CN100451269C - 一种耐脚轮性表面层压板和耐脚轮性地板材料 - Google Patents
一种耐脚轮性表面层压板和耐脚轮性地板材料 Download PDFInfo
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- CN100451269C CN100451269C CNB2005800015218A CN200580001521A CN100451269C CN 100451269 C CN100451269 C CN 100451269C CN B2005800015218 A CNB2005800015218 A CN B2005800015218A CN 200580001521 A CN200580001521 A CN 200580001521A CN 100451269 C CN100451269 C CN 100451269C
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- surface laminate
- synthetic resin
- resistant
- layer
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Abstract
本发明披露了一种使用合成树脂的耐脚轮性表面层压板以及一种包括该表面层压板的地板材料。该层压板利用了合成树脂层的缓冲特性,从而将对地板材料表面的损坏减到最小。该表面层压板使用选自PVC、PE、PET、PETG、PCTG和PU的树脂,以提高耐脚轮性、抗冲击性和抗水性。因此,与常规的表面层压板相比,在不发生由外部冲击引起的损坏,如曲成凹陷和破损的情况下,该表面层压板具有改善的物理性质。另外,该耐脚轮性表面层压板通过合成树脂层的染色而获得内部装饰效果。
Description
技术领域
本发明涉及一种具有优异的耐脚轮性(caster resistance)、抗冲击性和抗水性的表面层压板,以及一种包括所述表面层压板的地板材料。更具体地说,本发明涉及一种包括表面层压板和与该表面层压板层压的有槽基层(grooved base)(胶合板或木板)的耐脚轮性天然木地板材料,其中表面层压板包括从底部按顺序层压的高密度增强层、天然薄板层和合成树脂层。
背景技术
图1为示出用于地下加热系统的常规地板材料的结构的剖视图,其中天然薄板层层压在防水胶合板上。如图1所示,常规地板材料具有这样的结构,其中用UV涂料漆对天然薄板层22进行表面涂覆以形成一般UV涂层21’,或天然薄板层22浸渍树脂然后通过粘合层40层压在防水胶合板层10’上。
然而,用于地下加热系统的常规地板材料的缺点包括在某些负荷下抗划伤性和抗冲击性较差。具体地说,常规地板材料具有低至0.5~1N的表面抗划伤强度(surface scratch resistance)和低至5cm的冲击强度,表面抗划伤强度通过使用金刚石针刮擦地板材料而测得,冲击强度通过向地板材料落下重达225g的金属球而测得。这些较低的数值表明在其上放置和使用家用电器时易于损坏常规的地板材料。因此,常规地板材料引起消费者的不满并且不能满足消费者的不同需要的可能性较大。因此,存在对具有改善的抗刮伤性和抗冲击性的地板材料的需要。
通过将装饰薄板(印刷纸)粘结在胶合板上并涂覆该层压板,或通过使胶合板和中密度纤维板(MDF)彼此层压、将装饰薄板结合至MDF上并涂覆该层压板而制造的地板材料被广泛认为是另一种常规地板材料。这些地板材料的代表性例子通过将装饰薄板(印刷纸)粘结在胶合板上、或通过使胶合板和MDF彼此层压并将装饰薄板(印刷纸)粘结在层压板的中密度纤维板上而制造。
然而,以前的地板材料存在耐脚轮性较差的问题。另外,在地板材料上形成凸出(tongue)和凹槽的情况下,会发生起毛和边缘开裂,短袜和长袜的丝经常在其上被钩破并被拆散。另一方面,由于MDF具有较差的抗水性,近来的地板材料存在由于渗水引起MDF膨胀的问题,所以当使用木质装饰薄板(印刷纸)时,有时会损坏了地板材料的图案。
此外,在耐脚轮性方面,使用相对于胶合板具有优异物理性质的中密度纤维板具有优势,但会引起抗水性较差和浸入水中时出现剥落的问题。
因此,存在开发作为低价建筑材料的木地板材料的需要,这种木地板材料在满足所需的物理性质例如耐脚轮性和抗水性的同时,其相对温度变化,具有稳定的尺寸变化。
发明内容
技术问题
因此,考虑到现有技术存在的上述问题作出了本发明,本发明的一个目的是提供一种具有优异的耐脚轮性、抗冲击性和抗水性的表面层压板,该表面层压板包括增强层、合成树脂层和天然薄板层,所述层整体结合,从而在保持了天然纹理的同时,提高了表面层压板的表面强度,以及提供一种包括所述表面层压板的木地板材料。
本发明的另一个目的是提供一种通过染色能够获得内部装饰效果的耐脚轮性表面层压板,以及提供一种包括所述表面层压板的地板材料。
技术方案
根据达到上述目的的本发明的一个方面,提供了一种耐脚轮性表面层压板,该表面层压板包括具有增强层和合成树脂层的木薄板层,其中,所述木薄板层包括从底部按顺序层压的增强层、薄板层和合成树脂层。
本发明的表面层压板的特征在于:表现出基本的机械性能和缓冲性能的增强层和表现出优异的机械性能并对吸收外部冲击具有充分延展性的合成树脂层的层压使该表面层压板表现出优异的耐脚轮性和抗冲击性。增强层和合成树脂层以约40%∶60%的比率为表面层压板提供耐脚轮性。
本发明的耐脚轮性表面层压板包括从底部按顺序层压的增强层、薄板层和合成树脂层,或者包括从底部按顺序层压的增强层、合成树脂层和薄板层。
在通过使用压力机压制而整体结合木薄板层时,以前的耐脚轮性表面层压板能够阻止对薄板的损害,并且在冲击的吸收上是有效的。
本文所用术语“耐脚轮性”指的是由常用于住宅中的座椅轮子引起的曲成凹陷的程度。
本发明的耐脚轮性表面层压板的特征在于:改善的表面物理性质使地板材料的表面免于受到损坏,例如由较重的或尖锐的物体引起的凹陷和破损。针对这一点,合成树脂层优选由表现出优异机械性能并对吸收外部冲击具有充分延展性的合成树脂制得。作为合成树脂可使用(例如)聚氯乙烯(PVC)、聚二亚甲基环己撑(polycyclohexylenedimethylene)(PC)、聚乙烯(PE)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、乙二醇改性的PET(PETG)、环己烷二甲醇改性的PETG(PCTG)、异酞酸改性的PCTG(PCT-A)、高抗冲聚苯乙烯(HIPS)、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、聚氨酯(PU)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)、间同立构聚苯乙烯(SPS)、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)、丙烯酸酯等。其中,PVC、PETG和PCTG是优选的,并且PCTG是特别优选的。
PVC是对环境不友好的材料,并在焚烧时产生例如氯化氢气体(HCl)的有毒气体。相反,因为PCTG和PETG是环境友好的材料,在焚烧时产生二氧化碳(CO2)和水蒸汽(H2O),所以它们在使用中不受限制。另外,尽管使用减量的添加剂,PCTG和PETG在优异的光学性能和易加工方面仍然具有优势。具体地说,相对于PETG,PCTG具有优异的耐热性和抗冲击性,因此表现出极好的表面物理性质,例如对于由切割和冲击引起的损坏表现出改善的抵抗性。
合成树脂层优选的组成包含10~50重量份的增塑剂或乙烯乙酸乙烯酯(EVA)、1~5重量份的加工润滑剂和100重量份的至少一种选自PVC、PC、PE、PP、PET、PETG、PCTG、PCT-A、HIPS、ABS、PU、SBS、SEBS、SPS、SEPS和丙烯酸酯的合成树脂。合成树脂层可由单层或复合层组成,并且可由一种或多种混合树脂制成。
为了获得内部装饰效果,可向合成树脂层中添加诸如颜料的染色剂,从而赋予合成树脂层透明的颜色,使表面层压板能够具有染色效果。此外,可向合成树脂层中添加热敏性颜料,以确保颜色响应温度变化而变化。
用于制备彩色合成树脂的染色剂为有机和无机染料及颜料。有机颜料的例子包括偶氮和双偶氮颜料、色淀偶氮和双偶氮颜料、多环的颜料、酞菁颜料、喹吖啶酮(quinacridone)颜料、二萘嵌苯颜料、二噁嗪颜料、蒽醌颜料、硫靛颜料、二芳基蒽醌颜料和喹酞酮(quinophthalone)颜料。
无机颜料的例子包括可染色的金属氧化物、混合氧化物、硫酸铝、铬酸盐、金属粉末、珠光颜料、磷、氧化钛、氧化铁、炭黑、硅酸盐、钛酸镍、钴颜料和氧化铬。除了这些颜料之外,如果需要,可选择和使用其它颜料以产生适当的颜色。
在热敏性颜料中,产生颜色的成分的例子包括2,2-二丁氨基-6-甲基-7-苯胺基荧烷、2,2-丁基异戊基-6-甲基-7-苯胺基荧烷、3,3-二甲氨基-6-甲基-7-苯胺基荧烷等,显色剂的例子包括可与酚基化合物混合的化合物,例如双酚A和双酚S、对羟基苯甲基苯甲酸、对苯基苯酚和酸性石膏粉,从而产生或消除由电子的给予-受予机理引起的颜色。
用于本发明的热敏性染色剂仅用于说明性目的,应该理解本发明不以任何方式受此限制。各种热敏性染色剂可与合适的有机和无机颜料一起使用。根据所需的颜色,以不超过5%的含量使用有机和无机颜料。
本发明的表面层压板的特征在于:包括增强层和合成树脂层的木薄板层通过使用高压压力机压制而整体结合。这样做,可同时保持根据本发明的表面层压板的耐脚轮性和抗冲击性。
优选的是,本发明的耐脚轮性表面层压板进一步包括在其最上部的UV涂层。优选用于形成UV涂层的UV涂料漆为无溶剂型。使用无溶剂的UV涂料漆可防止致病建筑综合症(sick house syndrome)并提供环境友好的饰面材料。
使用诸如苯、甲苯和二甲苯的溶剂的UV涂料漆满足作为环境友好的建筑材料的质量等级的最低要求,然而无溶剂的UV涂料漆满足最高等级的要求。因此,无溶剂的UV涂料漆是环境最友好型涂料。
环境友好的建筑材料的质量等级被划分为下面五类:最高(标记为五个三叶草)、优异(标记为四个三叶草)、良好(标记为三个三叶草)、一般I(标记为两个三叶草)和一般II(标记为一个三叶草)。为了保持室内空气环境在最佳水平,推荐使用最高等级的材料。
用于制造本发明的表面层压板的增强层选自薄板、屏蔽纸(shielding paper)、高密度纤维板(HDF)和牛皮纸。低价的增强层和浸渍树脂层的使用以低成本改善了耐脚轮性和抗冲击性。
根据增强层和合成树脂层所需的厚度和价格,可层压一个或多个低重量或高重量的层。
本发明的耐脚轮性表面层压板可用于制造地板材料、壁橱、天花板和家具,特别是用于制造地板材料。
本发明进一步提供了一种耐脚轮性地板材料,该地板材料包括耐脚轮性表面层压板,该表面层压板包括具有增强层和合成树脂层的木薄板层,其中,所述木薄板层包括从底部按顺序层压的增强层、薄板层和合成树脂层。
本发明的耐脚轮性地板材料包括从底部按顺序层压的基层、粘合层和耐脚轮性表面层压板。
为了减少地板材料之间的噪声传播并赋予其改善的隔音性能,本发明的耐脚轮性地板材料可进一步包括至少一个隔音层,该隔音层层压在至少一个选自(a)基层与耐脚轮性表面层压板之间(b)基层之下的位置中。
用于制造本发明地板材料的基层选自聚氯乙烯树脂层、HDF、MDF、Paul刨花板(Paul strand board)和防水胶合板层,优选为背面开槽(back-grooved)以确保改善的尺寸稳定性并减少裂缝的出现。
附图说明
由下面结合附图给出的详细描述,将更清楚地了解本发明的上述和其它目的、特征和其它优点,其中:
图1为用于地下加热系统的常规地板材料的剖视图,其中天然薄板层压在防水胶合板上;
图2为根据本发明一个实施方式的耐脚轮性地板材料的剖视图,其中耐脚轮性表面层压板和背面开槽的基层彼此层压;以及
图3为根据本发明另一个实施方式的耐脚轮性地板材料的剖视图,其中将两个隔音层加入图2所示的地板材料中。
具体实施方式
现在参考下面的实施例和附图,将对本发明进行更详细的描述。然而,这些实施例和附图不能解释为限制本发明的范围。
用于地下加热系统的常规地板材料的剖视图示于图1。如图1所示,常规的地板材料具有从顶部按顺序层压的一般UV涂层21’、天然薄板层22、粘合层40和防水胶合板层10’的结构。
图2为根据本发明一个实施方式的耐脚轮性地板材料的剖视图。如图2所示,该地板材料具有在基层10上通过粘合层40层压的耐脚轮性表面层压板20的结构。
尽管未示于附图中,根据本发明的一个优选实施方式,耐脚轮性表面层压板20包括从底部按顺序层压的薄板(或至少一种选自屏蔽纸、HDF和牛皮纸的材料)高密度增强层24、天然薄板层22、合成树脂层23和无溶剂的UV涂层21。
根据本发明的另一个优选实施方式,图2所示的耐脚轮性表面层压板20包括从底部按顺序层压的薄板(或至少一种选自屏蔽纸、HDF和牛皮纸的材料)高密度增强层24、合成树脂层23、天然薄板层22和无溶剂的UV涂层21。
耐脚轮性表面层压板20通过以下步骤制造:从底部按顺序布置高密度增强层24、天然薄板层22和合成树脂层23或按顺序布置高密度增强层24、合成树脂层23和天然薄板层22;在压力机中20~200kg/cm2的压力下向该层压板加压,同时加热至温度110~180℃ 15~60分钟;然后在该压力下冷却加过压的层压板15~30分钟。
最后,通过粘合层40将这样制造的耐脚轮性表面层压板20和基层10彼此粘结。
可用于形成粘合层40的粘合剂的例子包括热固性三聚氰胺树脂、热固性或室温固化性聚氨酯和环氧树脂、聚乙烯醇、聚乙酸乙烯酯等。
当使用热固性三聚氰胺树脂作为粘合剂时,以80~300g/m2的量向基层10涂覆以而形成粘合层40。另一方面,当使用热固性或室温固化性聚氨酯或环氧树脂用作粘合剂时,以80~250g/m2的量向基层10涂覆以形成粘合层40。此后,将耐脚轮性表面层压板20布置在粘合层40上。当使用热固性三聚氰胺树脂作为粘合剂时,在10~15kgf/cm2的压力下向层压板加压并使其固化1~5分钟。同时,当使用室温固化性聚氨酯或环氧树脂用作粘合剂时,在10~15kgf/cm2的压力下向层压板加压1天。
在室温下对基层10和耐脚轮性表面层压板20的压制能够将热变形减到最少。
图3为根据本发明另一个实施方式的耐脚轮性地板材料的剖视图,在该耐脚轮性地板材料中将两个隔音层加入图2所示的地板材料中。如图3所示,将第一隔音层30插入基层10与粘合层40之间,将第二隔音层31置于基层10之下。然而,隔音层的位置和数量没有特别的限制。
可用作隔音层的材料为,例如,聚氯乙烯(PVC)、聚乙烯(PE)、乙烯乙酸乙烯酯(EVA)、聚丙烯(PP)、聚氨酯(PU)、聚酯无纺织物、氯丁二烯橡胶(CR)、丁腈橡胶(NBR)等。另外,隔音层的表面可通过压花和凹板技术、化学交联和发泡工艺以及高压发泡工艺进行加工处理。
实施例
1.基层10的制造
具有1.0~5.0mm厚度的聚氯乙烯树脂层由包含PVC树脂、增塑剂、填料、稳定剂和其它成分的组合物制成。基层可由至少一种选自热固性树脂和热塑性树脂的树脂制成。
刨花板和高密度纤维板通过以下步骤制得:向通过切割三聚氰胺树脂板材(lumber)或使三聚氰胺树脂板材纤维化而获得的线材(strand)或纤维加压,随后使其成形。
防水胶合板层通过以下步骤制得:使用三聚氰胺树脂使3至7层薄板以其纹理方向彼此成直角的方式一起成层,然后在压力机中压制该层压板。
2.耐脚轮性表面层压板20的制造
1)无溶剂的UV涂层21的制造
使用无溶剂的涂料漆进行6~10次的用于表面保护和高质量外观的UV涂覆。
2)天然薄板层22的制造
通过使用旋转车床或切片机切割天然原木(raw lumber)至0.12~5mm的厚度而制得天然薄板层22。
3)合成树脂层23的制造
通过压光处理由包含100重量份的PETG、30重量份的EVA和3重量份的加工润滑剂的组合物制得合成树脂层23。
4)高密度增强层24的制造
通过使用旋转车床或切片机切割天然原木至0.3~8mm的厚度而制得薄板。如果需要,为了防止在处理时在纹理方向出现裂纹,用胶带粘贴(tape)该薄板的两侧以用于储存。为了改善薄板的尺寸稳定性并将薄板的弯曲度减到最小,干燥该薄板至含水率为10%或更少。
屏蔽纸通过以下步骤制得:用酚或三聚氰胺树脂浸渍基本重量为50~150g/m2的纸张,随后在80~150℃的烘箱中干燥并半固化0.5~3分钟。根据所需的厚度,可使用两张或多张屏蔽纸。
HDF通过以下步骤制得:通过用酚树脂处理从针叶树或落叶树获得的纤维,随后使其成形、高温加压和固化。
牛皮纸通过以下步骤制得:用三聚氰胺或酚树脂浸渍基本重量为80~300g/m2的纸张,随后在80~150℃的烘箱中干燥并半固化0.5~3分钟。根据所需的厚度,可使用两张或多张牛皮纸。
5)高密度增强层24、天然薄板层22和合成树脂层23的整合(Integration)
在高密度增强层24与天然薄板层22之间布置合成树脂层23。或者,从底层按顺序布置高密度增强层24、天然薄板层22和合成树脂层23。在110~170℃的压力机中,分别以20、40、60、80、100、120和150kg/cm2的渐增压力向所得到的结构加压15、20、25和30分钟,然后在该压力下冷却25分钟,从而完整地结合各层。
3.基层10和耐脚轮性表面层压板20的层压
通过以150g/m2的量向基层10涂覆热固性三聚氰胺树脂而形成粘合层40。或者,通过以200g/m2的量向基层涂覆热固性或室温固化性聚氨酯或环氧树脂而形成粘合层40。其后,将耐脚轮性表面层压板20放置在粘合层40上。当使用热固性三聚氰胺树脂时,在12kgf/cm2的压力下向该层压板加压并固化2~5分钟。另一方面,当使用室温固化性树脂时,在15kgf/cm2的压力下向该层压板加压1天,以将耐脚轮性表面层压板粘结到基层上。
将根据本发明如此制造的高度耐脚轮性木地板材料(实施例1)的表面物理性质与图1所示的用于地下加热系统的常规地板材料(比较例1)的物理性质进行对比。其结果示于下表1中。
根据下面常用的方法测定地板材料的表面强度。首先,从地板材料上切割预定尺寸的测试片。通过使用金刚石针刮擦测试片的表面而测定抗刮伤性,且表示为0.5N单位。通过从渐增的高度(10cm的增量)向测试片的表面落下重物(225g)并在视觉上观察是否存在对测试片的损坏而测定抗冲击性。耐脚轮性通过以下步骤测定:在60kg负荷下以12m/min的速度压制测试片,重复压制100次,然后在视觉上或在光学显微镜下观察是否存在曲成凹陷或破损。
表1
实施例1 | 比较例1 | |
抗刮伤性(N) | 3~4 | 0.5~1 |
抗冲击性(cm) | ≥80 | 5~10 |
耐脚轮性(60kg) | ≥100次重复(无变化) | ≤10次重复(破坏涂层) |
从表1所示的数据显然可见,与用于地下加热系统的常规地板材料的表面物理性质相比,根据本发明的高度耐脚轮性天然木地板材料的表面物理性质被很大地改善了。具体地说,根据本发明的地板材料的抗刮伤性增至最大值4N,并且抗冲击性增至最大值100cm。此外,在根据本发明的地板材料的耐脚轮性中,即使在60kg的负荷下重复100次以后,也没有观察到表面曲成凹陷。天然薄板的耐脚轮性被显著改善,从而充分减少了消费者相当大程度不满的可能性,并且根据本发明的地板材料的表面物理性质被彻底改善,从而充分满足了消费者。
工业实用性
相对于常规的地板材料产品,通过整合包含高密度增强层和合成树脂层的木薄板层,本发明的地板材料表现出优异的耐脚轮性、抗水性、抗刮伤性和抗冲击性。特别地,向合成树脂层加入染色剂和热敏性颜料可提供内部装饰效果。
另外,无溶剂的UV涂覆处理有助于环境保护。通过使用高压压力机压紧而整合增强层、合成树脂层和天然薄板获得了表面强化。与用于地下加热系统的常规地板材料相比,在基层背面上形成凹槽改善了本发明的地板材料的表面强度,并且加入一个或多个隔音层能够向本发明的地板材料赋予改善的隔音性能。
Claims (16)
1、一种耐脚轮性表面层压板,该表面层压板包括具有增强层和合成树脂层的木薄板层,其中,所述木薄板层包括从底部按顺序层压的增强层、薄板层和合成树脂层。
2、根据权利要求1所述的耐脚轮性表面层压板,其中,所述合成树脂层由至少一种选自聚氯乙烯、聚二亚甲基环己撑、聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、乙二醇改性的PET、环己烷二甲醇改性的PETG、异酞酸改性的PCTG、高抗冲聚苯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚氨酯、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、间同立构聚苯乙烯、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物和丙烯酸酯的合成树脂制得。
3、根据权利要求2所述的耐脚轮性表面层压板,其中,所述合成树脂为乙二醇改性的PET或环己烷二甲醇改性的PETG。
4、根据权利要求1所述的耐脚轮性表面层压板,其中,所述合成树脂层包含染色剂。
5、根据权利要求1所述的耐脚轮性表面层压板,其中,所述合成树脂层包含热敏性颜料。
6、根据权利要求1所述的耐脚轮性表面层压板,其中,所述木薄板层通过使用高压压力机压紧而整体结合而成。
7、根据权利要求1所述的耐脚轮性表面层压板,该表面层压板在其最上部分进一步包括UV涂层。
8、根据权利要求7所述的耐脚轮性表面层压板,其中,所述UV涂层由无溶剂的UV涂料漆形成。
9、根据权利要求1所述的耐脚轮性表面层压板,其中,所述增强层选自薄板、屏蔽纸、高密度纤维板和牛皮纸。
10、根据权利要求1所述的耐脚轮性表面层压板,其中,根据所需厚度,几片增强层和合成树脂层被层压。
11、根据权利要求1所述的耐脚轮性表面层压板,其中,所述表面层压板用于制造地板材料、壁橱、天花板和家具。
12、一种耐脚轮性地板材料,该地板材料包括耐脚轮性表面层压板,该表面层压板包括具有增强层和合成树脂层的木薄板层,其中,所述木薄板层包括从底部按顺序层压的增强层、薄板层和合成树脂层。
13、根据权利要求12所述的耐脚轮性地板材料,其中,所述地板材料包括从底层按顺序层压的基层、粘合层和耐脚轮性表面层压板。
14、根据权利要求13所述的耐脚轮性地板材料,该地板材料进一步包括至少一个隔音层,其层压在至少一个选自(a)基层与耐脚轮性表面层压板之间和(b)基层之下的位置中。
15、根据权利要求13所述的耐脚轮性地板材料,其中,所述基层选自合成树脂层、高密度纤维板、中密度纤维板、Paul刨花板和防水胶合板。
16、根据权利要求13所述的耐脚轮性地板材料,其中,所述基层为背面开槽。
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KR100701891B1 (ko) * | 2006-04-11 | 2007-03-30 | 심대근 | 내충격성(耐衝擊性) 마루바닥재 |
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Also Published As
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TWI312314B (en) | 2009-07-21 |
KR20060109242A (ko) | 2006-10-19 |
EP1869269B1 (en) | 2012-09-05 |
US20060234009A1 (en) | 2006-10-19 |
EP1869269A1 (en) | 2007-12-26 |
EP1869269A4 (en) | 2008-05-21 |
US7462400B2 (en) | 2008-12-09 |
WO2006109914A1 (en) | 2006-10-19 |
KR100750479B1 (ko) | 2007-08-22 |
JP2007522980A (ja) | 2007-08-16 |
CN1922371A (zh) | 2007-02-28 |
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