CN111093993A - 层叠体、鞋底及鞋 - Google Patents

层叠体、鞋底及鞋 Download PDF

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Publication number
CN111093993A
CN111093993A CN201780094716.4A CN201780094716A CN111093993A CN 111093993 A CN111093993 A CN 111093993A CN 201780094716 A CN201780094716 A CN 201780094716A CN 111093993 A CN111093993 A CN 111093993A
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Prior art keywords
thermoplastic polymer
formula
laminate
laser beam
term
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CN201780094716.4A
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CN111093993B (zh
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北山裕教
立石纯一郎
原野健一
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Asics Corp
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Asics Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/023—Soles with several layers of the same material
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
    • A43D25/00—Devices for gluing shoe parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1603—Laser beams characterised by the type of electromagnetic radiation
    • B29C65/1612—Infrared [IR] radiation, e.g. by infrared lasers
    • B29C65/1616—Near infrared radiation [NIR], e.g. by YAG lasers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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    • B29C65/1629—Laser beams characterised by the way of heating the interface
    • B29C65/1635—Laser beams characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. laser transmission welding
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    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/53—Joining single elements to tubular articles, hollow articles or bars
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

本发明的层叠体具有：第一构件，包含热塑性高分子且透射激光；以及第二构件，包含热塑性高分子且吸收激光，第一构件直接粘着于第二构件，且由式1：A＝‑9×D+Wa‑45所表示的A大于零。所述D表示第一构件与第二构件的各热塑性高分子的汉森溶解度参数的距离，Wa表示根据第一构件与第二构件的各表面自由能计算出的附着功。此种第一构件与第二构件在不使用粘着用片的情况下相互牢固地粘着。

Description

层叠体、鞋底及鞋
技术领域
本发明涉及一种通过激光光束的照射而两个构件直接粘着而成的层叠体及其用途。
背景技术
鞋是通过将中底(midsole)等各构成构件粘着来制造。
在专利文献1中公开了一种通过激光光束的照射而粘着的至少三层结构的激光粘着用层叠体。所述层叠体具有：上部构件，对激光光束具有透射性；下部构件，由热塑性的发泡体形成；以及粘着用片，介隔存在于所述上部构件与下部构件之间，且通过照射激光光束而熔融，所述下部构件的熔点与粘着用片的熔点的差为-50℃～20℃，所述下部构件的熔融粘度与粘着用片的熔融粘度的差为3.0×105Pa·s～8.0×105Pa·s。
现有技术文献
专利文献
专利文献1：WO2011/045856号公报
发明内容
专利文献1的激光粘着用层叠体可通过照射激光光束而经由粘着用片将上部构件与由发泡体形成的下部构件良好地粘着，因此优选。
然而，在专利文献1中，由于使用粘着用片，因此不仅要准备上部构件和下部构件，还必须准备粘着用片。即，粘着对象本来是上部构件与下部构件，但必须使用用以将所述上部构件与下部构件粘着的粘着片。若使用粘着用片，则不仅原料成本上升，还需要进行将粘着用片夹入上部构件与下部构件之间的作业，生产成本也上升。
发明所要解决的问题
本发明的目的是提供一种在不使用粘着用片的情况下，通过激光光束将两个构件牢固地粘着而成的层叠体等。
解决问题的技术手段
本发明人等人在不介隔存在粘着用片而通过激光光束将两个构件(第一构件与第二构件)直接粘着的新颖目的之下进行了努力研究。
与使用粘着剂的粘着技术不同，使用激光光束进行的粘着是使热塑性材料熔融来使两种材料熔接，但难以使所述两种材料直接牢固地粘着。即，为了通过激光光束将两种材料直接牢固地粘着而需要选择相互适当的材料，但是其选择困难。
本发明人等人着眼于作为两种材料的混合指标的汉森溶解度参数(Hansensolubility parameter)的距离、以及作为两种材料密接、撕开所需的能量的附着功来作为利用激光光束的熔接因子。而且，努力研究后的结果确认了汉森溶解度参数的距离和附着功与使用激光光束的粘着强度的关联性高，从而完成了本发明。
本发明的层叠体具有：第一构件，包含热塑性高分子且透射激光光束；第二构件，包含热塑性高分子且吸收激光光束，所述第一构件直接粘着于所述第二构件，且由式1所表示的A大于零。
式1：A＝-9×D+Wa-45
式2：D＝{4×(δd1-δd2)2+(δp1-δp2)2+(δh1-δh2)2}1/2
式3：Wa＝2×(γd1×γd2)1/2+2×(γp1×γp2)1/2+2×(γh1×γh2)1/2
其中，式1中，D表示依据式2计算出的所述第一构件的热塑性高分子的汉森溶解度参数与所述第二构件的热塑性高分子的汉森溶解度参数的距离，Wa表示根据所述第一构件与所述第二构件的各表面自由能并依据式3计算出的附着功，式2中，δd1、δp1及δh1表示所述第一构件的热塑性高分子的汉森溶解度参数中的分散项、极性项及氢键项，δd2、δp2及δh2表示所述第二构件的热塑性高分子的汉森溶解度参数中的分散项、极性项及氢键项，式3中，γd1、γp1及γh1表示所述第一构件的表面自由能中的分散分量、极性分量及氢键分量，γd2、γp2及γh2表示所述第二构件的表面自由能中的分散分量、极性分量及氢键分量。
优选所述第一构件由非发泡体形成，所述第二构件由发泡体形成。
根据本发明的另一方面，提供一种鞋底及鞋。
所述鞋底具有外底，所述外底由所述第一构件或第二构件中的任一者形成。
另外，鞋具有所述鞋底。
发明的效果
本发明的层叠体在不介隔存在粘着用片的情况下将第一构件与第二构件牢固地粘着。所述层叠体可比较廉价地制造。另外，由于第一构件与第二构件牢固地粘着，因此本发明的层叠体可优选地用作在严酷的环境下使用的产品的构成构件，例如鞋底。
附图说明
图1是表示本发明的层叠体的制造过程的参考侧视图。
图2是表示本发明的层叠体的制造过程的参考侧视图。
图3是本发明的层叠体的一个实施方式的剖面图。
图4是本发明的层叠体的另一实施方式的剖面图。
图5是鞋的一个实施方式的侧视图。
图6是沿图5的VI-VI线切断而成的剖面图。
图7是表示各实施例及比较例的D与粘着强度的关系的曲线图。
图8是表示各实施例及比较例的Wa与粘着强度的关系的曲线图。
图9是表示各实施例及比较例的D与Wa的关系的曲线图。
图10是表示各实施例及比较例的粘着强度与A的关系的曲线图。
具体实施方式
以下，对本发明进行说明。
此外，在本说明书中，有时在用语的开头附加“第一”、“第二”，但所述第一等仅是为了区别用语而附加，并不表示其顺序或优劣等特别的含义。由“下限值X～上限值Y”所表示的数值范围是指下限值X以上、上限值Y以下的含义。在各别地记载有多个所述数值范围的情况下，可选择任意的下限值与任意的上限值来设定“任意的下限值～任意的上限值”的数值范围。应注意，各图中所示出的厚度及长度等尺寸有时与实际的尺寸不同。
本发明的层叠体具有直接层叠且经粘着的至少两层构件(第一构件及第二构件)，优选仅包含直接层叠且经粘着的两层构件(第一构件及第二构件)。第一构件包含热塑性高分子，且透射激光光束。第二构件包含热塑性高分子，且吸收激光光束。
本发明的特征在于：由第一构件和第二构件中所含的各热塑性高分子的汉森溶解度参数的距离D、与依据第一构件和第二构件的各表面自由能计算出的附着功Wa规定的A大于零。
＜第一构件＞
第一构件由包含热塑性高分子且可透射激光光束的材料形成。以下，有时将第一构件中所含的热塑性高分子称为“第一热塑性高分子”，将第二构件中所含的热塑性高分子称为“第二热塑性高分子”。
作为第一热塑性高分子，只要是具有热塑性的材料(可通过热而熔融的材料)，则并无特别限定。作为第一热塑性高分子，例如可列举热塑性树脂、热塑性弹性体、热塑性橡胶等。第一热塑性高分子可单独使用选自所述材料中的一种，或混合使用两种以上。
作为所述第一热塑性树脂，例如可列举低密度聚乙烯、高密度聚乙烯、聚丙烯、乙烯-乙酸乙烯酯共聚物(ethylene-vinyl acetate，EVA)、乙烯-α-烯烃共聚物等烯烃系树脂；聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯等酯系树脂；聚苯乙烯、丙烯腈-苯乙烯(acrylonitrile-styrene，AS)树脂、丙烯腈-丁二烯-苯乙烯(acrylonitrile-butadiene-styrene，ABS)树脂等苯乙烯系树脂；6-尼龙等酰胺系树脂；氯乙烯系树脂；聚甲基丙烯酸甲酯等丙烯酸系树脂；乙酸乙烯酯系树脂等。它们可单独使用一种，或混合使用两种以上。
作为所述热塑性弹性体，例如可列举烯烃系弹性体；苯乙烯丁二烯苯乙烯弹性体(styrene-butadiene-styrene，SBS)、苯乙烯异戊二烯苯乙烯弹性体(styrene-isoprene-styrene，SIS)、苯乙烯乙烯丁烯苯乙烯弹性体(styrene-ethylene-butylene-styrene，SEBS)、氢化苯乙烯系弹性体等苯乙烯系弹性体；聚氨酯系弹性体；酯系弹性体；氟类弹性体；聚酰胺系弹性体等。它们可单独使用一种，或混合使用两种以上。
作为所述热塑性橡胶，例如可列举丁二烯橡胶(butadiene rubber，BR)、异戊二烯橡胶(isoprene rubber，IR)、氯丁二烯(chloroprene rubber，CR)等合成橡胶；天然橡胶(natural rubber，NR)；苯乙烯丁二烯橡胶(styrene butadiene rubber，SBR)、苯乙烯丁二烯苯乙烯橡胶(styrene-butadiene-styrene rubber，SBSR)、丙烯腈丁二烯橡胶(acrylonitrile-butadiene rubber，NBR)、苯乙烯异戊二烯共聚物(styrene isoprenerubber，SIR)、丁基橡胶(异丁烯异戊二烯橡胶(isobutylene-isoprene rubber，IIR))等共聚物橡胶等。它们可单独使用一种，或混合使用两种以上。
此外，应注意，热塑性弹性体与热塑性橡胶根据其种类有时也无法明确地区分。
在第一构件中，第一热塑性高分子的含量并无特别限定，但若热塑性高分子过少，则第一构件有可能无法以充分的粘着强度粘着于第二构件。因此，相对于第一构件全体100质量％，第一热塑性高分子的调配量通常为60质量％以上，优选为70质量％以上。另一方面，第一热塑性高分子的调配量的上限在理论上为100质量％。
第一构件可具有橡胶弹性，或者也可不具有橡胶弹性。优选使用具有橡胶弹性的第一构件。例如，通过使用热塑性弹性体或热塑性橡胶作为第一热塑性高分子，可容易地形成具有橡胶弹性的第一构件。
第一构件可由发泡体形成，或者也可由非发泡体形成。优选第一构件为非发泡。此外，在第一构件由发泡体形成的情况下，所述发泡体的形成方法等的详细内容将引用下述＜第二构件＞一栏中的记载。
另外，第一构件中所含的第一热塑性高分子可经交联，或者也可未经交联。
在使热塑性高分子交联的情况下，其交联方法并无特别限定，例如可列举电子束交联、化学交联等。作为电子束，可列举X射线、α射线、β射线、γ射线等。另外，在进行化学交联的情况下，在热塑性高分子中调配过氧化物等交联剂。
形成第一构件的材料以包含所述第一热塑性高分子为条件，并无特别限制。例如，第一构件可仅由第一热塑性高分子形成，或者也可包含第一热塑性高分子及各种添加剂。
作为所述添加剂，可列举软化剂、交联剂、交联助剂、填充剂、耐候性剂、抗氧化剂、紫外线吸收剂、润滑剂、抗静电剂、分散剂、发泡剂等。
作为所述软化剂，例如可列举加工油、增量油(extender oil)等矿物油；妥尔油脂肪酸、蓖麻油、亚麻籽油等植物油等。作为所述交联剂，例如可列举有机过氧化物、马来酰亚胺系交联剂、硫系交联剂、酚系交联剂、肟类、多胺等。作为所述交联助剂，例如可列举脂肪酸、氧化锌、二乙烯基苯、三羟甲基丙烷三甲基丙烯酸酯、甲基丙烯酸1,6-己二醇酯、二甲基丙烯酸1,9-壬二醇酯、二甲基丙烯酸1,10-癸二醇酯、偏苯三酸三烯丙酯、三烯丙基异氰酸酯等。作为填充剂，例如可列举二氧化硅、碳酸钙、碳酸镁、氧化镁等。
第一构件的激光光束的透射率越高越优选。具体而言，第一构件的激光光束的透射率至少为10％以上，优选为20％以上，更优选为30％以上。此外，第一构件的激光光束的透射率的上限在理论上为100％。
其中，所述透射率是将第一构件的厚度设为2mm并对其照射波长808nm的激光光束时的所述激光光束的透射率。所述透射率例如可使用激光功率计(laser power meter)(俄菲(OPHIR)公司制造，产品名“NOVA II”)测定。
此外，第一构件也可包含可吸收激光光束的吸收剂。不过，为了使激光光束充分作用于第二构件，第一构件优选为实质上不包含可吸收激光的吸收剂。
第一构件的厚度并无特别限定，可根据使用目的设定为适宜的厚度。不过，若第一构件的厚度过薄，则有可能因激光光束照射时的热而在第一构件上产生孔。就所述观点而言，第一构件的厚度优选为1mm以上，更优选为1.5mm以上。第一构件的厚度的上限只要是不阻碍激光光束的透射的程度即可，例如第一构件的厚度为50mm以下。
第一构件可通过利用熔融压制法等现有公知的方法将包含第一热塑性高分子及视需要而调配的各种添加剂的材料成形来获得。
＜第二构件＞
第二构件由包含第二热塑性高分子且可吸收激光光束的材料形成。
作为第二热塑性高分子，只要是具有热塑性的材料(可通过热而熔融的材料)，则并无特别限定。作为第二热塑性高分子，例如可列举热塑性树脂、热塑性弹性体、热塑性橡胶等。第二热塑性高分子可单独使用选自所述材料中的一种，或混合使用两种以上。
作为第二热塑性高分子的热塑性树脂、热塑性弹性体及热塑性橡胶，可列举在所述＜第一构件＞一栏的第一热塑性高分子中所例示的物质。
此外，第一热塑性高分子及第二热塑性高分子可为相互相同的高分子，或者也可为同一系统的高分子，或者也可为相互不同的高分子。
形成第二构件的材料以包含第二热塑性高分子为条件，并无特别限定。例如，第二构件可仅由第二热塑性高分子形成，或者也可包含第二热塑性高分子及各种添加剂。作为添加剂，可列举在所述＜第一构件＞一栏中所例示的添加剂。
第二构件可具有橡胶弹性，或者也可不具有橡胶弹性。优选使用具有橡胶弹性的第二构件。例如，通过使用热塑性弹性体或热塑性橡胶作为第二热塑性高分子，可容易地形成具有橡胶弹性的第二构件。
为了在照射激光光束时发热，在第二构件中调配有可吸收激光光束的吸收剂。所述吸收剂是指通过添加所述吸收剂而可提高激光吸收率的试剂。作为所述吸收剂，例如可列举炭黑、氧化物系颜料等无机颜料；酞菁系颜料、色淀颜料、多环式系颜料等有机颜料；具有与所使用的激光光束相对应的吸收波长的染料等。
所述吸收剂的调配量并无特别限定，相对于第二构件全体100质量％，通常为0.1质量％～15质量％。
在第二构件中，第二热塑性高分子的含量并无特别限定，但若热塑性高分子的量过少，则第二构件有可能无法以充分的粘着强度粘着于第一构件。因此，相对于第二构件全体100质量％，第二热塑性高分子的调配量通常为60质量％以上，优选为70质量％以上。另一方面，第二热塑性高分子的调配量的上限在理论上为100质量％，但实际上为99.9质量％以下。
第二构件可由发泡体形成，或者也可由非发泡体形成。优选第二构件由发泡体形成。由发泡体形成的第二构件具有气泡。第二构件的表面成为基于所述气泡的凹凸面。即，在第二构件的表面，与气泡部分对应地存在无数小的凹陷。此外，为了使第二构件的表面成为平面状，也可在第二构件的表面形成表层。
发泡体是通过使包含热塑性高分子的材料发泡而获得。发泡方法可列举化学发泡法、物理发泡法或机械发泡法等现有公知的方法。此外，与所述发泡方法对应地，视需要调配适当的发泡剂。
发泡体的密度(表观密度)并无特别限定。不过，若所述密度过小或过大，则无法获得具有良好弹力性的发泡体。就所述观点而言，发泡体的密度(表观密度)优选为0.05g/cm3～0.8g/cm3。
第二构件的厚度并无特别限定，可根据使用目的设定为适宜的厚度。不过，若第二构件的厚度过薄，则有可能因激光光束照射时的热而在第二构件上产生孔。就所述观点而言，第二构件的厚度优选为1mm以上，更优选为1.5mm以上。
第二构件可通过利用熔融压制法等现有公知的方法将包含第二热塑性高分子、吸收剂及视需要而调配的各种添加剂的材料成形而获得。
＜汉森溶解度参数及附着功＞
所述第一构件与第二构件使用由式1所表示的A大于零的构件。
[数1]
式1：A＝-9×D+Wa-45
式1中，D表示依据下述式2计算出的第一构件的热塑性高分子的汉森溶解度参数与第二构件的热塑性高分子的汉森溶解度参数的距离。另外，式1中，Wa表示根据第一构件与第二构件的各表面自由能并依据下述式3计算出的附着功。
[数2]
式2：D＝{4×(δd1-δd2)2+(δp1-δp2)2+(δh1-δh2)2}1/2
[数3]
式3：Wa＝2×(γd1×γd2)1/2+2×(γp1×γp2)1/2+2×(γh1×γh2)1/2
式2中，δd1、δp1及δh1表示第一构件的热塑性高分子的汉森溶解度参数中的分散项、极性项及氢键项，δd2、δp2及δh2表示第二构件的热塑性高分子的汉森溶解度参数中的分散项、极性项及氢键项。
式3中，γd1、γp1及γh1表示第一构件的表面自由能中的分散分量、极性分量及氢键分量，γd2、γp2及γh2表示第二构件的表面自由能中的分散分量、极性分量及氢键分量。
δd1、δp1及δh1(第一热塑性高分子的分散项、极性项及氢键项)以及δd2、δp2及δh2(第二热塑性高分子的分散项、极性项及氢键项)也可使用文献值，但在本发明中，设为使用对基于高分子的结构的汉森溶解度参数进行计算而得的值。
第一热塑性高分子的汉森溶解度参数及第二热塑性高分子的汉森溶解度参数的算出可在温度23℃±2℃下，基于溶解度参数算出法并使用软件名“HSPiP”来计算。汉森溶解度参数的算出方法的详细情况可参照下述实施例一栏。
γd1、γp1及γh1(第一构件的分散分量、极性分量及氢键分量)以及γd2、γp2及γh2(第二构件的分散分量、极性分量及氢键分量)是指通过测定第一构件的接合面及第二构件的接合面的各表面自由能而获得的值。
表面自由能的测定是通过在温度23℃±2℃下，使水、二碘甲烷及乙二醇附着于第一构件的接合面及第二构件的接合面，使用接触角计测定接触角而获得。表面自由能的测定方法的详细情况可参照下述实施例一栏。
此外，如后所述，在成为层叠体的状态下，第一构件的接合面与第二构件的接合面经牢固地粘着。因此，在层叠体的状态下，难以测定第一构件的接合面及第二构件的接合面的各表面自由能。因此，当在层叠体的状态下测定第一构件及第二构件的各表面自由能时，分别将第一构件及第二构件切断来测定各切断面的表面的表面自由能。
＜层叠体及其制法＞
本发明的层叠体的制造方法具有使第一构件与第二构件重叠的步骤、自所述经重叠的双层物的第一构件侧照射激光光束的步骤。
具体而言，如图1所示，准备形成为所期望的形状的所述第一构件1与第二构件2。以所述第一构件1的下表面与第二构件2的上表面直接接触的方式，将第一构件1与第二构件2重叠(参照图2)。所述相互重叠的面是第一构件1的接合面1a与第二构件2的接合面2a。在图示例中，第一构件1的下表面为第一构件1的接合面1a，第二构件2的上表面为第二构件2的接合面2a。
此外，在图1及图2的纸面上，第一构件1与第二构件2是以第一构件1的下表面(接合面)与第二构件2的上表面(接合面)相接的状态经层叠，但也可为相反的。即，第一构件1与第二构件2也可以第二构件2的下表面与第一构件1的上表面直接相接的状态经层叠(未图示)。
也可使第一构件1的接合面1a及第二构件2的接合面2a分别独立地成为凹凸面。不过，由于可使两接合面整体密接地接触，因此优选使第一构件1的接合面1a及第二构件2的接合面2a均成为平滑的面。此外，平滑的面不仅可为平面，也包括平滑的曲面。
然后，自所述经重叠的双层物的第一构件1侧(第一构件1的与接合面1a为相反侧的面1b侧)照射激光光束。
所照射的激光光束的波长为780nm～1000nm，通常使用波长808nm的激光光束。激光光束的照射速度根据第一构件1及第二构件的形成材料适宜且适当地设定，例如为3mm/sec～15mm/sec。关于激光光束的输出，优选为使用4根～50根的每根为3W～25W的二极管，整体为100W～625W。
激光光束沿着第一构件1的厚度方向透射并到达第二构件2。第二构件2的吸收剂吸收激光光束，因此第二构件2发热。第二热塑性高分子因所述热而熔融，并且所述热经传递，从而第一热塑性高分子也熔融。散热后，第一热塑性高分子及第二热塑性高分子再次固化，由此获得第一构件1与第二构件2直接粘着而成的层叠体。
图3及图4是本发明的层叠体的剖面图。
本发明的层叠体3中，(1)第一构件1与第二构件2并无界面地经粘着(参照图3)，或者(2)在第一构件1与第二构件2的边界处具有界面且两构件经粘着(参照图4)。
参照图3，在一个实施方式中，本发明的层叠体3在第一构件1与第二构件2之间混杂有构成第一构件1的材料及构成第二构件2的材料。第一构件1与第二构件2以在结构上无法分离相互的材料的状态经牢固地粘着。图3的由×所表示的区域为第一构件1的材料与第二构件2的材料的混杂区域。
参照图4，在另一实施方式中，本发明的层叠体3在第一构件1与第二构件2的边界附近存在界面4。但是，并非在所述界面4处第一构件1的材料与第二构件2的材料被明确地分离，而是指可在结构上通过所述界面4将相互的材料大致分离。第一构件1与第二构件2在界面4处经牢固地粘着。
本发明的层叠体中，例如第一构件与第二构件的粘着强度为3kgf/2cm以上(约29.4N/2cm以上)，两个构件经牢固地粘着。
此种层叠体可通过使用由式1：A＝-9×D+Wa-45所表示的A大于零的第一构件与第二构件来获得。即，所述层叠体通过使用满足A＞0的关系的第一构件与第二构件来获得。
以往，在所谓的激光粘着的领域中，在两个构件之间插入粘着用片来粘着两构件。作为将两构件直接牢固粘着的一种方法，可列举选择通过激光而直接粘着般的两构件的材料。但是，所述材料选择是困难的。
根据本发明，通过满足A＞0的关系的材料(第一热塑性高分子及第二热塑性高分子)，可利用激光光束直接牢固地粘着第一构件与第二构件。在本发明的另一方面中，提供一种当使用激光光束直接粘着第一构件与第二构件时可容易地选择所述第一构件与第二构件的筛选方法。即，根据本发明的另一方面，当利用激光光束直接粘着第一构件与第二构件时，以A＞0为指标来选择第一构件与第二构件。满足A＞0的第一构件及第二构件可基于它们的汉森溶解度参数的距离D与附着功Wa而容易地进行取舍选择。
在式1中，只要A大于零则并无特别限制，但优选A为0.1以上，更优选为0.5以上。另外，A并无特别的上限，但实际上为20以下。
另外，式1中的D的数值的上限并无特别限制，但优选为3(J/cm3)1/2以下，更优选为2(J/cm3)1/2以下，进而优选为1(J/cm3)1/2以下。所述D的下限值在理论上为零。
式1中的Wa的数值并无特别限制，但优选为45mN/m～70mN/m，更优选为55mN/m～65mN/m。
＜层叠体的使用＞
本发明的层叠体的用途并无特别限定。层叠体可根据其用途而形成为适宜的平面形状或立体形状及厚度。
本发明的层叠体中，通过激光光束的照射而第一构件及第二构件经牢固地粘着，因此可优选地用作能够在严酷的环境下使用的产品的构成构件。层叠体的优选用途是鞋的构成构件。例如，本发明的层叠体可用作鞋底。鞋底具有外底，且由第一构件或第二构件的任一者形成所述外底。
优选鞋底具有中底、以及层叠粘着于所述中底的下表面上的外底，所述中底由第一构件或第二构件中的任一者构成，且外底由另一者构成。更优选中底由第一构件形成且外底由第二构件形成。
图5及图6表示一实施方式的鞋。
在图2及图3中，鞋5例如是运动鞋。鞋具有覆盖脚背的主体51、以及设置于主体的下方的鞋底52。
图示例的鞋底52包括中底521、以及直接粘着于中底521的下方的外底522。例如，可将非发泡的第一构件形成为既定形状来作为所述中底521，并将发泡的第二构件形成为既定形状来作为所述外底522。
此外，外底是鞋底中与地面相接的构件，中底是鞋底中介隔存在于外底与主体之间的构件。
实施例
以下，列举实施例及比较例对本发明进一步进行详细叙述。但本发明并不限定于下述实施例。
[使用材料]
(A)热塑性高分子
·LDPE：低密度聚乙烯。东曹股份有限公司制造，产品名“皮特罗森(Petrothene)226”。
·HDPE：高密度聚乙烯。东曹股份有限公司制造，产品名“尼泼龙硬(NipolonHard)1000”。
·EVA1：乙烯-乙酸乙烯酯共聚物。东曹股份有限公司制造，产品名“乌特拉森(Ultrathene)540”。
·EVA2：乙烯-乙酸乙烯酯共聚物。东曹股份有限公司制造，产品名“乌特拉森(Ultrathene)630”。
·EVA3：乙烯-乙酸乙烯酯共聚物。东曹股份有限公司制造，产品名“乌特拉森(Ultrathene)631”。
·SBS：苯乙烯丁二烯苯乙烯弹性体。JSR股份有限公司制造，产品名“TR2003”。
·SIS：苯乙烯异戊二烯苯乙烯弹性体。可乐丽(Kuraray)股份有限公司制造，产品名“海博拉(HYBRAR)7125F”。
·SEBS1：苯乙烯乙烯丁烯苯乙烯弹性体。旭化成股份有限公司制造，产品名“塔夫泰科(Tuftec)H1062”。
·SEBS2：苯乙烯乙烯丁烯苯乙烯弹性体。旭化成股份有限公司制造，产品名“塔夫泰科(Tuftec)H1041”。
·SEBS3：苯乙烯乙烯丁烯苯乙烯弹性体。旭化成股份有限公司制造，产品名“塔夫泰科(Tuftec)H1043”。
·ALLOY1：所述LDPE的70质量份与EVA1的30质量份的混合物。
·ALLOY2：所述LDPE的35质量份与HDPE的35质量份以及EVA1的30质量份的混合物。
(B)激光吸收剂
·炭黑：炭黑母粒类型(carbon black master-batches type)。盛强国际有限公司制造，产品名“黑粒50”。
·NIR1：酞菁系化合物。巴斯夫(BASF)公司制造，产品名“路慕根(lumogen)IR765”。
·NIR2：多环系化合物。昭和电工股份有限公司制造，产品名“IR-T”。
(C)各种添加剂
·填充剂：软质碳酸钙。丸尾钙股份有限公司制造。
·硬脂酸：新日本理化股份有限公司制造。
·氧化锌：活性氧化锌No.2。本庄化学股份有限公司制造。
·交联剂：过氧化物。日油股份有限公司制造，产品名“过异丙苯(Percumyl)D”。
·交联助剂：三烯丙基异氰酸酯。日本化成股份有限公司制造，产品名“TAICM60”。
·发泡剂：偶氮二甲酰胺。永和化成工业股份有限公司制造，产品名“维尼弗(Vinyfor)AC#3C”。
[第一构件(激光透射材)的制作]
按照以下工序，制作厚度2mm、横长20mm、纵长50mm的平板状的第一构件。此外，第一构件仅由热塑性高分子形成。
包含LDPE的第一构件(以下称为LDPE-第一构件)通过在射出成形机(喷嘴温度约200℃)中对LDPE进行成形来制作。
包含EVA1的第一构件(以下称为EVA1-第一构件)、包含EVA2的第一构件(以下称为EVA2-第一构件)、及包含EVA3的第一构件(以下称为EVA3-第一构件)通过在射出成形机(喷嘴温度约200℃)中分别对EVA1、EVA2、EVA3进行成形来制作。
包含SBS的第一构件(以下称为SBS-第一构件)通过在射出成形机(喷嘴温度约200℃)中对SBS进行成形来制作。
包含SIS的第一构件(以下称为SIS-第一构件)通在射出成形机(喷嘴温度约230℃)中对SIS进行成形来制作。
包含SEBS1的第一构件(以下称为SEBS1-第一构件)、包含SEBS2的第一构件(以下称为SEBS2-第一构件)、及包含SEBS3的第一构件(以下称为SEBS3-第一构件)通过在射出成形机(喷嘴温度约230℃)中分别对SEBS1、SEBS2、SEBS3进行成形来制作。
[第二构件(激光吸收材)的制作]
按照以下工序，制作厚度4mm、横长20mm、纵长50mm的平板状的包含LDPE的第二构件(以下称为LDPE(a)-第二构件)。
将LDPE、激光吸收剂(炭黑)、填充剂、发泡剂、交联剂等以表1所示的调配比例混合。此外，表1所示的数值为质量份表示。使用混炼机将所述混合物混炼后，使用压制机在160℃、压力15MPa下加压约20分钟，由此成形所述发泡体。所述发泡体为LDPE(a)-第二构件。
如表1所示改变调配比例，以同样的方式制作包含LDPE的另外的第二构件(以下称为LDPE(b)-第二构件、LDPE(c)-第二构件、LDPE(d)-第二构件)。
如表1所示改变热塑性高分子及调配比例，以同样的方式制作包含EVA3的第二构件(以下称为EVA3-第二构件)。
如表1所示改变热塑性高分子及调配比例，以同样的方式制作包含SBS的第二构件(以下称为SBS-第二构件)。
如表1所示改变热塑性高分子及调配比例，以同样的方式制作包含SIS的第二构件(以下称为SIS-第二构件)。
如表1所示改变热塑性高分子及调配比例，以同样的方式制作包含ALLOY1的第二构件(以下称为ALLOY1-第二构件)。
如表1所示改变热塑性高分子及调配比例，以同样的方式制作包含ALLOY2的第二构件(以下称为ALLOY2-第二构件)。
[表1]
Figure BDA0002403848650000151
[汉森溶解度参数的算出]
分别以如下方式计算出所述第一构件的热塑性高分子的汉森溶解度参数中的分散项δd1、极性项δp1及氢键项δh1、以及所述第二构件的热塑性高分子的汉森溶解度参数中的分散项δd2、极性项δp2及氢键项δh2。
基于查尔斯·汉森(Charles·Hansen)提出的溶解度参数算出法(文献名汉森C.M.(Hansen C.M.)；汉森溶解度参数(Hansen Solubility Parameters)，CRS出版社(CRSPress)(2000))，利用由查尔斯·汉森等人开发的软件(软件名：实际中的汉森溶解度参数(Hansen Solubility Parameter in Practice)(HSPiP)版本(Version)4.0.04)来求出。算出温度使用了作为基本设定的25℃。
将其结果示于表2。
[表2]
Figure BDA0002403848650000161
[表面自由能的测定]
测定所述各第一构件的表面自由能中的分散分量γd1、极性分量γp1及氢键分量γh1。
以同样的方式测定所述各第二构件的表面自由能中的分散分量γd2、极性分量γp2及氢键分量γh2。
表面自由能的测定使用了协和界面科学股份有限公司制造的接触角计“DMs-401”，表面自由能的各分量使用了已知的液体(水、二碘甲烷及乙二醇)。具体而言，在23℃±2℃、50％RH下，使用所述接触角计测定第一构件的接合面上的所述已知的液体的接触角θ，并使用协和界面科学股份有限公司制造的多功能综合软件“FAMAS”求出表面自由能的各分量(γd1、γp1及γh1)。第二构件的接合面上的表面自由能的γd2、γp2及γh2也以同样的方式求出。将其结果示于表3及表4。
接触角θ的测定条件。
测定：液滴法
液量：1μL
滴落识别：自动
图像处理：算法-无反射
[表3]
Figure BDA0002403848650000171
[表4]
Figure BDA0002403848650000172
[实施例1至实施例22及比较例1至比较例16]
将所述各第一构件及第二构件如表5及表6般加以组合。表5及表6中的D表示第一构件的热塑性高分子的汉森溶解度参数与所述第二构件的热塑性高分子的汉森溶解度参数的距离，Wa表示附着功。各D是在式2：D＝{4×(δd1-δd2)2+(δp1-δp2)2+(δh1-δh2)2}1/2中代入表2的数值而求出，各Wa是在式3：Wa＝2×(γd1×γd2)1/2+2×(γp1×γp2)1/2+2×(γh1×γh2)1/2中代入表3及表4的数值而求出。另外，A是根据式1：A＝-9×D+Wa-45而算出。
在各个组合中，在第二构件的上表面(接合面)上重叠第一构件的下表面(接合面)，并自所述第一构件的上表面侧以下述条件照射激光光束。
激光光束照射装置：日本爱默生(Emerson)股份有限公司制造。
激光光束的波长：波长808nm。
激光光束的照射速度：参照表5及表6。
每根二极管的激光光束的输出：4.5W。
二极管的根数：25根。
激光光束的照射时间：5秒。
通过照射激光光束，获得了第一构件与第二构件粘着而成的实施例1至实施例22以及比较例1至比较例16的各层叠体。
[表5]
Figure BDA0002403848650000191
[表6]
Figure BDA0002403848650000201
[剥离试验]
对于所述各实施例及比较例的层叠体，使用拉伸试验机进行剥离试验。
具体而言，对于各层叠体，利用拉伸试验机的各自的卡盘夹住第一构件的缘部与第二构件的缘部，以拉伸速度50mm/min将两卡盘拉开，由此将所述第一构件与第二构件剥离180度。换句话说，以第一构件的缘部与第二构件的缘部沿约180度的方向背离的方式，以50mm/min的拉伸速度对两者进行拉伸。而且，将第一构件与第二构件分离时的最大应力设为粘着强度。
将其结果示于表5及表6。
进而，以目视观察所述剥离试验后的状态。将其结果示于表5及表6。
再者，在表5及表6的剥离状态下，“材料破坏”表示在第一构件与第二构件的界面处两者未剥离且第二构件自身断裂的结果，“界面剥离”表示在第一构件与第二构件的界面处两者剥离的结果。
图7及图8是将剥离试验的结果制成图表而成，图7表示各实施例及比较例的溶解度参数的距离与粘着强度的关系，图8表示各实施例及比较例的附着功与粘着强度的关系。
此外，当粘着强度为3kgf/2cm以上(约29.4N/2cm以上)时，可以说第一构件与第二构件以充分的强度粘着。如根据图表可知，所有实施例的粘着强度均为3kgf/2cm以上。
图9是将各实施例及比较例的溶解度参数的距离与附着功的关系制成图表而成，横轴采取溶解度参数的距离，纵轴采取附着功。各实施例集中在所述图表的大致上侧(特别是上侧且左侧)，相反地，比较例集中在下侧。在所述图表中，划出各实施例与比较例的界线并决定所述界线的式子，结果为Wa＝9×D+45。推断所述界线的右上区域是相当于以充分的粘着强度粘着的第一构件与第二构件的组合的区域。所述区域是满足Wa-9×D-45＞0的区域。
图10是在横轴中采取图9中所决定的-9×D+Wa-45＝A来表示所述A与粘着强度的关系的图表。所有实施例均包含在A大于零的区域(A＞0的区域)中，所有比较例均包含在A为零以下的区域中。
产业上的可利用性
本发明的层叠体例如可用作鞋或运动用品等的构成构件。
符号的说明
1：第一构件
2：第二构件
3：层叠体
5：鞋
51：鞋的主体
52：鞋的鞋底
521：中底
522：外底

Claims (4)

1.一种层叠体，具有：第一构件，包含热塑性高分子且透射激光；以及第二构件，包含热塑性高分子且吸收激光，
所述第一构件直接粘着于所述第二构件，且
由下述式1所表示的A大于零；
其中，式1中，D表示依据下述式2计算出的所述第一构件的热塑性高分子的汉森溶解度参数与所述第二构件的热塑性高分子的汉森溶解度参数的距离，Wa表示根据所述第一构件与所述第二构件的各表面自由能并依据下述式3计算出的附着功，式2中，δd1、δp1及δh1表示所述第一构件的热塑性高分子的汉森溶解度参数中的分散项、极性项及氢键项，δd2、δp2及δh2表示所述第二构件的热塑性高分子的汉森溶解度参数中的分散项、极性项及氢键项，式3中，γd1、γp1及γh1表示所述第一构件的表面自由能中的分散分量、极性分量及氢键分量，γd2、γp2及γh2表示所述第二构件的表面自由能中的分散分量、极性分量及氢键分量；
[数1]
式1：A＝-9×D+Wa-45
式2：D＝{4×(δd1-δd2)2+(δp1-δp2)2+(δh1-δh2)2}1/2
式3：Wa＝2×(γd1×γd2)1/2+2×(γp1×γp2)1/2+2×(γh1×γh2)1/2。
2.根据权利要求1所述的层叠体，其中，所述第一构件由非发泡体形成，所述第二构件由发泡体形成。
3.一种鞋底，具有外底，
所述外底由如权利要求1或2所述的第一构件或第二构件中的任一者形成。
4.一种鞋，具有如权利要求3所述的鞋底。
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