WO2018177288A1 - 一种压敏胶黏剂及其制备方法 - Google Patents

一种压敏胶黏剂及其制备方法 Download PDF

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WO2018177288A1
WO2018177288A1 PCT/CN2018/080683 CN2018080683W WO2018177288A1 WO 2018177288 A1 WO2018177288 A1 WO 2018177288A1 CN 2018080683 W CN2018080683 W CN 2018080683W WO 2018177288 A1 WO2018177288 A1 WO 2018177288A1
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prepolymer
sensitive adhesive
pressure
weight
acrylate
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PCT/CN2018/080683
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English (en)
French (fr)
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泽登纯一
冈琦哲也
陈维
姜云
陈田安
高昂
杨春强
江华
邹学良
周玉波
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苏州凡赛特材料科技有限公司
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Priority to JP2019545274A priority Critical patent/JP6830281B2/ja
Publication of WO2018177288A1 publication Critical patent/WO2018177288A1/zh

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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
    • 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
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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

Definitions

  • the present application relates to the field of optical display, and in particular to an optical pressure sensitive adhesive for display device bonding and a preparation method thereof.
  • Acrylic resin is one of the commonly used pressure-sensitive adhesives. It is widely used because of its many advantages: 1. It exhibits high adhesion to transparent materials such as PET optical film or glass; 2. It is colorless and transparent and has good weather resistance. 3, no additives, simple formula; 4, the use of copolymerization and cross-linking can be made to meet a variety of different performance requirements of pressure-sensitive adhesives.
  • acrylic resin adhesives still have certain limitations. For example, in certain applications, adhesives are required to have a lower dielectric constant (typically 2 to 3 Dk is required at 1 kHz to 1 MHz), but conventional acrylic resins have double bonds and high dielectric constants, which is difficult to meet. .
  • a first object of the present application is to provide a pressure-sensitive adhesive having a low dielectric constant at a temperature of 1 kHz to 1 MHz, and having both high peel strength and high transmittance. The application prospects are more extensive.
  • a second object of the present application is to provide a method for preparing the above pressure-sensitive adhesive, which is simple in process and convenient in preparation, and thus is easy to promote new products.
  • a pressure-sensitive adhesive mainly composed of one or more acrylate monomers and oligomers polymerized by a photoinitiator
  • the acrylate monomer is a saturated acrylic acid ester or an alkyl alcohol saturated alcohol ester
  • the weight ratio of the acrylate monomer is 10% or more, preferably 15% or more, more preferably 20% or more;
  • the oligomer has a molecular weight of 20,000 or more and is selected from the group consisting of an acrylate prepolymer, an epoxy prepolymer, a silicone prepolymer, a polyurethane prepolymer, a polyether prepolymer, and a polyhydroxy polyolefin oligomer.
  • an acrylate prepolymer an epoxy prepolymer, a silicone prepolymer, a polyurethane prepolymer, a polyether prepolymer, and a polyhydroxy polyolefin oligomer.
  • One or more of a polybutadiene prepolymer and a fluorine-modified prepolymer are examples of a polybutadiene prepolymer.
  • the present application solves the technical problem that the dielectric constant cannot adapt to the new technology product.
  • the main principle used to solve the problem is to reduce the number of double bonds in the adhesive to lower the dielectric constant.
  • the adhesive prepared by the above formula has excellent comprehensive performance: the peel strength is maintained at 8N/25mm or more (180°), and the dielectric constant at 1 kHz to 1 MHz is maintained at 2-3.
  • the transmittance at a wavelength of 550 nm is 99% or more.
  • the alkyl group is selected from a C1-C10 alkyl group, preferably a C1-C6 alkyl group. That is, the substituent on the acrylic acid may be selected from methyl, ethyl, propyl, butyl, isobutyl and the like.
  • the saturated alcohol is selected from a C1-C18 saturated monohydric or polyhydric alcohol, preferably a C2-C8 saturated monohydric or polyhydric alcohol, preferably a C4-C8 saturated monohydric or polyhydric alcohol.
  • a C1-C18 saturated monohydric or polyhydric alcohol preferably a C2-C8 saturated monohydric or polyhydric alcohol, preferably a C4-C8 saturated monohydric or polyhydric alcohol.
  • the saturated alcohol herein refers to a saturated alcohol used in all of the above esters. It is to be noted that the kind of the saturated alcohol selected for each compound is independent, that is, any one of the above is independently selected.
  • the monomer type has a large influence on the peel strength of the adhesive, and secondly affects the dielectric constant.
  • the acrylate monomer is a mixture of isooctyl acrylate and 4-hydroxybutyl acrylate, and the weight ratio of the two is preferably 1: 1 or less, that is, the amount of 4-hydroxybutyl acrylate is preferably less than isooctyl acrylate.
  • the oligomer is selected from one or a mixture of an acrylate prepolymer, a polyurethane prepolymer.
  • the oligomer has a molecular weight of 20,000 to 40,000, or 30,000 to 60,000, or 40,000 to 70,000.
  • the type and molecular weight of the oligomer mainly affect the peel strength of the adhesive. If the choice is reasonable, the peel strength shown is much higher than that of the existing product.
  • the weight ratio of the oligomer is 20% or more, preferably 25% or more, more preferably 30% or more.
  • the weight ratio of the oligomer has an important influence on the peel strength and dielectric constant of the adhesive, preferably 20% or more, for example, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55. %, 60%, 65% or 70%, etc.
  • an additive at the time of polymerization, the additive being selected from the group consisting of a crosslinking agent, a tackifier, a plasticizer, an antistatic agent, a softener, a colorant, an antioxidant, and a leveling agent.
  • a crosslinking agent e.g., 1, 3-butanediol
  • a plasticizer e.g., 1, 3-butanediol
  • an antistatic agent e.g., 1, 3-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanethacrylate, 1, 4-butanedi
  • the additive is present in an amount of from 10 to 50% by weight.
  • the additive comprises a tackifier.
  • the additive comprises a tackifier, a light stabilizer, an antifoaming agent.
  • the various additives described above may be of a conventional type, but the effects of the type and amount on the peel strength and the dielectric constant are extremely different for the present application.
  • the tackifier is preferably selected from the group consisting of terpene phenolic resins, and the content of the tackifier is preferably 15% by weight or more, preferably 20% by weight or more, more preferably 25% by weight or more.
  • the light stabilizer is selected from the group consisting of phenoxytriazines in an amount of from 0.1 to 0.3% by weight, preferably from 0.1 to 0.2% by weight.
  • the antifoaming agent is selected from the group consisting of polysiloxanes in an amount of from 0.1 to 0.3% by weight, preferably from 0.1 to 0.2% by weight.
  • the crosslinking agent is a polybasic acryl polyol ester, and/or a polyhydric methacrylic polyol ester; the poly-acid poly-altery here indicates a plurality of ester groups.
  • the polyol is selected from the group consisting of a glycol, a trihydric alcohol, a tetrahydric alcohol or a polyethylene glycol, preferably a saturated alcohol or a cycloalkyl alcohol, more preferably 1,4-butanediol, 1,6- Hexanediol, 1,9-nonanediol, tripropylene glycol, tricyclodecane dimethanol, 1,10-nonanediol, polyethylene glycol 200, polyethylene glycol 400, trimethylolpropane, double three One or more of methylolpropane, ethoxylated pentaerythritol, pentaerythritol, and dipentaerythritol.
  • the crosslinking agent has a weight ratio of 0.1 to 3% by weight.
  • the pressure-sensitive adhesive described in the present application has another advantage: the hot pressing and curing process of the existing products can be used, thereby reducing the cost of product upgrade (including equipment replacement, process condition control, operator training, etc.) .
  • the photoinitiator is benzil dimethyl ether, dialkoxyacetophenone, methyl benzoylformate, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- Methyl-1-phenyl-1-propanone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-phenylbenzyl-2-dimethylamine 1-(4-morpholinebenzylphenyl)butanone, 2,4,6-trimethylbenzoylphenylphosphine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2 , 4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone and 4- a mixture of one or two or more of dimethylamino-benzoic acid ethy
  • Fig. 1 is a graph showing changes in dielectric constant with frequency of an adhesive obtained in Examples and Comparative Examples of the present application.
  • the present application solves the technical problem that the dielectric constant cannot adapt to the new technology product.
  • the main principle used to solve the problem is to reduce the number of double bonds in the adhesive to lower the dielectric constant.
  • it has been found that merely reducing the number of double bonds without considering other factors does not achieve good results, mainly because the peel strength is extremely low and thus the practical value is lost, or other properties such as transmittance are greatly reduced.
  • In order to obtain a practical adhesive in order to reduce the number of double bonds, it is also necessary to use a specific type, specific content of acrylate monomer to copolymerize with a specific type of prepolymer.
  • the basic plan is as follows:
  • the saturated acrylate monomer is formed from acrylic acid or alkyl acrylate and a saturated alcohol
  • the weight ratio of the acrylate monomer is 10% or more, preferably 15% or more, more preferably 20% or more;
  • the oligomer has a molecular weight of 20,000 or more and is selected from the group consisting of a urethane prepolymer, an acrylate prepolymer, an epoxy prepolymer, a silicone prepolymer, a polyester prepolymer, and a polyether prepolymer.
  • a polyhydric polyolefin oligomer a polybutadiene prepolymer, and a fluorine-modified prepolymer.
  • the application optimizes the types and amounts of monomers and oligomers, and introduces additives to optimize the types and additions of additives, and obtains superior comprehensive performance.
  • the optimization results are as follows:
  • the alkylacrylic acid is selected from a C1-C10 alkyl-substituted acrylic acid, preferably a C1-C6 alkyl-substituted acrylic acid;
  • the saturated alcohol is selected from a C1-C18 saturated monohydric or polyhydric alcohol, preferably a C2-C8 saturated monohydric or polyhydric alcohol, preferably a C4-C8 saturated monohydric or polyhydric alcohol;
  • the saturated acrylate monomer is a mixture of 4-hydroxybutyl acrylate and isooctyl acrylate, and the weight ratio of the two is preferably 1:1 or less.
  • the oligomer has a molecular weight of 20,000 to 40,000, or 30,000 to 60,000, or 40,000 to 70,000;
  • the weight ratio of the oligomer is 20% or more, preferably 25% or more, more preferably 30% or more.
  • the polymerization also introduces an appropriate amount of additives selected from the group consisting of a crosslinking agent, a tackifier, a plasticizer, an antistatic agent, a softener, a colorant, an antioxidant, a leveling agent, a light stabilizer, and a consumer.
  • additives selected from the group consisting of a crosslinking agent, a tackifier, a plasticizer, an antistatic agent, a softener, a colorant, an antioxidant, a leveling agent, a light stabilizer, and a consumer.
  • additives selected from the group consisting of a crosslinking agent, a tackifier, a plasticizer, an antistatic agent, a softener, a colorant, an antioxidant, a leveling agent, a light stabilizer, and a consumer.
  • the additive is present in an amount of from 10 to 50% by weight.
  • the additive comprises a tackifier.
  • the additive comprises a tackifier, a light stabilizer, an antifoaming agent.
  • the tackifier is preferably selected from the group consisting of terpene phenolic resins, and the content of the tackifier is preferably 15% by weight or more, preferably 20% by weight or more, more preferably 25% by weight or more;
  • the light stabilizer is selected from the group consisting of phenoxytriazines in an amount of 0.1 to 0.3% by weight, preferably 0.1 to 0.2% by weight;
  • the antifoaming agent is selected from the group consisting of polysiloxanes in an amount of from 0.1 to 0.3% by weight, preferably from 0.1 to 0.2% by weight.
  • the crosslinking agent is an acrylic polyol ester, and/or a methacrylic polyol ester;
  • the polyol is selected from the group consisting of a glycol, a trihydric alcohol, a tetrahydric alcohol or a polyethylene glycol, preferably a saturated alcohol or a cycloalkyl alcohol, more preferably 1,4-butanediol, 1,6- Hexanediol, 1,9-nonanediol, tripropylene glycol, tricyclodecane dimethanol, 1,10-nonanediol, polyethylene glycol 200, polyethylene glycol 400, trimethylolpropane, double three One or more of methylolpropane, ethoxylated pentaerythritol, pentaerythritol, and dipentaerythritol;
  • the crosslinking agent has a weight ratio of 0.1 to 3% by weight.
  • the photoinitiator is 2,4,6-trimethylbenzoylphenylphosphine, and/or methyl benzoylformate, preferably a mixture of the two; preferably, the weight ratio of the two is 1 to 2:1.
  • the oligomer described in Table 1 is an acrylate prepolymer.
  • the preparation method is as follows:
  • liquid pressure-sensitive adhesive composition which can be directly applied to a substrate and cured by uv irradiation.
  • Example 1 The only difference from Example 1 was that the prepolymer was replaced with an acrylate prepolymer having a molecular weight of 15,000.
  • the oligomer described in Table 2 is an acrylate prepolymer.
  • the adhesive of the present application can maintain a stable dielectric constant over a wide frequency range, such as the trend of the embodiment 1 and the comparative examples 3, 5, as shown in FIG.
  • the adhesive of the present application has excellent overall properties.

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Abstract

本申请提供了一种光学丙烯酸酯压敏胶黏剂及其制备方法。本申请的压敏胶黏剂在1kHz～1MHz条件下具有较低的介电常数，并且兼具剥离强度高、透过率高等优点，应用前景更广泛。一种压敏胶黏剂，由一个或多个丙烯酸酯单体与低聚物在光引发剂的作用下聚合而成；所述丙烯酸酯单体为丙烯酸饱和醇酯或烷基丙烯酸饱和醇酯；所述丙烯酸酯单体的重量比为10％以上，优选15％以上，更优选20％以上；所述低聚物的分子量为20000以上，选自丙烯酸酯类预聚物、环氧预聚物、有机硅预聚物、聚氨酯预聚物、聚醚预聚物、多羟基聚烯烃低聚物、聚丁二烯预聚物和氟改性的预聚物中的一种或多种。

Description

一种压敏胶黏剂及其制备方法
相关申请的交叉引用
本申请要求于2017年03月30日提交中国专利局的申请号为201710200648.7、名称为“一种压敏胶黏剂及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及光学显示领域，尤其是涉及一种显器件贴合用光学压敏胶黏剂及其制备方法。
背景技术
随着光学显示器的广泛应用和快速发展，对光学压敏胶粘剂的要求越来越高。丙烯酸树脂是常用压敏胶粘剂之一，由于其具有以下诸多优点被广泛应用：1、对PET光学膜或者玻璃等透明的材料表现出高粘着力；2、外观无色透明并有很好的耐候性；3、不需要添加剂，配方简单；4、利用共聚和交联可以制得满足各种不同性能要求的压敏胶粘剂。
然而随着电子产品的快速发展，丙烯酸树脂胶粘剂仍存在一定的局限性。例如，在特定的应用中需要胶粘剂具备较低的介电常数(通常要求1kHz～1MHz条件下Dk为2～3)，但传统的丙烯酸树脂具有双键和高介电常数，很难满足此要求。
有鉴于此，特提出本申请。
发明内容
本申请的第一目的在于提供一种压敏胶黏剂，所述的压敏胶黏剂在1kHz～1MHz条件下具有较低的介电常数，并且兼具剥离强度高、透过率高等优点，应用前景更广泛。
本申请的第二目的在于提供上述压敏胶黏剂的制备方法，所述的方法流程简单，制备方便，因此更易推广新产品。
为了实现以上目的，本申请提供了以下技术方案：
一种压敏胶黏剂，主要由一个或多个丙烯酸酯单体与低聚物在光引发剂的作用下聚合而成；
所述丙烯酸酯单体为丙烯酸饱和醇酯或烷基丙烯酸饱和醇酯；
所述聚合物中，所述丙烯酸酯单体的重量比为10％以上，优选15％以上，更优选20％以上；
所述低聚物的分子量为20000以上，选自丙烯酸酯类预聚物、环氧预聚物、有机硅预聚物、聚氨酯预聚物、聚醚预聚物、多羟基聚烯烃低聚物、聚丁二烯预聚物、氟改性的预聚物中的一种或多种。
本申请解决了介电常数无法适应新科技产品的技术问题，解决该问题所采用的主要原理是：减少胶黏剂中的双键数量来降低介电常数。
在实际研究中发现，仅仅减少双键数量而不考虑其它因素并不能获得较好的效果，主要表现为剥离强度极其低因而失去了实用价值，或者如透过率等其它性能大幅降低。为获得有实用价值的胶黏剂，在减少双键数量的同时，还必须选用特定种类、特定含量的丙烯酸酯单体与特定种类的预聚物共聚。
通过研究发现，采用上文所述配方制成的胶黏剂具有优异的综合性能：剥离强度均保持在8N/25mm以上(180°)，1kHz～1MHz时的介电常数保持在2～3之间，波长550nm的透过率在99％以上。
以上基础方案还可以进一步改进，以达到更多的技术效果，例如：
优选地，所述烷基选自C1-C10的烷基，优选C1-C6的烷基。即丙烯酸上的取代基可选甲基、乙基、丙基、丁基、异丁基等。
优选地，所述饱和醇选自C1-C18的饱和一元醇或多元醇，优选C2-C8的饱和一元醇或多元醇，优选C4-C8的饱和一元醇或多元醇。例如，甲醇、乙醇、丙醇、丙二醇、正丁醇、异丁醇、丁二醇、正辛醇、异辛醇、十六醇、十八醇等。此处的饱和醇是指上文所有酯中用到的饱和醇，需要注意的是，每个化合物选择的饱和醇的种类是独立的，即独立地选择上述任一种类。
单体种类对胶黏剂的剥离强度有较大影响，其次影响介电常数。
为获得较大的剥离强度以及较低的介电常数，优选地，所述丙烯酸酯单体为丙烯酸异辛酯与4-羟基丁基丙烯酸酯的混合物，且两者的重量比优选在1:1以下，即4-羟基丁基丙烯酸酯的用量以小于丙烯酸异辛酯为优。
优选地，所述低聚物选自丙烯酸酯类预聚物、聚氨酯预聚物中的一种或两者混合。
优选地，所述低聚物的分子量为20000～40000，或者30000～60000，或者40000～70000。
低聚物的种类和分子量主要影响胶黏剂的剥离强度，若选择合理，所显示的剥离强度远远高于现有产品。
优选地，所述低聚物的重量比为20％以上，优选25％以上，更优选30％以上。
低聚物的重量比对胶黏剂的剥离强度和介电常数都有重要影响，优选20％以上，例如20％、25％、30％、35％、40％、45％、50％、55％、60％、65％或70％等。
为了改善胶黏剂的稳定性，还可以在聚合时引入适量添加剂，所述添加剂选自交联剂、增粘剂、增塑剂、抗静电剂、柔软剂、着色剂、抗氧化剂、流平剂、耐光剂、消泡剂、稳定剂和防腐剂中的一种或多种。
优选地，所述添加剂的含量为10-50wt％。
优选地，所述添加剂包括增粘剂。
优选地，所述添加剂包括增粘剂、耐光剂、消泡剂。
上述各种添加剂可采用常规的类型，但是针对本申请，类别及用量对剥离强度和介电常数的影响极为不同。
优选地，所述增粘剂优选选自萜烯酚醛树脂，所述增粘剂的含量优选为15wt％以上，优选20wt％以上，更优选25wt％以上。
增粘剂用量和种类选择不当时，不仅介电常数提高、稳定性降低，而且剥离强度也不会显著提高。若采用上述类型和用量，则可以避免。
优选地，所述耐光剂选自苯氧基三嗪类，含量为0.1～0.3wt％，优选0.1～0.2wt％。
优选地，所述消泡剂选自聚硅氧烷，含量为0.1～0.3wt％，优选0.1～0.2wt％。
优选地，所述交联剂为多元丙烯酸多元醇酯，和/或多元甲基丙烯酸多元醇酯；此处的酸前的多元表示有多个酯基。
优选地，所述多元醇选自二元醇、三元醇、四元醇或聚乙二醇，优选为饱和醇或环烷基醇，更优选1,4-丁二醇、1,6-己二醇、1,9-壬二醇、三丙二醇、三环癸烷二甲醇、1,10-癸二醇、聚乙二醇200、聚乙二醇400、三羟甲基丙烷、双三羟甲基丙烷、乙氧基化季戊四醇、季戊四醇和双季戊四醇中的一种或多种。
优选地，所述聚合物中，所述交联剂的重量比为0.1～3wt％。
另外，本申请所述的压敏胶黏剂还有另一优势：可采用现有产品的热压、固化工艺，从而降低产品升级的成本(包括设备更换、工艺条件控制、操作人员培训等)。
其中，在聚合时，所述光引发剂为苯偶酰双甲醚，二烷氧基苯乙酮，苯甲酰甲酸甲酯，1-羟基环己基苯基甲酮，2-羟基-2-甲基-1-苯基-1-丙酮，2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮，2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮，2,4,6-三甲基苯甲酰基苯基膦，2,4,6-三甲基苯甲酰基二苯基氧化膦，2,4,6-三甲基苯甲酰基苯基膦酸乙酯，二苯甲酮，4,4'-双(二乙氨基)苯甲酮，2-异丙基硫杂蒽酮和4-二甲胺基-苯甲酸乙酯中的一种或两种或者两种以上的混合物，优选2,4,6-三甲基苯甲酰基苯基膦与苯甲酰甲酸甲酯二者的混合；优选二者的重量比为1～2:1。
综上，与现有技术相比，本申请达到了以下技术效果：
(1)胶黏剂的综合性能提升，包括剥离强度、介电常数、透过率、介电常数的稳定性等。
(2)胶黏剂的应用范围更广。
(3)生产工艺要求低。
附图说明
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单的介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施例及对比例所得胶黏剂的介电常数随频率变化图。
具体实施方式
下面将结合附图和具体实施方式对本申请的技术方案进行清楚、完整的描述，但是本领域技术人员将会理解，下列所描述的实施例是本申请一部分实施例，而不是全部的实施例，仅用于说明本申请，而不应视为限制本申请的范围。基于本申请中的实施例，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他实施例，都属于本申请保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本申请解决了介电常数无法适应新科技产品的技术问题，解决该问题所采用的主要原理是：减少胶黏剂中的双键数量来降低介电常数。在实际研究中发现，仅仅减少双键数量而不考虑其它因素并不能获得较好的效果，主要表现为剥离强度极其低因而失去了实用价值，或者透过率等其它性能大幅降低。为获得有实用价值的胶黏剂，在减少双键数量的同时，还必须选用特定种类、特定含量的丙烯酸酯单体与特定种类的预聚物共聚。基本方案如下：
主要由一个或多个饱和丙烯酸酯单体与低聚物在光引发剂的作用下聚合而成；
所述饱和丙烯酸酯单体由丙烯酸或烷基丙烯酸与饱和醇生成；
所述聚合物中，所述丙烯酸酯单体的重量比为10％以上，优选15％以上，更优选20％以上；
所述低聚物的分子量为20000以上，选自氨基甲酸酯预聚物、丙烯酸酯类预聚物、环氧预聚物、有机硅预聚物、聚酯预聚物、聚醚预聚物、多羟基聚烯烃低聚物、聚丁二烯预聚物和氟改性的预聚物中的一种或多种。
基于该宗旨，本申请优化了单体、低聚物的种类及用量，同时引入了添加剂，优化了添加剂的类型及添加量，获得了更优异的综合性能，优化结果如下：
所述烷基丙烯酸选自C1-C10烷基取代的丙烯酸，优选C1-C6烷基取代的丙烯酸；
优选地，所述饱和醇选自C1-C18的饱和一元醇或多元醇，优选C2-C8的饱和一元醇或多元醇，优选C4-C8的饱和一元醇或多元醇；
优选地，所述饱和丙烯酸酯单体为4-羟基丁基丙烯酸酯与丙烯酸异辛酯的混合物，且两者的重量比优选在1:1以下。
优选地，所述低聚物的分子量为20000～40000，或者30000～60000，或者40000～70000；
优选地，所述低聚物的重量比为20％以上，优选25％以上，更优选30％以上。
优选地，所述聚合时还引入适量添加剂，所述添加剂选自交联剂、增粘剂、增塑剂、抗静电剂、柔软剂、着色剂、抗氧化剂、流平剂、耐光剂、消泡剂、稳定剂和防腐剂中的一种或多种；
优选地，所述添加剂的含量为10-50wt％。
优选地，所述添加剂包括增粘剂。
优选地，所述添加剂包括增粘剂、耐光剂、消泡剂。
优选地，所述增粘剂优选选自萜烯酚醛树脂，所述增粘剂的含量优选为15wt％以上，优选20wt％以上，更优选25wt％以上；
优选地，所述耐光剂选自苯氧基三嗪类，含量为0.1～0.3wt％，优选0.1～0.2wt％；
优选地，所述消泡剂选自聚硅氧烷，含量为0.1～0.3wt％，优选0.1～0.2wt％。
优选地，所述交联剂为丙烯酸多元醇酯，和/或甲基丙烯酸多元醇酯；
优选地，所述多元醇选自二元醇、三元醇、四元醇或聚乙二醇，优选为饱和醇或环烷基醇，更优选1,4-丁二醇、1,6-己二醇、1,9-壬二醇、三丙二醇、三环癸烷二甲醇、1,10-癸二醇、聚乙二醇200、聚乙二醇400、三羟甲基丙烷、双三羟甲基丙烷、乙氧基化季戊四醇、季戊四醇和双季戊四醇中的一种或多种；
优选地，所述聚合物中，所述交联剂的重量比为0.1～3wt％。
优选地，所述光引发剂为2,4,6-三甲基苯甲酰基苯基膦，和/或苯甲酰甲酸甲酯，优选二者的混合；优选二者的重量比为1～2:1。
基于以上基础方案和优化方案，本申请提供了以下实施例。
实施例1至6
制备胶黏剂
配方如表1所示。
表1
Figure PCTCN2018080683-appb-000001
注：表1所述的低聚物为丙烯酸酯类预聚物。
制备方法如下：
将上述组分充分搅拌混合、抽真空，从而获得一种液体压敏粘合剂组合物，可直接应用于基材，采用uv照射方式固化。
对比例1
与实施例1的区别仅在于将预聚物替换为分子量为15000的丙烯酸酯类预聚物。
对比例2至6
对比例2至6的配方如表2所示，制备方法均与实施例1相同。
表2
Figure PCTCN2018080683-appb-000002
注：表2所述的低聚物为丙烯酸酯类预聚物。
测试以上所有实施例和对比例所得胶黏剂的性能，并列举如下表3和4所示，并且结果显示，实施例3至16所得胶黏剂的剥离强度均保持在8N以上，1kHz～1MHz时的介电常数保持在2～3之间，波长550nm的透过率在99％以上。
另外，本申请胶黏剂在较宽频率范围内能维持稳定的介电常数，例如实施例1以及对比例3、5的变化趋势，如图1所示。
综上，本申请的胶黏剂具有优异的综合性能。
表3
Figure PCTCN2018080683-appb-000003
表4
Figure PCTCN2018080683-appb-000004
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。

Claims (10)

  1. 一种压敏胶黏剂，其特征在于，主要由一个或多个丙烯酸酯单体与低聚物在光引发剂的作用下聚合而成；
    所述丙烯酸酯单体为丙烯酸饱和醇酯或烷基丙烯酸饱和醇酯；
    所述聚合物中，所述丙烯酸酯单体的重量比为10％以上，优选15％以上，更优选20％以上；
    所述低聚物的分子量为20000以上，选自丙烯酸酯类预聚物、环氧预聚物、有机硅预聚物、聚氨酯预聚物、聚醚预聚物、多羟基聚烯烃低聚物、聚丁二烯预聚物和氟改性的预聚物中的一种或多种。
  2. 根据权利要求1所述的压敏胶黏剂，其特征在于，所述烷基丙烯酸饱和醇酯中的所述烷基选自C1-C10的烷基，优选C1-C6的烷基；
    优选地，所述丙烯酸饱和醇酯以及所述烷基丙烯酸饱和醇酯中的饱和醇独立地选自C1-C18的饱和一元醇或多元醇，优选C2-C8的饱和一元醇或多元醇，优选C4-C8的饱和一元醇或多元醇；
    优选地，所述丙烯酸酯单体为丙烯酸异辛酯与4-羟基丁基丙烯酸酯的混合物，且两者的重量比优选在1:1以下。
  3. 根据权利要求1所述的压敏胶黏剂，其特征在于，所述低聚物选自丙烯酸酯类预聚物和聚氨酯预聚物中的一种或两者混合；
    优选地，所述低聚物的分子量为20000～40000，或者30000～60000，或者40000～70000；
    优选地，所述低聚物的重量比为20％以上，优选25％以上，更优选30％以上。
  4. 根据权利要求1-3任一项所述的压敏胶黏剂，其特征在于，所述聚合时还引入适量添加剂，所述添加剂选自交联剂、增粘剂、增塑剂、抗静电剂、柔软剂、着色剂、抗氧化剂、流平剂、耐光剂、消泡剂、稳定剂和防腐剂中的一种或多种；
    优选地，所述添加剂的含量为10-50wt％。
  5. 根据权利要求4所述的压敏胶黏剂，其特征在于，所述添加剂包括增粘剂。
  6. 根据权利要求4所述的压敏胶黏剂，其特征在于，所述添加剂为增粘剂、耐光剂和消泡剂。
  7. 根据权利要求4所述的压敏胶黏剂，其特征在于，所述增粘剂优选选自萜烯酚醛树脂，所述增粘剂的含量优选为15wt％以上，优选20wt％以上，更优选25wt％以上；
    优选地，所述耐光剂选自苯氧基三嗪类，含量为0.1～0.3wt％，优选0.1～0.2wt％；
    优选地，所述消泡剂选自聚硅氧烷，含量为0.1～0.3wt％，优选0.1～0.2wt％。
  8. 根据权利要求4所述的压敏胶黏剂，其特征在于，所述交联剂为多元丙烯酸多元醇酯，和/或多元甲基丙烯酸多元醇酯；
    优选地，所述交联剂中的多元醇选自二元醇、三元醇、四元醇或聚乙二醇，优选为饱和醇或环烷基醇，更优选1,4-丁二醇、1,6-己二醇、1,9-壬二醇、三丙二醇、三环癸烷二甲醇、1,10-癸二醇、聚乙二醇200、聚乙二醇400、三羟甲基丙烷、双三羟甲基丙烷、乙氧基化季戊四醇、季戊四醇和双季戊四醇中的一种或多种；
    优选地，所述聚合物中，所述交联剂的重量比为0.1～3wt％。
  9. 权利要求1-8任一项所述的压敏胶黏剂的制备方法，其特征在于，包括下列步骤：按照配方，将所有原料混合，在光引发剂的作用下聚合而成。
  10. 根据权利要求9所述的压敏胶黏剂的制备方法，其特征在于，所述光引发剂为苯偶酰双甲醚，二烷氧基苯乙酮，苯甲酰甲酸甲酯，1-羟基环己基苯基甲酮，2-羟基-2-甲基-1-苯基-1-丙酮，2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮，2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮，2,4,6-三甲基苯甲酰基苯基膦，2,4,6-三甲基苯甲酰基二苯基氧化膦，2,4,6-三甲基苯甲酰基苯基膦酸乙酯，二苯甲酮，4,4'-双(二乙氨基)苯甲酮，2-异丙基硫杂蒽酮和4-二甲胺基-苯甲酸乙酯中的一种或两种或者两种以上的混合物，优选2,4,6-三甲基苯甲酰基苯基膦与苯甲酰甲酸甲酯二者的混合；优选二者的重量比为1～2:1。
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