9．根据权利要求1的路面标记材料，其中顶层包含选自聚氨酯、聚脲、以及它们的混合物的聚合物。
10．根据权利要求1的路面标记材料，其中顶层包含一种聚氨酯，它是从下列反应物中得到的：
(a)包含一种或多种多羟基化合物的多羟基化合物组分，其中所述的多羟基化合物的平均分子量约为300到660，平均羟基当量约为100到220，每个多羟基化合物分子平均有三个或更多个的羟基；以及
(b)聚异氰酸酯，其中，所说的聚异氰酸酯的NCO基与多羟基化合物组分的OH基的当量比约为0.5到1.5。
11．根据权利要求10的路面标记材料，其中，
(a)所说的多羟基化合物组分包含约一当量的、羟基当量约为100的聚己酸内酯三醇；和0到0.33当量折，羟基当量约为300的聚己酸内酯三醇；和
(b)所说的聚异氰酸酯是1,6六亚甲基二异氰酸酯的加合物。
12．根据权利要求1的路面标记材料，其中所说的顶层包含一种聚氨酯，它是从下列反应物中得到的：
(a)约100份重量的聚己酸内酯三醇，其分子量约为300；和
(b)约10到25份重量的聚己酸内酯三醇，其分子量约为960；和
(c)约205份重量的1,6六亚甲基二异氰酸酯的缩二脲加合物，其异氰酸酯当量约为150到250。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US504.951 | 1990-04-05 | ||
| US07/504,951 US5077117A (en) | 1990-04-05 | 1990-04-05 | Pavement marking material with rupturing top layer |
| US504,951 | 1990-04-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1055703A CN1055703A (zh) | 1991-10-30 |
| CN1046893C true CN1046893C (zh) | 1999-12-01 |
Family
ID=24008400
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91101859A Expired - Lifetime CN1046893C (zh) | 1990-04-05 | 1991-03-25 | 路面标记材料 |
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| Country | Link |
|---|---|
| US (1) | US5077117A (zh) |
| EP (1) | EP0453135B1 (zh) |
| JP (1) | JP3045324B2 (zh) |
| KR (1) | KR100204183B1 (zh) |
| CN (1) | CN1046893C (zh) |
| AU (1) | AU629464B2 (zh) |
| BR (1) | BR9101317A (zh) |
| CA (1) | CA2037515A1 (zh) |
| DE (1) | DE69100423T2 (zh) |
| ES (1) | ES2044684T3 (zh) |
| GE (1) | GEP19981262B (zh) |
| HU (1) | HUT60794A (zh) |
| IE (1) | IE910694A1 (zh) |
| LT (1) | LTIP1471A (zh) |
| RU (1) | RU2083374C1 (zh) |
| YU (1) | YU51991A (zh) |
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| EP0346021A1 (en) * | 1988-06-09 | 1989-12-13 | Minnesota Mining And Manufacturing Company | Patterned pavement marking |
Also Published As
| Publication number | Publication date |
|---|---|
| US5077117A (en) | 1991-12-31 |
| DE69100423D1 (de) | 1993-11-04 |
| DE69100423T2 (de) | 1994-04-21 |
| RU2083374C1 (ru) | 1997-07-10 |
| KR920005744A (ko) | 1992-04-03 |
| GEP19981262B (en) | 1998-03-26 |
| EP0453135B1 (en) | 1993-09-29 |
| YU51991A (sh) | 1993-11-16 |
| HU910726D0 (en) | 1991-09-30 |
| KR100204183B1 (ko) | 1999-06-15 |
| EP0453135A1 (en) | 1991-10-23 |
| AU7277591A (en) | 1991-10-10 |
| JP3045324B2 (ja) | 2000-05-29 |
| ES2044684T3 (es) | 1994-01-01 |
| CN1055703A (zh) | 1991-10-30 |
| CA2037515A1 (en) | 1991-10-06 |
| IE910694A1 (en) | 1991-10-09 |
| LTIP1471A (en) | 1995-05-25 |
| BR9101317A (pt) | 1991-11-26 |
| AU629464B2 (en) | 1992-10-01 |
| JPH04223158A (ja) | 1992-08-13 |
| HUT60794A (en) | 1992-10-28 |
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| C20 | Patent right or utility model deemed to be abandoned or is abandoned |