WO2018184173A1 - 硫化橡胶物品及其制法与应用 - Google Patents

硫化橡胶物品及其制法与应用 Download PDF

Info

Publication number
WO2018184173A1
WO2018184173A1 PCT/CN2017/079613 CN2017079613W WO2018184173A1 WO 2018184173 A1 WO2018184173 A1 WO 2018184173A1 CN 2017079613 W CN2017079613 W CN 2017079613W WO 2018184173 A1 WO2018184173 A1 WO 2018184173A1
Authority
WO
WIPO (PCT)
Prior art keywords
vulcanized rubber
hot melt
melt adhesive
layer
rubber article
Prior art date
Application number
PCT/CN2017/079613
Other languages
English (en)
French (fr)
Inventor
林锦辉
黄亭凯
王雅琪
Original Assignee
三晃股份有限公司
达音创研股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 三晃股份有限公司, 达音创研股份有限公司 filed Critical 三晃股份有限公司
Priority to PCT/CN2017/079613 priority Critical patent/WO2018184173A1/zh
Publication of WO2018184173A1 publication Critical patent/WO2018184173A1/zh

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C4/00—Treatment of rubber before vulcanisation, not provided for in groups C08C1/00 - C08C3/02
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the present invention relates to a rubber article, and more particularly to a vulcanized rubber article having a thermoplastic polyurethane on its surface.
  • Vulcanized rubber articles have a wide range of applications due to their high hardness and good elasticity, such as sealing materials, tires, conveyor belts, soles, and soft synthetic leather.
  • vulcanized rubber articles have poor adhesion to other materials, so when it is necessary to join other objects, special processing is often required.
  • the outsole of general footwear is vulcanized rubber, and the outsole needs to be compounded with a midsole (such as TPU or EVA) to increase the lightweight comfort of the shoe.
  • a combination of a vulcanized rubber outsole and a midsole is a solvent-based adhesive.
  • the following procedures are usually required: cleaning and roughening baking, coating, and solvent drying.
  • the above steps are performed once for the outsole; then the midsole is applied;
  • the outsole and the midsole of the applied agent are baked again, and then the outsole is attached to the midsole, and then the two are hot pressed together.
  • the prior art also provides for the application of hot melt adhesive films to vulcanized rubber articles.
  • the hot melt adhesive film needs to be cut with the rubber skin shape, and the cutting process takes time and increases the labor cost.
  • the smooth surface of the hot melt adhesive film is also disadvantageous for its subsequent bonding with other objects.
  • the present invention disperses the hot melt adhesive powder on the surface of the unvulcanized rubber skin, and then heat-presses the unvulcanized rubber skin together with the hot melt adhesive powder to produce a vulcanized rubber article having an adhesive function on the surface. Because of the adhesive function, the combination of the vulcanized rubber article and the object can be completed by hot pressing or other suitable means without the aforementioned steps of cleaning and roughening baking, coating, and solvent removal.
  • the invention provides a method for producing a vulcanized rubber article, comprising: providing an unvulcanized rubber layer and a hot melt adhesive powder, the hot melt adhesive powder comprising a thermoplastic polyurethane; dispersing the hot melt adhesive powder on a surface of the unvulcanized rubber layer And hot pressing the unvulcanized rubber layer having the hot melt adhesive powder to obtain the vulcanized rubber article.
  • the unvulcanized rubber layer comprises polyisoprene rubber (IR), styrene butadiene Copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile butadiene copolymer rubber (NBR), isoprene, isobutylene copolymer rubber (IIR), ethylene. propylene-diene copolymer rubber (EPDM) Or halogenated butyl rubber (HR).
  • the thermoplastic polyurethane has a molecular weight (Mw) measured by a gel permeation chromatography (GPC) ranging from 5,000 to 100,000.
  • Mw molecular weight measured by a gel permeation chromatography
  • the thermoplastic polyurethane has a melt viscosity ranging from 1,000 to 20,000 cps.
  • the hot melt adhesive powder has a particle size ranging from 50 to 1,000 um as measured by a Laser Diffraction Particle Size Analyzer.
  • step of dispersing the hot melt adhesive powder on the surface of the unvulcanized rubber layer further comprises forming an adhesive layer on the surface.
  • the present invention also encompasses a vulcanized rubber article obtained by the aforementioned process.
  • the present invention provides a vulcanized rubber article comprising a vulcanized rubber layer and a hot melt adhesive layer over the vulcanized rubber layer, the hot melt adhesive layer comprising a thermoplastic polyurethane, wherein the hot melt adhesive layer has an uneven shape, and the unevenness The outer shape is formed by simultaneously pressing an unvulcanized rubber layer having a hot melt adhesive powder to form the vulcanized rubber layer.
  • an adhesive layer is further included between the hot melt adhesive layer and the vulcanized rubber layer.
  • the vulcanized rubber article has no stickiness at room temperature.
  • the present invention provides a method of bonding a vulcanized rubber article to a subject, comprising: providing a plurality of particles comprising a foamed thermoplastic polyurethane; placing the vulcanized rubber article of any of the foregoing And constituting the plurality of particles to form a subject, wherein the vulcanized rubber article is simultaneously bonded to the object.
  • the object is a midsole.
  • Figure 1 is a schematic view of an unvulcanized rubber layer of the present invention
  • 2A is a schematic view showing the surface of the present invention dispersing a hot melt adhesive powder on a surface of an unvulcanized rubber layer;
  • 2B is a schematic view showing the present invention, in which the hot melt adhesive powder is dispersed on an unvulcanized rubber layer having an adhesive layer on the surface;
  • FIG. 3A and 3B are schematic views of the front and back sides of a vulcanized rubber article of the present invention, wherein FIG. 3A is a front side (hot melt adhesive layer), and FIG. 3B is a back side (vulcanized rubber layer);
  • Figure 4 is a schematic view showing a vulcanized rubber article as a combination of an outsole and an object
  • Figure 5 is a schematic illustration of the sole of the present invention.
  • the method of making a vulcanized rubber article of the present invention mainly comprises the step A of providing an unvulcanized rubber layer 10 and a hot melt adhesive powder 20 (not shown in Figure 1).
  • the unvulcanized rubber layer 10 contains a rubber composition obtained by kneading a suitable rubber raw material with various additives, and may be any unvulcanized rubber material suitable for use as an outsole or other elastomer for shoes. This rubber composition can form a certain shape, so it is referred to herein as an unvulcanized rubber layer.
  • the rubber raw material may be selected from natural rubber, synthetic rubber or a mixture of the two.
  • Synthetic rubber such as polyisoprene rubber (IR), styrene butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile, butadiene copolymer rubber (NBR), isoprene .
  • Synthetic rubber such as polyisoprene rubber (IR), styrene butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile, butadiene copolymer rubber (NBR), isoprene .
  • SBR styrene butadiene copolymer rubber
  • BR polybutadiene rubber
  • NBR acrylonitrile
  • IIR butene copolymer rubber
  • EPDM propylene-diene copolymer rubber
  • HR halogenated butyl rubber
  • the additive in the rubber composition may be selected from a filler (including a material selected from the group consisting of carbon black, silica, talc, clay, aluminum hydroxide, titanium oxide, etc.), a sulfur component, a vulcanization accelerator, an anti-aging agent, an oil or a wax, and the like. .
  • the hot melt adhesive powder 20 of the present invention is mainly composed of a thermoplastic polyurethane.
  • the thermoplastic polyurethane can be obtained, for example, by mixing a diisocyanate, a polyester polyol, a chain extender, a catalyst, and other suitable additives at about 200 to 300 ° C.
  • the diisocyanate may be selected from the group consisting of 4,4-methylenebis(phenylisocyanate) (MDI), m-xylylene diisocyanate (XDI), phenylene-1,4-diisocyanate, 1,5-naphthalene.
  • the polyester polyol is a polyester of a dibasic acid and a glycol, the glycol may be a glycol having 2 to 10 carbon atoms, and the dibasic acid may be a linear chain having 4 to 12 carbon atoms or Branched dibasic acid. Preferred is 1,4-butanediol adipate.
  • the chain extender is a diol having 2 to 12 carbon atoms; for example: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3- At least one of butylene glycol, 1,5-pentanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, benzenediol, and xylene glycol.
  • the catalyst may be selected from at least one of triethylamine, dimethylcyclohexylamine, stannous dioctoate, dibutyltin dioctoate, dibutyltin dilaurate, and dibutyltin diacetate.
  • the hot-melt adhesive powder 20 of the present invention can be obtained by cooling and breaking the thermoplastic polyurethane in a molten state.
  • additives such as pigments, fillers, antioxidants, reinforcing agents, lubricants or plasticizers and the like can also be used in the above treatment.
  • the preferred molecular weight (Mw) of the thermoplastic polyurethane of the present invention ranges from 5,000 to 100,000 per mole (measured by gel permeation chromatography (GPC)); preferred melt viscosity ranges from 1,000 to 20,000 cps (by melt viscosity) Instrument (melt viscometer) determination).
  • the above hot melt adhesive powder preferably has a particle size ranging from 50 to 1,000 um (measured by a Laser Diffraction Particle Size Analyzer), and if the particle size is too large, a uniform adhesive surface cannot be formed on the carrier. On the other hand, if the particle size is too small, pores which are favorable for the subsequent formation on the carrier cannot be formed, and the adhesion is also lowered.
  • commercially available hot melt adhesive powders such as A-760, A-860, and A-1080 hot melt adhesive powders are used.
  • step B is then carried out: the hot melt adhesive powder 20 is dispersed on the surface 10a of the unvulcanized rubber layer.
  • the hot melt adhesive powder 20 may be sprinkled on the surface 10a of the unvulcanized rubber layer by any suitable method.
  • the adhesive layer 22 may be formed on the surface 10a (but not necessarily) as needed, wherein the composition of the adhesive layer 22 may be any suitable liquid phase adhesive, such as the shoe industry.
  • the surface treatment agent (such as 3M Primer) is used to surface pretreat the shoe material.
  • the hot melt adhesive powder 20 is dispersed on the adhesive layer 22 on the surface 10a.
  • first forming the adhesive layer 22 will help the hot melt adhesive powder 20 to be fixed to the watch. On the face 10a, it is possible to prevent the hot melt adhesive powder 20 from slipping when the unvulcanized rubber layer 10 is moved.
  • step C the unvulcanized rubber layer 10 having the hot melt adhesive powder 20 is hot pressed to obtain a vulcanized rubber article.
  • a rubber vulcanization hot press can be prepared, and both the upper mold and the lower mold can be sandwiched and held for hot pressing.
  • the unvulcanized rubber layer 10 having the hot melt adhesive powder 20 formed in Fig. 2A and/or Fig. 2B is placed in a lower mold, and then a release film is selectively placed on the hot melt adhesive powder 20 before the mold is placed on the cover ( This step can be used as needed, not necessary).
  • the upper and lower molds are combined and subjected to hot press vulcanization treatment, and the temperature condition is preferably 110 to 180 ° C. Other conditions can be referred to the general rubber vulcanization procedure.
  • the vulcanized rubber article can be obtained by appropriately cooling, removing the release film, and demolding.
  • FIG. 3A and 3B are photographs of the front and back sides of the vulcanized rubber article 30 obtained after the completion of the step C, FIG. 3A is the front side (hot melt adhesive layer), and FIG. 3B is the back side (vulcanized rubber layer).
  • the vulcanized rubber article 30 includes a vulcanized rubber layer 31 and a hot melt adhesive layer 32 above the vulcanized rubber layer 31.
  • the hot melt adhesive layer 32 as described above contains a thermoplastic polyurethane.
  • the hot melt adhesive layer 32 has an uneven shape as shown in FIG. 3A, and the uneven shape is formed by hot pressing an unvulcanized rubber layer 10 having a hot melt adhesive powder 20.
  • the vulcanized rubber article 30 does not have viscosity at room temperature, but the surface is viscous by proper heating or irradiation of microwaves. Therefore, when the vulcanized rubber article 30 is bonded to the object, the steps of cleaning and roughening the vulcanized rubber article 30, coating, and solvent drying can be eliminated.
  • the method includes providing a plurality of particles 40, and the plurality of particles 40 comprises a foamed thermoplastic polyurethane, the composition of which can be referred to the patent TW105129288, but is not limited thereto.
  • a plurality of particles 40 can be gathered therein using a suitable mold 41.
  • the vulcanized rubber article 45 is placed on a plurality of particles 40, wherein the face of the vulcanized rubber article 45 having a hot melt adhesive layer (not shown) is directed toward the plurality of particles 40.
  • a plurality of particles 40 are irradiated by microwaves to form a sole as shown in FIG. 5, in which a plurality of particles 40 form a midsole 51 (object 51), and during the microwave process, the vulcanized rubber article 45 is also combined with the object 51.
  • the vulcanized rubber article 45 is a shoe outsole.
  • the aforementioned vulcanized rubber article may also be combined with other objects by other methods, and is not limited to this method of the present invention.
  • the vulcanized rubber article of the present invention can be used for a variety of purposes, such as the outsole of the shoe as an example, but not limited thereto.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

一种硫化橡胶物品，其制法包含以下步骤：提供未硫化橡胶层及热熔胶粉末，热熔胶粉末包含热塑性聚氨酯；使热熔胶粉末分散于未硫化橡胶层上；及热压具有热熔胶粉末的未硫化橡胶层，以获得硫化橡胶物品。同时提供将此硫化橡胶物品与对象结合的应用。

Description

硫化橡胶物品及其制法与应用 技术领域
本发明涉及一种橡胶物品，特别是涉及其表面具有热塑性聚氨酯的硫化橡胶物品。
背景技术
硫化橡胶物品因高硬度及良好弹性的优点有相当广泛的应用，如密封材、轮胎、输送皮带、鞋底、软质合成皮等。但是，硫化橡胶物品与其他材料的黏合性差，因此当有必要与其他对象接合时，往往需要特殊的加工处理。举例而言，一般鞋类的大底是硫化橡胶，且大底有必要与中底(如TPU或EVA)复合以增加鞋子的轻便舒适性。实际操作中硫化橡胶大底和中底的结合采用溶剂型黏着剂。为使溶剂型黏着剂与大底与中底紧密结合通常需进行以下程序：清洁粗化烘烤、涂剂、烘除溶剂，上述各步骤对大底实施一次；然后对中底涂剂；上述已涂剂的大底与中底再次烘烤，然后进行大底与中底相贴，之后两者再一并热压。由此可知其流程相当繁琐。除溶剂型黏着剂以外，现有技术也提供热熔胶薄膜贴覆硫化橡胶物品的作法。利用热熔胶薄膜需配合橡胶皮外型进行裁切，裁切工程耗时且增加劳力成本。况且，热熔胶薄膜平滑的表面也不利其后续与其他对象的结合。
发明内容
为了解决上述问题，本发明的目的在于提供一种具有热熔胶层的硫化橡胶物品，该热熔胶层形成于对未硫化橡胶物品进行硫化过程中。利用本发明可简化硫化橡胶物品与其他对象结合的程序。具体地，本发明是将热熔胶粉末分散在未硫化橡胶皮的表面上，然后再将未硫化橡胶皮连同热熔胶粉末一起热压，进而产出表面带有黏着功能的硫化橡胶物品。因为带有黏着功能，硫化橡胶物品与对象的结合可将两者相贴经热压或其他合适方式即可完成，而无需前述的清洁粗化烘烤、涂剂、烘除溶剂等步骤。
一方面，本发明提供一种硫化橡胶物品的制法，包含：提供未硫化橡胶层及热熔胶粉末，该热熔胶粉末包含热塑性聚氨酯；使该热熔胶粉末分散于该未硫化橡胶层的表面上；及热压具有该热熔胶粉末的该未硫化橡胶层，以获得该硫化橡胶物品。
根据前述的制法，其中该未硫化橡胶层是包含聚异戊二烯橡胶(IR)、苯乙烯.丁二烯 共聚橡胶(SBR)、聚丁二烯橡胶(BR)、丙烯腈.丁二烯共聚橡胶(NBR)、异戊二烯.异丁烯共聚橡胶(IIR)、乙烯.丙烯-二烯共聚橡胶(EPDM)、或卤化丁基橡胶(HR)。
根据前述的制法，其中该热塑性聚氨酯以凝胶渗透层析仪(GPC)量测的分子量(Mw)范围为5,000至100,000。
根据前述的制法，其中该热塑性聚氨酯的熔融粘度范围为1,000到20,000cps。
根据前述的制法，其中以镭射粒径分析仪(Laser Diffraction Particle Size Analyzer)量测该热熔胶粉末的粒径范围为50-1,000um。
根据前述的制法，其中在使该热熔胶粉末分散于该未硫化橡胶层的该表面上的步骤前，还包含形成黏着层于该表面上。
本发明还包含一种硫化橡胶物品，是得自于前述的制法。
另一方面，本发明提供一种硫化橡胶物品，包含硫化橡胶层及热熔胶层于该硫化橡胶层上方，该热熔胶层包含热塑性聚氨酯，其中该热熔胶层具有凹凸不平的外形，该凹凸不平的外形是将具有热熔胶粉末的未硫化橡胶层进行热压以形成该硫化橡胶层时同时形成。
根据前述的硫化橡胶物品，其中该热熔胶层及该硫化橡胶层之间还包含黏着层。
根据前述的硫化橡胶物品，其中该硫化橡胶物品在室温下不具有黏性。
在更另一方面，本发明提供一种硫化橡胶物品与对象结合的方法，包含：提供复数个粒子，该复数个粒子包含发泡热塑性聚氨基甲酸酯；将前述任一种的硫化橡胶物品置放于该复数个粒子上；以及经微波照射该复数个粒子以形成对象，其中该硫化橡胶物品同时与该对象结合。
根据前述的方法，其中该硫化橡胶物品为鞋大底，该对象为鞋中底。
为让本发明的上述内容能更明显易懂，下文特举优选实施例，并结合附图，作详细说明如下。
附图说明
下面将结合附图对本发明的具体实施方式作进一步详细说明。
图1为本发明未硫化橡胶层的示意图；
图2A为本发明将热熔胶粉末分散于未硫化橡胶层的表面的示意图；
图2B为本发明将热熔胶粉末分散于表面上有黏着层的未硫化橡胶层的示意图；
图3A及图3B为本发明的一种硫化橡胶物品的正反两面示意图，图3A为正面(热熔胶层面)，图3B为背面(硫化橡胶层面)；
图4为硫化橡胶物品作为鞋大底与对象结合的示意图；
图5为本发明的鞋底的示意图。
元件标号说明
10未硫化橡胶层
10a表面
20热熔胶粉末
22黏着层
30硫化橡胶物品
31硫化橡胶层
32热熔胶层
40复数个粒子
41模具
45硫化橡胶物品
51鞋中底、对象
具体实施方式
以下由特定的具体实施例说明本发明的实施方式，本领域技术人员可由本说明书所揭示的内容轻易地了解本发明的其他优点及功效。虽然本发明的描述将结合优选实施例介绍，但这并不代表此发明的特征仅限于该实施方式。恰恰相反，结合实施方式作发明介绍的目的是为了覆盖基于本发明的权利要求而有可能延伸出的其它选择或改造。为了提供对本发明的深度了解，以下描述中将包含许多具体的细节。本发明也可以不使用这些细节实施。应注意为清楚呈现本发明，所附图式中的各组件并非按照实物的比例绘制，而且为避免模糊本发明的内容，以下说明还省略熟知的零组件、相关材料、及其相关处理技术。
参考图1及图2A，本发明的硫化橡胶物品的制法主要包含步骤A：提供未硫化橡胶层10及热熔胶粉末20(图1未示出)。关于步骤A，所述未硫化橡胶层10包含将合适橡胶原料与各种添加剂混炼而成的橡胶组合物，其可为任何适于用作鞋用大底或其它弹性体的未经硫化橡胶材。此橡胶组合物可形成一定的外型，因此本文称其未硫化橡胶层。橡胶原料可选自天然橡胶、合成橡胶或两者的混合。合成橡胶譬如聚异戊二烯橡胶(IR)、苯乙烯.丁二烯共聚橡胶(SBR)、聚丁二烯橡胶(BR)、丙烯腈.丁二烯共聚橡胶(NBR)、异戊二烯.异 丁烯共聚橡胶(IIR)、乙烯.丙烯-二烯共聚橡胶(EPDM)、卤化丁基橡胶(HR)等各种合成橡胶。橡胶组合物中的添加剂可选自填充剂(包含选自碳黑、二氧化硅、滑石、黏土、氢氧化铝、氧化钛等)、硫成份、硫化促进剂、抗老化剂、油或蜡等。
本发明所述热熔胶粉末20主要为热塑性聚氨酯所组成。热塑性聚氨酯的作法，举例而言，可将二异氰酸酯、聚酯多元醇、增链剂、催化剂和其他的合适添加剂相混合在约200～300℃下反应而得。二异氰酸酯可选自4，4-亚甲基双(苯基异氰酸酯)(MDI)、间-亚二甲苯基二异氰酸酯(XDI)、亚苯基-1，4-二异氰酸酯、1，5-萘二异氰酸酯、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)和二环己基甲烷-4,4-二异氰酸酯。较佳为MDI或TDI。聚酯多元醇为二元酸和二元醇的聚酯类，二元醇可为具有2-10个碳原子的二元醇，二元酸可为具有4-12个碳原子的直链或支链的二元酸。较佳为己二酸1，4-丁二醇酯。增链剂是具有2-12个碳原子的二醇；例如：乙二醇、二甘醇、丙二醇、二丙二醇、1，4-丁二醇、1，6-己二醇、1，3-丁二醇、1，5-戊二醇、1，4-环己烷二甲醇、新戊二醇、苯二醇和二甲苯二醇中的至少一种。催化剂可选自三乙胺、二甲基环己胺、二辛酸亚锡、二辛酸二丁基锡、二月桂酸二丁基锡、二乙酸二丁基锡中的至少一种。反应完成后，熔融状态的热塑性聚氨酯经冷却及打碎制程即可获得本发明所述热熔胶粉末20。上述处理过程中也可使用各种添加剂、譬如颜料、填料、抗氧剂、增强剂、润滑剂或增塑剂等等。本发明所述热塑性聚氨酯的较佳分子量(Mw)范围为5,000至100,000/摩尔(以凝胶渗透层析仪(GPC)量测)；较佳的熔融黏度范围为1,000到20,000cps(以熔融黏度仪(melt viscometer)测定)。上述热熔胶粉末较佳的粒径范围为50-1,000um(以镭射粒径分析仪(Laser Diffraction Particle Size Analyzer)量测)，若粉末粒径过大则无法在载体上形成均匀的接着面，以致接着性下降；另一方面，若粒径过小，则无法在载体上形成利于接着的孔洞，也同样导致接着性下降。本发明于较佳实施例使用商业上可取得的热熔胶粉末如三晃股份有限公司的品名为A-760、A-860、A-1080的热熔胶粉末。
参考图2A，接着进行步骤B：使该热熔胶粉末20分散于该未硫化橡胶层的表面10a上。可用任何合适的方法将热熔胶粉末20洒在未硫化橡胶层的表面10a上。而且，参考图2B，在B步骤之前，可视需要先形成黏着层22于该表面10a(但非必要)，其中该黏着层22的成分可以是任何合适的液相黏胶，如鞋界常使用的表面处理剂(譬如3M Primer)对鞋材进行表面预处理。如图2B所示，使热熔胶粉末20分散于表面10a上的黏着层22上。对于尺寸较小的未硫化橡胶层10，先形成黏着层22将有助于热熔胶粉末20固定于表 面10a上，可避免移动未硫化橡胶层10时造成热熔胶粉末20滑落。
接着进行步骤C：热压具有热熔胶粉末20的未硫化橡胶层10，以获得硫化橡胶物品。举例而言，可准备橡胶硫化热压机，具有上模及下模两者可上下夹合进行热压。将图2A及/或图2B所形成的具有热熔胶粉末20的未硫化橡胶层10置入下模具中，然后选择性地在盖上模具前铺上离型膜在热熔胶粉末20上(此步骤可视需要使用，并非必要)。接着将上下模合上进行热压硫化处理，温度条件较佳为110～180℃，其他条件可参考一般橡胶硫化程序。热压完成后经适当冷却、去除离型膜并脱模后即可取得硫化橡胶物品。
图3A及图3B为完成步骤C后所获得的硫化橡胶物品30的正反两面照片，图3A为正面(热熔胶层面)，图3B为背面(硫化橡胶层面)。由图可知硫化橡胶物品30包含硫化橡胶层31及热熔胶层32于该硫化橡胶层31上方。如前述热熔胶层32包含热塑性聚氨酯。如图3A所示热熔胶层32具有凹凸不平的外形，该凹凸不平的外形是经由热压具有热熔胶粉末20的未硫化橡胶层10所形成。硫化橡胶物品30于室温下不具有粘性，但经适当加热或照射微波可使其表面产生黏性。因此，将硫化橡胶物品30与对象结合时，可免除对硫化橡胶物品30进行清洁粗化烘烤、涂剂、烘除溶剂等步骤。
参考图4，提供一种将前述的硫化橡胶物品作为鞋大底与对象结合的方法。如图4所示，此方法包含提供复数个粒子40，复数个粒子40包含发泡热塑性聚氨基甲酸酯，其成分可参见专利TW105129288，但不以此为限。可利用合适的模具41将复数个粒子40聚集其中。接着，将硫化橡胶物品45置放于复数个粒子40上，其中硫化橡胶物品45具有热熔胶层(未示出)的面是朝向复数个粒子40。然后，经微波照射复数个粒子40以形成如图5所示的鞋底，其中复数个粒子40形成鞋中底51(对象51)，而且于微波过程中，硫化橡胶物品45同时也与对象51结合，硫化橡胶物品45即鞋大底。
也可以用其他方法使前述的硫化橡胶物品与其他对象结合，不以本发明的此方法为限。本发明的硫化橡胶物品可有多种用途，以鞋大底为例但不以此为限。
综上所述，本发明提供的上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (12)

  1. 一种硫化橡胶物品的制法，其特征在于，包含：
    提供未硫化橡胶层及热熔胶粉末，所述热熔胶粉末包含热塑性聚氨酯；
    使所述热熔胶粉末分散于所述未硫化橡胶层的表面上；及
    热压具有所述热熔胶粉末的所述未硫化橡胶层，以获得所述硫化橡胶物品。
  2. 如权利要求1所述的制法，其特征在于，其中所述未硫化橡胶层是包含聚异戊二烯橡胶(IR)、苯乙烯.丁二烯共聚橡胶(SBR)、聚丁二烯橡胶(BR)、丙烯腈.丁二烯共聚橡胶(NBR)、异戊二烯.异丁烯共聚橡胶(IIR)、乙烯.丙烯-二烯共聚橡胶(EPDM)、或卤化丁基橡胶(HR)。
  3. 如权利要求1所述的制法，其特征在于，其中所述热塑性聚氨酯以凝胶渗透层析仪(GPC)量测的分子量(Mw)范围为5,000至100,000。
  4. 如权利要求1所述的制法，其特征在于，其中所述热塑性聚氨酯的熔融黏度范围为1,000到20,000cps。
  5. 如权利要求1所述的制法，其特征在于，其中以镭射粒径分析仪(Laser Diffraction Particle Size Analyzer)量测所述热熔胶粉末的粒径范围为50-1,000um。
  6. 如权利要求1所述的制法，其特征在于，其中在使所述热熔胶粉末分散于所述未硫化橡胶层的所述表面上的步骤前，还包含形成黏着层于所述表面上。
  7. 一种硫化橡胶物品，其特征在于，是得自于以权利要求1所述的制法。
  8. 一种硫化橡胶物品，其特征在于，包含硫化橡胶层及热熔胶层于所述硫化橡胶层上方，所述热熔胶层包含热塑性聚氨酯，其中所述热熔胶层具有凹凸不平的外形，所述凹凸不平的外形是将具有热熔胶粉末的未硫化橡胶层进行热压以形成所述硫化橡胶层时同时形成。
  9. 如权利要求8所述的硫化橡胶物品，其特征在于，其中所述热熔胶层及所述硫化橡胶层之间还包含黏着层。
  10. 如权利要求8所述的硫化橡胶物品，其特征在于，其中所述硫化橡胶物品于室温下不具有黏性。
  11. 一种硫化橡胶物品与对象结合的方法，其特征在于，包含：
    提供复数个粒子，所述复数个粒子包含发泡热塑性聚氨基甲酸酯；
    将如权利要求7至10中所述任一项的硫化橡胶物品置放于所述复数个粒子上；以及
    经微波照射所述复数个粒子以形成对象，其中所述硫化橡胶物品同时与所述对象结合。
  12. 如权利要求11所述的方法，其特征在于，其中所述硫化橡胶物品为鞋大底，所述对象为鞋中底。
PCT/CN2017/079613 2017-04-06 2017-04-06 硫化橡胶物品及其制法与应用 WO2018184173A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/079613 WO2018184173A1 (zh) 2017-04-06 2017-04-06 硫化橡胶物品及其制法与应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/079613 WO2018184173A1 (zh) 2017-04-06 2017-04-06 硫化橡胶物品及其制法与应用

Publications (1)

Publication Number Publication Date
WO2018184173A1 true WO2018184173A1 (zh) 2018-10-11

Family

ID=63713043

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/079613 WO2018184173A1 (zh) 2017-04-06 2017-04-06 硫化橡胶物品及其制法与应用

Country Status (1)

Country Link
WO (1) WO2018184173A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101637976A (zh) * 2008-07-31 2010-02-03 张廷源 鞋组合物的制造方法
CN103522564A (zh) * 2013-09-05 2014-01-22 隆典实业股份有限公司 复合式鞋底的制法
CN104559843A (zh) * 2014-12-31 2015-04-29 广州鹿山新材料股份有限公司 一种橡胶/发泡eva复合鞋底粘接用热熔胶膜及其制备方法
TW201536202A (zh) * 2014-03-20 2015-10-01 Cherng Tay Technology Co Ltd 鞋底構造接著製程方法
CN105768345A (zh) * 2016-04-22 2016-07-20 福建登泰科技有限公司 一种模内一体成型鞋底及其制作工艺

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101637976A (zh) * 2008-07-31 2010-02-03 张廷源 鞋组合物的制造方法
CN103522564A (zh) * 2013-09-05 2014-01-22 隆典实业股份有限公司 复合式鞋底的制法
TW201536202A (zh) * 2014-03-20 2015-10-01 Cherng Tay Technology Co Ltd 鞋底構造接著製程方法
CN104559843A (zh) * 2014-12-31 2015-04-29 广州鹿山新材料股份有限公司 一种橡胶/发泡eva复合鞋底粘接用热熔胶膜及其制备方法
CN105768345A (zh) * 2016-04-22 2016-07-20 福建登泰科技有限公司 一种模内一体成型鞋底及其制作工艺

Similar Documents

Publication Publication Date Title
US2749960A (en) Composite structures
CN110272711A (zh) 可热硫化的压敏胶粘剂及其制造方法
JPS6176363A (ja) 加硫ゴム製品の製造法
TWI777932B (zh) 用於製造及黏結鞋用橡膠外底之方法
CN106490753B (zh) 劳保靴制作方法
KR20120062715A (ko) 다기능 프라이머를 이용한 신발의 제조 방법
KR101108549B1 (ko) 포화 신발용 수성형 프라이머 조성물
WO2018184173A1 (zh) 硫化橡胶物品及其制法与应用
Paiva et al. Importance of the surface treatment in the peeling strength of joints for the shoes industry
TW201836844A (zh) 硫化橡膠物品及其製法與應用
US20150283796A1 (en) Composition for laminated climbing shoes
CN109689356A (zh) 用于聚氨酯粘合剂的氨基甲酸盐树脂
KR101998314B1 (ko) 신발창의 제조 방법
KR101854475B1 (ko) 다기능 프라이머 및 이를 이용한 신발의 제조 방법
US20170297287A1 (en) Production method of glueless pasted integrally modeling shoe sole
JP3586418B2 (ja) 靴底補修剤及びそれを用いた靴底補修方法
CA2544102A1 (en) Application of film adhesive for post mold application
KR20000063527A (ko) 겉창과 중창의 동시 성형 및 접착으로 이루어진 신발용밑창 및 그 제조방법
KR20180001065A (ko) 고무시트층과 열가소성 합성수지층을 포함하는 복합 고무 시트 및 그 제조 방법
US2706698A (en) Method of manufacturing footwear from naturally tacky pre-cured rubber
KR870000952B1 (ko) 신발 밑창의 제조방법
TW201734075A (zh) 彈性體構件及工作機械用密封構件
KR20000059180A (ko) 겉창과 중창의 동시 성형 및 접착으로 이루어진 신발용밑창 및 그 제조방법
CN114075409B (zh) 具有聚氨酯载体的胶带
US20230202129A1 (en) Method for adhering cured rubber components

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17904803

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17904803

Country of ref document: EP

Kind code of ref document: A1