WO2020147310A1 - 一种含有微胶囊的水性多次可移压敏胶及其制备方法 - Google Patents

一种含有微胶囊的水性多次可移压敏胶及其制备方法 Download PDF

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WO2020147310A1
WO2020147310A1 PCT/CN2019/102266 CN2019102266W WO2020147310A1 WO 2020147310 A1 WO2020147310 A1 WO 2020147310A1 CN 2019102266 W CN2019102266 W CN 2019102266W WO 2020147310 A1 WO2020147310 A1 WO 2020147310A1
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sensitive adhesive
component
polymer
water
pressure
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PCT/CN2019/102266
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English (en)
French (fr)
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周广滨
纳赛尔纳比尔
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中山荣思东数码科技有限公司
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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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences
    • C09J183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to a removable pressure-sensitive adhesive with a special structure and a preparation method thereof, in particular to a water-based multi-removable pressure-sensitive adhesive containing microcapsules and a preparation method thereof.
  • Pressure sensitive adhesive is a type of adhesive that is sensitive to pressure. Pressure-sensitive adhesives can form a relatively strong bonding force under a small force. The bonding force formed between the surfaces of two objects is mainly van der Waals force and other polar forces. Therefore, after the bonding surface is formed, the structure of the bonding surface is mostly not destroyed, and its bonding force can be maintained for a relatively long time.
  • Solvent-based pressure-sensitive adhesives still contain organic solvents (VOC) such as toluene, xylene, and ethyl acetate after they are prepared into end products, so they are not suitable for indoor and unventilated occasions; water-based pressure-sensitive adhesives use water as a solvent.
  • VOC organic solvents
  • the finished product does not contain harmful substances such as VOC and can be used in various occasions with special requirements for health and environmental protection.
  • Pressure-sensitive adhesives can be divided into permanent adhesives, removable adhesives and multiple removable adhesives from the functional perspective. Permanent glue will leave residual glue on the sticking surface after use. It takes time and effort to clean up and easily destroys the original interface. Therefore, it can only be used for one time. Pressure sensitive glue containing solvents can also cause secondary pollution; solvent-based or a few water-based can be removed Glue removal is mostly two-component acrylic pressure-sensitive adhesives, which are often limited to a specific interface or substrate, so their use range is relatively small, which affects the widespread popularity of products. There are a few domestic acrylic water-based removable glue products, but they all have problems such as poor glue cohesion, residual glue on the sticking surface, poor stability, incompatibility with various substrates and different interfaces, and difficulty in achieving multiple removability.
  • the invention provides an aqueous multi-removable pressure-sensitive adhesive containing microcapsules and a preparation method thereof.
  • An aqueous multi-removable pressure-sensitive adhesive containing microcapsules which is characterized in that it contains the following components by weight:
  • Component 1 50 ⁇ 85 parts of microcapsule structure polymer
  • Component 2 10-30 parts of soft segment polymer
  • Component 3 5-15 parts of multi-component star polymer
  • Component 4 0.2 to 2 parts of pH regulator.
  • microcapsule structure polymer of the present invention is a capsular block polymer with a "core-arm-shell" structure containing high-viscosity groups, and its cross-sectional structure is shown in Figure 1.
  • the microcapsule structure polymer of the present invention is a white emulsion containing a microcapsule-like block polymer, with a solid content of 36%;
  • the soft segment polymer of the present invention is one or two of polyurethane or butyl acrylate.
  • the general structural formula of the multi-component star polymer of the present invention is:
  • R is selected from C1 ⁇ C12 straight-linked alkyl group, C1 ⁇ C12 branched chain alkyl group, substituted or unsubstituted C6 ⁇ C10 aryl group, halogen substituted C1 ⁇ C10 alkyl group , COO -, SO3H -, H 2 PO 4 - substituted alkyl.
  • the pH regulator in the present invention is one or more of ammonia, sodium carbonate, sodium bicarbonate and sodium hydroxide.
  • the multi-component star-shaped macromolecule polymer of the present invention is an amphiphilic macromolecule with a multifunctional silicon-oxygen cyclic compound as a core and a multi-component long-chain polymer as a branch.
  • the functional groups at the end of the long arm of the amphiphilic polymer can interact with polyacrylate latex particles to form a variety of reversible physical cross-linking networks, thereby enhancing the fluid
  • the rheological stability of the colloidal emulsion changes the characteristic that the viscosity of the colloidal emulsion fluctuates greatly with the change of the solid content; after most of the colloidal water is removed, the lipophilic core and outer arm functional groups on the amphiphilic polymer occupy the pressure-sensitive adhesive
  • the surface improves the adhesion of the colloid on the surface of various inert media (such as polyethylene, polypropylene, polyvinyl chloride, etc.), and reduces the unit number of polar groups on the col
  • the microcapsule structure polymer of the present invention is a micron soft latex particle with a "core-outer arm-shell" three-layer structure, and its center is a "core” formed by polymerization and crosslinking of a hydrophobic monomer.
  • the outer surface of the core is grafted with a large number of flexible hydrophilic long chains of polymers containing strong polar groups to form "outer arms”.
  • a hydrophobic segment of a certain molecular weight is connected to the end of each outer arm, and these hydrophobic ends are attracted to each other by van der Waals forces to form a semi-open "shell” that protects the polar groups on the inner outer arm .
  • the shell composed of each hydrophobic chain segment will open, exposing the flexible outer arm containing a large number of strong polar groups inside, and form a sticking effect with the interface; and when the external force is removed, the above contains a large amount of The outer arm of the strong polar group will shrink back into the "shell” to protect the polar group.
  • the viscosity of the pressure-sensitive adhesive system can be adjusted by the relative ratio of the microcapsule structure polymer to the soft segment polymer.
  • the area occupied by the microcapsule structure polymer belongs to the high-viscosity area, while the area occupied by the soft segment polymer belongs to the low-viscosity area.
  • the adhesive layer can be moved many times.
  • microsphere glue technology that is, the introduction of organic or inorganic hard microspheres into the pressure-sensitive adhesive system, so that the area occupied by the microspheres forms microscopic protrusions.
  • the gaps between the microspheres form microscopic depressions.
  • the addition of hard microspheres reduces the flexibility and deformability of the pressure-sensitive adhesive layer to a certain extent, resulting in traditional removable pressure-sensitive adhesives that tend to appear due to the small effective bonding area when pasting rough interfaces.
  • the phenomenon of shedding failure has greatly restricted its versatility.
  • the sticky groups in the traditional removable glue layer are always exposed, and it is easy to absorb dust in the air and lose its viscosity during storage. Therefore, it can only be moved, and it is difficult to move multiple times.
  • the present invention provides a water-based multi-removable pressure-sensitive adhesive containing microcapsules.
  • the key technology is to introduce soft microcapsule particles with a special three-layer structure into the pressure-sensitive adhesive system.
  • the addition of soft microcapsules not only enables the adhesive layer to form a high-viscosity-low-viscosity alternating microstructure to obtain removable properties, but also retains the flexibility and deformability of the pressure-sensitive adhesive layer to the greatest extent, making this
  • a pressure-sensitive adhesive is pasted with a relatively rough structure, it can still achieve sufficient contact with the pasting interface through a large deformation of the adhesive layer to prevent the product from falling off.
  • the outer shell of the soft microcapsule will be closed to protect the viscous groups on the inner and outer arms, thus making this pressure sensitive adhesive more Used repeatedly.
  • Figure 1 is a schematic diagram of the structure of a microcapsule structure polymer.
  • the invention provides a method for preparing a water-based multi-removable pressure-sensitive adhesive containing microcapsules.
  • the pressure-sensitive adhesive solves the problem that the existing solvent-based pressure-sensitive adhesive has poor environmental friendliness, while the performance of the water-based acrylic pressure-sensitive adhesive Poor technical problems.
  • the soft segment polymer comes from Guangzhou Aiport Digital Technology Co., Ltd.
  • the supplier of star polymer and microcapsule polymer is: Zhongshan Rongsidong Digital Technology Co., Ltd.
  • Component 1 50 parts of microcapsule structure polymer
  • Component 2 30 parts of soft segment polymer
  • Component 3 15 parts of multi-component star polymer
  • Component 4 0.2 parts of ammonia water.
  • Component 1 70 parts of microcapsule structure polymer
  • Component 2 20 parts of soft segment polymer
  • Component 3 10 parts of multi-component star polymer
  • Component 4 0.2 parts of ammonia water.
  • Example 1 The same preparation method as in Example 1 obtains multiple removable pressure-sensitive adhesives.
  • Component 1 85 parts of microcapsule structure polymer
  • Component 2 10 parts of soft segment polymer
  • Component 3 5 parts of multi-component star polymer
  • Component 4 0.2 parts of ammonia water.
  • Example 1 The same preparation method as in Example 1 obtains multiple removable pressure-sensitive adhesives.
  • the preparation method of the removable tape use an 80 ⁇ m wire rod coater to coat the prepared water-based microcapsule-containing multiple removable pressure-sensitive adhesive on a PET film, bake it in an oven at 105°C for 5 minutes, take it out, cool down, and cover Put on the release paper to obtain multiple removable pressure-sensitive adhesive tapes;
  • the initial adhesion test method uses: GBT 31125-2014 tape initial adhesion test method ring method method B;
  • the peel force test method uses: GB/T 2792-2014 Test method method 1 of the peel strength of adhesive tape;
  • Adhesive test method use: GB/T 4851-2014 Adhesive tape test method A;
  • the removable time ends with the appearance of residual glue.
  • test results show that the water-based removable pressure-sensitive adhesive prepared by the present invention, compared with the commercially available acrylate pressure-sensitive adhesive, maintains similar initial tack, but has a smaller peeling force, and has a far greater number of removals than ordinary acrylate adhesives. Removable time; at the same time, because of its safety and environmental protection, it has higher practical value in the fields of wallpaper, label, and packaging.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

本发明公开了一种含有微胶囊的水性多次可移压敏胶及其制备方法。该压敏胶由微胶囊结构聚合物，软链段聚合物，多组分星形高分子聚合物，pH调节剂组成。本发明将微胶囊结构聚合物和多组分星型高分子聚合物引入到水性压敏胶配方中，增强了胶体的稳定性，提高了胶体的内聚力；结合微胶囊结构聚合物的特殊性能，使胶体及其应用产品具备多次可移、粘贴表面不留残胶、内聚力好、通用性强、水性环保等特点，从而产生出各种特殊用途。

Description

一种含有微胶囊的水性多次可移压敏胶及其制备方法 技术领域：
本发明涉及一种具有特殊结构的可移压敏胶及其制备方法，尤其涉及一种含有微胶囊的水性多次可移压敏胶及其制备方法。
背景技术：
压敏胶是一类对压力具有敏感性的胶粘剂。压敏胶粘剂在较小的作用力下就能形成比较牢固的粘接力，它在两物体表面之间形成的粘接力主要是范德华力以及其它极性作用力。因此，粘接面形成后，粘接表面的结构大多没有被破坏，其粘接力能够保持相对较长的时间。
市场上压敏胶产品主要分为溶剂型和水性两大类。溶剂型压敏胶在制备成终端产品后仍含有甲苯、二甲苯和乙酸乙酯等有机溶剂(VOC)，因而不宜在室内和无通风的场合使用；水性压敏胶则以水为溶剂，制成终端产品后不含VOC等有害物质，可以在各种对健康和环保有特殊要求的场合使用。
压敏胶从使用功能上可分为永久性胶，可移胶和多次可移胶。永久性胶使用后会在粘贴表面遗留残胶，清理费时费力，容易破坏原有界面，因而只能一次性使用，含有溶剂的压敏胶还会造成二次污染；溶剂型或少数水性可移除胶大多为双组份丙烯酸类压敏胶，常常局限于某个特定的界面或基材，因而其使用范围较小，影响产品大范围普及。国内现有少数丙烯酸类水性可移胶产品，但都普遍存在胶水内聚力差，粘贴表面遗留残胶，稳定性差，不能兼容各种基材和不同界面，并难以达到多次可移等问题。
发明内容：
本发明提供了一种含有微胶囊的水性多次可移压敏胶及其制备方法。通过引入微胶囊结构的聚合物和多组分星型高分子聚合物，得到一种水性绿色环保、多次可移、粘贴表面不留残胶、内聚力好、通用性强的水性多次可移压敏胶。
为了实现上述特性，本发明采用如下技术方案：
一种含有微胶囊的水性多次可移压敏胶，其特征在于包含以下重量份数组分：
组分1：微胶囊结构聚合物50～85份；
组分2：软链段聚合物10～30份；
组分3：多组分星形高分子聚合物5～15份；；
组分4：pH调节剂0.2～2份。
本发明所述的微胶囊结构聚合物是一种具有“核‐臂‐壳”结构内含高粘性基团的囊状嵌段聚合物，其剖面结构示意如图1所示。
本发明所述的微胶囊结构聚合物为含有微胶囊状嵌段聚合物的白色乳液，固含量为36％；
本发明所述的软链段聚合物为聚氨酯或丁基丙烯酸酯中的一种或两种。
本发明所述的多组分星形高分子聚合物的结构通式为：
Figure PCTCN2019102266-appb-000001
其中n1＝4～5,n2＝3～39，R选自C1～C12直连烷基，C1～C12支链烷基，取代或未取代的C6～C10芳基，卤素取代C1～C10烷基，COO -、SO3H -、H 2PO 4 -取代烷基。
本发明所述的pH调节剂为氨水，碳酸钠，碳酸氢钠，氢氧化钠中的一种或几种。
本发明中一种制备上述水性多次可移压敏胶的方法，其特征在于包括以下具体步骤:
(1)将组分1与组分2倒入反应器中混合，以较低转速(300±100rpm)缓慢均匀分散15min以上；
(2)将组分3和水混合溶解后加入反应器中，继续以较低转速(300±100rpm)缓慢搅拌30min以上；
(3)加入组分4调节乳液pH至9-10，搅拌30min即可。
本发明所述的多组分星型高分子聚合物是一种以多官能团硅氧环状类化合物为核体，以多组分长链聚合物为支链的两亲性高分子。将其应用于胶体乳液的配方中，其两亲性高分子聚合物长臂末端的功能性基团可以与聚丙烯酸酯类乳胶粒相互作用，形成多种可逆的物理交联网络，从而增强流体的流变稳定性，改变了胶体乳液的黏度随固含量改变而大起大落的特性；在胶体水分大部分去除后，两亲性高分子上亲油性核心和外臂功能性基团占据压敏胶的表面，改善了胶体在各种惰性介质表面(如聚乙烯，聚丙烯，聚氯乙烯等)的粘着力，又可减少胶体表面极性基团的单位数量从而调节胶体对粘贴表面(家具，各种塑料平面，玻璃，皮革，涂过乳胶漆的墙面，等等)的剥离强度，使胶体具备移除时不留残胶 的特性。
本发明所述的微胶囊结构聚合物是具有“核‐外臂‐壳”三层结构的微米软性乳胶粒，其中心是由疏水性单体聚合并交联而形成的“核”。在核的外表面接枝大量含有强极性基团高分子柔性亲水性长链，从而形成“外臂”。在每个外臂的末端连接着一定分子量的疏水性链段，且这些疏水性末端通过范德华力相互吸引，形成半开放的“壳”，起到保护内部外臂上的极性基团的作用。在外界压力作用下，由各疏水链段组成的壳，将会打开，暴露出内部含有大量强极性基团的柔性外臂，并与界面形成粘贴作用；而当外力撤去后，上述含有大量强极性基团的外臂将收缩回“壳”内，从而将极性基团保护起来。当微胶囊结构聚合物和软链段聚合物以及多组分星形高分子聚合物混合后，压敏胶体系的粘性可以由微胶囊结构聚合物与软链段聚合物的相对比例来调节。从微观结构上看，被微胶囊结构聚合物占据的区域属于高粘区，而被软链段聚合物占据的区域属于低粘区，借助自身这种高粘‐低粘交替的微观结构，赋予了胶层多次可移的功能。
本发明的创新点与有益效果：
传统的可移压敏胶，绝大多数是采用微球胶技术，即在压敏胶体系中引入有机或无机的硬质微球，使得被微球占据的区域形成微观凸起，微球与微球之间的间隙则形成了微观的凹陷。当压敏胶与被粘贴界面粘合时，凸起部分能够与粘贴表面充分接触，形成高粘区，而凹陷部分仅能部分或不与粘贴表面接触，形成低粘区。借助上述这种高粘-低粘交替的微观结果，赋予压敏胶可移特性。然而，硬质微球的加入在一定程度上降低了压敏胶胶层的柔韧性和可变形性，导致传统可移压敏胶在粘贴较粗糙界面时，容易由于有效粘贴面积过小而出现脱落失效的现象，其通用性受到了极大的限制。此外，传统可移胶胶层中的粘性基团始终处于裸露状态，在存放过程中极易吸附空气中的粉尘而失去粘性，因而只能做到可移，而难以实现多次可移。
如前文所述，本发明所提供的是一种含有微胶囊的水性多次可移压敏胶，其技术关键在于在压敏胶体系中引入具有特殊三层结构的软质微胶囊微粒。软质微胶囊的加入，不仅能够使胶层形成高粘‐低粘交替排列的微观结构以获得可移特性，而且最大程度的保留的压敏胶胶层的柔韧性和可变形性，使得这种压敏胶在粘贴较粗糙结构时，仍能够通过胶层的大幅度变形实现与粘贴界面的充分接触，防止产品脱落。另一方面，在无外界压力作用下(即存放条件下)，软质微胶囊外部的壳将会闭合，将内部外臂上的粘性基团保护起来，因而使得此种压敏胶能够实现多次反复使用。
附图说明：
图1为微胶囊结构聚合物的结构示意图。
具体实施方式：
本发明提供了一种含有微胶囊的水性多次可移压敏胶的制备方法，该压敏胶解决了现有的溶剂型压敏胶环境友好性较差，而水性丙烯酸酯压敏胶性能较差的技术问题。
为使得本发明的发明目的、特征、优点能够更加的明显和易懂，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述。显然，下面所描述的实施例仅仅是本发明一部分实施例，而非全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
原料说明：
软链段聚合物来自广州爱波特数码科技有限公司
星型聚合物和微胶囊聚合物的供应商为：中山荣思东数码科技有限公司
实施例1：
1.水性可移压敏胶重量组分：
组分1：微胶囊结构聚合物50份；
组分2：软链段聚合物30份；
组分3：多组分星形高分子聚合物15份；；
组分4：氨水0.2份。
2.压敏胶的制备步骤：
取30份软链段聚合物于反应器中，加入50份微胶囊结构聚合物，用搅拌器以300rpm转速缓慢搅拌20min，使乳液均匀混合。加入15份多组分星形高分子聚合物和14.6份水混合后继续搅拌30min，最后将0.2份氨水加入乳液中继续搅拌30min，得到含微胶囊的水性多次可移压敏胶成品。
实施例2：
1.水性可移压敏胶重量组分：
组分1：微胶囊结构聚合物70份；
组分2：软链段聚合物20份；
组分3：多组分星形高分子聚合物10份；
组分4：氨水0.2份。
2.压敏胶的制备步骤：
同实施例1的制备方法得到多次可移压敏胶。
实施例3：
1.水性可移压敏胶重量组分：
组分1：微胶囊结构聚合物85份；
组分2：软链段聚合物10份；
组分3：多组分星形高分子聚合物5份；
组分4：氨水0.2份。
2.压敏胶的制备步骤：
同实施例1的制备方法得到多次可移压敏胶。
对比例1：
为了充分说明本发明的有益效果，选取市售某化工厂型号为1008‐55A的OPP水性丙烯酸酯压敏胶带作为对比例，与本发明实施例进行部分性能的对比。
实施例1‐3与对比例所制备的压敏胶带性能测试如表1所示：
表1：
Figure PCTCN2019102266-appb-000002
表1说明：
可移胶带的制备方法：用80μm线棒涂布器将制得的含微胶囊的水性多次可移压敏胶涂附于PET膜上，于105℃烘箱中烘5分钟，取出降温，覆盖上离型纸，即得到多次可移压敏胶胶带；
初粘力测试方法使用：GBT 31125-2014胶带初粘性试验方法环形法方法B；
剥离力测试方法使用：GB/T 2792-2014胶粘带剥离强度的试验方法方法1；
持粘性测试方法使用：GB/T 4851-2014胶粘带持粘性的试验方法方法A；
可移次数测试以粘黏力明显下降或出现残胶为终点；
可移时间以出现残胶为终点。
测试结果表明：本发明制备的水性可移压敏胶相对于市售丙烯酸酯压敏胶，在保持类似初粘力的同时，剥离力更小，具有远大于普通丙烯酸酯胶的可移次数与可移时间；同时由于其安全环保，在墙纸，标签，包装等领域，拥有更高的实用价值。

Claims (6)

  1. 一种含有微胶囊的水性多次可移压敏胶，其特征在于包含以下重量份数组分：
    组分1：微胶囊结构聚合物50～85份；
    组分2：软链段聚合物10～30份；
    组分3：多组分星形高分子聚合物5～15份；
    组分4：pH调节剂0.2～2份。
  2. 根据权利要求1所述的一种含有微胶囊的水性多次可移压敏胶，其特征在于所述的微胶囊结构聚合物为具有“核‐臂‐壳”结构，内含高粘性基团的囊状嵌段聚合物。
  3. 根据权利要求1所述的一种含有微胶囊的水性多次可移压敏胶，其特征在于所述的软链段聚合物为聚氨酯或丁基丙烯酸酯中的一种或两种。
  4. 根据权利要求1所述的一种含有微胶囊的水性多次可移压敏胶，其特征在于所述的多组分星形高分子聚合物的结构通式为：
    Figure PCTCN2019102266-appb-100001
    其中n1＝4～5,n2＝3～39，R选自C1～C12直连烷基，C1～C12支链烷基，取代或未取代的C6～C10芳基，卤素取代C1～C10烷基，COO -、SO 3H -、H 2PO 4 -、OH -、NH 2、SO 3 -取代烷基。
  5. 根据权利要求1所述的一种含有微胶囊的水性多次可移压敏胶，其特征在于所述的pH调节剂为氨水，碳酸钠，碳酸氢钠，氢氧化钠中的一种或几种。
  6. 根据权利要求1所述的一种含有微胶囊的水性多次可移压敏胶的制备方法，其特征在于包含以下具体步骤：
    (1)将组分1与组分2倒入反应器中混合，以较低转速(300±100rpm)缓慢均匀分散15min以上；
    (2)将组分3和水混合溶解后加入反应器中，继续以较低转速(300±100rpm)缓慢搅拌30min以上；
    (3)加入组分4调节乳液pH至9-10，搅拌30min即可。
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