CN102719205B - Pressure-sensitive adhesive, pressure-sensitive adhesive tape, preparation method of the pressure-sensitive adhesive tape and medical dressing - Google Patents

Pressure-sensitive adhesive, pressure-sensitive adhesive tape, preparation method of the pressure-sensitive adhesive tape and medical dressing Download PDF

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CN102719205B
CN102719205B CN 201110388243 CN201110388243A CN102719205B CN 102719205 B CN102719205 B CN 102719205B CN 201110388243 CN201110388243 CN 201110388243 CN 201110388243 A CN201110388243 A CN 201110388243A CN 102719205 B CN102719205 B CN 102719205B
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sensitive adhesive
acrylate
monomer
pressure sensitive
monomers
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CN 201110388243
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CN102719205A (en )
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王蔚南
马静
曹俊峰
黄静
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明尼苏达矿业制造医用器材(上海)有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08Homopolymers or copolymers of acrylic acid esters
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/58Adhesives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/21Paper; Textile fabrics
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • C09J201/02Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J2201/60Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups by other properties
    • C09J2201/622Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups by other properties the parameters being the characterising features
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00Presence of inorganic and organic materials
    • C09J2400/20Presence of organic materials
    • C09J2400/26Presence of textile or fabric
    • C09J2400/263Presence of textile or fabric in the substrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of acrylic polymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00Presence of polyurethane
    • C09J2475/006Presence of polyurethane in the substrate

Abstract

本发明涉及压敏胶、压敏胶带及其制备方法和医用敷料。 The present invention relates to pressure-sensitive adhesive, pressure sensitive adhesive tape and a preparation method and medical dressing. 本发明的压敏胶是丙烯酸酯类压敏胶,包括由以下单体通过自由基共聚形成的聚合物,以所有单体的总重量按100%计:a)10%-30%的带羟基或乙氧基的亲水性丙烯酸酯单体;b)50%-70%的短链的疏水性丙烯酸酯类单体,所述短链的疏水性丙烯酸酯类单体的结构式为CH2=CHCOOR1,R1是含1-5个碳原子的烷基;c)10%-35%的长链的疏水性丙烯酸酯类单体,所述长链的疏水性丙烯酸酯类单体结构式为CH2=CHCOOR2,R2是含6-14个碳原子的烷基;和d)0.5%-5%的可与上述单体ac共聚的具有极性基团的丙烯类单体。 Pressure-sensitive adhesive of the present invention are acrylate pressure sensitive adhesive comprising a polymer formed from the following monomers by free radical copolymerization of, based on the total weight of all monomers in 100% basis: a) 10% -30% of the hydroxyl ethoxy or hydrophilic acrylate monomer; b) a hydrophobic acrylate monomer 50% -70% of the short chain, the hydrophobic structural formula short chain acrylic acid ester monomer is CH2 = CHCOOR1 , Rl is an alkyl group having 1-5 carbon atoms; c) a hydrophobic acrylic acid ester monomer is 10% to 35% of the long chain of the long chain hydrophobic acrylic acid ester monomer of the formula CH2 = CHCOOR2 , R2 is an alkyl group having 6-14 carbon atoms; and d) 0.5% -5% of ac monomers copolymerizable with the above acrylic monomer having a polar group.

Description

压敏胶、压敏胶带及其制备方法和医用敷料 Pressure-sensitive adhesive, pressure sensitive adhesive tape and a preparation method and medical dressing

技术领域 FIELD

[0001] 本发明涉及压敏胶及其应用,更具体地,涉及丙烯酸酯类压敏胶及其作为压敏胶带和医用敷料的应用。 [0001] The present invention relates to pressure-sensitive adhesive and its application, and more particularly, relates to their use as pressure-sensitive acrylic pressure sensitive adhesive tape and medical dressing.

背景技术 Background technique

[0002] 丙烯酸酯类压敏胶广泛应用于各种压敏胶带和医用敷料,例如伤口敷料。 [0002] The acrylate pressure sensitive adhesive and a pressure sensitive adhesive tape widely used in medical dressings, for example wound dressings. 伤口敷料是包扎伤口的用品,用以覆盖疮、伤口或其他损害的材料。 Wound dressing is a wound dressing supplies, materials for covering sores, wounds or other damage. 一个典型的伤口敷料的结构包括一层涂布于背衬上的压敏胶,和一层附着于胶面上的离型膜(见图1)。 A typical wound dressing comprising a layer structure applied to the pressure sensitive adhesive backing, and a layer of adhesive adhered to the surface of the release film (see FIG. 1). 有的伤口敷料耐水,但不透汽,也有的伤口敷料既耐水也透汽。 Some wound dressings water, but not vapor-permeable, and some wound dressings are also both water vapor permeable. 近几年来,随着科学进步和人民生活水平的提高,后一种既耐水也透汽的伤口敷料越来越得到人们的重视。 In recent years, with the scientific progress and the improvement of people's living standards, the latter also both water vapor permeable wound dressing more and more attention.

[0003] WO 84/03837披露了一种对干湿两性皮肤都具有良好粘接效果的溶剂型丙烯酸酯类压敏胶。 [0003] WO 84/03837 discloses a solvent-wet kind of acrylate pressure sensitive adhesive having good adhesion amphoteric skin effect. 该压敏胶成分中有大量的亲水性单体,因此具有在高湿环境下良好的粘接力。 The pressure sensitive adhesive component in a large number of hydrophilic monomers, and therefore has good adhesion in high humidity environments. 但是该专利文件没有涉及丙烯酸酯类压敏胶的透汽性。 However, this patent document does not relate to moisture vapor transmission of acrylate pressure sensitive adhesive.

[0004] US6, 680, 113披露了一种具有较高水汽透过率和较好粘性的敷料用压敏胶。 [0004] US6, 680, 113 discloses a dressing having a moisture vapor transmission rate and a high viscosity is preferably pressure-sensitive. 它是一种多层结构,包含有一层或多层高透汽性的膜,和一层高粘性的压敏胶。 It is a multilayer structure, comprising one or more layers of high moisture vapor transmission films, pressure sensitive adhesive and a layer of highly viscous. 其整体水汽透过率为1200g/m 2/24hrs/37°C,粘性为15g/inch。 Overall water vapor transmission rate of 1200g / m 2 / 24hrs / 37 ° C, a viscosity of 15g / inch. 该敷料用压敏胶的高透汽性主要通过一层或多层高透汽性膜实现,而未讨论所使用的压敏胶对透汽性的影响。 The dressing with high moisture vapor transmission through the primary pressure-sensitive adhesive layer or layers of the film to achieve a high moisture vapor transmission, whereas the pressure-sensitive adhesive used to discuss the influence of the water vapor permeability.

[0005] 目前,还没有一种丙烯酸酯类压敏胶,既具有高透汽性,同时还具有良好的粘性, 尤其是在用于伤口敷料时,对干、湿性皮肤均有良好的粘性。 [0005] Currently, there is not a pressure sensitive adhesive acrylate, both a high vapor permeability, and also has good adhesion, especially when used in wound dressings, dry, wet skin, have good tack.

发明内容 SUMMARY

[0006] 本发明旨在解决上述技术问题,并提供一种具有高透汽性,高亲水性,并且具有良好粘性的丙烯酸酯类压敏胶。 [0006] The present invention is intended to solve the above problems and to provide acrylate pressure sensitive adhesive having a high vapor permeability, high hydrophilicity, and has good adhesion.

[0007] 具体地,本发明涉及一种丙烯酸酯类压敏胶,所述压敏胶包括由以下单体通过自由基共聚形成的聚合物: [0007] In particular, the present invention relates to an acrylic pressure sensitive adhesive, said pressure sensitive adhesive comprises a polymer formed from a monomer copolymerizable by free-radical:

[0008] a). 10% -30%的带羟基或乙氧基的亲水性丙烯酸酯单体,以所有单体的总重量按100 %计; . [0008] a) 10% -30% of a hydroxyl group or an ethoxy hydrophilic acrylate monomer, based on the total weight of all monomers in 100% basis;

[0009] b). 50% -70%的短链的疏水性丙烯酸酯类单体,以所有单体的总重量按100% 计;所述短链的疏水性丙烯酸酯类单体的结构式为CH 2 = CHCOOR1, R1是含1-5个碳原子的烧基; [0009] b) hydrophobic acrylic acid ester monomer is 50% -70% of the short chain, based on the total weight of all monomers in 100% basis; Structural formula hydrophobic acrylic acid ester monomer as the short-chain CH 2 = CHCOOR1, R1 is burned group having 1-5 carbon atoms;

[0010] c). 10% -35%的长链的疏水性丙烯酸酯类单体,以所有单体的总重量按100% 计;所述长链的疏水性丙烯酸酯类单体的结构式为CH 2 = CHCOOR2, R2是含6-14个碳原子的烧基; [0010] c) a hydrophobic acrylate monomer 10% to 35% of long-chain, based on the total weight of all monomers in 100% basis; Structural formula hydrophobic acrylic acid ester monomer as the long-chain CH 2 = CHCOOR2, R2 is the group containing roast 6-14 carbon atoms;

[0011] d). 0. 5% -5%的可与上述单体ac共聚的具有极性基团的丙烯类单体,以所有单体的总重量按100 %计。 [0011] d). 0. 5% -5% of ac monomers copolymerizable with the above acrylic monomer having a polar group, based on the total weight of all the monomers to 100% by weight.

[0012] 本发明通过从以上四类单体中每一类各选一个或多个单体加以组合,以自由基共聚反应的方式形成丙烯酸酯类压敏胶,不但可以具有良好的水汽透过率,还会对无论是干性还是湿性的皮肤具有良好的粘性,同时还会有刺激性小,无残胶等特性。 [0012] The invention is by the above four monomers from each of one or more monomers selected from each type of composition, so as to free-radical copolymerization of the acrylate pressure sensitive adhesive is formed, not only has good moisture vapor transmission rate, will have to either dry or moist skin good adhesion, while there will be a little irritating, no adhesive residue and other features.

[0013] 本发明还涉及一种高透汽性的压敏胶带,其包括涂布在背衬上的一层本发明提供的的丙烯酸酯类压敏胶,所述压敏胶带在正杯法测试中,其水汽透过率可以达到1900g/ m2/24hrs/37°C (在25微米聚氨酯膜上涂一层25微米的干胶测得)。 [0013] The present invention further relates to a high moisture vapor transmission of pressure sensitive adhesive tape, pressure sensitive adhesive comprising acrylic coated on the backing layer of the present invention is provided, the pressure-sensitive tape n-cup method test, the water vapor transmission rate which can reach 1900g / m2 / 24hrs / 37 ° C (25 [mu] m polyurethane film coated with a 25 micron Adhesive measured).

[0014] 本发明还涉及一种制备压敏胶带的方法,所述方法包括在背衬上涂布一层本发明提供的的丙烯酸酯类压敏胶,并且通过使丙烯酸酯类压敏胶交联而固化。 [0014] The present invention further relates to a method for preparing a pressure-sensitive adhesive tape, said method comprising the acrylate pressure sensitive adhesive coated on the backing layer of the present invention is provided, and by making the cross-acrylate pressure sensitive adhesive linked cured.

[0015] 本发明另外还涉及一种医用敷料,其包括上述的压敏胶带,并且在所述压敏胶带的胶面上附上一层离型膜。 [0015] The present invention further relates to a medical dressing comprising a pressure sensitive adhesive tape described above, and a layer of release film attached on the surface of the pressure-sensitive adhesive tape. 该医用敷料在干性皮肤上的初始粘性为〜lOOg/inch,在湿性皮肤上初始粘性有〜45g/inch,在干性或湿性皮肤上经过72小时后的粘性为〜170g/ inch,在干性或湿性皮肤上经过168小时后的粘性为〜110g/inch。 The medical dressing on initial tack to dry skin ~lOOg / inch, initial tack on the skin with a wet ~45g / inch, the viscosity after 72 hours ~170g / inch on a dry or wet skin, dry after 168 hours the viscosity ~110g / inch or wet on the skin. (本文中使用的"〜"表示平均值,因为不同人的皮肤差别很大,所以对皮肤的粘性以取平均值的方式表示。) ( "~" As used herein indicates an average value, because a large individual differences in the skin, so the representation of the viscosity of the skin to averaging.)

[0016] 根据本发明的丙烯酸酯类压敏胶(带)和医用敷料具有高透汽性,良好的粘性和很好的亲水性,而且成本低廉。 [0016] having a high vapor permeability, good adhesion and good hydrophilicity according acrylate pressure sensitive adhesive (tape) of the present invention and medical dressing, and low cost. 同时它还具有粘性高,残胶少,对皮肤刺激性低等优点。 It also has a high viscosity, low residue, and low irritation to the skin. 即使是在高湿度的环境下仍然可以保持很高的粘接力。 Even still maintain a high adhesive strength under high humidity environment.

附图说明 BRIEF DESCRIPTION

[0017] 图1是本发明一个示例性伤口敷料的结构切面图。 [0017] FIG. 1 is illustrative of the present invention a wound dressing structure section in FIG.

[0018] 图2显示了丙烯酸2-(2-乙氧乙氧基)乙酯(EEEA)单体比例和特征粘度IV以及水汽透过率MVTR的关系。 [0018] FIG. 2 shows the relationship acrylate, 2- (2-ethoxyethoxy) ethyl acrylate (EEEA) and monomer ratio and intrinsic viscosity IV of moisture vapor transmission rate MVTR.

[0019] 图3显示了本发明的压敏胶的粘性的内部临床测试结果。 [0019] Figure 3 shows the results of clinical testing internal viscous pressure sensitive adhesive of the present invention.

[0020] 图4是水汽透过率(MVTR)测试方法的示意图。 [0020] FIG. 4 is a schematic diagram of a test method for water vapor transmission rate (MVTR).

具体实施方式 Detailed ways

[0021] 本发明的丙烯酸酯类压敏胶包括由以下四种单体共聚形成的聚合物: [0021] The acrylate pressure sensitive adhesive of the present invention comprises a polymer formed from the monomers of the following four:

[0022] a).带羟基或乙氧基的亲水性丙烯酸酯单体; [0022] a) a hydrophilic acrylate monomer with a hydroxyl or ethoxy.;

[0023] b).短链的疏水性丙烯酸酯类单体,其结构式为CH2 = CHCOOR1, R1是含1-5个碳原子的烧基; . [0023] b) a hydrophobic acrylate monomer short-chain having the formula CH2 = CHCOOR1, R1 is burned group having 1-5 carbon atoms;

[0024] c).长链的疏水性丙烯酸酯类单体,其结构式为CH2 = CHCOOR2, R2是含6-14个碳原子的烧基; [0024] c) a hydrophobic long-chain acrylic acid ester monomers, having the formula CH2 = CHCOOR2, R2 is the group containing roast 6-14 carbon atoms.;

[0025] d).可与上述单体ac共聚的具有极性基团的丙烯类单体。 [0025] d). Ac monomers copolymerizable with the above acrylic monomer having a polar group.

[0026] 共聚方法可以是常规的自由基聚合方法。 [0026] The method of copolymerization may be a conventional radical polymerization method. 在一个具体实施方案中,聚合反应的具体条件如下: In one particular embodiment, the specific conditions of polymerization are as follows:

[0027] 将所有单体及溶剂依次加入1000加仑反应釜中,单体和溶剂比例如表二所示,搅拌半个小时,搅拌子的速率为70转每分钟。 [0027] All monomers and solvents were added 1,000 gallons reactor, the monomer and solvent ratios shown in Table II was stirred for half an hour, a stirring rate of 70 revolutions per minute. 通氮气除氧,除氧的时间大约为15-30分钟。 Oxygen nitrogen, oxygen takes about 15-30 minutes. 然后将反应釜中物料(单体、溶剂和引发剂)的温度升高到59摄氏度。 The temperature of the autoclave was then materials (monomer, solvent, and initiator) was increased to 59 degrees Celsius. 将引发剂(例如AIBN) 以1 : 10的比例溶解在乙酸乙酯中,并加入物料中(见表二)。 The initiator (e.g., AIBN) in a ratio of 1: 10 was dissolved in ethyl acetate, and the material was added (see Table II). 大约10-15分钟后,反应开始,这时物料温度会明显升高1-2摄氏度。 After about 10-15 minutes, the reaction began, the temperature of the material at this time will be significantly increased 1-2 ° C. 控制物料温度在60摄氏度,搅拌速率为70转每分钟,反应24小时,这时的转化率应该在99%以上,反应结束。 Controlling the material temperature at 60 ° C, stirring rate of 70 revolutions per minute, for 24 hours, at a conversion rate should be above 99%, the reaction was completed. 最后将物料冷却到43摄氏度出料。 Finally, the mass is cooled to 43 ° C the material. 最后得到的聚合物IV在0.9-1. ldl/g之间,重均分子量Mw在500, 000-900, OOO 之间。 The resulting polymer IV in / between 0.9-1. Ldl g, weight average molecular weight 500, 000-900, OOO between Mw.

[0028] 其中转化率的测量方法为:取约3克物料,放入105摄氏度烘箱2个小时,取出置于干燥皿中15分钟,然后称重。 [0028] wherein the method for measuring the conversion rate: taking about 3 grams of material, placed in an oven at 105 ° C two hours, taken out was placed in a desiccator for 15 minutes and weighed. 其公式为 The formula is

[0029] [0029]

Figure CN102719205BD00061

[0030] 在本发明中涉及的化学品均以缩写表示,具体解释见表一。 [0030] In the present invention relates to chemical abbreviations are specifically explained in Table I.

[0031] 表一本发明所涉及到的代表性的化学品及供应商 [0031] TABLE representative invention relates to a chemical supplier and

[0032] [0032]

[0033] [0033]

Figure CN102719205BD00062

[0034] 表二单体、溶剂及引发剂的比例,表中比例均为重量比 [0034] Table II monomer ratio, solvent, and initiator, the ratio in the table are weight ratios

[0035] [0035]

Figure CN102719205BD00063

[0036] *注:此处的EtOAc包括了用于溶解AIBN的EtOAc. [0036] * Note: EtOAc to EtOAc herein include dissolution of AIBN.

[0037] 下面将详细描述用于本发明的丙烯酸酯类压敏胶的各种单体。 [0037] The monomers for acrylate pressure sensitive adhesive of the present invention will be described in detail below.

[0038] a)亲水性丙烯酸酯单体 [0038] a) a hydrophilic acrylate monomer

[0039] 早在1984年,William R. Snyder及其同事就在WO 84/03837中提出如果一种具有良好的亲水性的单体和其它单体甚至疏水单体聚合,生成的高分子也会带有良好的亲水性,因此可大大提高在湿性皮肤上的粘性。 [0039] In 1984, William R. Snyder and his colleagues proposed in WO 84/03837 if a polymer having a good hydrophilic monomers and hydrophobic monomers even other monomers, is also generated will be with good hydrophilicity, it can greatly improve wet tack on the skin. 他们建议这种单体占总的聚合物单体的重量百分比为5% -30%。 They suggested that such a polymer weight percent of the total monomers of the monomer 5% to 30%. 我们研究发现在这一类的亲水单体中,带羟基或乙氧基的亲水性丙烯酸酯单体不但可以有效的增强聚合物的亲水性,还可以增强其透汽性。 We found that in this type of hydrophilic monomers, the hydrophilic acrylate monomer with a hydroxyl or ethoxy group can not only effectively enhance the hydrophilic polymer, may further enhance its vapor permeability.

[0040] 本发明的带羟基或乙氧基的亲水性丙烯酸酯单体包括但不限于:三羟甲基丙烷二丙烯酸酯,季戊四醇三丙烯酸酯,双三羟甲基丙烷三丙烯酸酯,丙烯酸2-羟基乙酯(2-HEA),丙烯酸4-羟基苄酯(4-HBA),丙烯酸2-(2-乙氧乙氧基)乙酯(EEEA)。 [0040] a hydroxyl group or an ethoxy group of the present invention, hydrophilic acrylate monomers include, but are not limited to: trimethylol propane diacrylate, pentaerythritol triacrylate, trimethylol propane trimethacrylate bis acrylate, 2-hydroxyethyl acrylate (2-HEA), benzyl acrylate, 4-hydroxybutyl (4-HBA), 2- (2-ethoxyethoxy) ethyl acrylate (EEEA). 最优选EEEA、2-HEA 和4-HBA。 Most preferably EEEA, 2-HEA and 4-HBA.

[0041] 另外,不同种类的亲水性单体对透汽性的影响各不相同。 [0041] Further, the effects of different types of hydrophilic monomer vapor permeability varies. 如表三所示,在单体的重量百分比相同的情况下,含乙氧基的EEEA比含羟基的2-HEA和4-HBA对MVTR的提高效果更好一点。 As shown in Table III, at the same weight percent of monomers, the ratio of EEEA containing ethoxy 2-HEA hydroxyl-containing 4-HBA and the effect of improving a little better MVTR. 但是考虑到对胶粘剂其它性能的影响,例如玻璃化转变温度上升导致持粘性下降,该类亲水性单体的量不宜太高。 However, consider the impact on other properties of the adhesive, such as glass transition temperature increases leading to decrease holding adhesive, such an amount of hydrophilic monomer is not too high. 从图二可以看出,以EEEA为例,当EEEA从占单体总含量的5%提高到10%时,其MVTR提高了56g/m 2/24hrs·但当EEEA从15%提高到22%,其MVTR仅提高了5g/m2/24hrs。 Can be seen in Figure II, an example in EEEA, EEEA when increased from 5% of the total monomer content to 10%, which increased MVTR 56g / m 2 / 24hrs · EEEA but from 15% to 22% its MVTR increased only 5g / m2 / 24hrs. 另一方面,当EEEA浓度提高后,其特征粘度IV也有大幅度的上升,而过高的IV被发现会降低对皮肤表面的粘性,包括初粘性以及持粘性。 On the other hand, when the concentration increase EEEA, characterized in viscosity IV has increased substantially, and IV were found to be too high to lower the viscosity of the surface of the skin, including initial adhesion and holding power.

[0042] 综合考虑到高透水性和其他性能之间的平衡,带羟基或乙氧基的亲水性丙烯酸酯单体的比例优选占所有单体的总重量的10% -30%,更优选15% -25%。 [0042] Considering the balance between the ratio of the high water permeability and other properties, a hydroxyl group or ethoxy hydrophilic acrylic monomer is preferably 10% -30% of the total weight of all monomers, and more preferably 15% -25%.

[0043] 表三不同亲水性单体对水汽透过率(MVTR)的影响,表中比例均为重量比 [0043] Table Effects of three different moisture vapor transmission rate of the hydrophilic monomer (the MVTR) in the table of ratios are by weight

[0044] [0044]

Figure CN102719205BD00071

[0045] [0045]

Figure CN102719205BD00081

[0046] 图4显示了MVTR测试的装置和安装测试样品的方法。 [0046] Figure 4 shows the mounting apparatus and method for testing MVTR test sample. 该MVTR测试是根据TMS0759,在温度37°C进行的,使用的I3U薄膜是由拜耳供应的聚氨酯膜。 The MVTR test according TMS0759, carried out at a temperature of 37 ° C, I3U film using a polyurethane film supplied by Bayer. 具体步骤和条件如下: Specific steps and conditions are as follows:

[0047] 1.向玻璃瓶内装入约50ml水 [0047] 1 to about 50ml of water was charged into a glass bottle

[0048] 2.将试样贴在铝箔环5的粘胶面上,注意试样应置于铝箔环的椭圆洞的中心。 [0048] 2. The sample was attached to the adhesive surface of the aluminum foil ring 5, the specimen should be placed in the center of attention of the elliptical hole foil ring.

[0049] 3.为保证与第二个铝箔环对齐,将第一个铝箔环5 (胶面朝上)放在一个平面上。 [0049] 3. In order to ensure the ring is aligned with a second foil, the first ring 5 a foil (adhesive side up) on a flat surface. 将试样3对准中央,贴在第一个铝箔环上。 The sample was aligned with the center 3, a foil attached to the first ring. 然后将第二个铝箔环2 (胶面朝下)贴在试样3 上,使得两个铝箔环的椭圆洞重合。 Then a second aluminum ring 2 (glue face down) 3 attached to the sample, so that the two foil rings oval holes coincides. 用手指将铝箔/试样/铝箔压平整,注意不要有褶皱或空隙。 Finger aluminum foil / sample / foil pressed flat, careful not wrinkled or voids.

[0050] 4.将橡胶垫圈4放在瓶口上(见图4),再将铝箔/试样/铝箔组件置于垫圈4上。 [0050] 4. The rubber gasket 4 placed on the bottle (see FIG. 4), and then an aluminum foil / sample / foil assembly was placed on the gasket 4. 如果试样上有涂胶,则将胶面朝下。 If there is adhesive, adhesive face on the sample will be lower. (如果试样一面是薄膜,一面是布或无纺布,则将薄膜一面朝下)。 (If the sample side of a film, a cloth or a nonwoven fabric on one side, then the film side down).

[0051] 5.轻轻地旋上瓶盖1,将瓶子放在金属架上,并将其放入老化箱。 [0051] 5. Gently screw on the cap 1, the bottle was placed in a metal frame and placed in the aging tank. 老化箱按以下的条件设置,放4个小时:401:±11:(104°?±1.8°?),相对湿度为20%±2%。 Aging tank is provided under the following conditions, release 4 hours: 401: ± 11: (104 ° ± 1.8 °??), A relative humidity of 20% ± 2%.

[0052] 6.在老化箱内旋紧瓶盖1 (食指放在瓶盖和试样上面,这样试样才会与瓶盖水平, 避免产生膨胀),橡胶垫圈4放在确切的位置。 [0052] The aging in tightly closed box 6. 1 (index finger on the top cap and the sample, so that only the sample with the level of the cap, to avoid the expansion), the rubber washer 4 in the exact position.

[0053] 7.将样品从老化箱里拿出来,立即用分析天平称重(初始重量Wl),天平的精确到0. Olg0 [0053] 7. The sample was aged out of the box, the balance immediately weighed (Wl of the initial weight) by analytical balance accurate to 0. Olg0

[0054] 8.将瓶子放回老化箱,至少放置18个小时。 [0054] 8. The bottle was returned to the aging tank for at least 18 hours.

[0055] 9.将样品从老化箱里拿出来,立即用分析天平称重(最终重量W2),天平的精确到0. Olg0 [0055] 9. The samples aged out of the box to immediately weighed by analytical balance (W2 of final weight), the balance accurate to 0. Olg0

[0056] 10.计算湿气透过率,单位是g/m2/24hrs [0056] 10. The moisture vapor transmission rate is calculated in units of g / m2 / 24hrs

[0057] MVTR = (W1_W2)/S/TX24 小时 [0057] MVTR = (W1_W2) / S / TX24 hr

[0058] Wl =初始重量(g) [0058] Wl = initial weight (g)

[0059] W2 =最终重量(g) [0059] W2 = final weight (g)

[0060] S =试样的测试面积(m2) [0060] S = the sample test area (m2)

[0061] T =试验时间(小时),试验时间应大于18h。 [0061] T = test time (hr), the test time should be greater than 18h.

[0062] b)短链的疏水性丙烯酸酯类单体和c)长链的疏水性丙烯酸酯类单体 Hydrophobic acrylic acid ester monomer [0062] b) a hydrophobic acrylate monomer and short-chain c) long chain

[0063] 除上述亲水性单体之外,本发明人还研究了疏水性丙烯酸酯类单体对压敏胶的透汽性和粘性的影响。 [0063] In addition to the above hydrophilic monomers, the present inventors have also studied the influence of hydrophobic pressure-sensitive acrylate monomer vapor permeability and viscosity. 发现:通过将疏水性丙烯酸酯类单体分成短链的疏水性丙烯酸酯类单体和长链的疏水性丙烯酸酯类单体两类,并且适当地控制两者之间的比例,可以在MVTR和粘性之间取得一个良好的平衡。 Found: by adding a hydrophobic acrylic acid ester monomer into short-chain hydrophobic acrylic acid ester monomer and the acrylate monomer types hydrophobic long chain, and the ratio between the two suitably controlled, may MVTR between viscosity and achieve a good balance.

[0064] 本发明的短链的疏水性丙烯酸酯类单体是指结构式为CH2 = CHCOOR1的丙烯酸酯类单体,其中R1是含1-5个碳原子的烷基。 [0064] Short-chain hydrophobic acrylic acid ester monomer of the present invention refers to an acrylate monomer of formula CH2 = CHCOOR1, wherein R1 is an alkyl group having 1-5 carbon atoms. 具体实例包括但不限于:丙烯酸甲酯,丙烯酸乙酯,丙烯酸丁酯,甲基丙烯酸甲酯,甲基丙烯酸乙酯,甲基丙烯酸丁酯等,优选丙烯酸甲酯, 丙烯酸乙酯,丙烯酸丁酯,最优选丙烯酸丁酯(BA)。 Specific examples include, but are not limited to: methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, preferably methyl acrylate, ethyl acrylate, butyl , most preferably butyl acrylate (BA).

[0065] 本发明的长链的疏水性丙烯酸酯类单体是指结构式为CH2 = CHCOOR2的丙烯酸酯类单体,其中R2是含6-14个碳原子的烷基。 Long chain hydrophobic acrylic acid ester monomer [0065] The present invention refers to an acrylate monomer of formula CH2 = CHCOOR2, wherein R2 is an alkyl group having 6-14 carbon atoms. 具体实例包括但不限于:丙烯酸-2-乙基己酯, 丙烯酸异辛酯,辛基丙烯酸酯,癸基丙烯酸酯,十二烷基丙烯酸酯,十三烷基丙烯酸酯等,优选丙烯酸-2-乙基己酯(2-EHA),丙烯酸异辛酯。 Specific examples include, but are not limited to: 2-ethylhexyl acrylate, isooctyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, tridecyl acrylate, preferably acrylic acid -2 - ethylhexyl acrylate (2-EHA), isooctyl acrylate.

[0066] 本发明的b)短链的疏水性丙烯酸酯类单体和c)长链的疏水性丙烯酸酯类单体之间的比例对压敏胶的MVTR和粘性有显著影响。 The ratio between the hydrophobic long chain acrylate monomer acrylic hydrophobic monomer b) [0066] The short chain of the present invention and c) have a significant impact on the MVTR of the pressure sensitive adhesive and sticky. 如表四所示,如果保持EEEA的含量不变,提高BA的比例并降低2-EHA的比例,则MVTR将会有很大的提高。 As shown in Table IV, if the content remains unchanged EEEA, increase the proportion of BA and reduce the proportion of 2-EHA, the MVTR will be greatly improved. 当BA占所有单体的重量百分比从0提高到75份时,其MVTR从〜1500g/m 2/24hrs升高到〜2200g/m2/24hrs。 When the weight of all monomers BA account the percentage increased from 0 to 75 parts, from which rises MVTR ~1500g / m 2 / 24hrs to ~2200g / m2 / 24hrs. 但同时其粘性也会有显著的下降。 But its viscosity will be significantly decreased. 因此,要在MVTR和粘性之间取得一个良好的平衡,单体的比例必须保持在一个适当的范围。 Therefore, to achieve a good balance between MVTR and viscous, the proportion of the monomers must be kept in a proper range. 本发明优选的范围是:短链的疏水性丙烯酸酯类单体占总单体重量的50% -70 %,最优选55% -65% ;长链的疏水性丙烯酸酯类单体占总单体重量的10% -35%,最优选20% -30%。 The preferred range of the present invention: 50% -70% of the total monomer weight of a hydrophobic acrylic acid ester monomer is a short chain, most preferably 55% -65%; hydrophobic acrylic acid ester monomer of the total single-long-chain 10% to 35% by weight thereof, and most preferably 20% -30%.

[0067] 表四BA和2-EHA对MVTR以及粘性的影响 Effects [0067] Table IV BA and 2-EHA and viscosity of MVTR

[0068] [0068]

Figure CN102719205BD00091

[0069] 粘性测试基材:不锈钢板 [0069] Adhesive Test material: stainless steel plate

[0070] 粘度测试方法:180。 [0070] Viscosity Test Method: 180. 剥离,ASTMD3330 Peeling, ASTMD3330

[0071] IV:特征粘度,测试方法:TM0148 [0071] IV: intrinsic viscosity, Test Method: TM0148

[0072] PU薄膜:聚氨酯,供应商Vix Co.韩国,20. 3微米空白PU膜,MVTR3000g/m2/24hrs [0072] PU film: polyurethane, supplier Vix Co. Korea, blank 203 [mu] m PU film, MVTR3000g / m2 / 24hrs

[0073] MVTR 测试方法:TMS0759,温度37°C [0073] MVTR Test Method: TMS0759, temperature 37 ° C

[0074] IV测试方法具体如下: [0074] IV test method as follows:

[0075] 测试仪器:LAUDA Proline PV24 [0075] test equipment: LAUDA Proline PV24

[0076] 1.取少量样品溶于乙酸乙酯中,配成大约为0.25g(干胶)/100毫升(乙酸乙酯) 溶液。 [0076] 1. A small sample was dissolved in ethyl acetate, dubbed about 0.25 g (Adhesive) / 100 ml (ethyl acetate) was added.

[0077] 2.将1中配得的溶液取25mL放入一个已知重量的铝皿中,置于105°C烘箱烘烤两个小时。 [0077] 2. The solution 1 was taken with a known weight of 25mL placed in an aluminum dish and placed in an oven at 105 ° C baked for two hours. 取出称重,减去错皿的重量,得到25mL溶液中的实际干胶重wl。 Remove the weighing dish by subtracting the weight error, and the actual weight wl 25mL Adhesive solution.

[0078] 3.取9. 00克分析纯的乙酸乙酯为标准液体流过仪器毛细管,记录通过这段毛细管所用时间tl.再将1中配得的溶液取9. 00克流过同一段毛细管,得到时间t2. [0078] 3. Take 9.00 g of analytically pure ethyl acetate as the standard flow through the capillary liquid instrument, recording the time spent by this capillary tl. Then the resulting solution with a 9.00 g take some flowing with capillary, to give time t2.

[0079] 4.将溶液实际固含量wl,标准液体通过毛细管时间tl,样品通过毛细管时间t2输入相应软件,即可获得该压敏胶的特征粘度IV. [0079] 4. The actual solids content of the solution WL, standard liquid t2 corresponding software input time through a capillary tube by capillary time tl, the sample, the pressure-sensitive adhesive can be obtained intrinsic viscosity IV.

[0080] 粘度测试方法:180°剥离,ASTMD3330,测试仪器:IMASS SP-2000 [0080] Viscosity Test method: 180 ° peeling, ASTMD3330, test equipment: IMASS SP-2000

[0081] 1.准备一块4英寸X 10英寸的钢板 [0081] 1. Prepare a 4-inch X 10 inch sheet

[0082] 2.裁一条1英寸X 12英寸的样品 [0082] 2. A cutting a 1 inch X 12 inches sample

[0083] 3.首先用异丙醇擦拭钢板表面,以除去灰尘和污物。 [0083] 3. The steel sheet is first cleaned with isopropyl alcohol to remove dust and dirt.

[0084] 4.将样品剥去离型纸,胶面向下贴在钢板表面,用刮刀刮平。 [0084] 4. The sample was peeled off the release paper, affixed to the plastic surface of the steel facing Calibrating with a doctor blade. 因为样品比钢板长, 所以样品一端露在钢板外。 Since the sample is longer than the sheet, so the sample is exposed outside the end plate.

[0085] 5.静置20分钟 [0085] The stand 20 minutes

[0086] 6.将钢板水平固定在仪器样品台上,将样品露在钢板外的一端顺着钢板方向弯折180度,并固定于仪器夹具中。 [0086] 6. The horizontal plate fixed to the instrument on the sample stage, the sample is exposed outside one end of the steel sheet is bent along the direction of the steel sheet by 180 degrees, and is fixed to the instrument holder. 仪器参数设置为: Instrument parameter is set to:

[0087] 速度:12英尺每分钟 [0087] Speed: 12 feet per minute

[0088] 测试方式:剥离力 [0088] Test mode: peel force

[0089] 迟滞时间:2秒 [0089] The lag time: 2 seconds

[0090] 测试时间:5秒 [0090] Test Time: 5 seconds

[0091] 7.按"start"开始测试,自动停止并记录数据。 [0091] 7. press "start" to start the test, and automatically stops recording data.

[0092] d).可与上述单体ac共聚的具有极性基团的丙烯类单体 [0092] d). Copolymerizable with the monomer ac propylene monomer having a polar group

[0093] 本发明的可与上述单体ac共聚的具有极性基团的丙烯类单体优选为具有高玻璃化转变温度的丙烯类单体,更优选具有羧基或酰胺基的丙烯类单体,其具体实例包括但不限于:丙烯酰胺,丙烯酸,甲基丙烯酰胺,甲基丙烯酸;优选丙烯酰胺和丙烯酸,因为它们极性较强;最优选丙烯酰胺,因为它无刺激性。 [0093] copolymerizable with the monomer of the present invention having ac polar group is preferably a propylene-based monomer having a high glass transition temperature of the acrylic monomers, more preferably acrylic monomers having a carboxyl group or an amide group , specific examples thereof include but are not limited to: acrylamide, acrylic acid, methacrylamide, methacrylic acid; preferably acrylamide and acrylic acid, because they are polar; most preferably acrylamide, because it is non-irritating. 可与上述单体ac共聚的具有极性基团的丙烯类单体在全部单体中的重量比例优选为〇. 5% -5%,优选1% -3%。 Copolymerizable with the monomer ac propylene monomer having a polar group in a proportion by weight of all the monomers is preferably square. 5% -5%, preferably 1% to 3%.

[0094] 发明人发现,要合成一个具有高水汽透过率,高粘性,低残胶的丙烯酸类压敏胶, 其单体组成主要有四部分。 [0094] The inventors have found that, to be synthesized with a high moisture vapor transmission rate, high viscosity, low residual acrylic pressure-sensitive adhesive with a monomer mainly composed of four parts. 其一是带羟基或乙氧基的亲水性单体,它们占整个单体的比例为10% -30%。 One is a hydrophilic monomer with a hydroxyl or ethoxy, it is the total monomer ratio of 10% -30%. 它们主要是提供一定的透汽性,同时还可提高对湿性皮肤的粘结力;其二是疏水性的短链丙烯酸酯类单体,CH2 = CHCOOR1, R1是含1-5个碳原子的烷基,它们占所有单体的总重量的50% -70%,如丙烯酸甲酯,丙烯酸乙酯,丙烯酸丁酯等。 They mainly provide a water vapor permeability, while also enhancing adhesion to wet skin; the other is a short-chain hydrophobic acrylate monomer, CH2 = CHCOOR1, R1 containing 1-5 carbon atoms alkyl, which accounted for 50% -70% of the total weight of all monomers, such as methyl acrylate, ethyl acrylate, butyl acrylate and the like. 这一类单体虽然通常被认为是疏水性的,但相比长链的丙烯酸酯单体,它们具有更好的透汽性(表四),可调节粘性和透汽性的平衡,并提供一定的内聚强度。 Although this type of monomer is generally considered to be hydrophobic, but as compared to long-chain acrylate monomer, which has a better vapor permeability (Table IV), and the viscosity may be adjusted vapor permeability balance, and to provide some cohesive strength. 第三类是长链的疏水性丙烯酸酯类单体,其结构式为CH 2 = CHCOOR2, R2是含6-14个碳原子的烷基,它们占所有单体的总重量的10 %-35 %。 The third category is a hydrophobic long-chain acrylic acid ester monomers, having the formula CH 2 = CHCOOR2, R2 is an alkyl group having 6-14 carbon atoms, which accounts for 10% -35% of the total weight of all monomers . 这些长链单体的柔顺性好,可以增强胶的浸润性,提高初粘力和剥离力,从而提高整个胶的粘性。 The flexibility of the long-chain monomers, and can enhance the wettability of the adhesive, enhance tack and peel forces, thereby increasing the viscosity of the entire gel. 第四类是如丙烯酰胺,丙烯酸,甲基丙烯酰胺,甲基丙烯酸等极性单体,它们通常带有羧基或酰胺基等极性基团,可以给胶粘剂带来良好的内聚强度,易于交联,并且能和被粘结的基材形成牢固的氢键。 The fourth category is such as acrylamide, acrylic acid, methacrylamide, methacrylic acid, polar monomers, typically having a carboxyl group or a polar group such as an amide group, can bring good cohesive strength to the adhesive, easy cross-linked, and can form strong hydrogen bonds and the bonded substrates. 这一类单体占所有单体的总重量0. 5〜5%。 This monomer based on the total weight of all monomers 0. 5~5%.

[0095] 如果从以上四类单体中每一类各选一个或多个单体加以组合,以自由基共聚反应的方式生成的丙烯酸胶粘剂,不但可以具有良好的水汽透过率,还会对无论是干性还是湿性的皮肤具有良好的粘性,同时还会有刺激性小,无残胶等特性。 [0095] If each of the four categories selected from a monomer or monomers each class are combined, so as to generate a free-radical copolymerization of acrylic adhesive, not only has good moisture vapor transmission rate, but also on whether it is dry or moist skin has good adhesion, while there will be a little irritating, no adhesive residue and other features. 表五所示的配方是本发明优选的几个组合。 Five formulations are shown in Table A presently preferred combination of several.

[0096] 表五本发明中四种优化配方及其测试结果 [0096] Table V optimized formulation of the present invention and of four test results

[0097] [0097]

Figure CN102719205BD00111

[0099] *通过改变聚合反应条件来控制IV,使得IV减小。 [0099] * by controlling the polymerization conditions were varied IV, IV is reduced so.

[0100] IV:特征粘度,测试方法:TM0148 [0100] IV: intrinsic viscosity, Test Method: TM0148

[0101] PU薄膜:聚氨酯,供应商Vix Co.韩国,20. 3微米空白PU膜,MVTR3000g/m2/24h [0101] PU film: polyurethane, supplier Vix Co. Korea, blank 203 [mu] m PU film, MVTR3000g / m2 / 24h

[0102] MVTR 测试方法:TMS0759,温度37°C [0102] MVTR Test Method: TMS0759, temperature 37 ° C

[0103] Tegaderm std,Tegaderm HP 及MMD 均为3M 的产品。 [0103] Tegaderm std, Tegaderm HP and MMD are 3M products.

[0104] IV-3000 为Smith&N印hew (施乐辉)的产品。 [0104] IV-3000 is a Smith & N printing HEW (Smith & Nephew) of product.

[0105] 从表五可以看出,与市售的几款产品相比,HPA-14/14-L和HPA-12/12-L的MVTR_1837g/m2/24hrs 和1900g/m2/24hrs 要大大高于Tegadem std 的900g/m2/24hrs 和Tegaderm HP 的1100g/m2/24hrs,略高于MMD 的1700g/m2/24hrs,低于IV-3000 的2700g/ m2/24hrs。 [0105] As can be seen from Table V, compared to several commercially available products, HPA-14/14-L and HPA-12/12-L of MVTR_1837g / m2 / 24hrs and 1900g / m2 / 24hrs to be much higher in Tegadem std of 900g / m2 / 24hrs of Tegaderm HP and 1100g / m2 / 24hrs, slightly higher MMD of 1700g / m2 / 24hrs, IV-3000 of less than 2700g / m2 / 24hrs. 低于IV-3000的主要原因是基材和胶层厚度不同。 The main reason is lower than the IV-3000 and the layer thickness different substrates. IV-3000的胶层厚度只有12 微米,是HPA-14/14-L和HPA-12/12-L的一半,且基材的透气性也比供应商Vix Co.提供的基材要高。 IV-3000 layer thickness of only 12 microns, is HPA-14/14-L and HPA-12 12-L / half, and permeability of the substrate than the base material suppliers Vix Co. providing greater. MMD采用了点状涂胶的方式,干胶在PU膜上呈点状分布,胶点和胶点之间有很大的空隙可以透汽。 MMD using the dot coating manner, spotty distribution Adhesive PU film, a large gap may be vapor permeable adhesive spots and adhesive between points. 相比于传统的连续涂布,在使用相同的压敏胶的情况下,可以大大提高胶带的MVTR。 Compared to conventional continuous coating, in the case of using the same pressure sensitive adhesive, can greatly improve the MVTR of the adhesive tape. 尽管这样,与采用了高透汽性压敏胶,并使用传统的连续涂布的HPA-14/14-L 和HPA-12/12-L相比,仍略有不如。 Despite this, and with a high moisture vapor transmission adhesive, and coated using a conventional continuous HPA-14/14-L and HPA-12/12-L compared, still slightly better. 而相对于基材,胶层厚度,涂布方式均类似的Tegaderm std,Tegaderm HP 而言,HPA-14/14-L 和HPA-12/12-L 在MVTR 上具有明显的的优势。 Relative to the substrate, layer thickness, coating method are similar Tegaderm std, Tegaderm HP terms, HPA-14/14-L and HPA-12/12-L has a significant advantage in MVTR.

[0106] 压敏胶带和医用敷料: [0106] pressure sensitive adhesive tape and medical dressing:

[0107] 本发明的丙烯酸类压敏胶可广泛应用于需要高水汽透过率的各种胶粘剂领域,包括工业、医疗和家用胶粘剂。 Acrylic pressure-sensitive [0107] The present invention can be widely applied to various fields requiring high moisture vapor transmission rate of the adhesive, including industrial, medical and household adhesives. 作为最普遍的一种使用方式,可以将本发明的丙烯酸类压敏胶涂布在背衬上以形成压敏胶带。 As the most common way of use, it may be acrylic pressure-sensitive coating of the present invention on a backing to form a pressure sensitive adhesive tape.

[0108] 背衬可以是已知的常规背衬,例如,纺织织物,无纺织物,纸张或合成材料。 [0108] The backing may be a backing conventionally known, for example, woven fabric, non-woven fabric, paper or synthetic material. 为了提供高水汽透过率的压敏胶带,背衬除提供支撑作用之外,还应具有高透汽性。 In order to provide a high moisture vapor transmission rate of pressure sensitive adhesive tape, in addition to provide support backing, it should also have a high vapor permeability. 这样的背衬可以由具有高透汽性的材料制成,例如聚氨酯膜。 Such backing may be made of a material having a high vapor permeability, such as a polyurethane film.

[0109] 在将丙烯酸类压敏胶涂布在背衬上之后,需要使丙烯酸类压敏胶交联而固化。 [0109] After the acrylic pressure-sensitive coating on the backing, it is necessary to crosslink the acrylic pressure-sensitive adhesive is cured. 所述交联,可以通过用射线照射或者添加交联剂来实现。 The crosslinking by adding a crosslinking agent or irradiation with radiation to achieve. 所述射线,可以选用伽玛射线,也可以选用电子束。 The rays, gamma rays can be selected, the electron beam may be selected. 所述交联剂,可以选自下列的一种或多种:金属离子交联剂、氮丙啶交联剂、 异氰酸酯交联剂;所述交联剂的用量为占整个单体的重量的0. 01% -5%。 The crosslinking agent may be selected from one or more of: metal ion crosslinking agent, aziridine crosslinking agent, an isocyanate crosslinking agent; the crosslinking agent is used in an amount accounting for the weight of the total monomer 0.01% to 5%.

[0110] 本发明的丙烯酸类压敏胶特别适合用于医用敷料。 [0110] The acrylic pressure-sensitive adhesive of the present invention are particularly suitable for medical dressings. 当用于医用敷料时,可以在上述压敏胶带的胶面上附上一层离型膜,以对于压敏胶可以表现出极轻且稳定的离型力。 When used in medical dressings, one can attach the plastic film from the surface of the pressure-sensitive adhesive tape, pressure-sensitive adhesive in order for the light and may exhibit very stable release force. [0111] 离型膜包括但不限于:由具有涂层的基材制成的离型膜。 [0111] The release film include, but are not limited to: a release film made of a base material with a coating. 所述基材包括但不限于: 纸类基材、膜类基材、铝箔类基材、聚烯烃类材料基材。 The substrates include, but are not limited to: paper-based substrate, a film-based substrate, an aluminum foil-based substrate, polyolefin-based substrate material. 上述离型膜至少有一面具有一个低表面能的涂层,所述涂层包含一种或者几种如下化合物:有机硅、氟化物、氟硅共聚物、侧链为长链聚烯烃的化合物。 Above at least one side with a release film having a low surface energy coating, the coating comprising one or several following compounds: Compound long polyolefin chain silicones, fluorides, silicone copolymers, the side chains. 所述离型膜,优选克重80-120g/m 2之间的纸质离型膜,供应商有宝燕、Ioparex等。 Paper from the film of the release film, the preferred weight between 2 80-120g / m, suppliers Po Yan, Ioparex like.

[0112] 一个典型的医用敷料结构见图1,从上往下依次为聚氨酯膜1,压敏胶2,离型膜3。 [0112] A typical medical dressing structure shown in Figure 1, from top to bottom of a polyurethane film, pressure-sensitive adhesive 2, 3 from the film. 聚氨酯膜1由供应商ViX Co.韩国供应,厚度20.3微米。 Polyurethane film 1 supplied by the vendor ViX Co. Korea, a thickness of 20.3 microns. 压敏胶2为本发明的丙烯酸酯类压敏胶,胶层厚度25微米,转移涂布法涂布。 2 of the present invention, the pressure-sensitive acrylate pressure sensitive adhesive, 25 micron layer thickness, coating method, transfer coating. 离型纸3是80g单面离型纸,上海宝燕提供。 3-sided release paper release paper is 80g, Shanghai Yan Bao provided. 交联固化及灭菌是用伽马射线实现的。 Crosslinking and sterilization is achieved with gamma rays. 由上海金鹏源辐照技术有限公司,采用钴源进行辐照交联和灭菌,剂量范围:25-50kGy。 By the Shanghai Ltd. Jinpeng source of radiation, cobalt source radiation cross-linking and sterilization dose range: 25-50kGy.

[0113] 内部临床实验 [0113] internal clinical trials

[0114] 为了更好的验证本发明中优选实施例的使用性能,进行内部的临床实验。 [0114] In order to verify the performance of an embodiment of the present invention, preferably, the inside of the clinical trials. 即在评估实施例中样品在健康人身上的使用情况,观察敷料的MVTR,粘性、残胶、卷边及皮肤反应等。 That is the case in evaluating the use of the healthy person's samples embodiment, the MVTR of the dressing was observed, viscosity, adhesive residue, curling and skin reactions.

[0115] 以市售样品Tegaderm std,Tegaderm HP, IV-3000及MMD做参比,样品制备过程如下:选用本发明中HPA-12, HPA-12L,HPA-14, HPA-14L四个配方。 [0115] In the commercially available sample Tegaderm std, Tegaderm HP, IV-3000 and MMD do reference, samples were prepared as follows: Using the present invention, HPA-12, HPA-12L, HPA-14, HPA-14L four formulations. 采用的涂布方法是:先将胶水涂在离型纸上,再在胶面上涂上PU膜。 The coating method is adopted: first glue applied to the release paper, and then coated with the PU film on surface of the plastic. PU膜厚为20. 3 μ m,胶水的涂布量为20g/m2,干胶厚25微米。 PU film thickness of 20. 3 μ m, the amount of glue applied was 20g / m2, thickness 25 m Adhesive. 上述样品经常规伽马射线灭菌并交联,然后裁成2. 5 X 8cm的样品,贴于志愿者背部进行临床实验。 In the sample by conventional gamma sterilization and crosslinking, and then cut into the sample 2. 5 X 8cm, affixed to the back of volunteers for clinical trials. 选择12个志愿者,对所贴的样品位置做随机分布。 Select the 12 volunteers, affixed to the sample position to do random distribution. 评估样品在初始Oh (TO),72小时(T72)及168小时(T168)的粘性、残胶、卷边及皮肤反应。 The samples were evaluated in the initial viscosity Oh (TO), 72 hours (T72 is) and 168 hours (T168), and adhesive residue, skin reactions and curling. 测试方法如下: Test methods are as follows:

[0116] 步骤: [0116] Step:

[0117] 1.临床研究工程师将首先用稀释的肥皂水溶液清洁实验者背部的皮肤。 [0117] 1. Clinical Study engineer soap solution is first diluted cleaning experimenter back skin.

[0118] 2.临床研究工程师将在实验者背部左侧贴上8条敷料(干性)(每个样品各一条);在实验者背部右侧洒少量温水,再贴上另外8条敷料(湿性)(每个样品各一条),并在5分钟后ASTMD3330方法测试这些样品,记录为T0。 [0118] 2. Clinical research engineer will be affixed at the back left of the experimenter 8 dressing (dry) (one per each sample); a small amount of hot water sprinkled on the right back of the experimenter, and then paste additional 8 dressing ( wet) (one per each sample) and the samples were tested ASTMD3330 method after 5 minutes, is recorded as T0. 样品大小为2. 5 X 8cm2。 The sample size of 2. 5 X 8cm2.

[0119] 3.临床研究工程师将在实验者背部同样的位置再贴上同样的敷料。 [0119] 3. Clinical study engineer then paste the same dressing experimenter back in the same position.

[0120] 4.临床研究工程师将要求实验者在72小时后返回IHP试验室,评估所有样品的浮起率和皮肤反应。 [0120] 4. Clinical Study engineer asked subjects returned IHP test chamber 72 hours later, floating evaluation of all samples and skin reactions. 一半样品会被撕去,评估粘性和残胶率(T72)。 Half of the sample is torn off, and the residual gum tackiness assessment (T72).

[0121] 5.临床研究工程师将要求实验者在168小时后返回IHP试验室做样品的评估。 [0121] 5. Clinical Study engineer asked subjects return to the laboratory doing IHP samples were evaluated after 168 hours. 剩余的另一半样品会被撕去,并评估浮起率、粘性、残胶率和皮肤反应(T168)。 The remaining half will be torn off the sample, and evaluated floating rate, viscosity, and the residual gum skin reactions (T168).

[0122] 图3显示了粘性临床测试的结果。 [0122] FIG. 3 shows the results of clinical tests of tack. 粘性测试方法与ASTMD3330相似,只不过把钢板换成人体背部,180度剥离,12inch/min。 Viscous and ASTMD3330 test method is similar, except that the back plate into the human body, 180 ° peeling, 12inch / min. 图3中,TO (Dry)表示所测样品在干性皮肤上的初始粘性,TO(Wet)表示所测样品在湿性皮肤上的初始粘性,T72表示所测样品在干性或湿性皮肤上经过72小时后的粘性,T168表示所测样品在干性或湿性皮肤上经过168小时后的粘性。 In FIG. 3, TO (Dry) indicates sample being measured on dry skin initial tack, TO (Wet) represents the initial viscous samples on wet skin measured, T72 represents a sample being tested passes on dry or wet skin after 72 hours the viscosity, T168 denotes the viscosity measured after the samples after 168 hours in dry or wet skin.

[0123] 从图3中可以看出,在TO时,以上所测样品对皮肤的粘性均大于40g/inch。 [0123] As can be seen from Figure 3, when the TO, more viscous sample being tested to the skin greater than 40g / inch. HPA-12/12L,HPA-14/14L在干性皮肤上的初始粘性为90-110g/inch,优选〜100g/inch,在湿性皮肤上的初始粘性为30-50g/inch,优选〜45g/inch,在干性或湿性皮肤上经过72小时后的粘性为160_190g/inch,优选〜170g/inch,在干性或湿性皮肤上经过168小时后的粘性为l〇〇_120g/inch,优选〜110g/inch。 HPA-12 / 12L, HPA-14 / 14L on initial tack to dry skin 90-110g / inch, preferably ~100g / inch, initial wet tack on the skin of 30-50g / inch, preferably ~45g / inch, after dry or wet on the skin after 72 hours the viscosity was 160_190g / inch, preferably ~170g / inch, after dry or wet on the skin for adhesion after 168 hours l〇〇_120g / inch, preferably ~ 110g / inch. 在T72 和T168 时,与市售样品Tegaderm std, Tegaderm HP,IV-3000相比,HPA-12L和HPA-14L具有相类似的粘性,且其粘性高于参比样品MMD,说明以上两种配方具有良好的持粘性。 In time T72, T168, commercially available samples Tegaderm std, Tegaderm HP, IV-3000 compared, HPA-12L and HPA-14L having a similar viscosity, and the viscosity thereof is higher than the reference sample MMD, the two formulations described above have good holding power. HPA-12及HPA-14则与MMD具有相似的粘性, 但是它们在T72和T168时粘性低于与市售样品Tegaderm std,Tegaderm HP,IV-3000。 HPA-12 and HPA-14 and then the MMD having similar viscosity, but the viscosity thereof is lower than the commercially available samples Tegaderm std, Tegaderm HP, IV-3000 at time T72 and T168.

[0124] 除了粘性,残胶和卷边也是影响敷料使用性能的重要因素。 [0124] In addition to the important factors sticky, adhesive residue and also affect the curling of the dressing performance. 本发明中采用0-5评价敷料的残胶、卷边。 0-5 of the present invention employed in the evaluation of the dressing adhesive residue, crimping. 〇分为无残胶或卷边,依次递增,5分为全部残胶或者样品掉落。 Square divided into no residue or crimping, in ascending order, is divided into 5 sample all the adhesive residue or falling.

[0125] 所评估样品在T72时的残胶及卷边如表六所示。 [0125] The samples were evaluated at the time T72 and the residual gum bead as shown in Table VI. 从表六中的残胶评价结果可以看出,本发明中的配方HPA-12L,HPA-14L,HPA-12及HPA-14在内部临床实验中均没有观察到残胶,较之市售产品Tegaderm HP及IV-3000具有明显的优势。 As can be seen from the evaluation results of six tables residue, HPA-12L formulation of the present invention, HPA-14L, HPA-12 and HPA-14 had no adhesive residue was observed in clinical trials in the interior, compared with commercial products Tegaderm HP and IV-3000 has a distinct advantage.

[0126] 从表六中的卷边评价结果可以看出,在评估的72h内,所评估样品均未出现脱落。 [0126] As can be seen from the table in six bead evaluation result in the evaluation 72h, no fall off the sample evaluation. HPA-12L及HPA-14L在T72没有观察到卷边或只有轻微的卷边,与市售产品Tegaderm HP, Tegaderm Std及IV-3000相同。 HPA-12L and HPA-14L was not observed in the T72 or only slight crimping bead,, Tegaderm Std IV-3000 and the same commercial products Tegaderm HP. HPA-12及HPA-14的卷边情况较之上述样品严重,但其评估结果仍好于MMD。 Crimping situation HPA-12 and HPA-14 of the above samples than serious, but still better than the results of its assessment MMD.

[0127] 所评估样品在T1682时的残胶及卷边评价结果如表七所示。 [0127] The samples were evaluated in the bead and the adhesive residue at the time of the evaluation results are shown in Table T1682 VII. 从表七中的残胶评价结果可以看出,本发明中的配方HPA-12L,HPA-14L,HPA-12及HPA-14在长达168h即7天的内部临床实验中均没有观察到残胶,较之市售产品Tegaderm HP及IV-3000具有明显的优势。 As can be seen from the evaluation results of Table VII residue, HPA-12L formulation of the present invention, HPA-14L, HPA-12 and HPA-14 residues were not observed in clinical trials within 7 days i.e. up to 168h in plastic, compared with commercially available products Tegaderm HP and IV-3000 has a distinct advantage.

[0128] 从表七的卷边评价结果可以看出,在长达7天的试验中(T168)HPA-12L及HPA-14L 与市售产品Tegaderm HP及IV-3000具有相似的卷边性能,均有一个样品或两个样品脱落。 [0128] As can be seen from the evaluation results of Table VII bead, test of up to 7 days (T168) HPA-12L and the commercially available HPA-14L product Tegaderm HP and IV-3000 has similar performance bead, a sample or samples have two off. HPA-12及HPA-14的卷边及脱落情况较之上述样品严重,出现3-4个样品的脱落。 Crimping and shedding HPA-12 and HPA-14 is severe than the above samples, sample 3-4 shedding occurs.

[0129] 表六T72残胶及卷边的内部临床测试结果 [0129] Table VI internal clinical test results and adhesive residue bead T72

[0130] [0130]

Figure CN102719205BD00141

[0132] 表七T168残胶及卷边的内部临床测试结果 [0132] Table VII T168 inner bead and an adhesive residue clinical tests results

[0133] [0133]

Figure CN102719205BD00142

[0134] [0134]

Figure CN102719205BD00151

[0135] 综合评估本发明中配方在各个时间点的性能,可以看出HPA-12L及HPA-14L较之HPA-12及HPA-14具有更好的粘性、更少的残胶,更好的卷边性能。 [0135] Comprehensive evaluation of performance of the present invention in the formulation of various points in time, it can be seen HPA-12L and HPA-14L than HPA-12 and HPA-14 has better tack, less adhesive residue, better hemming performance. 而且,HPA-12L及HPA-14L 较之HPA-12及HPA-14具有更高的MVTR。 Further, HPA-12L and HPA-14L than HPA-12 and HPA-14 has a higher MVTR. 因此,适宜作为更透汽,残胶更少的新一代的敷料、胶带产品。 Thus, as a more suitable vapor-permeable, adhesive residue is less generation dressings, tape products.

[0136] 综上所述,本发明披露了一种同时具有高透汽性(MVTR〜1900g/m2/24hrs),高粘性(7天不脱落,不卷边,剥离力有lOOg/inch),低刺激性的压敏胶。 [0136] In summary, while the present invention discloses a high moisture vapor transmission (MVTR~1900g / m2 / 24hrs), high viscosity (7 days does not fall off, not curling, there peel force lOOg / inch), low irritation of pressure sensitive adhesive. 它主要由四类单体构成,带羟基或乙氧基的亲水性丙烯酸酯单体,短链的和长链的疏水性丙烯酸酯类软单体、以及带极性基团的丙烯类硬单体。 It is mainly composed of four monomers, hydrophilic acrylate monomer with a hydroxyl or ethoxy, hydrophobic acrylic acid ester monomer and long chain soft short chain of propylene and a polar group with hard monomer. 这种压敏胶在人体测试中显示出了相比市场同类产品在性能上的巨大优势,是下一代医用敷料的首选。 This pressure-sensitive display in human testing in the market compared to similar products a huge advantage in terms of performance, the next generation of medical dressing of choice. 同时在其它需要高水汽透过率的工业胶粘剂领域,如电子行业也会有广阔的前景。 While in other areas of industrial adhesives requiring high water vapor transmission rate, such as the electronics industry will have broad prospects.

Claims (21)

  1. 1. 一种丙烯酸酯类压敏胶,所述压敏胶包括由以下单体通过自由基共聚形成的聚合物: a) . 10% -30%的带羟基或乙氧基的亲水性丙烯酸酯单体,以所有单体的总重量按100 %计; b) . 50% -70 %的短链的疏水性丙烯酸酯类单体,以所有单体的总重量按100 %计;所述短链的疏水性丙烯酸酯类单体的结构式为CH2 = CHCOORp &是含1-5个碳原子的烷基; c) . 10% -35 %的长链的疏水性丙烯酸酯类单体,以所有单体的总重量按100 %计;所述长链的疏水性丙烯酸酯类单体的结构式为CH2 = CHC00R2,R2是含6-14个碳原子的烷基; d) . 0. 5% -5%的可与上述单体ac共聚的具有极性基团的丙烯类单体,以所有单体的总重量按100 %计。 An acrylate pressure sensitive adhesive, said pressure sensitive adhesive comprises a polymer of the following monomers by free radical copolymerization of:. A) 10% -30% of a hydroxyl group or ethoxy hydrophilic acrylic ester monomer, based on the total weight of all monomers in 100% basis;. b) hydrophobic acrylic acid ester monomer is 50% -70% of the short chain, based on the total weight of all monomers in 100% basis; the formula hydrophobic acrylic acid ester monomer is a short chain CH2 = CHCOORp & alkyl group containing 1-5 carbon atoms; c) a hydrophobic acrylic acid ester monomer is 10% to 35% of the long chain to. total weight of all monomers in 100% basis; structural formula of the long chain hydrophobic acrylic acid ester monomer is CH2 = CHC00R2, R2 is an alkyl group having 6-14 carbon atoms; d) 0. 5%. 5% of the monomer copolymerizable with propylene ac monomer having a polar group, based on the total weight of all the monomers to 100% by weight.
  2. 2. 根据权利要求1所述的丙烯酸酯类压敏胶,其中所述带羟基或乙氧基的亲水性丙烯酸酯单体在所有单体的总重量中所占的比例为15% -25%。 The acrylate pressure sensitive adhesive of claim 1, wherein the ratio of the hydrophilic acrylic monomer is a hydroxyl group or an ethoxy group in the total weight of all monomers is 15% -25 %.
  3. 3. 根据权利要求1所述的丙烯酸酯类压敏胶,其中所述短链的疏水性丙烯酸酯类单体在所有单体的总重量中所占的比例为55% -65%。 3. The acrylate pressure sensitive adhesive according to claim 1, the ratio of hydrophobic acrylic acid ester monomer wherein the short-chain in the total weight of all monomers was 55% -65%.
  4. 4. 根据权利要求1所述的丙烯酸酯类压敏胶,其中所述长链的疏水性丙烯酸酯类单体在所有单体的总重量中所占的比例为20% -30%。 According to claim acrylate pressure sensitive adhesive of claim 1, wherein the ratio of the hydrophobic acrylic acid ester monomer is a long chain in the total weight of all the monomers is 20% -30%.
  5. 5. 根据权利要求1所述的丙烯酸酯类压敏胶,其中所述可与单体ac共聚的丙烯类单体在所有单体的总重量中所占的比例为1% -3%。 The acrylate pressure sensitive adhesive of claim 1, wherein the ratio of the ac monomers copolymerizable with the propylene monomer relative to the total weight of all monomers is 1% -3%.
  6. 6. 根据权利要求1所述的丙烯酸酯类压敏胶,其中所述带羟基或乙氧基的丙烯酸酯类单体选自下列的一种或多种:2-(2-乙氧基乙氧基)乙基丙烯酸酯,丙烯酸羟乙酯,丙烯酸4_轻基节酯。 According to claim acrylate pressure sensitive adhesive of claim 1, wherein the acrylate monomer with a hydroxyl or ethoxy one or more selected from the group consisting of: 2- (2-ethoxyethyl oxy) ethyl acrylate, hydroxyethyl acrylate, 4_ section light-yl ester.
  7. 7. 根据权利要求1所述的丙烯酸酯类压敏胶,其中所述短链的疏水性丙烯酸酯类单体选自下列的一种或多种:丙烯酸甲酯,丙烯酸乙酯,丙烯酸丁酯。 The acrylate pressure sensitive adhesive of claim 1, wherein the hydrophobic acrylic acid ester monomer selected from the group consisting of short chain one or more of: methyl acrylate, ethyl acrylate, butyl acrylate, .
  8. 8. 根据权利要求1所述的丙烯酸酯类压敏胶,其中所述长链的疏水性丙烯酸酯类单体选自下列的一种或多种:丙烯酸-2-乙基己酯,丙烯酸异辛酯。 The acrylate pressure sensitive adhesive according to claim 1, wherein the hydrophobic acrylic acid ester monomer is selected from the group consisting of long-chain one or more of: 2-ethylhexyl acrylate, isobutyl acrylate, octyl ester.
  9. 9. 根据权利要求1所述的丙烯酸酯类压敏胶,其中所述丙烯类单体选自具有羧基或酰胺基的丙烯类单体。 According to claim acrylate pressure sensitive adhesive of claim 1, wherein said propylene monomer is selected from acrylic monomers having a carboxyl group or an amide group.
  10. 10. 根据权利要求9所述的丙烯酸酯类压敏胶,其中所述具有羧基或酰胺基的丙烯类单体选自下列的一种或多种:丙烯酰胺,丙烯酸,甲基丙烯酰胺,甲基丙烯酸。 10. The propylene-based monomer acrylate pressure sensitive adhesive according to claim 9, wherein said group having a carboxyl group or an amide of one or more selected from the group consisting of: acrylamide, acrylic acid, methacrylamide, methyl methacrylic acid.
  11. 11. 一种高透汽性的压敏胶带,其包括涂布在背衬上的一层根据权利要求1所述的丙烯酸酯类压敏胶,所述压敏胶带在正杯法测试中,在20. 3微米聚氨酯膜上涂一层25微米的干胶测得的水汽透过率可以达到1900g/m2/24hrs/37°C。 A high moisture vapor transmission of pressure sensitive adhesive tape which comprises a coating layer on a backing according to claim 1, the acrylate pressure sensitive adhesive, the pressure-sensitive tape n Cup test, in the 20.3 micron polyurethane film coated with a 25 micron Adhesive measured water vapor transmission rate can reach 1900g / m2 / 24hrs / 37 ° C.
  12. 12. 根据权利要求11所述的压敏胶带,其中所述背衬是聚氨酯膜。 12. The pressure sensitive adhesive tape as claimed in claim 11, wherein said backing is a polyurethane film.
  13. 13. -种制备根据权利要求11所述的压敏胶带的方法,所述方法包括在背衬上涂布一层根据权利要求1所述的丙烯酸酯类压敏胶,并且通过使丙烯酸酯类压敏胶交联而固化。 13. - Method according to claim kind of pressure sensitive adhesive tape prepared according to claim 11, said method comprising the backing coated with a layer according to claim 1 of the acrylate pressure sensitive adhesive, and by making the acrylate crosslinked pressure-sensitive adhesive cured.
  14. 14. 根据权利要求13所述的方法,其中所述交联是通过用射线照射或者添加交联剂而实现的。 14. The method according to claim 13, wherein said crosslinked by adding a crosslinking agent or irradiation with radiation achieved.
  15. 15. 根据权利要求14所述的方法,其中所述交联剂选自下列的一种或多种:异氰酸酯交联剂,氮丙啶交联剂,金属离子交联剂;所述交联剂的含量占总的单体的重量的0• 01% -5%。 15. The method according to claim 14, wherein said crosslinker is selected from one or more of the following: an isocyanate crosslinking agent, aziridine crosslinking agent, metal ion crosslinking agent; the crosslinking agent 0 • 01% -5% of the total content of the monomer weight.
  16. 16. 根据权利要求14所述的方法,其中所述射线是伽马射线。 16. The method according to claim 14, wherein said radiation is gamma rays.
  17. 17. -种医用敷料,其包括权利要求11所述的压敏胶带,并且在所述压敏胶带的胶面上附上一层离型膜。 17. - kind of medical dressing, in which the pressure sensitive adhesive tape 11 including the claims, and attached on one surface of the plastic film off the pressure-sensitive tape.
  18. 18. 根据权利要求17所述的医用敷料,其中所述离型膜由具有涂层的基材制成的,所述基材选自下列的一种或多种:纸类基材、膜类基材、铝箔类基材、聚烯烃类材料基材。 18. A medical dressing according to claim 17, wherein the release film is made of a substrate having a coating, said substrate is selected from one or more of the following: paper-based substrate, the film type substrate, aluminum-based substrate, polyolefin-based substrate material.
  19. 19. 根据权利要求18所述的医用敷料,其中所述涂层含一种或者几种如下化合物:有机硅、氟化物、氟硅共聚物、侧链为长链聚烯烃的化合物。 19. A medical dressing according to claim 18, wherein said coating comprises one or several following compounds: Compound long polyolefin chain silicones, fluorides, silicone copolymers, the side chains.
  20. 20. 根据权利要求17所述的医用敷料,其在干性皮肤上的初始粘性为90-1 lOg/inch, 在湿性皮肤上的初始粘性为30-50g/inch,在干性或湿性皮肤上经过72小时后的粘性为160-190g/inch,在干性或湿性皮肤上经过168小时后的粘性为100-120g/inch。 20. A medical dressing according to claim 17, in which the initial tack to dry skin 90-1 lOg / inch, initial wet tack on the skin of 30-50g / inch, a dry or wet skin after 72 hours the viscous 160-190g / inch, viscosity after 168 hours after 100-120g / inch on a dry or wet skin.
  21. 21. 根据权利要求20所述的医用敷料,其在干性皮肤上的初始粘性为〜lOOg/inch, 在湿性皮肤上的初始粘性为〜45g/inch,在干性或湿性皮肤上经过72小时后的粘性为〜 170g/inch,在干性或湿性皮肤上经过168小时后的粘性为〜110g/inch,其中的〜表示平均值。 21. A medical dressing according to claim 20, in which the initial tack to dry skin ~lOOg / inch, initial tack on the skin is wet ~45g / inch, after dry or wet on the skin 72 hours after the viscosity was ~ 170g / inch, viscosity after 168 hours after ~110g / inch on a dry or wet skin, where ~ represents the average value.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101798491A (en) * 2010-02-25 2010-08-11 北京高盟新材料股份有限公司 Pressure sensitive adhesive for protective film and preparation method thereof
CN101875828A (en) * 2009-04-28 2010-11-03 中国科学院过程工程研究所 Medicinal hydrophilic polyacrylic ester pressure-sensitive adhesive and preparation method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0140941A1 (en) 1983-04-07 1985-05-15 Minnesota Mining And Manufacturing Company Adhesive and adhesive-coated sheet material for moist skin
US6680113B1 (en) 1989-12-29 2004-01-20 3M Innovative Properties Company Multi-layered dressing
JP3717952B2 (en) * 1994-04-01 2005-11-16 ミネソタ マイニング アンド マニュファクチャリング カンパニー Medical pressure-sensitive adhesive and a medical dressing with this
US6558790B1 (en) * 1999-11-30 2003-05-06 Avery Dennison Corporation Water vapor-permeable, pressure-sensitive adhesives
WO2007038323A1 (en) * 2005-09-23 2007-04-05 National Starch And Chemical Investment Holding Corporation Acrylic polymer-based adhesives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101875828A (en) * 2009-04-28 2010-11-03 中国科学院过程工程研究所 Medicinal hydrophilic polyacrylic ester pressure-sensitive adhesive and preparation method
CN101798491A (en) * 2010-02-25 2010-08-11 北京高盟新材料股份有限公司 Pressure sensitive adhesive for protective film and preparation method thereof

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