TW201930519A

TW201930519A - Ultra-removable and solvent resistant pressure-sensitive adhesives

Info

Publication number: TW201930519A
Application number: TW107144745A
Authority: TW
Inventors: 沈驃; 楊宇潤; 王一華
Original assignee: 美商艾維利丹尼森公司
Priority date: 2017-12-12
Filing date: 2018-12-12
Publication date: 2019-08-01
Also published as: CN110003818B; WO2019113780A1; CN110003818A; TWI813606B

Abstract

Provided herein is a pressure sensitive adhesive (PSA) composition having high levels of removability, peel strength and solvent resistance. This PSA composition comprises a unique mixture of a polyacrylate base polymer, an epoxy crosslinker, and an optional isocyanate crosslinker. The PSA contains less than 6 wt. % of tackifier. The polyacrylate base polymer has an acid value ranging from 2 to 90 mg KOH/g and has a Tg above -41 DEG C. The PSA is solvent-based and can be prepared in any of a number of solvents, including toluene and ethyl acetate.

Description

具有超可去除性和耐溶劑性的壓敏粘合劑Pressure-sensitive adhesive with ultra-removability and solvent resistance

本發明總體涉及壓敏粘合劑(PSA)，尤其涉及改進的壓敏粘合劑，其具有良好平衡的機械性能、可去除性和耐溶劑性。本申請也涉及含有改進的壓敏粘合劑的標籤及其製備方法。The present invention relates generally to pressure-sensitive adhesives (PSA), and more particularly to improved pressure-sensitive adhesives, which have a good balance of mechanical properties, removability and solvent resistance. The present application also relates to labels containing improved pressure-sensitive adhesives and methods of making the same.

已知壓敏粘合劑(PSA)是當在室溫下施用時能向各種基材提供粘附性或粘性的組合物。該粘附性可以提供在擠壓時對基材的暫態粘著力。PSA通常易於以固體形式處理，並具有長的貯存期，所以它們廣泛用於生產例如自粘標籤。Pressure-sensitive adhesives (PSA) are known as compositions that can provide adhesion or tackiness to various substrates when applied at room temperature. This adhesion can provide transient adhesion to the substrate during extrusion. PSAs are generally easy to handle in solid form and have a long shelf life, so they are widely used in the production of, for example, self-adhesive labels.

PSA通常可以分為兩類：永久性PSA和可去除性PSA。通常，永久性PSA用於粘附基材且不會出現邊緣翹起。這些PSA不能在不損害標籤或基材的情況下被去除。可去除性PSA能粘附基材且不會出現邊緣翹起，並能在不損害標籤或基材的情況下被去除。當需要在粘附於物品上後去除和/或重新定位PSA時，可去除性PSA是尤其有用的。實例包括帶有標籤的包裝和/或容器，其可以在取出內容物後經受清潔或再迴圈處理以再使用它們或者回收實際的包裝/容器材料。這類處理通常要求將標籤從它固著的包裝或容器上完全分離，且不會在所述製品的表面上留下粘合劑殘留，以便簡化清潔或再迴圈過程。可再迴圈使用和可重新佈置的PSA也改進了PSA的環境友好性，並促進其易於處理性。PSA can generally be divided into two categories: permanent PSA and removable PSA. Generally, permanent PSAs are used to adhere to a substrate without edge warping. These PSAs cannot be removed without damaging the label or substrate. Removable PSA adheres to the substrate without edge warping and can be removed without damaging the label or substrate. Removable PSA is particularly useful when it is necessary to remove and / or reposition the PSA after adherence to the article. Examples include labeled packaging and / or containers that can be subjected to cleaning or re-cycling after the contents have been removed to reuse them or to recycle actual packaging / container materials. This type of treatment typically requires complete separation of the label from the package or container to which it is affixed without leaving adhesive residue on the surface of the article in order to simplify the cleaning or re-cycling process. Recyclable and repositionable PSAs also improve the environmental friendliness of PSAs and promote their ease of handling.

另一方面，在一些應用中，希望PSA具有高的剝離強度，從而使標籤能穩定地固定在製品上達到理想的時間。具有高剝離強度的PSA要求較大的從粘附的基材或製品上剝離PSA的力。例如，對於濕紙巾包裝袋，希望具有被高可去除性粘合劑層壓的蓋子，從而當包裝被重複打開和關閉時當包裝被打開時（標籤是與基材分開的），在包裝表面上沒有粘合劑殘留物。在一些情況下，PSA施用於濕的基材表面上，或基材經常暴露於有機清潔溶劑或洗滌劑。與這些溶劑例如水和醇的接觸會導致變渾濁和弱化PSA和基材之間的結合。這些應用要求PSA具有優良的耐溶劑性並且可以耐受這些溶劑的劣化影響。On the other hand, in some applications, it is desired that PSA has high peel strength, so that the label can be stably fixed on the product for the desired time. A PSA with high peel strength requires a large force to peel the PSA from the adhered substrate or article. For example, for wet tissue packaging bags, it is desirable to have a lid laminated with a highly removable adhesive so that when the package is opened and closed repeatedly when the package is opened (the label is separated from the substrate), on the packaging surface No adhesive residue on it. In some cases, PSA is applied to a wet substrate surface, or the substrate is often exposed to an organic cleaning solvent or detergent. Contact with these solvents such as water and alcohol can cause turbidity and weaken the bond between the PSA and the substrate. These applications require PSA to have excellent solvent resistance and to withstand the degradation effects of these solvents.

現有技術的PSA不能滿足這些要求。所以，仍然需要能提供具有平衡的性能特性的PSA，這包括優良剝離粘合性、高的可去除性和優異耐溶劑性的組合。Prior art PSAs cannot meet these requirements. Therefore, there is still a need to provide PSAs with balanced performance characteristics, including a combination of excellent peel adhesion, high removability, and excellent solvent resistance.

在一些實施方案中，本發明提供一種粘合劑組合物，其包含：聚丙烯酸酯基礎聚合物，其具有2-90 mgKOH/g的酸值並具有高於-41ºC的Tg；包含環氧樹脂的第一交聯劑，其中第一交聯劑的存在量是基於粘合劑組合物的總乾重計的大於0.15重量%；和其中粘合劑組合物含有小於6重量%的增粘劑。In some embodiments, the present invention provides an adhesive composition comprising: a polyacrylate base polymer having an acid value of 2-90 mgKOH / g and a Tg higher than -41ºC; comprising an epoxy resin A first cross-linking agent, wherein the first cross-linking agent is present in an amount greater than 0.15% by weight based on the total dry weight of the adhesive composition; and wherein the adhesive composition contains less than 6% by weight of a tackifier .

在一些實施方案中，粘合劑組合物包含：聚丙烯酸酯基礎聚合物，其具有2-90 mgKOH/g的酸值並具有高於-41ºC的Tg；包含環氧樹脂的第一交聯劑，其中第一交聯劑的存在量是基於粘合劑組合物的總乾重計的大於0.15重量%；和其中粘合劑組合物含有小於6重量%的增粘劑。在一些實施方案中，當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，粘合劑組合物具有小於15%的霧度值。在一些實施方案中，實施方案2的粘合劑組合物，其中溶劑是水或乙醇。In some embodiments, the adhesive composition comprises: a polyacrylate base polymer having an acid value of 2-90 mgKOH / g and a Tg above -41ºC; a first cross-linking agent comprising an epoxy resin Wherein the first crosslinking agent is present in an amount of greater than 0.15% by weight based on the total dry weight of the adhesive composition; and wherein the adhesive composition contains less than 6% by weight of a tackifier. In some embodiments, the adhesive composition has a haze value of less than 15% after the adhesive composition is immersed in a solvent for at least 3 days when tested in accordance with ASTM D1003 experiments. In some embodiments, the adhesive composition of embodiment 2, wherein the solvent is water or ethanol.

在一些實施方案中，當從已經與粘合劑接觸的基材的表面去除粘合劑組合物時，粘合劑在小於3%的表面積上留下殘留物。In some embodiments, when the adhesive composition is removed from the surface of a substrate that has been in contact with the adhesive, the adhesive leaves a residue on a surface area of less than 3%.

在一些實施方案中，粘合劑組合物的聚丙烯酸酯基礎聚合物具有4-76 mg KOH/g的酸值。在一些實施方案中，聚丙烯酸酯基礎聚合物具有36-76 mg KOH/g的酸值，其中環氧樹脂的存在量是0.2-0.5重量%，和其中增粘劑的存在量是小於1重量%，其中當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，粘合劑具有小於10%的霧度值。In some embodiments, the polyacrylate base polymer of the adhesive composition has an acid value of 4-76 mg KOH / g. In some embodiments, the polyacrylate base polymer has an acid value of 36-76 mg KOH / g, wherein the epoxy resin is present in an amount of 0.2-0.5% by weight, and wherein the tackifier is present in an amount of less than 1 weight %, Where the adhesive has a haze value of less than 10% after the adhesive composition is soaked in a solvent for at least 3 days when tested in accordance with ASTM D1003.

在一些實施方案中，粘合劑組合物的聚丙烯酸酯基礎聚合物具有60-76 mg KOH/g的酸值，並且環氧樹脂的存在量是0.2-0.5重量%。在這些實施方案中，在粘合劑組合物中的增粘劑的存在量是小於0.5重量%，並且當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，粘合劑具有小於8%的霧度值。在這些實施方案中，當從已經與粘合劑接觸的基材的表面去除粘合劑組合物時，粘合劑在小於3%的表面積上留下殘留物。In some embodiments, the polyacrylate base polymer of the adhesive composition has an acid value of 60-76 mg KOH / g, and the epoxy resin is present in an amount of 0.2-0.5% by weight. In these embodiments, the tackifier is present in the adhesive composition in an amount of less than 0.5% by weight, and when tested in accordance with ASTM D1003 experiments, the adhesive composition is sticky after soaking in the solvent for at least 3 days The mixture has a haze value of less than 8%. In these embodiments, when the adhesive composition is removed from the surface of a substrate that has been in contact with the adhesive, the adhesive leaves a residue on a surface area of less than 3%.

在一些實施方案中，聚丙烯酸酯基礎聚合物具有60-76 mgKOH/g的酸值。在這些實施方案中，環氧樹脂含有一個或多個叔胺基團，並且其存在量是0.2-0.5重量%。在這些實施方案中，增粘劑的存在量是小於0.5重量%，並且當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，粘合劑具有小於8%的霧度值。在這些實施方案中，當從已經與粘合劑接觸的基材的表面去除粘合劑組合物時，粘合劑在小於3%的表面積上留下殘留物。In some embodiments, the polyacrylate base polymer has an acid value of 60-76 mgKOH / g. In these embodiments, the epoxy resin contains one or more tertiary amine groups, and is present in an amount of 0.2-0.5% by weight. In these embodiments, the tackifier is present in an amount of less than 0.5% by weight, and the adhesive has a haze of less than 8% after the adhesive composition is soaked in a solvent for at least 3 days when tested according to ASTM D1003. Degree value. In these embodiments, when the adhesive composition is removed from the surface of a substrate that has been in contact with the adhesive, the adhesive leaves a residue on a surface area of less than 3%.

在一些實施方案中，聚丙烯酸酯基礎聚合物具有在-40°C至 -5°C範圍內的玻璃化轉變溫度(Tg)。在一些實施方案中，聚丙烯酸酯基礎聚合物不是嵌段共聚物。在一些實施方案中，聚丙烯酸酯基礎聚合物含有具有2-14個碳原子的烷基。在一些實施方案中，聚丙烯酸酯基礎聚合物的平均分子量在50000-1500000g/mol的範圍內。在一些實施方案中，聚丙烯酸酯聚合物的分子量分佈指數在2-8的範圍內。在一些實施方案中，聚丙烯酸酯基礎聚合物不含不飽和基團。在一些實施方案中，聚丙烯酸酯基礎聚合物含有羥基，並具有0-100 mgKOH/g的羥值。In some embodiments, the polyacrylate base polymer has a glass transition temperature (Tg) in the range of -40 ° C to -5 ° C. In some embodiments, the polyacrylate base polymer is not a block copolymer. In some embodiments, the polyacrylate base polymer contains an alkyl group having 2-14 carbon atoms. In some embodiments, the average molecular weight of the polyacrylate base polymer is in the range of 50,000-1500000 g / mol. In some embodiments, the molecular weight distribution index of the polyacrylate polymer is in the range of 2-8. In some embodiments, the polyacrylate base polymer is free of unsaturated groups. In some embodiments, the polyacrylate base polymer contains a hydroxyl group and has a hydroxyl value of 0-100 mgKOH / g.

在一些實施方案中，粘合劑組合物含有0.10-1.0重量%的第一交聯劑。在一些實施方案中，第一交聯劑是環氧樹脂並具有60-300 g/eq的環氧當量重量。在一些實施方案中，環氧樹脂在其化學結構中含有一個或多個叔胺基團。在一些實施方案中，第一交聯劑的環氧樹脂含有一個或多個叔胺基團並具有選自由以下的化學結構所構成群組：
;
;
;
;
以及它們的混合物。In some embodiments, the adhesive composition contains 0.10-1.0% by weight of the first crosslinking agent. In some embodiments, the first crosslinking agent is an epoxy resin and has an epoxy equivalent weight of 60-300 g / eq. In some embodiments, the epoxy resin contains one or more tertiary amine groups in its chemical structure. In some embodiments, the epoxy resin of the first cross-linking agent contains one or more tertiary amine groups and has a chemical structure selected from the group consisting of:
;
;
;
;
And their mixtures.

在一些實施方案中，粘合劑組合物還含有包含異氰酸酯樹脂的第二交聯劑。在一些實施方案中，粘合劑組合物含有0.05-0.8重量%的第二交聯劑。在一些實施方案中，異氰酸酯樹脂具有10-30重量%的NCO含量。在一些實施方案中，實施方案20-22中任一項的粘合劑組合物，其中第一交聯劑與第二交聯劑之間的重量比在0.6-20的範圍內。In some embodiments, the adhesive composition further contains a second crosslinking agent comprising an isocyanate resin. In some embodiments, the adhesive composition contains 0.05-0.8% by weight of a second crosslinking agent. In some embodiments, the isocyanate resin has an NCO content of 10-30% by weight. In some embodiments, the adhesive composition of any one of embodiments 20-22, wherein the weight ratio between the first crosslinking agent and the second crosslinking agent is in the range of 0.6-20.

在一些實施方案中，聚丙烯酸酯基礎聚合物與第一交聯劑之間的重量比在100:0.9至100:0.01(較佳100:0.6至100:0.03)的範圍內，並且根據FINAT-1方法檢測，粘合劑組合物在不銹鋼上的剝離強度是2-10 N/英寸。在一些實施方案中，粘合劑組合物具有40-95重量%的凝膠含量。在一些實施方案中，粘合劑組合物具有大於4小時的貯存期。在一些實施方案中，當在120°C下固化時，粘合劑組合物具有0.3-5分鐘的固化時間。在一些實施方案中，粘合劑實質上不含天然橡膠。In some embodiments, the weight ratio between the polyacrylate base polymer and the first crosslinking agent is in the range of 100: 0.9 to 100: 0.01 (preferably 100: 0.6 to 100: 0.03), and according to FINAT- 1 method, the peel strength of the adhesive composition on the stainless steel was 2-10 N / inch. In some embodiments, the adhesive composition has a gel content of 40-95% by weight. In some embodiments, the adhesive composition has a shelf life of more than 4 hours. In some embodiments, the adhesive composition has a curing time of 0.3-5 minutes when cured at 120 ° C. In some embodiments, the adhesive is substantially free of natural rubber.

在一些實施方案中，本發明提供包含粘合劑層的標籤，所述粘合劑層包含本發明的粘合劑組合物。在一些實施方案中，標籤含有與粘合劑層接觸的面材(facestock)層。In some embodiments, the present invention provides a label comprising an adhesive layer comprising the adhesive composition of the present invention. In some embodiments, the label contains a facestock layer in contact with the adhesive layer.

在一些實施方案中，本發明提供一種製備粘合劑配製劑的方法，包括：在小於50°C的溫度下在溶劑中溶解以下組分：a)聚丙烯酸酯基礎聚合物，和b)包含環氧樹脂的第一交聯劑，其中第一交聯劑的存在量是基於粘合劑組合物的總乾重計的大於0.15重量%，其中粘合劑配製劑含有小於6重量%的增粘劑。在一些實施方案中，第一交聯劑含有一種或多種催化單元。在一些實施方案中，一種或多種催化單元是一種或多種叔胺。在一些實施方案中，第一交聯劑的量是基於粘合劑組合物乾重計的0.15-0.9重量%。在一些實施方案中，第一交聯劑的環氧樹脂具有60-300 g/eq的環氧當量重量。在一些實施方案中，溶劑選自由甲苯、乙酸乙酯、異丙醇、二甲苯、正己烷、正庚烷、甲基環己烷、乙酸丁酯、丙酮、丁酮和2-乙醯氧基-1-甲氧基丙烷所構成群組。在一些實施方案中，此方法還包括：用粘合劑配製劑塗覆面材，和乾燥所述粘合劑配製劑。在一些實施方案中，其中此方法還包括向基材施用包含粘合劑的標籤。In some embodiments, the present invention provides a method for preparing an adhesive formulation, comprising: dissolving the following components in a solvent at a temperature of less than 50 ° C: a) a polyacrylate base polymer, and b) comprising The first cross-linking agent for epoxy resin, wherein the first cross-linking agent is present in an amount of greater than 0.15% by weight based on the total dry weight of the adhesive composition, wherein the adhesive formulation contains less than 6% by weight Adhesive. In some embodiments, the first crosslinking agent contains one or more catalytic units. In some embodiments, the one or more catalytic units are one or more tertiary amines. In some embodiments, the amount of the first crosslinking agent is 0.15-0.9% by weight based on the dry weight of the adhesive composition. In some embodiments, the epoxy resin of the first cross-linking agent has an epoxy equivalent weight of 60-300 g / eq. In some embodiments, the solvent is selected from the group consisting of toluene, ethyl acetate, isopropanol, xylene, n-hexane, n-heptane, methylcyclohexane, butyl acetate, acetone, methyl ethyl ketone, and 2-acetamyloxy A group of -1-methoxypropane. In some embodiments, the method further comprises: coating the facestock with an adhesive formulation, and drying the adhesive formulation. In some embodiments, wherein the method further comprises applying a label comprising an adhesive to the substrate.

在一些實施方案中，本發明提供粘合劑系統，其包含：第一組分，其包含i)具有酸基團並且酸值為2-90 mgKOH/g的聚丙烯酸酯基礎聚合物，ii)溶劑；和第二組分，其包含在溶劑中的含有環氧樹脂的第一交聯劑；和其中第一組分是與第二組分分開的。In some embodiments, the present invention provides an adhesive system comprising: a first component comprising i) a polyacrylate base polymer having an acid group and an acid value of 2-90 mgKOH / g, ii) A solvent; and a second component comprising a first crosslinking agent containing an epoxy resin in a solvent; and wherein the first component is separated from the second component.

在一些實施方案中，本發明提供帶有標籤的容器，其包含本發明的粘合劑組合物。In some embodiments, the present invention provides a labeled container comprising the adhesive composition of the present invention.

具體實施方式
本發明總體涉及壓敏粘合劑(PSA)，其能提供有利的性能特性，尤其是良好平衡的剝離強度、可去除性以及耐溶劑性。當PSA用於要求粘合劑將標籤牢固地保持在適當位置且在去除標籤時不會留下粘合劑殘留物時，並且要求粘合劑對各種溶劑具有耐溶劑性時，這些特性的組合可以是特別重要的。DETAILED DESCRIPTION The present invention relates generally to pressure-sensitive adhesives (PSA), which can provide advantageous performance characteristics, especially well-balanced peel strength, removability, and solvent resistance. A combination of these properties when PSA is used to require an adhesive to hold a label firmly in place without leaving adhesive residue when removing the label, and when the adhesive is required to be solvent resistant to various solvents Can be particularly important.

如上所述，各種常規 PSA是本領域公知的。但是，許多這些粘合劑已經開發用於其中較佳高的可去除性或高的剝離強度的應用。通常，現有技術的PSA 不能同時具有高的可去除性和高的剝離強度。實際上，用於改進粘合性(進而提高剝離強度)的許多組分通常對PSA的可去除性和耐溶劑性具有不利影響。相似地，已知的在去除時在基材上不會形成或留下顯著量殘留物的PSA一般具有差的粘合性。As mentioned above, various conventional PSAs are well known in the art. However, many of these adhesives have been developed for applications in which high removability or high peel strength is preferred. Generally, prior art PSAs cannot have both high removability and high peel strength. In fact, many components used to improve adhesion (and thus peel strength) often have a negative impact on PSA removability and solvent resistance. Similarly, known PSAs that do not form or leave a significant amount of residue on the substrate upon removal generally have poor adhesion.

例如，美國專利申請No. 2016/0280967A1描述了水性乳液PSA，其中聚合物在水中在表面活性劑的存在下乳化。並且為了穩定乳液，表面活性劑通常是必需的。表面活性劑不利地影響所需聚合物的交聯，所以降低了PSA的可去除性和耐溶劑性。另外，美國專利申請No. 2016/0280967A1沒有公開丙烯酸酯聚合物的酸值和羥值或其環氧樹脂的環氧當量重量和含量。中國專利申請103827238A描述了PSA，其包含丙烯酸酯基礎聚合物和環氧樹脂。這種PSA不含增粘劑。丙烯酸酯基礎聚合物是從第一單體和第二單體形成的，其中第一單體是伯醇R1- OH、(甲基)丙烯酸烷基酯，第二單體是烯屬飽和基團。此聚合物不含任何酸單體，因此不具有足夠的酸值，這將不利地影響可去除性，這是因為在環氧樹脂和丙烯酸酯基礎聚合物之間的交聯不是有效的。For example, U.S. Patent Application No. 2016/0280967 A1 describes an aqueous emulsion PSA in which a polymer is emulsified in water in the presence of a surfactant. And in order to stabilize the emulsion, a surfactant is usually necessary. Surfactants adversely affect the cross-linking of the desired polymer, so reducing the PSA's removability and solvent resistance. In addition, U.S. Patent Application No. 2016 / 0280967A1 does not disclose the acid value and hydroxyl value of the acrylate polymer or the epoxy equivalent weight and content of the epoxy resin thereof. Chinese patent application 103827238A describes a PSA that includes an acrylate base polymer and an epoxy resin. This PSA contains no tackifiers. The acrylate base polymer is formed from a first monomer and a second monomer, wherein the first monomer is a primary alcohol R1-OH, an alkyl (meth) acrylate, and the second monomer is an ethylenically saturated group. . This polymer does not contain any acid monomers and therefore does not have a sufficient acid value, which would adversely affect removability because the crosslinking between the epoxy resin and the acrylate base polymer is not effective.

本發明人發現，聚丙烯酸酯基礎聚合物、含環氧樹脂的交聯劑的特定組合，視需要按照特定量使用，令人驚奇地提供高性能的PSA，其同時具有高的剝離強度、高水準的可去除性和優異的耐溶劑性。重要的是，本發明人發現，增粘劑對所得PSA的耐溶劑性具有不利影響。鑒於此發現，本發明的PSA含有極少的（如果有的話）增粘劑，例如小於6重量%，小於5重量%，較佳0重量%的增粘劑。例如，當具有酸基團、例如羧基並且酸值為2-90 mgKOH/g的聚丙烯酸酯基礎聚合物與含環氧樹脂的交聯劑一起使用時(不含增粘劑或含有極少的增粘劑)，所得的PSA令人驚奇地和有利地具有高的剝離強度和可去除性以及優異的耐溶劑性。重要的是，發現PSA可以通過將各組分溶解在特定溶劑中製備(如下文所述)。在一些情況下，溶劑基PSA可以用於生產標籤或其它商業產品，其同時具有優良的可去除性並具有高的剝離強度和耐溶劑性。The inventors have discovered that a specific combination of a polyacrylate-based polymer and an epoxy-containing cross-linking agent is used in a specific amount as needed, surprisingly providing a high-performance PSA, which also has high peel strength, Level of removability and excellent solvent resistance. Importantly, the present inventors have found that the tackifier has an adverse effect on the solvent resistance of the resulting PSA. In light of this finding, the PSA of the present invention contains very little, if any, tackifiers, such as less than 6% by weight, less than 5% by weight, and preferably 0% by weight. For example, when a polyacrylate base polymer having an acid group, such as a carboxyl group, and an acid value of 2-90 mgKOH / g is used with a crosslinking agent containing an epoxy resin (without a tackifier or containing very little Adhesive), the resulting PSA has surprisingly and advantageously a high peel strength and removability as well as excellent solvent resistance. Importantly, it was found that PSA can be prepared by dissolving the components in a specific solvent (as described below). In some cases, solvent-based PSAs can be used to produce labels or other commercial products that have both good removability and high peel strength and solvent resistance.

下面詳細描述本發明的一些具體組分。除非另有說明，所有百分是基於PSA的總乾重計的重量百分比。Some specific components of the present invention are described in detail below. Unless otherwise stated, all percentages are weight percentages based on the total dry weight of the PSA.

聚丙烯酸酯基礎聚合物溶劑基PSA的聚合物含有聚丙烯酸酯基礎聚合物。各種丙烯酸酯聚合物是本領域公知的，並且這些聚合物通常含有基於丙烯酸結構的單體，例如由乙烯基和羧酸端基組成的單體，或其衍生物。在一些情況下，聚合物可以含有單種類型的丙烯酸酯單體，而在其它情況下，聚合物可以含有不同類型丙烯酸酯單體的組合。在一些實施方案中，用於聚丙烯酸酯基礎聚合物中的丙烯酸酯單體包括丙烯酸丁基酯。Polyacrylate-Based Polymer The polymer of the solvent-based PSA contains a polyacrylate-based polymer. Various acrylate polymers are well known in the art, and these polymers usually contain monomers based on an acrylic structure, such as monomers composed of vinyl and carboxylic acid end groups, or derivatives thereof. In some cases, the polymer may contain a single type of acrylate monomer, while in other cases, the polymer may contain a combination of different types of acrylate monomers. In some embodiments, the acrylate monomer used in the polyacrylate base polymer includes butyl acrylate.

在一些實施方案中，聚丙烯酸酯基礎聚合物含有酸基團和/或羥基。在一些實施方案中，用於形成聚丙烯酸酯基礎聚合物的單體包括丙烯酸單體和/或丙烯酸酯單體。在一些實施方案中，用於形成聚丙烯酸酯基礎聚合物的單體還包括含有羥基的單體(“羥基供體”)，並且其在聚合物中的存在量直接與聚丙烯酸酯基礎聚合物的羥值相關。非示例性的羥基供體包括丙烯酸羥基乙基酯(HEA)，藻酸羥基丙基酯(HPA)和羥基苯甲酸(HBA)。羥基供體的量可以是基於用於形成聚丙烯酸酯基礎聚合物的單體的總重量計的0.3-3重量%，例如0.4-2重量%或0.5-1重量%。關於上限，羥基供體的量可以小於3重量%，小於2重量%，或小於1重量%。關於下限，羥基供體的存在量可以是大於0.3重量%，大於0.4重量%或大於0.5重量%。In some embodiments, the polyacrylate base polymer contains acid groups and / or hydroxyl groups. In some embodiments, the monomers used to form the polyacrylate base polymer include acrylic monomers and / or acrylate monomers. In some embodiments, the monomers used to form the polyacrylate base polymer also include hydroxyl-containing monomers ("hydroxy donors"), and their presence in the polymer is directly related to the polyacrylate base polymer Related to the hydroxyl value. Non-exemplary hydroxyl donors include hydroxyethyl acrylate (HEA), hydroxypropyl alginate (HPA), and hydroxybenzoic acid (HBA). The amount of the hydroxyl donor may be 0.3 to 3% by weight, for example, 0.4 to 2% by weight or 0.5 to 1% by weight based on the total weight of the monomers used to form the polyacrylate base polymer. Regarding the upper limit, the amount of the hydroxyl donor may be less than 3% by weight, less than 2% by weight, or less than 1% by weight. Regarding the lower limit, the hydroxyl donor may be present in an amount of more than 0.3% by weight, more than 0.4% by weight, or more than 0.5% by weight.

重要的是，被引入聚丙烯酸酯的丙烯酸單體的量可以直接與在聚丙烯酸酯基礎聚合物中的酸基團的量相關，例如羧酸；並且被引入聚丙烯酸酯基礎聚合物的丙烯酸酯單體的量可以直接與在聚丙烯酸酯基礎聚合物中的羥基的量相關。本發明人發現，保持單體與酸基團或羥基之間的特定比率能獲得具有上述所需性能特性組合的PSA，例如高的剝離強度和高的可去除性。在一些實施方案中，PSA不含任何丙烯酸酯單體。在一些實施方案中，丙烯酸酯單體與丙烯酸單體之間的比率可以是在5.6:1至499:1的範圍內，例如10:1 至400:1，20:1至300:1，30:1至200:1，50:1至100:1，或70:1至90:1，例如約82:1。關於上限，丙烯酸酯單體與丙烯酸單體之間的比率是小於499:1，小於200:1，小於150:1，小於100:1，或小於90:1。關於下限，丙烯酸酯單體與丙烯酸單體之間的比率是大於5.6:1，大於8:1，大於10:1或大於20:1，例如大於9:1。不受任何理論的束縛，認為具有很少或不含酸基團（酸值是0）的基礎聚合物不能被（環氧基）交聯劑交聯。Importantly, the amount of acrylic monomers introduced into the polyacrylate can be directly related to the amount of acid groups in the polyacrylate base polymer, such as carboxylic acids; and the acrylates introduced into the polyacrylate base polymer The amount of monomer can be directly related to the amount of hydroxyl groups in the polyacrylate base polymer. The present inventors have found that maintaining a specific ratio between a monomer and an acid group or a hydroxyl group can obtain a PSA having the desired combination of performance characteristics described above, such as high peel strength and high removability. In some embodiments, the PSA is free of any acrylate monomer. In some embodiments, the ratio between the acrylate monomer and the acrylic monomer may be in a range of 5.6: 1 to 499: 1, such as 10: 1 to 400: 1, 20: 1 to 300: 1, 30 : 1 to 200: 1, 50: 1 to 100: 1, or 70: 1 to 90: 1, such as about 82: 1. Regarding the upper limit, the ratio between the acrylate monomer and the acrylic monomer is less than 499: 1, less than 200: 1, less than 150: 1, less than 100: 1, or less than 90: 1. With regard to the lower limit, the ratio between the acrylate monomer and the acrylic monomer is greater than 5.6: 1, greater than 8: 1, greater than 10: 1, or greater than 20: 1, such as greater than 9: 1. Without being bound by any theory, it is believed that a base polymer with little or no acid groups (acid value is 0) cannot be crosslinked by a (epoxy) crosslinking agent.

在一些情況下，在聚丙烯酸酯基礎聚合物中的酸基團的量由酸值表示。聚丙烯酸酯基礎聚合物的酸值是為了中和1克聚丙烯酸酯基礎聚合物所需的氫氧化鉀(KOH)的毫克品質。在一些實施方案中，聚丙烯酸酯基礎聚合物的酸值是2-90 mgKOH/g，例如4-75mgKOH/g，5-35mgKOH/g，4-36mgKOH/g，或8-75mgKOH/g。關於上限，聚丙烯酸酯基礎聚合物的酸值是小於90mgKOH/g，小於80mgKOH/g，小於75mgKOH/g，小於50mgKOH/g，或小於40mgKOH/g。關於下限，聚丙烯酸酯基礎聚合物的酸值是大於2mgKOH/g，大於4mgKOH/g，大於10mgKOH/g，大於20 mgKOH/g，或大於25mgKOH/g。本發明人驚奇地發現，當聚丙烯酸酯基礎聚合物具有在上述範圍內的酸值並且當環氧樹脂的量也在恰當範圍內（如下文所述）時，聚合物的交聯可以更有效地進行，這進而導致優良的可去除性和耐溶劑性的優良性能。In some cases, the amount of acid groups in the polyacrylate base polymer is represented by an acid value. The acid value of the polyacrylate base polymer is the milligram quality of potassium hydroxide (KOH) required to neutralize 1 gram of the polyacrylate base polymer. In some embodiments, the acid value of the polyacrylate base polymer is 2-90 mgKOH / g, such as 4-75 mgKOH / g, 5-35 mgKOH / g, 4-36 mgKOH / g, or 8-75 mgKOH / g. Regarding the upper limit, the acid value of the polyacrylate base polymer is less than 90 mgKOH / g, less than 80 mgKOH / g, less than 75 mgKOH / g, less than 50 mgKOH / g, or less than 40 mgKOH / g. Regarding the lower limit, the acid value of the polyacrylate base polymer is greater than 2 mgKOH / g, greater than 4 mgKOH / g, greater than 10 mgKOH / g, greater than 20 mgKOH / g, or greater than 25 mgKOH / g. The inventors have surprisingly found that when the polyacrylate base polymer has an acid value within the above range and when the amount of the epoxy resin is also in the proper range (as described below), the polymer can be more effectively crosslinked This, in turn, results in excellent properties of excellent removability and solvent resistance.

在一些實施方案中，在聚丙烯酸酯基礎聚合物中的羥基的量由羥值表示。聚丙烯酸酯基礎聚合物的羥值是為了中和在1克聚丙烯酸酯基礎聚合物進行醯化時被吸收的乙酸所需的氫氧化鉀(KOH)的毫克品質。在一些實施方案中，聚丙烯酸酯基礎聚合物的羥值是0-100 mgKOH/g，例如0-90 mg KOH/g，1-50mgKOH/g，5-50mgKOH/g，10-50mgKOH/g，20-80mg KOH/g，例如30-55mgKOH/g。值得注意的是，PSA的一些實施方案包括不含遊離羥基的聚丙烯酸酯基礎聚合物。因此，這些實施方案包括羥值等於0 mg KOH/g的聚丙烯酸酯基礎聚合物。關於上限，聚丙烯酸酯基礎聚合物的羥值是小於100mg KOH/g，小於80mgKOH/g，小於50mgKOH/g，小於20 mg KOH/g，小於10 mgKOH/g，小於5 mgKOH/g。關於下限，聚丙烯酸酯基礎聚合物的酸值是大於0 mg KOH/g，大於1 mgKOH/g，大於5 mg KOH/g，大於10 mgKOH/g，大於20 mgKOH/g，或大於25 mgKOH/g。In some embodiments, the amount of hydroxyl groups in the polyacrylate base polymer is represented by a hydroxyl value. The hydroxyl value of the polyacrylate base polymer is the milligram quality of potassium hydroxide (KOH) required to neutralize the acetic acid that is absorbed when 1 g of the polyacrylate base polymer is subjected to amination. In some embodiments, the hydroxyl value of the polyacrylate base polymer is 0-100 mgKOH / g, such as 0-90 mg KOH / g, 1-50 mgKOH / g, 5-50 mgKOH / g, 10-50 mgKOH / g, 20-80 mg KOH / g, such as 30-55 mg KOH / g. It is worth noting that some embodiments of the PSA include a polyacrylate base polymer that does not contain free hydroxyl groups. Therefore, these embodiments include a polyacrylate base polymer having a hydroxyl value equal to 0 mg KOH / g. Regarding the upper limit, the hydroxyl value of the polyacrylate base polymer is less than 100 mg KOH / g, less than 80 mg KOH / g, less than 50 mg KOH / g, less than 20 mg KOH / g, less than 10 mg KOH / g, and less than 5 mg KOH / g. Regarding the lower limit, the acid value of the polyacrylate base polymer is greater than 0 mg KOH / g, greater than 1 mg KOH / g, greater than 5 mg KOH / g, greater than 10 mgKOH / g, greater than 20 mgKOH / g, or greater than 25 mgKOH / g.

在較佳實施方案中，聚丙烯酸酯基礎聚合物不是嵌段共聚物。嵌段共聚物是由兩種或更多種單體形成的共聚物，這些單體聚集在一起並形成重複單元的嵌段。例如，由X和Y單體一起形成的聚合物：Y-Y-Y-Y-Y-X-X-X-X-X-Y-Y-Y-Y-Y-X-X-X-X-X-是嵌段共聚物，其中-Y-Y-Y-Y-Y-和-X-X-X-X-X-基團是嵌段。雖然本發明的聚丙烯酸酯基礎聚合物可以含有多於一種類型的單體，但是這些單體均勻地分佈在聚合物鏈中，且不會形成重複單元的嵌段。In a preferred embodiment, the polyacrylate base polymer is not a block copolymer. Block copolymers are copolymers formed from two or more monomers that come together and form blocks of repeating units. For example, a polymer formed from X and Y monomers together: Y-Y-Y-Y-Y-X-X-X-X-X-Y-Y-Y-Y-Y-X-X-X-X-X- is a block copolymer in which the -Y-Y-Y-Y-Y- and -X-X-X-X-X-X- groups are blocks. Although the polyacrylate base polymer of the present invention may contain more than one type of monomer, these monomers are uniformly distributed in the polymer chain without forming blocks of repeating units.

在一些實施方案中，聚丙烯酸酯基礎聚合物可以含有還包含烷基鏈的丙烯酸酯單體。這些烷基鏈可以在寬範圍內變化，例如是直鏈、支化、環狀、脂族、芳族、飽和或不飽和的。在丙烯酸酯單體的烷基鏈中的碳原子數目可以在1-20個碳原子範圍內變化，例如2-15、2-13、4-10、4-8 個碳原子。在較佳實施方案中，這些烷基鏈含有不大於20個碳原子，例如不大於15個碳原子，不大於12個碳原子，不大於8個碳原子，不大於6個碳原子，不大於5個碳原子，或不大於4個碳原子。在較佳實施方案中，這些烷基鏈含有大於1個碳原子，例如大於1、大於3、大於4或大於5個碳原子。In some embodiments, the polyacrylate base polymer may contain an acrylate monomer further comprising an alkyl chain. These alkyl chains can vary over a wide range, such as being linear, branched, cyclic, aliphatic, aromatic, saturated or unsaturated. The number of carbon atoms in the alkyl chain of the acrylate monomer can vary from 1-20 carbon atoms, such as 2-15, 2-13, 4-10, 4-8 carbon atoms. In a preferred embodiment, these alkyl chains contain no more than 20 carbon atoms, such as no more than 15 carbon atoms, no more than 12 carbon atoms, no more than 8 carbon atoms, no more than 6 carbon atoms, and no more than 5 carbon atoms, or no more than 4 carbon atoms. In preferred embodiments, these alkyl chains contain more than 1 carbon atom, such as greater than 1, greater than 3, greater than 4 or greater than 5 carbon atoms.

聚丙烯酸酯基礎聚合物可以含有不飽和碳基團；但較佳的是，丙烯酸酯聚合物不含任何不飽和碳基團。在一些情況下，聚合物的丙烯酸酯單體可以含有芳環；但較佳的是，聚合物的丙烯酸酯單體不含芳環。具有芳環的單體通常不能達到高的聚合度，因此與不含芳環的單體相比具有降低的粘結力和粘附性能。The polyacrylate base polymer may contain unsaturated carbon groups; however, it is preferred that the acrylate polymer does not contain any unsaturated carbon groups. In some cases, the polymer's acrylate monomer can contain aromatic rings; however, it is preferred that the polymer's acrylate monomer does not contain aromatic rings. A monomer having an aromatic ring generally cannot achieve a high degree of polymerization, and thus has reduced adhesion and adhesion properties compared to a monomer having no aromatic ring.

在一些實施方案中，聚丙烯酸酯基礎聚合物具有在合適範圍和/或限度內的玻璃化轉變溫度(Tg)。玻璃化轉變溫度定義了聚合物從硬的玻璃態材料向軟的橡膠態材料轉化的區域。驚奇地發現，當聚丙烯酸酯基礎聚合物具有在-40°C至-15°C範圍內的Tg(包括端點)時，例如-40ºC至-15ºC，-35°C至-15°C，-35°C至-20°C，-31ºC至-25 ºC，或約-26.8 °C，可以實現優異的性能特徵的組合，例如優化的剝離粘合性和可去除性。In some embodiments, the polyacrylate base polymer has a glass transition temperature (Tg) within a suitable range and / or limit. The glass transition temperature defines the region where the polymer transitions from a hard glassy material to a soft rubbery material. Surprisingly, when the polyacrylate base polymer has a Tg in the range of -40 ° C to -15 ° C (inclusive), such as -40 ° C to -15 ° C, -35 ° C to -15 ° C, -35 ° C to -20 ° C, -31ºC to -25 ºC, or about -26.8 ° C, can achieve a combination of excellent performance characteristics, such as optimized peel adhesion and removability.

聚丙烯酸酯基礎聚合物的平均分子量可以在寬範圍內變化。在一些情況下，平均分子量可以是50,000-1,500,000g/mol，例如70,000-1,200,000 g/mole，100,000-600,000 g/mole，200,000-800,000 g/mole，300,000-600,000 g/mole或約450,000g/mole。關於上限，聚丙烯酸酯基礎聚合物可以具有小於1,500,000g/mole的平均分子量，例如小於800,000 g/mole，小於600,000 g/mole。關於下限，聚丙烯酸酯基礎聚合物可以具有大於50,000g/mole的平均分子量，例如大於100,000g/mole，或小於300,000g/mole。在一些實施方案中，聚丙烯酸酯基礎聚合物含有2-40重量%、例如6-30重量%、10-20重量%的分子量為10,000g/mole或更低的聚合物，基於聚丙烯酸酯基礎聚合物的總乾重計。The average molecular weight of the polyacrylate base polymer can vary over a wide range. In some cases, the average molecular weight can be 50,000-1,500,000 g / mol, such as 70,000-1,200,000 g / mole, 100,000-600,000 g / mole, 200,000-800,000 g / mole, 300,000-600,000 g / mole, or about 450,000 g / mole . With regard to the upper limit, the polyacrylate base polymer may have an average molecular weight of less than 1,500,000 g / mole, such as less than 800,000 g / mole, and less than 600,000 g / mole. With regard to the lower limit, the polyacrylate base polymer may have an average molecular weight greater than 50,000 g / mole, such as greater than 100,000 g / mole, or less than 300,000 g / mole. In some embodiments, the polyacrylate base polymer contains 2-40% by weight, for example 6-30% by weight, 10-20% by weight of a polymer having a molecular weight of 10,000 g / mole or less, based on the polyacrylate base Total dry weight of polymer.

聚丙烯酸酯基礎聚合物可以具有在2-8範圍內的分子量分佈指數，例如2-5，1-4，2-3，3- 4，或3-4。分子量分佈指數表示聚合物的分子量分佈的寬度，該指數越大，分子量分佈就越寬。The polyacrylate base polymer may have a molecular weight distribution index in the range of 2-8, such as 2-5, 1-4, 2-3, 3-4, or 3-4. The molecular weight distribution index indicates the width of the molecular weight distribution of a polymer, and the larger the index, the wider the molecular weight distribution.

合適的市售聚丙烯酸酯基礎聚合物包括來自YASUSA Chemical的Y-1510、Y-1310、Y-1500W、Y-1210、Y-2100，來自Toyo Ink的BPS5375 ，來自Eternal的Etrac7017B、Etarc77307、Etarac7709、Etarac7055，來自Sumei的PS8249和PS8245，來自Henkel的Ulrta-Reclo 236A、Ulrta-Reclo 247A，來自Soken的NC-310。Suitable commercially available polyacrylate base polymers include Y-1510, Y-1310, Y-1500W, Y-1210, Y-2100 from YASUSA Chemical, BPS5375 from Toyo Ink, Etrac7017B, Etarc77307, Etarac7709 from Eternal, Etarac7055, PS8249 and PS8245 from Sumei, Ulrta-Reclo 236A from Henkel, Ulrta-Reclo 247A, and NC-310 from Soken.

交聯劑本發明的PSA含有一種或多種交聯劑。此交聯劑用於將一個聚合物鏈與另一個聚合物鏈連接。在較佳實施方案中，一種交聯劑、例如第一交聯劑含有環氧樹脂，其可以與在聚丙烯酸酯基礎聚合物中的酸基團反應。環氧樹脂開環並產生一個羥基。PSA可以含有0.16-1.0重量%的第一交聯劑，例如0.16-1.0重量%，0.18-0.9重量%，0.25-1重量%，0.20-0.75重量%，0.3-0.70重量%和0.35-0.5重量%，例如約0.25重量%，基於PSA的總乾重計。關於上限，PSA含有小於1重量%、小於0.9重量%或小於0.7重量%的環氧交聯劑，基於PSA的總乾重計。關於下限，PSA含有大於0.15重量%、例如大於0.20重量%、大於0.25重量%的環氧交聯劑，基於PSA的總乾重計。Cross-linking agent The PSA of the present invention contains one or more cross-linking agents. This crosslinker is used to link one polymer chain to another. In a preferred embodiment, a cross-linking agent, such as a first cross-linking agent, contains an epoxy resin that can react with acid groups in the polyacrylate base polymer. The epoxy ring opens and generates a hydroxyl group. PSA may contain 0.16-1.0% by weight of the first cross-linking agent, such as 0.16-1.0% by weight, 0.18-0.9% by weight, 0.25-1% by weight, 0.20-0.75% by weight, 0.3-0.70% by weight, and 0.35-0.5% by weight %, Such as about 0.25% by weight, based on the total dry weight of the PSA. Regarding the upper limit, the PSA contains less than 1% by weight, less than 0.9% by weight, or less than 0.7% by weight of epoxy crosslinking agent, based on the total dry weight of the PSA. With regard to the lower limit, the PSA contains more than 0.15% by weight, such as more than 0.20% by weight, and more than 0.25% by weight, based on the total dry weight of the PSA.

在較佳實施方案中，環氧樹脂可以含有一種、兩種、三種或更多種叔胺。有利的是，當按照上述合適量使用時，發現具有所述性能的環氧樹脂能與聚丙烯酸酯基礎聚合物以較高的速率和在較溫和的溫度下反應，尤其與具有上述酸值的聚丙烯酸酯基礎聚合物反應。結果，交聯所需的時間、即固化時間有利地顯著縮短。換句話說，驚奇地發現，使用具有特定性能的環氧基交聯劑，例如具有一種或多種叔胺的環氧交聯劑，能有利地提高交聯效率，例如縮短固化時間和/或降低固化所需的溫度。與在120-130ºC溫度下通常需要30分鐘至1小時固化的常規 PSA不同，本發明的PSA可以在相似溫度下在數分鐘內固化，並在一些情況下在甚至更溫和的更低溫度下固化，例如30-100ºC，或50-90ºC、45-80ºC或50-70ºC。關於上限，PSA的固化溫度可以小於100ºC，小於90ºC，小於80ºC，或小於70ºC。關於下限，PSA的固化溫度可以大於30ºC，大於40ºC，或大於45ºC。In a preferred embodiment, the epoxy resin may contain one, two, three or more tertiary amines. Advantageously, when used in the appropriate amounts described above, it has been found that epoxy resins having the properties described can react with polyacrylate base polymers at a higher rate and at a milder temperature, especially with those having an acid value as described above. Polyacrylate base polymer reaction. As a result, the time required for crosslinking, that is, the curing time is advantageously significantly shortened. In other words, it has been surprisingly found that the use of epoxy-based crosslinkers with specific properties, such as epoxy crosslinkers with one or more tertiary amines, can advantageously increase the efficiency of crosslinks, such as shortening the curing time and / or The temperature required for curing. Unlike conventional PSAs, which typically require 30 minutes to 1 hour to cure at 120-130ºC, the PSAs of the present invention can be cured at similar temperatures in minutes, and in some cases at even milder lower temperatures , Such as 30-100ºC, or 50-90ºC, 45-80ºC, or 50-70ºC. Regarding the upper limit, the curing temperature of PSA can be less than 100ºC, less than 90ºC, less than 80ºC, or less than 70ºC. Regarding the lower limit, the curing temperature of PSA can be greater than 30ºC, greater than 40ºC, or greater than 45ºC.

本文中的固化時間表示聚合物組合物通過聚合物鏈的交聯而固化或硬化所需的時間。一般而言，如果使用較高的固化溫度，則可以預期較短的固化時間。The curing time herein means the time required for the polymer composition to be cured or hardened by crosslinking of the polymer chain. In general, shorter curing times can be expected if higher curing temperatures are used.

適用於本發明的環氧樹脂可以包括但不限於以下物質：
(I) 間-苯撐二甲胺的縮水甘油醚

(II) 間-環己基二胺的縮水甘油醚

(III) N,N-二(2,3-環氧基丙基)異丙基胺

(IV) N,N-二(2,3-環氧基丙基)環己基胺
The epoxy resin suitable for the present invention may include, but is not limited to, the following substances:
(I) Glycidyl ether of m-phenylene dimethylamine

(II) Glycidyl ether of m-cyclohexyldiamine

(III) N, N-bis (2,3-epoxypropyl) isopropylamine

(IV) N, N-bis (2,3-epoxypropyl) cyclohexylamine

合適的市售環氧樹脂交聯劑包括、但不限於：來自CVC的ERISYS GA-240(具有結構I)，來自Toyoink 的BXX5983(具有結構II)，和來自YASUSA Chemical的Y-202(具有結構III)。Suitable commercially available epoxy crosslinkers include, but are not limited to: ERISYS GA-240 (with structure I) from CVC, BXX5983 (with structure II) from Toyoink, and Y-202 (with structure) from YASUSA Chemical III).

認為所用環氧樹脂的高的環氧當量重量與增加的反應速率和/或基礎聚丙烯酸酯聚合物的交聯度有關。環氧當量重量(EEW)是限定含有1克當量環氧基的樹脂的重量克數的參數。在較佳實施方案中，PSA的環氧樹脂具有60-300 g/eq的EEW，例如60-100g/eq，60-150g/eq，60-250g/eq，75-125 g/eq，75-200g/eq，90-120g/eq，和100-200g/eq，或約100g/eq。關於上限，PSA的環氧樹脂具有小於300g/eq、小於250g/eq或小於200g/eq的EEW。關於下限，PSA的環氧樹脂具有大於60 g/eq、大於75g/eq或大於80 g/eq的EEW。The high epoxy equivalent weight of the epoxy resin used is believed to be related to the increased reaction rate and / or the degree of crosslinking of the base polyacrylate polymer. Epoxy equivalent weight (EEW) is a parameter that defines the weight in grams of a resin containing 1 gram equivalent epoxy group. In a preferred embodiment, the epoxy resin of PSA has an EEW of 60-300 g / eq, such as 60-100 g / eq, 60-150 g / eq, 60-250 g / eq, 75-125 g / eq, 75- 200 g / eq, 90-120 g / eq, and 100-200 g / eq, or about 100 g / eq. Regarding the upper limit, the epoxy resin of PSA has an EEW of less than 300 g / eq, less than 250 g / eq, or less than 200 g / eq. Regarding the lower limit, the epoxy resin of PSA has an EEW of more than 60 g / eq, more than 75 g / eq, or more than 80 g / eq.

在一些實施方案中，PSA中的聚丙烯酸酯基礎聚合物與第一交聯劑之間的重量比是在111至10,000的範圍內，例如166至3333，1000至5000，或2000至3000。關於上限，聚丙烯酸酯基礎聚合物與第一交聯劑之間的重量比是小於10,000，小於5000，或小於4000。關於下限，聚丙烯酸酯基礎聚合物與第一交聯劑之間的重量比是大於100，例如大於200，大於1000，大於2000，或大於3000。In some embodiments, the weight ratio between the polyacrylate base polymer and the first crosslinking agent in the PSA is in the range of 111 to 10,000, such as 166 to 3333, 1000 to 5000, or 2000 to 3000. Regarding the upper limit, the weight ratio between the polyacrylate base polymer and the first crosslinking agent is less than 10,000, less than 5000, or less than 4000. With regard to the lower limit, the weight ratio between the polyacrylate base polymer and the first crosslinking agent is greater than 100, such as greater than 200, greater than 1000, greater than 2000, or greater than 3000.

在一些實施方案中，PSA也可以包括第二交聯劑，其可以含有異氰酸酯樹脂。異氰酸酯樹脂可以與聚丙烯酸酯基礎聚合物的羥基反應，如以下反應路線所示。
In some embodiments, the PSA may also include a second crosslinking agent, which may contain an isocyanate resin. Isocyanate resins can react with the hydroxyl groups of the polyacrylate base polymer as shown in the following reaction scheme.

在一些實施方案中，PSA含有基於PSA總乾重計的0.05-0.8重量%的第二交聯劑，例如0.005-0.4重量%，0.01-0.4重量%，0.03-0.3重量%，0.05-0.2重量%，和0.08-0.15重量%。關於上限，PSA含有小於0.4重量%、小於0.3重量%、小於0.2重量%或小於0.15重量%的第二交聯劑。關於下限，PSA含有大於0.005重量%、大於0.01重量%、大於0.03重量%或大於0.05重量%的第二交聯劑。In some embodiments, the PSA contains 0.05-0.8% by weight of the second cross-linking agent based on the total dry weight of the PSA, such as 0.005-0.4% by weight, 0.01-0.4% by weight, 0.03-0.3% by weight, 0.05-0.2% %, And 0.08-0.15% by weight. Regarding the upper limit, the PSA contains less than 0.4% by weight, less than 0.3% by weight, less than 0.2% by weight, or less than 0.15% by weight of the second crosslinking agent. Regarding the lower limit, PSA contains more than 0.005 wt%, more than 0.01 wt%, more than 0.03 wt%, or more than 0.05 wt% of a second crosslinking agent.

認為任何異氰酸酯樹脂的NCO含量會影響交聯反應的速率和效率，NCO含量表示基於樹脂總量計的N=C=O官能團的重量百分比。在較佳實施方案中，第二交聯劑是具有基於異氰酸酯樹脂的總乾重計10-30重量%的NCO含量的異氰酸酯樹脂，NCO含量例如是10-15重量%，10-20重量%，12-15重量%，15-25重量%，或15-30重量%。具有在此範圍內的較高NCO含量的異氰酸酯樹脂通常具有低分子量和高揮發性，因此可能是對環境或使用者有害的。關於上限，PSA的第二交聯劑具有小於30重量%、小於25重量%或小於20重量%的NCO含量。關於下限，PSA的第二交聯劑具有大於10重量%、大於12重量%或大於15重量%的NCO含量，基於異氰酸酯樹脂的總乾重計。It is believed that the NCO content of any isocyanate resin will affect the rate and efficiency of the crosslinking reaction. The NCO content represents the weight percentage of N = C = O functional groups based on the total resin. In a preferred embodiment, the second crosslinking agent is an isocyanate resin having an NCO content of 10-30% by weight based on the total dry weight of the isocyanate resin, and the NCO content is, for example, 10-15% by weight, 10-20% by weight, 12-15% by weight, 15-25% by weight, or 15-30% by weight. Isocyanate resins with a higher NCO content in this range typically have a low molecular weight and high volatility, and may therefore be harmful to the environment or the user. Regarding the upper limit, the second crosslinking agent of PSA has an NCO content of less than 30% by weight, less than 25% by weight, or less than 20% by weight. Regarding the lower limit, the second crosslinking agent of PSA has an NCO content of more than 10% by weight, more than 12% by weight, or more than 15% by weight, based on the total dry weight of the isocyanate resin.

合適的市售異氰酸酯樹脂交聯劑包括、但不限於來自Covestro的Desmodur L75、Desmodur N100和Desmodur N3390。Suitable commercially available isocyanate resin crosslinkers include, but are not limited to, Desmodur L75, Desmodur N100, and Desmodur N3390 from Covestro.

在一些實施方案中，PSA同時含有第一交聯劑和第二交聯劑。一方面，發現環氧樹脂交聯了聚丙烯酸酯基礎聚合物並產生比使用異氰酸酯樹脂時更高的交聯密度。因此，具有過高量的環氧樹脂的PSA會具有過高的交聯密度，這可以導致當通過轉移塗覆施用於基材上時的固定性差。另一方面，發現增加異氰酸酯樹脂的量能提高貯存期，但會降低可去除性。因此，具有過高量的異氰酸酯樹脂的PSA可以顯示差的可去除性。因此，本發明人發現，環氧樹脂與異氰酸酯樹脂之間的特定比率能有利地提供出人意料的性能特徵的組合。例如，如上所述，環氧基交聯劑與異氰酸酯交聯劑之間的重量比可以在0.6-20的範圍內，例如0.7-15，1-10，1-8，1-4，例如約1.25、1.33或約3.5。關於上限，第一交聯劑與第二交聯劑之間的重量比是小於20，小於15，小於10，小於8，小於4。關於下限，第一交聯劑與第二交聯劑之間的重量比是大於0.5，大於0.7，或大於1。發現對於控制固化反應速度而言，保持第一和第二交聯劑之間的合適比率是重要的，使得PSA能有效地固化並且也具有理想的貯存期和可操作性，如下文所示。第一和第二交聯劑之間的合適比率也有益於改進PSA的剝離強度。In some embodiments, the PSA contains both a first crosslinker and a second crosslinker. On the one hand, epoxy resins were found to crosslink the polyacrylate base polymer and produce a higher crosslink density than when isocyanate resins were used. Therefore, a PSA having an excessively high amount of an epoxy resin may have an excessively high crosslinking density, which may result in poor fixability when applied to a substrate by transfer coating. On the other hand, it has been found that increasing the amount of isocyanate resin can improve the shelf life, but reduce the removability. Therefore, a PSA having an excessively high amount of an isocyanate resin may show poor removability. Therefore, the present inventors have found that a specific ratio between an epoxy resin and an isocyanate resin can advantageously provide a combination of unexpected performance characteristics. For example, as described above, the weight ratio between the epoxy-based crosslinking agent and the isocyanate-based crosslinking agent may be in the range of 0.6-20, such as 0.7-15, 1-10, 1-8, 1-4, such as about 1.25, 1.33, or about 3.5. Regarding the upper limit, the weight ratio between the first crosslinking agent and the second crosslinking agent is less than 20, less than 15, less than 10, less than 8, and less than 4. Regarding the lower limit, the weight ratio between the first crosslinking agent and the second crosslinking agent is greater than 0.5, greater than 0.7, or greater than 1. It was found that for controlling the curing reaction speed, it is important to maintain a proper ratio between the first and second cross-linking agents so that the PSA can be effectively cured and also has ideal shelf life and operability, as shown below. A suitable ratio between the first and second cross-linking agents is also beneficial to improve the peel strength of the PSA.

增粘劑增粘劑是用於提高粘合劑表面的粘性和粘合性的化合物。常規使用的增粘劑包括松香樹脂，多萜樹脂，烴樹脂(例如C₉ 增粘劑)，酚醛樹脂，或其組合。重要的是，本發明的PSA含有小於5重量%、小於2.5重量%、小於1重量%、小於0.5重量%、小於0.1重量%、例如小於0.05重量%的增粘劑。較佳地，本發明的PSA不含任何增粘劑。本發明人驚奇地發現，增粘劑會不利地影響PSA的耐溶劑性，參見實施例2，因此有益的是從PSA排除增粘劑。Tackifier Tackifier is a compound used to improve the tackiness and adhesion of the adhesive surface. Conventionally used tackifiers include rosin resins, polyterpene resins, hydrocarbon resins (such as C ₉ tackifiers), phenolic resins, or combinations thereof. It is important that the PSA of the invention contains less than 5% by weight, less than 2.5% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, for example less than 0.05% by weight tackifiers. Preferably, the PSA of the present invention does not contain any tackifiers. The inventors have surprisingly found that tackifiers adversely affect the solvent resistance of PSA, see Example 2, so it is beneficial to exclude tackifiers from PSA.

標籤在一些情況下，溶劑基PSA可以用於生產同時具有優良可去除性和高剝離強度的標籤或其它商業產品。因此，本發明也提供含有上述PSA的標籤。標籤可以包含面材層，以及含PSA的粘合劑層。在一些情況下，標籤還包含一個或多個底塗層(primer layer)和/或襯墊，如下文所述。Labels In some cases, solvent-based PSAs can be used to produce labels or other commercial products that have both good removability and high peel strength. Therefore, the present invention also provides a label containing the PSA. The label may include a facestock layer, and a PSA-containing adhesive layer. In some cases, the label also includes one or more primer layers and / or pads, as described below.

在一些實施方案中，標籤含有PSA層，該層可以具有10-40微米的厚度，例如15-35微米，18-30微米，20-40微米，或在上述量內的其它範圍。關於下限，面材層可以具有至少10微米的厚度，例如至少15微米，至少18微米。關於上限，聚烯烴膜可以具有小於40微米的厚度，例如小於35微米，或小於30微米。In some embodiments, the tag contains a PSA layer, which may have a thickness of 10-40 microns, such as 15-35 microns, 18-30 microns, 20-40 microns, or other ranges within the above amounts. With regard to the lower limit, the facestock layer may have a thickness of at least 10 microns, such as at least 15 microns, at least 18 microns. With regard to the upper limit, the polyolefin film may have a thickness of less than 40 microns, such as less than 35 microns, or less than 30 microns.

面材層
標籤可以具有一個或多個面材層。在一個實施方案中，從朝下觀看基材的方向，面材層是標籤的頂表面，其暴露於環境，並且設計成用於接受可印刷的資訊，例如條碼或字母數位元元元字元。Facing material labels may have one or more facing material layers. In one embodiment, the facestock layer is the top surface of the label when viewed from the downward direction of the substrate, which is exposed to the environment and is designed to accept printable information, such as barcodes or alphanumeric characters .

面材層可以例如包括格拉辛紙(glassine)、牛皮紙和聚酯，例如聚對苯二甲酸乙二醇酯(PET)，聚醯胺(PA)，聚萘二甲酸乙二醇酯(PEN)，棉，紙巾，紙，玻璃纖維，合成織物，以及聚烯烴，例如聚丙烯(PP)，乙烯-丙烯共聚物，聚乙烯(PE)，以及它們的組合。其它聚合物膜材料包括基於聚氨酯的聚合物，例如聚醚聚氨酯和聚酯聚氨酯；基於醯胺的聚合物，包括聚醚聚醯胺共聚物；基於丙烯醯的聚合物，包括聚丙烯酸酯，和乙烯/乙酸乙烯酯共聚物；基於聚酯的聚合物，包括聚醚聚酯；氯乙烯；偏二氯乙烯；聚苯乙烯；聚丙烯腈；聚碳酸酯；聚醯亞胺；ABS；聚丙烯酸酯；聚碳酸酯(PC)；聚醯胺；聚醯亞胺(PI)；聚醯氨基醯亞胺；聚縮醛；聚苯醚(PPO)；聚碸，聚醚碸(PES)；聚苯硫醚；聚醚醚酮(PEEK)；聚醚醯亞胺(PEl)；金屬化的聚對苯二甲酸乙二醇酯(PET)；聚氟乙烯(PVF)；聚乙烯醚(PEE)；氟化乙烯丙烯共聚物(FEP)；聚氨酯(PUR)；液晶聚合物(LCP，屬於芳族聚酯)；聚偏二氟乙烯(PVDF)；芳族聚醯胺纖維；DIALAMY(聚合物合金)；聚萘二甲酸乙二醇酯(PEN)；乙烯/四氟乙烯共聚物(E/TFE)；聚苯碸(PPSU)；以及含有一種或多種這些材料的聚合物或聚合物合金。The facestock layer may include, for example, glassine, kraft paper, and polyester, such as polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN) , Cotton, paper towels, paper, fiberglass, synthetic fabrics, and polyolefins, such as polypropylene (PP), ethylene-propylene copolymer, polyethylene (PE), and combinations thereof. Other polymer film materials include polyurethane-based polymers, such as polyether polyurethanes and polyester polyurethanes; fluorene-based polymers, including polyether polyfluorene copolymers; acrylic-based polymers, including polyacrylates, and Ethylene / vinyl acetate copolymer; polyester-based polymers including polyether polyester; vinyl chloride; vinylidene chloride; polystyrene; polyacrylonitrile; polycarbonate; polyimide; ABS; polyacrylic acid Esters; Polycarbonate (PC); Polyamidine; Polyamidoimine (PI); Polyamidoamidoimine; Polyacetal; Polyphenylene ether (PPO); Polyfluorene, Polyetherfluorene (PES); Polyester Phenyl sulfide; polyetheretherketone (PEEK); polyetherimide (PEl); metalized polyethylene terephthalate (PET); polyvinyl fluoride (PVF); polyvinyl ether (PEE) ; Fluorinated ethylene propylene copolymer (FEP); polyurethane (PUR); liquid crystal polymer (LCP, which is an aromatic polyester); polyvinylidene fluoride (PVDF); aromatic polyamide fibers; DIALAMY (polymer alloy ); Polyethylene naphthalate (PEN); ethylene / tetrafluoroethylene copolymer (E / TFE); polyphenylene terephthalate (PPSU); and those containing one or more of these materials Polymer or polymer alloy.

面材層的厚度或塗覆重量可以根據對於具體應用所需的標籤的勁度而變化。根據本發明的某些實施方案，面材層可以具有100-1000微米的厚度，例如200-800微米，150-500微米，300-600微米，或450-900微米，或上述量的其它範圍。關於下限，面材層可以具有至少100微米的厚度，例如至少150微米，至少200微米，或至少300微米。關於上限，聚烯烴膜可以具有小於1000微米的厚度，例如小於800微米，小於500微米，小於400微米，或小於300微米。在一些實施方案中，面材層是125微米。The thickness or coating weight of the facestock layer can vary depending on the stiffness of the label required for a particular application. According to certain embodiments of the present invention, the facestock layer may have a thickness of 100-1000 microns, such as 200-800 microns, 150-500 microns, 300-600 microns, or 450-900 microns, or other ranges of the above amounts. With regard to the lower limit, the facestock layer may have a thickness of at least 100 microns, such as at least 150 microns, at least 200 microns, or at least 300 microns. With regard to the upper limit, the polyolefin film may have a thickness of less than 1000 microns, such as less than 800 microns, less than 500 microns, less than 400 microns, or less than 300 microns. In some embodiments, the facestock layer is 125 microns.

面材層可以視需要地設計成能接受印刷。例如，面材層可以含有一個或多個可印刷的層，該層含有用於形成印刷資訊的油墨接受性組合物。各種這類組合物是本領域公知的，這些組合物通常包括粘合劑和分散在粘合劑中的顏料，例如二氧化矽或滑石。視需要地，可印刷的層含有交聯劑CX-100 (DSM的多官能乙烯亞胺液體交聯劑)。美國專利No. 6,153,288描述了許多這類油墨接受性組合物，將其公開內容引入本文以供參考。可印刷的資訊可以使用各種印刷技術佈置在面材層上，例如絲網印刷，點陣式印刷，噴墨印刷，鐳射印刷，鐳射標記，熱轉移印刷等等。在一些情況下，面材層可接受熱轉移印刷。The facestock layer can be designed to accept printing as needed. For example, the facestock layer may contain one or more printable layers containing an ink-receptive composition for forming printed information. Various such compositions are well known in the art, and these compositions generally include a binder and a pigment dispersed in the binder, such as silica or talc. Optionally, the printable layer contains a cross-linking agent CX-100 (DSM's multifunctional ethyleneimine liquid cross-linking agent). U.S. Patent No. 6,153,288 describes many such ink receiving compositions, the disclosure of which is incorporated herein by reference. Printable information can be arranged on the surface layer using various printing technologies, such as screen printing, dot matrix printing, inkjet printing, laser printing, laser marking, thermal transfer printing and so on. In some cases, the facestock layer can be subjected to thermal transfer printing.

用於在面材層上印刷的油墨可以在寬範圍內變化，可以包括市售的水性、溶劑基或可輻照固化的油墨。這些油墨的例子包括 Sun Sheen(Sun Chemical的產品，是可用醇稀釋的聚醯胺油墨)，SUNTEX® MP(Sun Chemical的產品，是溶劑基油墨，配製用於表面印刷帶丙烯醯基塗層的基材、被PVDC塗覆的基材和聚烯烴膜)，X-Cel(Water Ink Technologies的產品，是用於印刷膜基材的水性膜油墨)，Uvilith AR-109 Rubine Red(Daw Ink的產品，是UV油墨)和CLA91598F(Sun Chemical的產品，是多重連接的黑色溶劑基油墨)。The inks used to print on the facestock layer can vary over a wide range and can include commercially available water-based, solvent-based, or radiation-curable inks. Examples of these inks include Sun Sheen (a product of Sun Chemical, a polyamine-based ink that can be diluted with alcohol), SUNTEX® MP (a product of Sun Chemical, a solvent-based ink, formulated for surface printing with acryl-based coatings) Substrate, PVDC-coated substrate, and polyolefin film), X-Cel (a product of Water Ink Technologies, an aqueous film ink for printed film substrates), Uvilith AR-109 Rubine Red (a product of Daw Ink , UV ink) and CLA91598F (a product of Sun Chemical, a multi-linked black solvent-based ink).

面材層可以含有一個或多個頂塗層，其改進印刷性能、耐久性和/或耐溶劑性。在一個實施方案中，頂塗層設計為其頂表面與在面材層中的可印刷層的底表面接觸。在一個實施方案中，標籤的頂塗層通常含有樹脂。適合用作頂塗層的樹脂的非限制性例子包括聚酯-氨基樹脂和苯氧基樹脂，聚酯-異氰酸酯，聚氨酯，和聚丙烯酸酯。The facestock layer may contain one or more topcoats that improve printability, durability, and / or solvent resistance. In one embodiment, the top coat is designed such that its top surface is in contact with the bottom surface of the printable layer in the facestock layer. In one embodiment, the top coat of the label typically contains a resin. Non-limiting examples of resins suitable for use as the top coat include polyester-amino resins and phenoxy resins, polyester-isocyanates, polyurethanes, and polyacrylates.

在一些情況下，面材層可以是使用可活化的油墨的面材，例如可刺激活化的油墨，例如(例如)鐳射活化的油墨、壓力活化的油墨或溫度活化的油墨。In some cases, the facestock layer may be a facestock using an activatable ink, such as a stimulable ink, such as, for example, a laser activated ink, a pressure activated ink, or a temperature activated ink.

根據本發明的某些實施方案，頂塗層可以通過本領域公知的任何技術施塗到面材層的面材部分上，例如噴塗、輥塗、刷塗或其它技術。可印刷的層可以通過沉積、凹版印刷等技術在頂塗層上形成，其中底表面與頂塗層的頂表面接觸。According to certain embodiments of the present invention, the topcoat may be applied to the facestock portion of the facestock layer by any technique known in the art, such as spray coating, roller coating, brushing, or other techniques. The printable layer can be formed on the top coating by techniques such as deposition, gravure printing, etc., where the bottom surface is in contact with the top surface of the top coating.

底塗層
視需要地，本發明的標籤含有一個或多個底塗層，並且一個或多個底塗層可以位於面材層和粘合劑層之間。Undercoat layer Optionally, the label of the present invention contains one or more undercoat layers, and one or more undercoat layers may be located between the facestock layer and the adhesive layer.

視需要組分在一些情況下，PSA、面材層、頂塗層或底塗層可以視需要地包含一種或多種填料、抗氧化劑、UV吸收劑、光穩定劑和/或填料。這些添加劑可以使用常規設備和技術按照常規量引入粘合劑中。例如，代表性的填料可以包括滑石，碳酸鈣，有機粘土，玻璃纖維，大理石粉，水泥粉，長石，二氧化矽或玻璃，熱解法二氧化矽，矽酸鹽，氧化鋁，各種磷化合物，溴化銨，二氧化鈦，三氧化銻，三氧化銻，氧化鋅，硼酸鋅，硫酸鋇，有機矽，矽酸鋁，矽酸鈣，玻璃微球，白堊，雲母，粘土，矽灰石，八鉬酸銨，膨脹化合物以及兩種或更多種這些材料的混合物。填料也可以攜帶或包含各種表面塗料或處理劑，例如矽烷、脂肪酸等。其它填料可以包括阻燃劑，例如鹵化有機化合物。在某些實施方案中，頂塗層可以包含一種或多種能與該層的其它組分相容的熱塑性彈性體，例如醚化蜜胺、羥基化聚酯、聚酯蜜胺以及其它合適的彈性體。Optional Components In some cases, the PSA, facestock, topcoat, or basecoat may optionally include one or more fillers, antioxidants, UV absorbers, light stabilizers, and / or fillers. These additives can be incorporated into the adhesive in conventional amounts using conventional equipment and techniques. For example, representative fillers may include talc, calcium carbonate, organoclay, fiberglass, marble powder, cement powder, feldspar, silica or glass, pyrogenic silica, silicate, alumina, various phosphorus compounds, Ammonium bromide, titanium dioxide, antimony trioxide, antimony trioxide, zinc oxide, zinc borate, barium sulfate, organic silicon, aluminum silicate, calcium silicate, glass microspheres, chalk, mica, clay, wollastonite, octamolybdenum Ammonium acid, swelling compounds, and mixtures of two or more of these materials. Fillers can also carry or contain various surface coatings or treatment agents, such as silanes, fatty acids, and the like. Other fillers may include flame retardants, such as halogenated organic compounds. In certain embodiments, the topcoat may include one or more thermoplastic elastomers that are compatible with other components of the layer, such as etherified melamine, hydroxylated polyester, polyester melamine, and other suitable elastomers. body.

襯墊在一些實施方案中，標籤還包括位於與面材層接觸的反應性粘合劑層表面的另一側上的襯墊。可釋放的襯墊可以位於與反應性粘合劑層相鄰的位置，使得反應性粘合劑層直接或間接地位於或夾在面材層的底表面和可釋放的襯墊之間。可釋放的襯墊可以起到保護蓋的作用，使得可釋放的襯墊保持在適當位置直到標籤即將用於粘附到物體上。如果標籤中包括襯墊或可釋放的襯墊，則多種材料和結構可以用於襯墊。在許多實施方案種，襯墊是紙或紙基材料。在許多其它實施方案中，襯墊是一種或多種聚合物材料的聚合物膜。通常，襯墊的至少一個面塗有可釋放的材料，例如矽氧烷或基於矽氧烷的材料。據理解，襯墊的可釋放的塗覆面與粘合劑層的另外暴露面接觸。在將標籤施用于有意義的表面上以前，將襯墊除去，從而暴露標籤的粘合劑面。襯墊可以是單一薄片的形式。作為選擇，襯墊可以是多段或板的形式。Liner In some embodiments, the label further includes a liner on the other side of the surface of the reactive adhesive layer in contact with the facestock layer. The releasable liner may be located adjacent to the reactive adhesive layer such that the reactive adhesive layer is directly or indirectly located or sandwiched between the bottom surface of the facestock layer and the releasable liner. The releasable pad can serve as a protective cover, keeping the releasable pad in place until the label is about to be used to adhere to an object. If the label includes a cushion or a releasable cushion, a variety of materials and structures can be used for the cushion. In many embodiments, the liner is paper or a paper-based material. In many other embodiments, the gasket is a polymer film of one or more polymer materials. Typically, at least one side of the pad is coated with a releasable material, such as a siloxane or a siloxane-based material. It is understood that the releasable coated side of the pad is in contact with another exposed side of the adhesive layer. Before applying the label to a meaningful surface, the liner is removed, exposing the adhesive side of the label. The cushion may be in the form of a single sheet. Alternatively, the pad may be in the form of a multi-segment or plate.

用於標籤中的襯墊可以具有20-150微米的厚度，例如30-120微米，60-100微米，或50-90微米。關於上限，標籤的厚度是小於150微米，例如小於130微米，或小於100微米。關於下限，標籤的厚度是大於20微米，例如大於30微米，或大於40 微米。The liner used in the label may have a thickness of 20-150 microns, such as 30-120 microns, 60-100 microns, or 50-90 microns. With regard to the upper limit, the thickness of the label is less than 150 microns, such as less than 130 microns, or less than 100 microns. With regard to the lower limit, the thickness of the label is greater than 20 microns, such as greater than 30 microns, or greater than 40 microns.

也可將各種添加劑加入面材、底塗層、粘合劑層或襯墊層中的一個或多個中以得到某些所需特性。這些添加劑可包括例如一種或多種蠟、表面活性劑、滑石、粉狀矽酸鹽、填料劑、消泡劑、著色劑、抗氧化劑、UV穩定劑、發光劑、交聯劑、緩衝劑、防結塊劑、潤濕劑、消光劑、抗靜電劑、酸清除劑、阻燃劑、加工助劑、擠出助劑和其它。Various additives may also be added to one or more of the facestock, basecoat, adhesive layer, or backing layer to obtain certain desired characteristics. These additives may include, for example, one or more waxes, surfactants, talc, powdered silicates, fillers, defoamers, colorants, antioxidants, UV stabilizers, luminescent agents, crosslinkers, buffers, anti-oxidants Caking agents, wetting agents, matting agents, antistatic agents, acid scavengers, flame retardants, processing aids, extrusion aids and others.

剝離強度本發明的PSA具有高的剝離強度。剝離強度是為了在恒定速度和特定角度下從基材去除在特定條件下層壓到基材上的粘合劑所需的平均力。剝離強度的評估可以通過根據FINAT測試方法1(2017)(“FINAT-1”)檢測180°不銹鋼剝離20分鐘和24小時進行。當施加於不銹鋼上，PSA可以顯示根據FINAT-1方法檢測的剝離強度為2-10 N/英寸，例如2-7 N/英寸，3-9 N/英寸，5-10 N/英寸，和7-10 N/英寸。關於上限，PSA顯示在不銹鋼上的剝離強度小於10 N/英寸，例如小於9 N/英寸，或小於8 N/英寸。關於下限，PSA顯示在不銹鋼上的剝離強度大於2 N/英寸，大於3 N/英寸，或大於5 N/英寸。Peel strength The PSA of the present invention has high peel strength. Peel strength is the average force required to remove an adhesive laminated to a substrate under specific conditions from a substrate at a constant speed and a specific angle. Evaluation of peel strength can be performed by detecting 180 ° stainless steel peeling for 20 minutes and 24 hours according to FINAT test method 1 (2017) ("FINAT-1"). When applied to stainless steel, PSA can show peel strengths of 2-10 N / inch as measured by FINAT-1, such as 2-7 N / inch, 3-9 N / inch, 5-10 N / inch, and 7 -10 N / inch. Regarding the upper limit, PSA shows a peel strength on stainless steel of less than 10 N / inch, such as less than 9 N / inch, or less than 8 N / inch. Regarding the lower limit, PSA shows peel strength on stainless steel greater than 2 N / inch, greater than 3 N / inch, or greater than 5 N / inch.

可去除性
如上所述，本發明的PSA具有高度的可去除性。認為這種高度的可去除性至少部分地歸功於上述交聯劑的存在。交聯劑的存在提高了PSA的粘結力性能，使得粘合劑可以在不留下殘留物的情況下從基材表面去除。 PSA的可去除性能可以通常通過以下方式確定：
· 將PSA粘附到基材的表面(例如不銹鋼)達到一段時間，例如至少3天，至少5天，至少10天，從而使PSA在高溫和具有80%以上濕度的環境下老化。溫度範圍通常是40-90ºC；然後
· 從表面剝離PSA；然後
· 目測觀察表面上保留的任何粘合劑殘留物—保留在基材表面上的較少殘留物表示可去除性較高；然後
· 基於保留的粘合劑量確定數值。Removability As described above, the PSA of the present invention is highly removable. It is believed that this high degree of removability is due, at least in part, to the presence of the aforementioned crosslinking agents. The presence of a cross-linking agent improves the PSA's cohesive properties, allowing the adhesive to be removed from the surface of the substrate without leaving residues. PSA's removable performance can usually be determined by:
· Adhere PSA to the surface of the substrate (such as stainless steel) for a period of time, such as at least 3 days, at least 5 days, at least 10 days, so that the PSA is aged under high temperature and 80% humidity. The temperature range is usually 40-90ºC; then · PSA is peeled from the surface; then · any adhesive residue remaining on the surface is visually observed-less residue remaining on the surface of the substrate indicates higher removability; then · The value is determined based on the amount of adhesive retained.

該數值可以基於1-5的評級，其中5表示在剝離標籤後在基材上沒有留下殘留物(例如在小於3%的與PSA接觸的表面積上留下殘留物)，3 表示留下很少的殘留物(例如在小於20%的與PSA接觸的表面積上留下殘留物)，和1表示在基材上留下顯著量(例如大於40%)的殘留物。一般而言，對於大多數應用而言，認為4或5的可去除性是可接受的。This value can be based on a rating of 1-5, where 5 means no residue is left on the substrate after peeling off the label (for example, less than 3% of the surface area in contact with PSA is left), and 3 means very Fewer residues (for example, leaving less than 20% of the surface area in contact with PSA), and 1 means leaving a significant amount (for example, more than 40%) of residue on the substrate. In general, a removability of 4 or 5 is considered acceptable for most applications.

固化時間
本發明的PSA令人驚奇地和出人意料地具有高的交聯效率。認為這種高的交聯效率歸功於在PSA中所用的一種或多種交聯劑的合適用量和性能。例如，具有一種或多種叔胺的環氧基交聯劑可以顯著改進固化效率。這通常反映為與常規PSA相比，本發明的PSA具有較短的固化時間(參見上文)。在較佳實施方案中，當在120°C下固化時，PSA的固化時間可以是0.5-5分鐘，例如0.5-1分鐘，1-2分鐘，1-3分鐘，2-4分鐘，或4-5分鐘。關於此範圍的上限，固化時間是小於7分鐘，小於6分鐘，小於5分鐘，或小於3分鐘。關於此範圍的下限，固化時間是大於0.5分鐘，大於1分鐘，大於2分鐘，或大於3分鐘。Curing time The PSA of the present invention has surprisingly and unexpectedly high crosslinking efficiency. It is believed that this high crosslinking efficiency is attributed to the appropriate amount and performance of one or more crosslinking agents used in the PSA. For example, epoxy-based crosslinkers with one or more tertiary amines can significantly improve curing efficiency. This is generally reflected in the shorter curing time of the PSA of the present invention compared to conventional PSAs (see above). In a preferred embodiment, when cured at 120 ° C, the curing time of the PSA may be 0.5-5 minutes, such as 0.5-1 minutes, 1-2 minutes, 1-3 minutes, 2-4 minutes, or 4 -5 minutes. Regarding the upper limit of this range, the curing time is less than 7 minutes, less than 6 minutes, less than 5 minutes, or less than 3 minutes. Regarding the lower limit of this range, the curing time is more than 0.5 minutes, more than 1 minute, more than 2 minutes, or more than 3 minutes.

凝膠含量
本發明的PSA也具有高的凝膠含量，這是由於聚丙烯酸酯基礎聚合物被交聯劑充分交聯。凝膠含量通常通過將粘合劑溶解在合適的溶劑中達到至少一天，並從粘合劑的不可溶級分分離含有粘合劑可溶性級分的溶液來確定。不可溶級分，即凝膠，進行乾燥和相對於粘合劑的總乾重計稱重。凝膠含量一般與交聯度、PSA的粘附強度和PSA的可去除性成正比。在一些實施方案中，PSA的凝膠含量是基於PSA總乾重計的40- 95重量%，例如45-95重量%，50-90重量%，或60-85重量%。Gel Content The PSA of the present invention also has a high gel content because the polyacrylate base polymer is sufficiently crosslinked by a crosslinking agent. The gel content is generally determined by dissolving the binder in a suitable solvent for at least one day and separating the solution containing the binder-soluble fraction from the insoluble fraction of the binder. The insoluble fraction, ie the gel, is dried and weighed relative to the total dry weight of the binder. The gel content is generally directly proportional to the degree of cross-linking, PSA adhesion strength, and PSA removability. In some embodiments, the gel content of the PSA is 40-95% by weight, such as 45-95% by weight, 50-90% by weight, or 60-85% by weight based on the total dry weight of the PSA.

耐溶劑性本發明的PSA具有優異的耐溶劑性。此特徵對於其中PSA與溶劑接觸的應用而言是理想的，溶劑例如是水、乙醇和油。耐溶劑性可以通過將PSA在溶劑中浸泡長時間來檢測，例如至少60分鐘，至少5小時，或至少3天。然後評估在溶劑處理之前和之後的PSA的外觀和/或性能，並進行比較。因為溶劑通常導致PSA的外觀不透明，因此在一個實施方案中，耐溶劑性可以通過光學方法檢測PSA的不透明度來測定。對於具有優異耐水性的粘合劑，在浸泡于水中之前和之後，不透明度的增加是很少的，目測沒有區別或區別很小。一種常用的檢測不透明度的方法是霧度實驗；霧度反映了當光通過PSA時的光散射的量，並且可以用於定量表面或內部試樣的表現為不透明的缺陷。在溶劑處理之前，PSA通常是透明的，所以霧度值接近0。在溶劑處理之後PSA的低霧度值表示低的不透明度，表明PSA的耐溶劑性較高。PSA的霧度值可以根據ASTM D 1003檢測。Solvent resistance The PSA of the present invention has excellent solvent resistance. This feature is ideal for applications where PSA is in contact with solvents such as water, ethanol, and oil. Solvent resistance can be measured by immersing the PSA in a solvent for a long time, for example at least 60 minutes, at least 5 hours, or at least 3 days. The appearance and / or performance of PSA before and after solvent treatment was then evaluated and compared. Because solvents often cause the appearance of PSA to be opaque, in one embodiment, solvent resistance can be determined by optically detecting the opacity of the PSA. For adhesives with excellent water resistance, there is little increase in opacity before and after immersion in water, and there is no difference or small difference visually. A commonly used method for detecting opacity is the haze experiment; the haze reflects the amount of light scattering when light passes through the PSA, and can be used to quantify defects that appear as opaque on the surface or inside the sample. Prior to solvent treatment, PSA is usually transparent, so the haze value is close to zero. The low haze value of PSA after solvent treatment indicates low opacity, indicating that the solvent resistance of PSA is higher. The haze value of PSA can be detected according to ASTM D 1003.

含有獨特組合和比例的本發明PSA具有0-15%的霧度值，例如 1-10%，2-8%，3-7%，或4-6%。關於上限，霧度值是小於15%，小於12%，小於10%。關於下限，霧度值是大於0%，大於1%，或大於2%。本發明人發現，通過使用具有2-90 mg KOH/g的酸值和具有高於-41 ºC的Tg的聚丙烯酸酯基礎聚合物、使用大於0.15重量%的環氧樹脂和使用極少增粘劑或不使用增粘劑，能提高PSA的耐溶劑性。不受任何理論的束縛，認為優良的霧度值可以至少部分地歸因於當使用上述組分時實現的優異的交聯效率。其它的有貢獻的因素包括高的凝膠含量，以及非常少量的低分子量組分，例如增粘劑。The PSA of the present invention containing unique combinations and ratios has a haze value of 0-15%, such as 1-10%, 2-8%, 3-7%, or 4-6%. Regarding the upper limit, the haze value is less than 15%, less than 12%, and less than 10%. Regarding the lower limit, the haze value is greater than 0%, greater than 1%, or greater than 2%. The inventors have found that by using a polyacrylate base polymer having an acid value of 2-90 mg KOH / g and a Tg above -41 ºC, using an epoxy resin of more than 0.15% by weight, and using very little tackifier Or without using a tackifier, it can improve the solvent resistance of PSA. Without being bound by any theory, it is believed that the excellent haze value can be attributed at least in part to the excellent cross-linking efficiency achieved when the above-mentioned components are used. Other contributing factors include high gel content and very small amounts of low molecular weight components such as tackifiers.

貯存期本發明的PSA具有改進的貯存期。貯存期表示初始混合的組合物達到雙倍粘度所需的時間。貯存期是指示PSA的固化速度和PSA的可操作性的優良指標。通常，從產品混合的時刻開始，並在操作溫度、例如室溫下檢測。為了工業生產PSA，重要的是貯存期足夠長以允許在生產線上處理組合物，但是不會太長以致減慢生產工藝。本發明的PSA含有合適量的交聯劑，例如環氧交聯劑，使得可以達到優化的貯存期。本發明的PSA通常具有4-32小時的貯存期，例如4-8小時，4-16小時，8-10小時，8-16小時，和16-32小時。關於下限，PSA具有大於4小時的貯存期，例如大於8小時，大於10小時，或大於15小時。關於上限，PSA具有小於32小時的貯存期，例如小於25小時，小於20小時，或大於16小時。Shelf life The PSA of the present invention has an improved shelf life. The shelf life indicates the time required for the initially mixed composition to reach double viscosity. The shelf life is an excellent indicator of the curing speed of PSA and the operability of PSA. Usually, it starts at the moment of product mixing and is detected at an operating temperature, such as room temperature. For the industrial production of PSA, it is important that the storage period is long enough to allow the composition to be processed on the production line, but not so long as to slow down the production process. The PSA of the present invention contains a suitable amount of a cross-linking agent, such as an epoxy cross-linking agent, so that an optimal shelf life can be achieved. The PSA of the present invention typically has a shelf life of 4 to 32 hours, such as 4 to 8 hours, 4 to 16 hours, 8 to 10 hours, 8 to 16 hours, and 16 to 32 hours. With regard to the lower limit, PSA has a shelf life of more than 4 hours, such as more than 8 hours, more than 10 hours, or more than 15 hours. Regarding the upper limit, PSA has a shelf life of less than 32 hours, such as less than 25 hours, less than 20 hours, or more than 16 hours.

粘合劑配製劑本發明也提供粘合劑配製劑，其含有溶劑、聚丙烯酸酯基礎聚合物、增粘劑、含環氧樹脂的第一交聯劑和視需要地含異氰酸酯樹脂的第二交聯劑，如上所述。合適的溶劑包括但不限於甲苯和乙酸乙酯。Adhesive formulation The present invention also provides an adhesive formulation comprising a solvent, a polyacrylate base polymer, a tackifier, a first cross-linking agent containing an epoxy resin, and a second isocyanate-containing resin, if necessary. Crosslinking agent, as described above. Suitable solvents include, but are not limited to, toluene and ethyl acetate.

生產PSA 本發明也涉及生產PSA的方法。此方法包括提供溶劑，含環氧樹脂的第一交聯劑，視需要地第二交聯劑，和具有酸值為2-90 mg KOH/g的聚丙烯酸酯基礎聚合物；並且混合所述溶劑、第一交聯劑和聚合物以形成粘合劑配製劑。聚丙烯酸酯基礎聚合物、第一交聯劑和/或第二交聯劑的任何上述實施方案可以用於生產粘合劑配製劑。示例性的PSA 配製劑如表1所示。此方法通常稱為配混(compounding)。可以在小於50°C的溫度下，例如在20°C和40°C之間，或在20°C和30°C之間，或者在低於用於固化的觸發溫度的任何溫度下進行配混。Producing PSA The present invention also relates to a method for producing PSA. This method includes providing a solvent, a first cross-linking agent containing an epoxy resin, and optionally a second cross-linking agent, and a polyacrylate base polymer having an acid value of 2-90 mg KOH / g; and mixing the A solvent, a first crosslinking agent, and a polymer to form an adhesive formulation. Any of the above embodiments of the polyacrylate base polymer, the first cross-linking agent, and / or the second cross-linking agent can be used to produce an adhesive formulation. Exemplary PSA formulations are shown in Table 1. This method is commonly referred to as compounding. Can be formulated at temperatures less than 50 ° C, such as between 20 ° C and 40 ° C, or between 20 ° C and 30 ° C, or at any temperature below the trigger temperature for curing Mixed.

各種溶劑可以用於溶解PSA的各組分。合適的溶劑包括具有適當蒸發速率的那些，且各種組分在此溶劑中顯示優良的溶解度。在較佳實施方案中，溶劑是基於石油的溶劑。合適的溶劑包括但不限於：芳族溶劑，脂族溶劑，酯溶劑，二甲苯，乙苯，異丙醇，以及它們的混合物。芳族溶劑的例子包括具有烷基取代基的芳環（例如甲苯）。酯溶劑的例子包括3或更多個碳原子的酯（例如乙酸甲酯或乙酸乙酯）。在一些實施方案中，兩種或更多種溶劑可以用於溶解上述各種組分以生產粘合劑配製劑。Various solvents can be used to dissolve the components of the PSA. Suitable solvents include those with a suitable evaporation rate, and the various components show excellent solubility in this solvent. In a preferred embodiment, the solvent is a petroleum-based solvent. Suitable solvents include, but are not limited to, aromatic solvents, aliphatic solvents, ester solvents, xylene, ethylbenzene, isopropanol, and mixtures thereof. Examples of the aromatic solvent include an aromatic ring having an alkyl substituent (for example, toluene). Examples of the ester solvent include an ester of 3 or more carbon atoms (for example, methyl acetate or ethyl acetate). In some embodiments, two or more solvents can be used to dissolve the various components described above to produce an adhesive formulation.

用於生產粘合劑配製劑的一種或多種溶劑的量可以根據適用於在基材或其它層上塗覆的所需粘度而變化。通常，在粘合劑配製劑中的溶劑的存在量是5-50重量%，例如8-45重量%，10-40重量%，15-25重量%，例如約17重量%。關於下限，溶劑的存在量是大於5重量%，例如大於8重量%，大於10重量%，或大於12重量%，大於15重量%，或約17重量%，基於粘合劑配製劑的總重量計。關於上限，溶劑的存在量是小於50重量%，例如小於40重量%，小於30重量%，或小於20重量%，基於粘合劑配製劑的總重量計。The amount of one or more solvents used to produce the adhesive formulation may vary depending on the desired viscosity suitable for coating on a substrate or other layer. Generally, the solvent is present in the adhesive formulation in an amount of 5-50% by weight, such as 8-45% by weight, 10-40% by weight, 15-25% by weight, such as about 17% by weight. With regard to the lower limit, the solvent is present in an amount greater than 5 wt%, such as greater than 8 wt%, greater than 10 wt%, or greater than 12 wt%, greater than 15 wt%, or about 17 wt%, based on the total weight of the adhesive formulation meter. With regard to the upper limit, the solvent is present in an amount of less than 50% by weight, such as less than 40% by weight, less than 30% by weight, or less than 20% by weight, based on the total weight of the adhesive formulation.

通常，當儲存時，含有聚丙烯酸酯基礎聚合物的溶液保持與交聯劑分開，從而防止不需要的交聯。可以剛好在生產粘合劑和/或標籤之前將交聯劑加入含有聚丙烯酸酯基礎聚合物的溶液中。因此，在一些實施方案中，本發明提供粘合劑系統，其包含：具有酸基團且酸值為2-90 mg KOH/g的聚丙烯酸酯基礎聚合物，含有環氧樹脂的第一交聯劑；其中交聯劑是與聚丙烯酸酯基礎聚合物分開的。Generally, when stored, the solution containing the polyacrylate base polymer remains separate from the crosslinking agent, thereby preventing unwanted crosslinking. The crosslinker can be added to the solution containing the polyacrylate base polymer just before the adhesive and / or label is produced. Therefore, in some embodiments, the present invention provides an adhesive system comprising: a polyacrylate base polymer having an acid group and an acid value of 2-90 mg KOH / g, and a first cross-link containing an epoxy resin. Crosslinker; where the crosslinker is separate from the polyacrylate base polymer.

如上所述製備的粘合劑配製劑具有優良的可塗覆性，典型的粘度是100-5000 cps，例如200-4000 cps，300-3000 cps，400-2000 cps，300-600 cps，或約500 cps。關於下限，粘度是大於100cps，例如大於200 cps，大於300 cps，或大於400 cps。關於上限，粘度是小於5000 cps，小於4000cps，小於2000cps，小於1000cps。檢測粘度的方法是公知的，例如使用Brookfield粘度計方法，其中通過低速和中速旋轉檢測流體的流動阻力。The adhesive formulations prepared as described above have excellent coatability, and typical viscosities are 100-5000 cps, such as 200-4000 cps, 300-3000 cps, 400-2000 cps, 300-600 cps, or about 500 cps. With regard to the lower limit, the viscosity is greater than 100 cps, such as greater than 200 cps, greater than 300 cps, or greater than 400 cps. Regarding the upper limit, the viscosity is less than 5000 cps, less than 4000 cps, less than 2000 cps, and less than 1000 cps. Methods for detecting viscosity are well known, such as the Brookfield viscometer method, in which the resistance to flow of a fluid is detected by low and medium speed rotation.

在一些實施方案中，如上所述製備的粘合劑配製劑可以然後使用溶劑塗覆器通過在輥上的刮刀、狹縫式模口或刮刀式(comma)塗覆方法塗覆到面材上。配製劑可以塗覆形成粘合劑層，其具有至少5克/平方米(gsm)的塗覆重量，例如至少10 gsm或至少15 gsm。關於上限，配製劑可以塗覆形成塗覆重量為60 gsm或更低的粘合劑層，例如50 gsm或更低，或40 gsm或更低。關於此範圍，配製劑可以塗覆形成具有塗覆重量為5-60 gsm、例如10-50gsm或15-40gsm的粘合劑層，這取決於粘合劑層的最終用途。被上述配製劑塗覆的面材/襯墊然後可以如下文所述進行乾燥，並加工成標籤。在一些情況下，其用作轉移粘合劑且與面材不相關。In some embodiments, the adhesive formulation prepared as described above can then be applied to the facestock using a solvent applicator by a doctor blade, slot die or comma coating method on a roller . The formulation can be applied to form an adhesive layer having a coating weight of at least 5 grams per square meter (gsm), such as at least 10 gsm or at least 15 gsm. With regard to the upper limit, the formulation can be applied to form an adhesive layer having a coating weight of 60 gsm or less, such as 50 gsm or less, or 40 gsm or less. With regard to this range, the formulation can be coated to form an adhesive layer having a coating weight of 5-60 gsm, such as 10-50 gsm or 15-40 gsm, depending on the end use of the adhesive layer. The facestock / liner coated with the above formulation can then be dried as described below and processed into a label. In some cases, it is used as a transfer adhesive and is not related to the facestock.

塗覆工藝通常在具有多個溫度區域的烘箱中進行，例如至少2個區域，至少3個區域，至少4個區域，至少5個區域，或至少6個區域。這些溫度區域可以處於30-200ºC，例如40-150ºC或60-130ºC。溫度可以從第一區域向最後一個區域提高，但是多個區域可以處於相同的溫度。The coating process is usually performed in an oven with multiple temperature zones, such as at least 2 zones, at least 3 zones, at least 4 zones, at least 5 zones, or at least 6 zones. These temperature zones can be at 30-200ºC, such as 40-150ºC or 60-130ºC. The temperature may increase from the first region to the last region, but multiple regions may be at the same temperature.

塗覆後，粘合劑可以在烘箱中乾燥預定的乾燥時間。乾燥烘箱可以具有高於100ºC的溫度。溶劑蒸發的速率隨著溫度的升高而提高。乾燥時間可以是至少2分鐘，至少4分鐘，至少6分鐘，至少8分鐘，至少10分鐘，至少15分鐘，至少20分鐘，至少25分鐘，至少30分鐘，至少40分鐘，至少50分鐘，或至少1小時。After coating, the adhesive can be dried in an oven for a predetermined drying time. Drying ovens can have temperatures above 100ºC. The rate of solvent evaporation increases with increasing temperature. The drying time can be at least 2 minutes, at least 4 minutes, at least 6 minutes, at least 8 minutes, at least 10 minutes, at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 40 minutes, at least 50 minutes, or at least 1 hour.

在一些實施方案中，粘合劑可以層壓到襯墊上。合適的襯墊如上所述。In some embodiments, the adhesive may be laminated to the cushion. Suitable pads are as described above.

向製品施加標籤本發明也涉及向製品施加包含PSA的標籤的方法，以及帶有標籤的製品。此方法包括提供限定外表面的製品，以及根據一個實施方案的標籤。此方法還包括將標籤固定在製品的外表面上，從而向製品施加標籤。在一些實施方案中，製品是容器，書，或帶有蓋子的包裝，通常要求蓋子能重新關閉和重新定位。粘合劑可以固定在蓋子上。The present invention also relates to a method for applying a PSA-containing label to an article, and to a labeled article. This method includes providing an article defining an outer surface, and a label according to one embodiment. The method also includes securing the label to an outer surface of the article, thereby applying the label to the article. In some embodiments, the article is a container, book, or package with a lid, which typically requires the lid to be recloseable and repositionable. The adhesive can be fixed on the lid.

標籤可以按照分批、連續或半連續的方式固定在製品上。在施用以前，可將一個或多個襯墊從標籤上去除，從而暴露標籤的粘合劑面。然後將粘合劑面和標籤與容器或製品接觸並將標籤施用於其上。粘附還可包括一個或多個擠壓或者將擠壓力施加於標籤上的操作，從而促進與容器的接觸和/或粘附；將粘合劑活化和/或固化，例如通過加熱和/或暴露於UV光進行；和/或乾燥操作。The label can be fixed to the product in a batch, continuous or semi-continuous manner. Prior to application, one or more liners can be removed from the label, exposing the adhesive side of the label. The adhesive side and label are then contacted with the container or article and the label is applied thereon. Adhesion may also include one or more squeezes or operations that apply a squeeze force to the label to promote contact and / or adhesion to the container; activating and / or curing the adhesive, such as by heating and / or Or by exposure to UV light; and / or drying operations.

粘合劑系統本發明還提供粘合劑系統，其包含第一組分，此第一組分含有具有酸基團且酸值為2-90mgKOH/g的聚丙烯酸酯基礎聚合物，和溶劑。第一組分可以通過將聚丙烯酸酯基礎聚合物溶解在溶劑中製備。此系統還含有第二組分，其包含在溶劑中的含環氧樹脂的第一交聯劑。通常，第一組分和第二組分是分開儲存的，並且僅僅在施用於基材上之前的短時間進行混合以製備上文所述的PSA，例如在施用之前小於16小時、小於8小時或小於4小時。這能防止聚丙烯酸酯聚合物的過早交聯，並提高可操作性。在第一組分中所用的溶劑可以與在第二組分中所用的溶劑相同或不同。Binder System The present invention also provides a binder system comprising a first component, the first component containing a polyacrylate base polymer having an acid group and an acid value of 2-90 mgKOH / g, and a solvent. The first component can be prepared by dissolving a polyacrylate base polymer in a solvent. This system also contains a second component, which contains a first epoxy-containing crosslinker in a solvent. Generally, the first and second components are stored separately and mixed only shortly before application to the substrate to prepare the PSA described above, such as less than 16 hours, less than 8 hours before application Or less than 4 hours. This prevents premature crosslinking of the polyacrylate polymer and improves workability. The solvent used in the first component may be the same as or different from the solvent used in the second component.

在一些實施方案中，第二組分可以還含有包含異氰酸酯的第二交聯劑，如上文所述。In some embodiments, the second component may further contain a second crosslinking agent comprising an isocyanate, as described above.

在粘合劑系統的第一和/或第二組分中的各材料可以按照使得所得PSA具有本文所述的性能的量存在。Each material in the first and / or second component of the adhesive system may be present in an amount such that the resulting PSA has the properties described herein.

實施方案本發明的示例性實施方案如下所示：
實施方案1：一種粘合劑組合物，其包含：具有2-90 mg KOH/g的酸值並具有高於-41ºC的Tg的聚丙烯酸酯基礎聚合物，包含環氧樹脂的第一交聯劑，其中第一交聯劑的存在量是基於粘合劑組合物的總乾重計的大於0.15重量%，其中粘合劑組合物含有小於6重量%的增粘劑。
實施方案2：根據實施方案1的粘合劑組合物，其中當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，粘合劑組合物具有小於15%的霧度值。
實施方案3：根據實施方案2的粘合劑組合物，其中溶劑是水或乙醇。
實施方案4：根據實施方案1的粘合劑組合物，其中當從已經與粘合劑接觸的基材的表面去除粘合劑組合物時，粘合劑在小於3%的表面積上留下殘留物。
實施方案5：根據實施方案1的粘合劑組合物，其中聚丙烯酸酯基礎聚合物具有4-76 mgKOH/g的酸值。
實施方案6：根據實施方案1的粘合劑組合物，其中聚丙烯酸酯基礎聚合物具有36-76 mg KOH/g的酸值，其中環氧樹脂的存在量是0.2-0.5重量%，和其中增粘劑的存在量是小於1重量%，其中當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，粘合劑具有小於10%的霧度值。
實施方案7：根據實施方案1的粘合劑組合物，其中聚丙烯酸酯基礎聚合物具有60-76 mg KOH/g的酸值，其中環氧樹脂的存在量是0.2-0.5重量%，和其中增粘劑的存在量是小於0.5重量%，其中當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，粘合劑具有小於8%的霧度值，和其中當從已經與粘合劑接觸的基材的表面去除粘合劑組合物時，粘合劑在小於3%的表面積上留下殘留物。
實施方案8：根據實施方案1的粘合劑組合物，其中丙烯酸酯基礎聚合物具有60-76 mgKOH/g的酸值，其中環氧樹脂的存在量是0.2-0.5重量%，其中環氧樹脂含有一個或多個叔胺基團，其中增粘劑的存在量是小於0.5重量%，其中當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，粘合劑具有小於8%的霧度值，和其中當從已經與粘合劑接觸的基材的表面去除粘合劑組合物時，粘合劑在小於3%的表面積上留下殘留物。
實施方案9：根據前述實施方案中任一項的粘合劑組合物，其中聚丙烯酸酯基礎聚合物具有在-40°C至-5°C範圍內的玻璃化轉變溫度(Tg)。
實施方案10：根據前述實施方案中任一項的粘合劑組合物，其中聚丙烯酸酯基礎聚合物不是嵌段共聚物。
實施方案11：根據前述實施方案中任一項的粘合劑組合物，其中聚丙烯酸酯基礎聚合物含有具有2-14個碳原子的烷基。
實施方案12：根據前述實施方案中任一項的粘合劑組合物，其中聚丙烯酸酯基礎聚合物的平均分子量在50000-1500000 g/mol的範圍內。
實施方案13：根據前述實施方案中任一項的粘合劑組合物，其中聚丙烯酸酯聚合物的分子量分佈指數在2-8的範圍內。
實施方案14：根據前述實施方案中任一項的粘合劑組合物，其中聚丙烯酸酯基礎聚合物不含不飽和基團。
實施方案15：根據前述實施方案中任一項的粘合劑組合物，其中聚丙烯酸酯基礎聚合物含有羥基，並且具有0-100 mg KOH/g的羥值。
實施方案16：根據前述實施方案中任一項的粘合劑組合物，其中粘合劑組合物含有0.10-1.0重量%的第一交聯劑。
實施方案17：根據前述實施方案中任一項的粘合劑組合物，其中第一交聯劑的環氧樹脂具有60-300 g/eq的環氧當量重量。
實施方案18：根據前述實施方案中任一項的粘合劑組合物，其中第一交聯劑的環氧樹脂在其化學結構中含有一個或多個叔胺基團。
實施方案19：根據前述實施方案中任一項的粘合劑組合物，其中第一交聯劑的環氧樹脂含有一個或多個叔胺基團並具有選自由以下的化學結構所構成群組：
；
；
；
；
以及它們的混合物。
實施方案20：根據前述實施方案中任一項的粘合劑組合物，其中粘合劑組合物還含有包含異氰酸酯樹脂的第二交聯劑。
實施方案21：根據實施方案20的粘合劑組合物，其中粘合劑組合物含有0.05-0.8重量%的第二交聯劑。
實施方案22：根據實施方案20或21的粘合劑組合物，其中異氰酸酯樹脂具有10-30重量%的NCO含量。
實施方案23：根據實施方案20-22中任一項的粘合劑組合物，其中第一交聯劑與第二交聯劑之間的重量比在0.6-20的範圍內。
實施方案24：根據前述實施方案中任一項的粘合劑組合物，其中聚丙烯酸酯基礎聚合物與第一交聯劑之間的重量比在100:0.9至100:0.01的範圍內(較佳100:0.6至100:0.03)。
實施方案25：根據前述實施方案中任一項的粘合劑組合物，其中根據FINAT-1方法檢測，粘合劑組合物在不銹鋼上的剝離強度是2-10 N/英寸。
實施方案26：根據前述實施方案中任一項的粘合劑組合物，其中粘合劑組合物具有40-95重量%的凝膠含量。
實施方案27：根據前述實施方案中任一項的粘合劑組合物，其中粘合劑組合物具有大於4小時的貯存期。
實施方案28：根據前述實施方案中任一項的粘合劑組合物，其中粘合劑組合物在120°C下固化時具有0.3-5分鐘的固化時間。
實施方案29：根據前述實施方案中任一項的粘合劑組合物，其中粘合劑實質上不含天然橡膠。
實施方案30：一種包含粘合劑層的標籤，所述粘合劑層包含根據實施方案1-29中任一項的粘合劑組合物。
實施方案31：根據實施方案30的標籤，其還包含與粘合劑層接觸的面材層。
實施方案32：一種製備粘合劑配製劑的方法，包括：在小於50°C的溫度下在溶劑中溶解以下組分：a)聚丙烯酸酯基礎聚合物和b)包含環氧樹脂的第一交聯劑，其中第一交聯劑的存在量是基於粘合劑組合物的總乾重計的大於0.15重量%，其中粘合劑配製劑含有小於6重量%的增粘劑。
實施方案33：根據實施方案32的方法，其中第一交聯劑含有一種或多種催化單元。
實施方案34：根據實施方案32-33中任一項的方法，其中一種或多種催化單元是一種或多種叔胺。
實施方案35：根據實施方案32的方法，其中第一交聯劑的量是基於粘合劑組合物的乾重計的0.15-0.9重量%。
實施方案36：根據實施方案32或35的方法，其中第一交聯劑的環氧樹脂具有60-300 g/eq的環氧當量重量。
實施方案37：根據實施方案32-36中任一項的方法，其中溶劑選自由甲苯、乙酸乙酯、異丙醇、二甲苯、正己烷、正庚烷、甲基環己烷、乙酸丁酯、丙酮、丁酮和2-乙醯氧基-1-甲氧基丙烷所構成群組。
實施方案38：根據實施方案32-37中任一項的方法，還包括：用粘合劑配製劑塗覆面材，和乾燥所述粘合劑配製劑。
實施方案39：根據實施方案32-38中任一項的方法，其中此方法還包括向基材施用含有粘合劑的標籤。
實施方案40：一種粘合劑系統，其包含：第一組分，其包含i)具有酸基團並且酸值為2-90 mg KOH/g的聚丙烯酸酯基礎聚合物，ii)溶劑；和第二組分，其包含在溶劑中的含有環氧樹脂的第一交聯劑；和其中第一組分是與第二組分分開的。
實施方案41：一種帶有標籤的容器，其包含根據實施方案1-29中任一項的粘合劑組合物。Embodiments Exemplary embodiments of the present invention are as follows:
Embodiment 1: An adhesive composition comprising: a polyacrylate base polymer having an acid value of 2-90 mg KOH / g and a Tg higher than -41ºC, and a first cross-linking comprising an epoxy resin Agent, wherein the first crosslinking agent is present in an amount of greater than 0.15% by weight based on the total dry weight of the adhesive composition, and wherein the adhesive composition contains less than 6% by weight of a tackifier.
Embodiment 2: The adhesive composition according to Embodiment 1, wherein the adhesive composition has a haze of less than 15% after the adhesive composition is soaked in a solvent for at least 3 days when tested in accordance with ASTM D1003. value.
Embodiment 3: The adhesive composition according to Embodiment 2, wherein the solvent is water or ethanol.
Embodiment 4: The adhesive composition according to Embodiment 1, wherein when the adhesive composition is removed from the surface of a substrate that has been in contact with the adhesive, the adhesive leaves a residue on a surface area of less than 3% Thing.
Embodiment 5: The adhesive composition according to Embodiment 1, wherein the polyacrylate base polymer has an acid value of 4-76 mgKOH / g.
Embodiment 6: The adhesive composition according to Embodiment 1, wherein the polyacrylate base polymer has an acid value of 36 to 76 mg KOH / g, wherein the epoxy resin is present in an amount of 0.2 to 0.5% by weight, and wherein The tackifier is present in an amount of less than 1% by weight, wherein the adhesive has a haze value of less than 10% after the adhesive composition is soaked in a solvent for at least 3 days when tested in accordance with ASTM D1003.
Embodiment 7: The adhesive composition according to Embodiment 1, wherein the polyacrylate base polymer has an acid value of 60 to 76 mg KOH / g, wherein the epoxy resin is present in an amount of 0.2 to 0.5% by weight, and wherein The tackifier is present in an amount of less than 0.5% by weight, wherein the adhesive has a haze value of less than 8% after the adhesive composition is soaked in a solvent for at least 3 days when tested in accordance with ASTM D1003, and where When the adhesive composition is removed from the surface of the substrate that has been in contact with the adhesive, the adhesive leaves a residue on a surface area of less than 3%.
Embodiment 8: The adhesive composition according to Embodiment 1, wherein the acrylate base polymer has an acid value of 60 to 76 mgKOH / g, wherein the epoxy resin is present in an amount of 0.2 to 0.5% by weight, wherein the epoxy resin is Containing one or more tertiary amine groups, where the tackifier is present in an amount of less than 0.5% by weight, wherein when tested in accordance with ASTM D1003, the adhesive has at least 3 days after the adhesive composition is soaked in a solvent. A haze value of less than 8%, and wherein when the adhesive composition is removed from the surface of a substrate that has been in contact with the adhesive, the adhesive leaves a residue on a surface area of less than 3%.
Embodiment 9: The adhesive composition according to any one of the preceding embodiments, wherein the polyacrylate base polymer has a glass transition temperature (Tg) in a range of -40 ° C to -5 ° C.
Embodiment 10: The adhesive composition according to any one of the preceding embodiments, wherein the polyacrylate base polymer is not a block copolymer.
Embodiment 11: The adhesive composition according to any one of the preceding embodiments, wherein the polyacrylate base polymer contains an alkyl group having 2 to 14 carbon atoms.
Embodiment 12: The adhesive composition according to any one of the preceding embodiments, wherein the average molecular weight of the polyacrylate base polymer is in the range of 50000-1500000 g / mol.
Embodiment 13: The adhesive composition according to any one of the preceding embodiments, wherein the molecular weight distribution index of the polyacrylate polymer is in the range of 2-8.
Embodiment 14: The adhesive composition according to any one of the preceding embodiments, wherein the polyacrylate base polymer is free of unsaturated groups.
Embodiment 15: The adhesive composition according to any one of the preceding embodiments, wherein the polyacrylate base polymer contains a hydroxyl group and has a hydroxyl value of 0-100 mg KOH / g.
Embodiment 16: The adhesive composition according to any one of the preceding embodiments, wherein the adhesive composition contains 0.10 to 1.0% by weight of the first crosslinking agent.
Embodiment 17: The adhesive composition according to any one of the preceding embodiments, wherein the epoxy resin of the first crosslinking agent has an epoxy equivalent weight of 60 to 300 g / eq.
Embodiment 18: The adhesive composition according to any one of the preceding embodiments, wherein the epoxy resin of the first crosslinking agent contains one or more tertiary amine groups in its chemical structure.
Embodiment 19: The adhesive composition according to any one of the preceding embodiments, wherein the epoxy resin of the first crosslinking agent contains one or more tertiary amine groups and has a group selected from the group consisting of the following chemical structures :
;
;
;
;
And their mixtures.
Embodiment 20: The adhesive composition according to any one of the preceding embodiments, wherein the adhesive composition further contains a second crosslinking agent including an isocyanate resin.
Embodiment 21: The adhesive composition according to Embodiment 20, wherein the adhesive composition contains 0.05-0.8% by weight of the second crosslinking agent.
Embodiment 22: The adhesive composition according to embodiment 20 or 21, wherein the isocyanate resin has an NCO content of 10 to 30% by weight.
Embodiment 23: The adhesive composition according to any one of embodiments 20-22, wherein a weight ratio between the first crosslinking agent and the second crosslinking agent is in a range of 0.6-20.
Embodiment 24: The adhesive composition according to any one of the preceding embodiments, wherein a weight ratio between the polyacrylate base polymer and the first crosslinking agent is in a range of 100: 0.9 to 100: 0.01 (compared to (100: 0.6 to 100: 0.03).
Embodiment 25: The adhesive composition according to any one of the preceding embodiments, wherein the peel strength of the adhesive composition on the stainless steel is 2-10 N / inch as measured according to the FINAT-1 method.
Embodiment 26: The adhesive composition according to any one of the preceding embodiments, wherein the adhesive composition has a gel content of 40 to 95% by weight.
Embodiment 27: The adhesive composition according to any one of the preceding embodiments, wherein the adhesive composition has a shelf life of more than 4 hours.
Embodiment 28: The adhesive composition according to any one of the preceding embodiments, wherein the adhesive composition has a curing time of 0.3-5 minutes when cured at 120 ° C.
Embodiment 29: The adhesive composition according to any one of the preceding embodiments, wherein the adhesive is substantially free of natural rubber.
Embodiment 30: A label comprising an adhesive layer comprising the adhesive composition according to any one of embodiments 1-29.
Embodiment 31: A label according to embodiment 30, further comprising a facestock layer in contact with the adhesive layer.
Embodiment 32: A method of preparing an adhesive formulation, comprising: dissolving the following components in a solvent at a temperature of less than 50 ° C: a) a polyacrylate base polymer and b) a first epoxy resin-containing Cross-linking agent, wherein the first cross-linking agent is present in an amount greater than 0.15% by weight based on the total dry weight of the adhesive composition, wherein the adhesive formulation contains less than 6% by weight of a tackifier.
Embodiment 33: The method according to embodiment 32, wherein the first crosslinking agent contains one or more catalytic units.
Embodiment 34: The method according to any one of embodiments 32-33, wherein the one or more catalytic units are one or more tertiary amines.
Embodiment 35: The method according to embodiment 32, wherein the amount of the first crosslinking agent is 0.15-0.9% by weight based on the dry weight of the adhesive composition.
Embodiment 36: The method according to embodiment 32 or 35, wherein the epoxy resin of the first crosslinking agent has an epoxy equivalent weight of 60 to 300 g / eq.
Embodiment 37: The method according to any one of embodiments 32-36, wherein the solvent is selected from the group consisting of toluene, ethyl acetate, isopropanol, xylene, n-hexane, n-heptane, methylcyclohexane, butyl acetate , Acetone, methyl ethyl ketone, and 2-ethoxyl-1-methoxypropane.
Embodiment 38: The method according to any one of embodiments 32-37, further comprising: coating the facestock with an adhesive formulation, and drying the adhesive formulation.
Embodiment 39: The method according to any one of embodiments 32-38, wherein the method further comprises applying an adhesive-containing label to the substrate.
Embodiment 40: An adhesive system comprising: a first component comprising i) a polyacrylate base polymer having an acid group and an acid value of 2-90 mg KOH / g, and ii) a solvent; and A second component comprising a first crosslinking agent containing an epoxy resin in a solvent; and wherein the first component is separate from the second component.
Embodiment 41: A labelled container comprising the adhesive composition according to any one of embodiments 1-29.

實施例
以下實施例用於說明本發明，但不限制本發明。Examples The following examples are used to illustrate the present invention, but not to limit the present invention.

實施例I：增粘劑對耐溶劑性的影響
示例性的PSA組合物(實施例1)如下表1所示。PSA組合物含有來自YASUSA Chemical的聚丙烯酸酯基礎聚合物 Y-1130，來自CVC的環氧樹脂 GA-240(第一交聯劑)，來自Covestro的異氰酸酯樹脂 L75(第二交聯劑)，其NCO含量是基於異氰酸酯樹脂的總乾重計的13.3重量%。通過旋轉流變分析測定此聚合物具有-20 ºC的Tg。使用上述方法法檢測PSA的可去除性、耐溶劑性和剝離強度。結果如表1所示。
*評估的級別是1至5，其中1是最差的，5是最好的。
如表1所示，具有酸值為60 mgKOH/g和羥值為10 mgKOH/g的聚丙烯酸酯基礎聚合物、0.35重量%環氧交聯劑和0.15重量%異氰酸酯交聯劑的PSA顯示優異的可去除性、耐溶劑性以及優良的機械性能。Example I: Effect of Tackifier on Solvent Resistance An exemplary PSA composition (Example 1) is shown in Table 1 below. The PSA composition contains polyacrylate base polymer Y-1130 from YASUSA Chemical, epoxy resin GA-240 from CVC (first crosslinker), and isocyanate resin L75 (second crosslinker) from Covestro, which The NCO content is 13.3% by weight based on the total dry weight of the isocyanate resin. This polymer has a Tg of -20 ºC as determined by rotational rheological analysis. The removability, solvent resistance, and peel strength of PSA were measured using the method described above. The results are shown in Table 1.
* Evaluated on a scale of 1 to 5, with 1 being the worst and 5 being the best.
As shown in Table 1, the PSA having a polyacrylate base polymer having an acid value of 60 mgKOH / g and a hydroxyl value of 10 mgKOH / g, 0.35 wt% epoxy crosslinking agent, and 0.15% wt isocyanate crosslinking agent showed excellent Removability, solvent resistance and excellent mechanical properties.

實施例 II: 增粘劑對耐溶劑性的影響
如上所述製備四種粘合劑組合物。粘合劑組合物含有來自YASUSA Chemical的Y-1130作為聚丙烯酸酯基礎聚合物，來自YASUSA Chemical的Y-202作為環氧樹脂(第一交聯劑)。在一些實施例中，PSA還含有L75作為異氰酸酯樹脂(第二交聯劑)。聚丙烯酸酯基礎聚合物具有36 mg KOH/g的酸值，羥值為 3 mg KOH/g，並且Tg為-27℃。如表2所示改變交聯劑和增粘劑的量，並且聚丙烯酸酯基礎聚合物構成PSA的餘量。
*評估的級別是1至5，其中1是最差的，5是最好的。
如上所示，當暴露于乙醇或水時，含有0.4重量%環氧樹脂、但不含異氰酸酯樹脂的實施例2具有低的霧度值(即，高的耐溶劑性)。相比之下，當暴露於乙醇時，不含環氧樹脂但含有0.5重量%異氰酸酯樹脂的對比例A具有20的高霧度值(表示低的耐溶劑性)，並且具有低的可去除性為3。這些結果表明使用環氧樹脂令人驚奇地能提供在可去除性和耐溶劑性方面的優異結果(與異氰酸酯相比)。
另外，當暴露于乙醇和水時，實施例3和4的霧度值分別是5和6。相比之下，對比例B含有20重量%的增粘劑，並當暴露于乙醇或水時顯示顯著更高的霧度值，即分別是23和20。這些結果表明增粘劑的存在令人驚奇地損害PSA的耐溶劑性。向PSA加入5重量%的增粘劑(實施例4)，雖然PSA的可去除性和凝膠含量略有降低，但是PSA 保持優良的耐溶劑性，並且仍然適用於許多應用。Example II: Effect of Tackifiers on Solvent Resistance Four adhesive compositions were prepared as described above. The adhesive composition contains Y-1130 from YASUSA Chemical as a polyacrylate base polymer, and Y-202 from YASUSA Chemical as an epoxy resin (first crosslinking agent). In some embodiments, the PSA also contains L75 as an isocyanate resin (second crosslinker). The polyacrylate base polymer had an acid value of 36 mg KOH / g, a hydroxyl value of 3 mg KOH / g, and a Tg of -27 ° C. The amounts of the crosslinking agent and the tackifier were changed as shown in Table 2, and the polyacrylate base polymer constituted the balance of the PSA.
* Evaluated on a scale of 1 to 5, with 1 being the worst and 5 being the best.
As shown above, Example 2 containing 0.4% by weight of an epoxy resin but not containing an isocyanate resin had a low haze value (ie, high solvent resistance) when exposed to ethanol or water. In contrast, Comparative Example A, which contains no epoxy resin but contains 0.5% by weight of isocyanate resin, has a high haze value of 20 (indicating low solvent resistance) and low removability when exposed to ethanol. Is 3. These results indicate that the use of epoxy resins surprisingly provides excellent results in terms of removability and solvent resistance (compared to isocyanates).
In addition, the haze values of Examples 3 and 4 were 5 and 6 when exposed to ethanol and water, respectively. In comparison, Comparative Example B contained 20% by weight of a tackifier and showed significantly higher haze values when exposed to ethanol or water, which were 23 and 20, respectively. These results indicate that the presence of a tackifier surprisingly impairs the solvent resistance of PSA. Adding 5 wt% tackifier to PSA (Example 4), although PSA's removability and gel content are slightly reduced, PSA maintains excellent solvent resistance and is still suitable for many applications.

實施例 III: 酸值和羥值對霧度和可去除性的影響
製備七種(7)含有聚丙烯酸酯基礎聚合物的粘合劑組合物。如表3所示改變環氧交聯劑和/或異氰酸酯交聯劑的量。這些粘合劑組合物不含增粘劑。基礎聚合物的酸值、羥值如表3所示。也檢測可去除性和霧度值(耐溶劑性)。
*評估的級別是1至5，其中1是最差的，5是最好的。Example III: Effect of Acid Value and Hydroxyl Value on Haze and Removability Seven (7) adhesive compositions containing a polyacrylate base polymer were prepared. As shown in Table 3, the amount of the epoxy crosslinking agent and / or the isocyanate crosslinking agent was changed. These adhesive compositions are free of tackifiers. The acid value and hydroxyl value of the base polymer are shown in Table 3. Removability and haze values (solvent resistance) were also tested.
* Evaluated on a scale of 1 to 5, with 1 being the worst and 5 being the best.

這些結果顯示在不存在增粘劑的情況下，實施例5 – 9顯示優良的耐溶劑性，這表現為霧度值小於5%，這進一步證明瞭增粘劑不利地影響PSA的耐溶劑性。These results show that in the absence of a tackifier, Examples 5-9 show excellent solvent resistance, which is manifested by a haze value of less than 5%, which further proves that the tackifier adversely affects the solvent resistance of PSA .

另外，不具有酸基團的對比例C(酸值為0)顯示9%的低凝膠含量和1的低可去除性。認為這是由於在不存在酸基團的情況下，環氧基不能交聯聚丙烯酸酯基礎聚合物。In addition, Comparative Example C (acid value of 0) without an acid group showed a low gel content of 9% and a low removability of 1. This is believed to be due to the inability of the epoxy group to crosslink the polyacrylate base polymer in the absence of acid groups.

與對比例C相比，實施例5-8都具有76 mgKOH/g的酸值，並具有優異的可去除性和高的凝膠含量，這表明在聚丙烯酸酯基礎聚合物中存在酸基團是有益的。另外，與具有0.2重量%的額外異氰酸酯樹脂交聯劑的實施例6相比，含有0.3重量%的環氧樹脂、但不含異氰酸酯樹脂的實施例5具有相當的霧度值(耐溶劑性)，但具有較低的可去除性，這表明當環氧樹脂的存在量較低時，例如 0.3重量%，額外的異氰酸酯樹脂可以改進去除性和提高凝膠含量。實施例7和8 雖然都具有羥值為0，但是顯示優良的可去除性，這表明在聚丙烯酸酯聚合物中的羥基的存在雖然是較佳的，但是對於保持PSA的可去除性而言並不是必需的。Compared with Comparative Example C, Examples 5-8 all had an acid value of 76 mgKOH / g, and had excellent removability and high gel content, which indicates the presence of acid groups in the polyacrylate base polymer Is helpful. In addition, Example 5 containing 0.3% by weight of an epoxy resin but not containing an isocyanate resin had a comparable haze value (solvent resistance) compared to Example 6 with an additional isocyanate resin crosslinking agent of 0.2% by weight. However, it has lower removability, which indicates that when the epoxy resin is present in a low amount, such as 0.3% by weight, the additional isocyanate resin can improve the removability and increase the gel content. Although Examples 7 and 8 both had a hydroxyl value of 0, they showed excellent removability, which indicates that the presence of hydroxyl groups in the polyacrylate polymer is better, but it is important for maintaining the removability of PSA. It is not required.

儘管已經詳細描述了本發明，但是在本發明的精神和範圍內的修改對於本領域技術人員而言將是顯而易見的。鑒於前面的討論，本領域的相關知識和上面結合背景和詳細描述討論的參考文獻，其公開內容全部通過引用併入本文。此外，應該理解的是，本發明的各方面和各種實施方案的部分以及下面所述和/或所附申請專利範圍中所述的各種特徵可以整體或部分地組合或互換。在對各種實施方案的前述描述中，參考另一實施方案的那些實施方案可以與本領域技術人員將理解的其他實施方案適當地組合。此外，本領域的普通技術人員將會理解，前面的描述僅僅是作為示例，並不意圖限制本發明。Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. In light of the foregoing discussion, the relevant knowledge in the art and the references discussed above in connection with the background and detailed description, the disclosures of which are all incorporated herein by reference. In addition, it should be understood that aspects of the invention and portions of various embodiments, as well as various features described below and / or described in the scope of the appended application patents, may be combined or interchanged in whole or in part. In the foregoing description of the various embodiments, those referring to another embodiment may be appropriately combined with other embodiments that will be understood by those skilled in the art. In addition, those of ordinary skill in the art will understand that the foregoing description is merely an example and is not intended to limit the present invention.

Claims

一種粘合劑組合物，其包含：聚丙烯酸酯基礎聚合物，其具有2-90 mgKOH/g的酸值並具有高於-41°C的Tg，包含環氧樹脂的第一交聯劑，其中第一交聯劑的存在量是基於粘合劑組合物的總乾重計的大於0.15重量%，其中粘合劑組合物含有小於6重量%的增粘劑。An adhesive composition comprising: Polyacrylate base polymer with an acid value of 2-90 mgKOH / g and a Tg above -41 ° C, A first crosslinking agent comprising an epoxy resin, wherein the first crosslinking agent is present in an amount greater than 0.15% by weight based on the total dry weight of the adhesive composition, The adhesive composition contains less than 6% by weight of a tackifier.

如請求項1的粘合劑組合物，其中當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，該粘合劑組合物具有小於15%的霧度值。The adhesive composition of claim 1, wherein the adhesive composition has a haze value of less than 15% after the adhesive composition is immersed in a solvent for at least 3 days when tested in accordance with ASTM D1003.

如請求項2的粘合劑組合物，其中該溶劑是水或乙醇。The adhesive composition of claim 2, wherein the solvent is water or ethanol.

如請求項1的粘合劑組合物，其中當從已經與粘合劑接觸的基材的表面去除粘合劑組合物時，粘合劑在小於3%的表面積上留下殘留物。The adhesive composition as claimed in claim 1, wherein when the adhesive composition is removed from the surface of the substrate that has been in contact with the adhesive, the adhesive leaves a residue on a surface area of less than 3%.

如請求項1的粘合劑組合物，其中該聚丙烯酸酯基礎聚合物具有4-76 mgKOH/mg的酸值。The adhesive composition of claim 1, wherein the polyacrylate base polymer has an acid value of 4-76 mgKOH / mg.

如請求項1的粘合劑組合物，其中該聚丙烯酸酯基礎聚合物具有36-76 mgKOH/g的酸值，其中該環氧樹脂的存在量是0.2-0.5重量%，和其中該增粘劑的存在量是小於1重量%，其中當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，該粘合劑具有小於10%的霧度值。The adhesive composition of claim 1, wherein the polyacrylate base polymer has an acid value of 36 to 76 mgKOH / g, Wherein the epoxy resin is present in an amount of 0.2-0.5% by weight, and where the tackifier is present in an amount of less than 1% by weight, Wherein when tested according to ASTM D1003, the adhesive has a haze value of less than 10% after the adhesive composition is soaked in a solvent for at least 3 days.

如請求項1的粘合劑組合物，其中該聚丙烯酸酯基礎聚合物具有60-76 mgKOH/g的酸值，其中該環氧樹脂的存在量是0.2-0.5重量%，和其中該增粘劑的存在量是小於0.5重量%，其中當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，該粘合劑具有小於8%的霧度值，和其中當從已經與粘合劑接觸的基材的表面去除粘合劑組合物時，粘合劑在小於3%的表面積上留下殘留物。The adhesive composition of claim 1, wherein the polyacrylate base polymer has an acid value of 60 to 76 mgKOH / g, Wherein the epoxy resin is present in an amount of 0.2-0.5% by weight, and wherein the tackifier is present in an amount of less than 0.5% by weight, Wherein when tested in accordance with ASTM D1003, the adhesive has a haze value of less than 8% after the adhesive composition is soaked in a solvent for at least 3 days, and Wherein when the adhesive composition is removed from the surface of the substrate that has been in contact with the adhesive, the adhesive leaves a residue on a surface area of less than 3%.

如請求項1的粘合劑組合物，其中該丙烯酸酯基礎聚合物具有60-76 mg KOH/g的酸值，其中該環氧樹脂的存在量是0.2-0.5重量%，其中該環氧樹脂含有一個或多個叔胺基團，其中該增粘劑的存在量是小於0.5重量%，其中當根據ASTM D1003實驗檢測時，在粘合劑組合物在溶劑中浸泡至少3天后，粘合劑具有小於8%的霧度值，和其中當從已經與粘合劑接觸的基材的表面去除粘合劑組合物時，粘合劑在小於3%的表面積上留下殘留物。As in the adhesive composition of claim 1, Wherein the acrylate base polymer has an acid value of 60-76 mg KOH / g, Wherein the epoxy resin is present in an amount of 0.2-0.5% by weight, Wherein the epoxy resin contains one or more tertiary amine groups, Wherein the tackifier is present in an amount of less than 0.5% by weight, Wherein when tested in accordance with ASTM D1003, the adhesive has a haze value of less than 8% after the adhesive composition is soaked in a solvent for at least 3 days, and Wherein when the adhesive composition is removed from the surface of the substrate that has been in contact with the adhesive, the adhesive leaves a residue on a surface area of less than 3%.

如前述請求項中任一項的粘合劑組合物，其中該聚丙烯酸酯基礎聚合物具有在-40°C至-5°C範圍內的玻璃化轉變溫度(Tg)。The adhesive composition of any one of the preceding claims, wherein the polyacrylate base polymer has a glass transition temperature (Tg) in the range of -40 ° C to -5 ° C.

如前述請求項中任一項的粘合劑組合物，其中該聚丙烯酸酯基礎聚合物不是嵌段共聚物。The adhesive composition of any of the preceding claims, wherein the polyacrylate base polymer is not a block copolymer.

如前述請求項中任一項的粘合劑組合物，其中該聚丙烯酸酯基礎聚合物含有具有2-14個碳原子的烷基。The adhesive composition of any of the preceding claims, wherein the polyacrylate base polymer contains an alkyl group having 2 to 14 carbon atoms.

如前述請求項中任一項的粘合劑組合物，其中該聚丙烯酸酯基礎聚合物的平均分子量在50000-1500000 g/mol的範圍內。The adhesive composition of any one of the preceding claims, wherein the average molecular weight of the polyacrylate base polymer is in the range of 50,000-1500000 g / mol.

如前述請求項中任一項的粘合劑組合物，其中該聚丙烯酸酯聚合物的分子量分佈指數在2-8的範圍內。The adhesive composition according to any one of the preceding claims, wherein the molecular weight distribution index of the polyacrylate polymer is in a range of 2-8.

如前述請求項中任一項的粘合劑組合物，其中該聚丙烯酸酯基礎聚合物不含不飽和基團。The adhesive composition of any one of the preceding claims, wherein the polyacrylate base polymer is free of unsaturated groups.

如前述請求項中任一項的粘合劑組合物，其中該聚丙烯酸酯基礎聚合物含有羥基，並且具有0-100 mg KOH/g的羥值。The adhesive composition according to any one of the preceding claims, wherein the polyacrylate base polymer contains a hydroxyl group and has a hydroxyl value of 0-100 mg KOH / g.

如前述請求項中任一項的粘合劑組合物，其中該粘合劑組合物含有0.10-1.0重量%的第一交聯劑。The adhesive composition according to any one of the preceding claims, wherein the adhesive composition contains 0.10-1.0% by weight of the first crosslinking agent.

如前述請求項中任一項的粘合劑組合物，其中該第一交聯劑的環氧樹脂具有60-300 g/eq的環氧當量重量。The adhesive composition according to any one of the preceding claims, wherein the epoxy resin of the first crosslinking agent has an epoxy equivalent weight of 60 to 300 g / eq.

如前述請求項中任一項的粘合劑組合物，其中該第一交聯劑的環氧樹脂在其化學結構中含有一個或多個叔胺基團。The adhesive composition of any one of the preceding claims, wherein the epoxy resin of the first crosslinking agent contains one or more tertiary amine groups in its chemical structure.

如前述請求項中任一項的粘合劑組合物，其中該第一交聯劑的環氧樹脂含有一個或多個叔胺基團，並具有選自由以下的化學結構所構成群組：；；；；及其混合物。The adhesive composition according to any one of the preceding claims, wherein the epoxy resin of the first cross-linking agent contains one or more tertiary amine groups and has a group selected from the group consisting of the following chemical structures: ; ; ; ; And its mixtures.

如前述請求項中任一項的粘合劑組合物，其中該粘合劑組合物還含有包含異氰酸酯樹脂的第二交聯劑。The adhesive composition according to any one of the preceding claims, wherein the adhesive composition further contains a second crosslinking agent containing an isocyanate resin.

如請求項20的粘合劑組合物，其中該粘合劑組合物含有0.05-0.8重量%的第二交聯劑。The adhesive composition of claim 20, wherein the adhesive composition contains 0.05-0.8% by weight of the second cross-linking agent.

如請求項20或21的粘合劑組合物，其中該異氰酸酯樹脂具有10-30重量%的NCO含量。The adhesive composition as claimed in claim 20 or 21, wherein the isocyanate resin has an NCO content of 10-30% by weight.

如請求項20-22中任一項的粘合劑組合物，其中該第一交聯劑與該第二交聯劑之間的重量比在0.6-20的範圍內。The adhesive composition of any one of claims 20-22, wherein a weight ratio between the first crosslinking agent and the second crosslinking agent is in a range of 0.6-20.

如前述請求項中任一項的粘合劑組合物，其中該聚丙烯酸酯基礎聚合物與該第一交聯劑之間的重量比在100:0.9至100:0.01的範圍內(較佳100:0.6至100:0.03)。The adhesive composition according to any one of the preceding claims, wherein a weight ratio between the polyacrylate base polymer and the first crosslinking agent is in a range of 100: 0.9 to 100: 0.01 (preferably 100 : 0.6 to 100: 0.03).

如前述請求項中任一項的粘合劑組合物，其中根據FINAT-1方法檢測，該粘合劑組合物在不銹鋼上的剝離強度是2-10 N/英寸。The adhesive composition according to any one of the preceding claims, wherein the peel strength of the adhesive composition on stainless steel is 2-10 N / inch as measured according to the FINAT-1 method.

如前述請求項中任一項的粘合劑組合物，其中該粘合劑組合物具有40-95重量%的凝膠含量。The adhesive composition according to any one of the preceding claims, wherein the adhesive composition has a gel content of 40 to 95% by weight.

如前述請求項中任一項的粘合劑組合物，其中該粘合劑組合物具有大於4小時的貯存期。The adhesive composition of any of the preceding claims, wherein the adhesive composition has a shelf life of more than 4 hours.

如前述請求項中任一項的粘合劑組合物，其中該粘合劑組合物在120°C下固化時具有0.3-5分鐘的固化時間。The adhesive composition of any one of the preceding claims, wherein the adhesive composition has a curing time of 0.3-5 minutes when cured at 120 ° C.

如前述請求項中任一項的粘合劑組合物，其中該粘合劑實質上不含天然橡膠。The adhesive composition of any of the preceding claims, wherein the adhesive is substantially free of natural rubber.

一種包含粘合劑層的標籤，所述粘合劑層包含如請求項1-29中任一項的粘合劑組合物。A label comprising an adhesive layer comprising the adhesive composition according to any one of claims 1-29.

如請求項30的標籤，其還包含與粘合劑層接觸的面材層。The label of claim 30, further comprising a facestock layer in contact with the adhesive layer.

一種製備粘合劑配製劑的方法，包括：在小於50°C的溫度下在溶劑中溶解以下組分： a)聚丙烯酸酯基礎聚合物，和 b)包含環氧樹脂的第一交聯劑，其中該第一交聯劑的存在量是基於粘合劑組合物的總乾重計的大於0.15重量%，其中粘合劑配製劑含有小於6重量%的增粘劑。A method for preparing an adhesive formulation, comprising: Dissolve the following components in solvents at temperatures below 50 ° C: a) a polyacrylate base polymer, and b) a first crosslinking agent comprising an epoxy resin, wherein the first crosslinking agent is present in an amount greater than 0.15% by weight based on the total dry weight of the adhesive composition, The adhesive formulation contains less than 6% by weight of a tackifier.

如請求項32的方法，其中該第一交聯劑含有一種或多種催化單元。The method of claim 32, wherein the first crosslinking agent contains one or more catalytic units.

如請求項32-33中任一項的方法，其中該一種或多種催化單元是一種或多種叔胺。The method of any of claims 32-33, wherein the one or more catalytic units are one or more tertiary amines.

如請求項32的方法，其中該第一交聯劑的量是基於粘合劑組合物的乾重計的0.15-0.9重量%。The method of claim 32, wherein the amount of the first crosslinking agent is 0.15-0.9% by weight based on the dry weight of the adhesive composition.

如請求項32或35的方法，其中該第一交聯劑的環氧樹脂具有60-300 g/eq的環氧當量重量。The method of claim 32 or 35, wherein the epoxy resin of the first crosslinking agent has an epoxy equivalent weight of 60 to 300 g / eq.

如請求項32-36中任一項的方法，其中該溶劑選自由甲苯、乙酸乙酯、異丙醇、二甲苯、正己烷、正庚烷、甲基環己烷、乙酸丁酯、丙酮、丁酮和2-乙醯氧基-1-甲氧基丙烷所構成群組。The method of any one of claims 32-36, wherein the solvent is selected from the group consisting of toluene, ethyl acetate, isopropanol, xylene, n-hexane, n-heptane, methylcyclohexane, butyl acetate, acetone, Methyl ethyl ketone and 2-ethoxyl-1-methoxypropane form a group.

如請求項32-37中任一項的方法，還包括：用粘合劑配製劑塗覆面材，和乾燥所述粘合劑配製劑。The method of any one of claims 32-37, further comprising: Coating the facestock with an adhesive formulation, and The adhesive formulation is dried.

如請求項32-38中任一項的方法，其中此方法還包括向基材施用含有該粘合劑的標籤。The method of any one of claims 32-38, wherein the method further comprises applying a label containing the adhesive to the substrate.

一種粘合劑系統，其包含：第一組分，其包含：i)具有酸基團並且酸值為2-90 mg KOH/g的聚丙烯酸酯基礎聚合物，ii)溶劑；和第二組分，其包含在溶劑中的含有環氧樹脂的第一交聯劑；和其中該第一組分是與該第二組分分開的。An adhesive system comprising: A first component comprising: i) a polyacrylate base polymer having an acid group and an acid value of 2-90 mg KOH / g, ii) a solvent; and A second component comprising a first crosslinking agent containing an epoxy resin in a solvent; and Wherein the first component is separated from the second component.

一種帶有標籤的容器，其包含如請求項1-29中任一項的粘合劑組合物。A labeled container comprising an adhesive composition as claimed in any one of claims 1-29.