WO2019052203A1 - 一种嵌段结构的丙烯酸压敏胶乳液的制备方法 - Google Patents

一种嵌段结构的丙烯酸压敏胶乳液的制备方法 Download PDF

Info

Publication number
WO2019052203A1
WO2019052203A1 PCT/CN2018/086236 CN2018086236W WO2019052203A1 WO 2019052203 A1 WO2019052203 A1 WO 2019052203A1 CN 2018086236 W CN2018086236 W CN 2018086236W WO 2019052203 A1 WO2019052203 A1 WO 2019052203A1
Authority
WO
WIPO (PCT)
Prior art keywords
emulsion
sensitive adhesive
acrylate monomer
block structure
monomer pre
Prior art date
Application number
PCT/CN2018/086236
Other languages
English (en)
French (fr)
Inventor
吴培龙
孙大伟
Original Assignee
江苏景宏新材料科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 江苏景宏新材料科技有限公司 filed Critical 江苏景宏新材料科技有限公司
Publication of WO2019052203A1 publication Critical patent/WO2019052203A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers

Definitions

  • the invention belongs to the field of pressure sensitive adhesives, and in particular relates to a block structure acrylate pressure sensitive adhesive emulsion and a preparation method thereof.
  • Acrylate pressure sensitive adhesive types mainly include solvent-based pressure-sensitive adhesives, water-based pressure-sensitive adhesives and hot melt pressure sensitive adhesives.
  • Solvent-based pressure-sensitive adhesive is not only costly, but also contains a large amount of flammable and toxic organic solvents, which adversely affects the health of workers and seriously pollutes the environment.
  • the hot-melt pressure-sensitive adhesive has aging resistance, poor surface resistance and comprehensive performance. It can't meet the application requirements in the middle and high-end fields; and the water-based acrylate pressure sensitive adhesive is widely used in more and more fields due to its environmental friendliness, non-toxicity, no VOC emission, large molecular weight, high solid content and low price. application.
  • the water-based acrylate pressure-sensitive adhesive has disadvantages such as water resistance, heat resistance, wettability, and poor coating property, and the crosslinking effect is not satisfactory. If an external curing agent is added, the curing agent reacts with water and is difficult to mix with the glue. Evenly, it will produce more foam; if the internal cross-linking method is used, the cross-linking is incomplete, and the high-temperature aging resistance is poor, so in some areas, the water-based pressure-sensitive adhesive is difficult to replace the solvent-based pressure-sensitive adhesive, such as the alkaline dry battery label.
  • the pressure-sensitive adhesives are almost all solvent-based acrylate pressure-sensitive adhesives.
  • the battery labels have high requirements on the comprehensive performance of the glue, that is, they have good initial adhesion, holding strength and peel strength, especially the glue has a prominent 90° peeling. Sticky, otherwise, the interface of the battery label is easy to reverse.
  • the invention aims at the deficiencies of the prior art, and proposes a block structure acrylate pressure-sensitive adhesive emulsion, which has the advantages of ingenious structure, low cost, excellent comprehensive performance, and particularly good surface resistance.
  • the invention is prepared by the following steps:
  • the acrylate monomer pre-emulsion adding a part of the acrylate monomer pre-emulsion to the emulsion of the step (2), and the second initiator, the acrylate monomer is pre-emulsified and then immersed for 10 to 30 minutes, and then all the styrene is added dropwise.
  • the body pre-emulsion after the completion of the drop, the temperature is kept for 10 to 30 minutes, and finally the residual acrylate monomer pre-emulsion is added dropwise, and the total pre-emulsified droplets of the monomer are added for 3 to 5 hours;
  • step (1) the weight ratio is
  • the acrylate monomer pre-emulsion obtained in the step (1) is 65-80% by weight of the acrylate monomer, and the styrene monomer pre-emulsion styrene weight percentage is 55-70%;
  • the first initiator in the step (2) accounts for 0.08 to 0.2% of the total amount of the monomers, and the second initiator in the step (3) accounts for 0.15 to 0.5% of the total amount of the monomers;
  • the acrylate monomer is butyl acrylate, isooctyl acrylate, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, methylol acrylamide, hydroxyethyl acrylamide, A One or more of glycidyl acrylate, isobornyl methacrylate, and ureido methacrylate.
  • the emulsifier is sodium 2-acrylamido-2-methylpropane sulfonate (AMPS), 1-allyloxy-3-(4-nonylphenol)-2-polyoxyethylene ether ammonium sulfate ( DNS-86), allyloxynonylphenoxypropanol polyoxyethylene ether (SN-10), allyloxynonylphenoxypropanol polyoxyethylene ether ammonium sulfate (SE-10), hydrazine
  • the base emulsifier is sodium alkyl alkoxylated sodium sulfate (AS-801), nonylphenol ethoxylated ammonium sulfate (NPES-4)
  • AES-4 the C12 alkyl alcohol ethoxylated sodium sulfate salt
  • AES-4 the emulsification amount of the base is 0.6 to 6% of the total amount of the total amount
  • first initiator is one of ammonium persulfate or potassium persulfate
  • second initiator is one of ammonium persulfate or potassium persulfate
  • step (3) part of the acrylate monomer pre-emulsion accounts for 30-60% of the total acrylate monomer pre-emulsion, and step (4) adjusts the pH value to 7-8 with ammonia water.
  • the finally obtained pressure-sensitive adhesive emulsion has a block structure composed of a soft segment of polyacrylate and a hard segment of polystyrene, and the weight percentage of the soft segment and the hard segment is: 65% to 95%: 5 % ⁇ 35%.
  • the invention has the following advantages: the pressure sensitive adhesive polymer molecular chain is composed of a polyacrylate soft segment and a polystyrene hard segment, and the polyacrylate segment has a low glass transition temperature. It has good wettability and provides adhesive properties.
  • the polystyrene segment is hard and provides the physical cross-linking point by the force between the segments, providing cohesive force and holding force for the pressure sensitive adhesive.
  • the pressure sensitive adhesive has low cost, good initial tack, holding strength and peel strength, outstanding comprehensive performance and good surface resistance, and can be widely used in the field of curved labels.
  • Step (1) Weigh 30 parts of deionized water, 0.3 parts of emulsifier SE-10, 0.25 parts of emulsifier TX-4SA, add to the pre-emulsified kettle, start stirring, add 80 parts of butyl acrylate, 10 parts of isooctyl acrylate Stir for 30min to obtain acrylate monomer pre-emulsion; weigh 6 parts of deionized water, 0.12 parts of emulsifier SE-10, add to another pre-emulsion kettle, start stirring, add 10 parts of styrene, stir for 30min to get styrene Monomer pre-emulsion;
  • Step (2) Add 40 parts of deionized water, 0.02 parts of AS-801 to the reactor, heat up to 65-70 ° C to open the condensing reflux device, stir to 80 ° C, add 2.5% acrylate monomer pre-emulsion, and then 0.12 parts of ammonium persulfate dissolved in 3 parts of water and added to the reaction vessel at one time, the reaction was carried out for 30 min;
  • Step (3) adding 38% acrylate monomer pre-emulsion, 0.24 parts of ammonium persulfate of the second initiator is dissolved in 18 parts of water, and the monomer pre-emulsion is simultaneously added to the reaction kettle; after the completion of the dropwise addition Insulation for 15 min; add all the styrene monomer pre-emulsion, add 3-5 h, add 15 min after the completion of the addition, and finally add the remaining 59.5% acrylate monomer emulsion, step (4) drop to complete the insulation 1h, the temperature was lowered to 45 ° C, and the pH was adjusted to 7 by adding ammonia water to obtain a block type acrylate pressure-sensitive adhesive emulsion.
  • Step (1) Weigh 30 parts of deionized water, 0.36 parts of DNS-86, 0.24 parts of emulsifier SN-10, add to the pre-emulsified kettle, start stirring, add 70 parts of butyl acrylate, 16 parts of isooctyl acrylate, 2 A portion of methacrylic acid, stirred for 30min to obtain an acrylate monomer pre-emulsion; weigh 6 parts of deionized water, 0.12 parts of emulsifier SE-10 was added to another pre-emulsion kettle, start stirring, add 12 parts of styrene, stir 30min to obtain a styrene monomer pre-emulsion;
  • Step (2) adding 36 parts of deionized water and 0.012 parts of emulsifier AES-4 to the reaction kettle, heating to 65-70 ° C to open the condensing reflux device, stirring and heating to 80 ° C, adding 3.5% acrylate monomer pre-emulsion, Then, 0.09 parts of ammonium persulfate was dissolved in 3 parts of water and added to the reaction vessel at one time, and the reaction was carried out for 30 minutes;
  • Step (3) dropwise adding 26% acrylate monomer pre-emulsion, dissolving 0.27 parts of ammonium persulfate of the second initiator in 18 parts of water, and dropping the monomer pre-emulsion into the reaction kettle simultaneously; after the completion of the dropwise addition Insulation for 15 min; add all the styrene monomer pre-emulsion, add 3-5 h, add 20 min after the completion of the addition, and finally add the remaining 70.5% acrylate monomer pre-emulsion.
  • Step (4) is completed by adding dropwise for 1 hour, and the temperature is lowered to 45 ° C, and the pH is adjusted to 7 by adding ammonia water to obtain a block type acrylate pressure-sensitive adhesive emulsion.
  • Step (1) Weigh 30 parts of deionized water, 0.3 parts of emulsifier SE-10, 0.45 parts of emulsifier AMPS, add to the pre-emulsified kettle, start stirring, add 70 parts of butyl acrylate, 18 parts of isooctyl acrylate, 2 Part of hydroxyethyl methacrylate, 2 parts of glycidyl methacrylate, stirred for 30min to obtain acrylate monomer pre-emulsion; weigh 6 parts of deionized water, 0.09 parts of emulsifier SE-10 was added to another pre-emulsion kettle In the middle, stirring was started, 8 parts of styrene was added, and stirred for 30 minutes to obtain a styrene monomer pre-emulsion;
  • Step (2) Add 45 parts of deionized water and 0.018 parts of NPES-4 to the reactor, raise the temperature to 65-70 ° C to open the condensing reflux device, stir the temperature to 80 ° C, add 2.5% acrylate monomer pre-emulsion, and then 0.12 parts of ammonium persulfate dissolved in 3 parts of water and added to the reaction vessel at one time, the reaction was carried out for 30 min;
  • Step (3) dropwise adding 50% acrylate monomer pre-emulsion, 0.24 parts of second initiator ammonium persulfate is dissolved in 18 parts of water, and the monomer pre-emulsion is simultaneously added dropwise to the reaction kettle; After heat preservation for 20 min; add all the styrene monomer pre-emulsion, add 3-5 h, add 20 5% acrylate monomer pre-emulsion after the completion of the addition.
  • Step (4) is completed by adding dropwise for 1 hour, and the temperature is lowered to 45 ° C, and the pH is adjusted to 7 by adding ammonia water to obtain a block type acrylate pressure-sensitive adhesive emulsion.
  • Step (1) Weigh 27 parts of deionized water, 0.24 parts of emulsifier SE-10, 0.24 parts of emulsifier SN-10, add to the pre-emulsified kettle, start stirring, add 42 parts of butyl acrylate, 40 parts of isooctyl acrylate 1 part of acrylic acid, 2 parts of ureido methacrylate, stirred for 30 minutes to obtain acrylate monomer pre-emulsion; weigh 9 parts of deionized water, 0.15 parts of emulsifier SE-10 was added to another pre-emulsion kettle, and opened Stirring, adding 15 parts of styrene, stirring for 30min to obtain a styrene monomer pre-emulsion;
  • Step (2) adding 40 parts of deionized water and 0.012 parts of emulsifier AS-801 to the reaction kettle, heating to 65-70 ° C to open the condensing reflux device, stirring and heating to 80 ° C, adding 3% acrylate monomer pre-emulsion, Then 0.12 parts of ammonium persulfate was dissolved in 3 parts of water and added to the reaction kettle at one time, and the reaction was carried out for 30 minutes;
  • Step (3) dropwise adding 32% acrylate monomer pre-emulsion, and dissolving 0.3 parts of ammonium persulfate of the second initiator in 18 parts of water, and dropping the monomer pre-emulsion into the reaction kettle simultaneously; after the completion of the dropwise addition Insulation for 15 min; add all the styrene monomer pre-emulsion, add 3-5 h, add 20 min after the completion of the addition, and finally add the remaining 65% acrylate monomer pre-emulsion.
  • Step (4) is completed by adding dropwise for 1 hour, and the temperature is lowered to 45 ° C, and the pH is adjusted to 7 by adding ammonia water to obtain a block type acrylate pressure-sensitive adhesive emulsion.
  • test method of pressure sensitive adhesive performance is as follows:
  • the block structure acrylate pressure sensitive adhesive prepared by the invention has excellent comprehensive performance, especially 90° peeling and good adhesion, and is particularly suitable for fields requiring high surface resistance, such as alkaline dry battery labels.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明公开了一种嵌段结构的丙烯酸酯压敏胶乳液的制备方法，将丙烯酸酯单体和苯乙烯单体分别与去离子水、乳化剂混合均匀，搅拌乳化分别得到丙烯酸酯单体预乳化液和苯乙烯单体预乳化液；将去离子水和打底乳化剂搅拌混合均匀，升温冷凝回流；加入丙烯酸酯单体预乳化液，再加入第一引发剂；向步骤(2)的乳液中滴加部分丙烯酸酯单体预乳化液，以及第二引发剂，然后滴加全部苯乙烯单体预乳化液，最后滴加剩余丙烯酸酯单体预乳化液，出料得到乳液，该乳液玻璃化温度低，浸润性好，提供粘附性能，压敏胶成本低廉，兼具良好初粘力、持粘力和剥离强度，综合性能突出，耐曲面性佳，可以在曲面标签领域有广泛应用。

Description

一种嵌段结构的丙烯酸压敏胶乳液的制备方法 技术领域
本发明属于压敏胶领域，具体涉及一种嵌段结构的丙烯酸酯压敏胶乳液及其制备方法。
背景技术
丙烯酸酯压敏胶类型主要有溶剂型压敏胶、水性压敏胶和热熔压敏胶。溶剂型压敏胶不仅成本高，而且含有大量易燃、有毒的有机溶剂，对工作人员健康造成不利影响，而且严重污染环境；热熔压敏胶存在耐老化性能、耐曲面性能差，综合性能达不到中高端领域应用要求；而水性丙烯酸酯压敏胶由于其环境友好、无毒、无VOC排放、分子量大、固含量高、价格低廉等优点，在越来越多的领域获得广泛的应用。
但是，水性丙烯酸酯压敏胶存在耐水性、耐热性、浸润性、涂布性差等缺点，且交联效果不理想，若采用外添加固化剂，固化剂会与水反应，与胶水难以混合均匀，还会产生较多泡沫；若采用内交联方法，交联不完全，高温耐老化性能差，所以在某些领域水性压敏胶难以取代溶剂型压敏胶，如碱性干电池标签用的压敏胶几乎都是溶剂型丙烯酸酯压敏胶，电池标签对胶水综合性能要求较高，即要具有良好的初粘力、持粘力和剥离强度，尤其要求胶水具有突出的90°剥离持粘性，否则，电池标签的接口处容易反翘。
发明内容
本发明针对现有技术的不足，提出一种嵌段结构丙烯酸酯压敏胶乳液，结构巧妙，低成本，综合性能优异，尤其耐曲面性能佳。
本发明是通过以下步骤制备的：
(1)将丙烯酸酯单体和苯乙烯单体分别与去离子水、乳化剂混合均匀，充分搅拌乳化分别得到丙烯酸酯单体预乳化液和苯乙烯单体预乳化液；
(2)将去离子水和打底乳化剂搅拌混合均匀，升温至65～70℃，冷凝回流；加入占步骤(1)丙烯酸酯单体预乳液重量的0.5wt％～5wt％丙烯酸酯单体预乳化液，再加入第一引发剂，升温至78～84℃，反应20～40min；
(3)将步骤(2)的乳液中滴加部分丙烯酸酯单体预乳化液，以及第二引发剂，丙烯酸酯单体预乳化液滴完后保温10～30min，然后滴加全部苯乙烯单体预乳化液，滴完后保温10～30min，最后滴加剩余丙烯酸酯单体预乳化液，全部单体预乳化液滴加时间为3～5h；
(4)全部滴完后保温1～2h，然后降温至50℃以下，调节乳液pH值至7～8，出料得到嵌段结 构丙烯酸酯压敏胶乳液。
步骤(1)中按重量比为
Figure PCTCN2018086236-appb-000001
其中步骤(1)得到的丙烯酸酯单体预乳化液中丙烯酸酯单体重量百分比的65～80％，苯乙烯单体预乳化液中苯乙烯重量百分比为55～70％；
步骤(2)所述的第一引发剂占单体总量0.08～0.2％，步骤(3)第二引发剂占单体总量的0.15～0.5％；
进一步地，丙烯酸酸酯单体为丙烯酸丁酯、丙烯酸酸异辛酯、丙烯酸、甲基丙烯酸、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、羟甲基丙烯酰胺、羟乙基丙烯酰胺、甲基丙烯酸缩水甘油酯、甲基丙烯酸酸异冰片酯、甲基丙烯酸脲基酯中的一种或多种。
进一步地，乳化剂为2-丙烯酰胺基-2-甲基丙磺酸钠(AMPS)、1-烯丙氧基-3-(4-壬基苯酚)-2-聚氧乙烯醚硫酸铵(DNS-86)、烯丙氧基壬基苯氧基丙醇聚氧乙烯醚(SN-10)、烯丙氧基壬基苯氧基丙醇聚氧乙烯醚硫酸铵(SE-10)、壬基酚聚氧乙烯醚硫酸铵(TX4SA)中一种或多种，打底乳化剂为烷基醇烷氧基化硫酸钠(AS-801)、壬基酚乙氧基硫酸铵(NPES-4)、C12烷基醇乙氧基化硫酸钠盐(AES-4)中一种或多种，打底乳化剂量占乳化剂总量的0.6～6％。
其中第一引发剂为过硫酸铵或过硫酸钾中的一种；第二引发剂为为过硫酸铵或过硫酸钾中的一种。
步骤(3)中部分丙烯酸酯单体预乳化液占总丙烯酸酯单体预乳液的30～60％，步骤(4)用氨水调节PH值至7-8。
根据本发明的技术方案，最终制得的压敏胶乳液由聚丙烯酸酯软段和聚苯乙烯硬段构成的嵌段结构，软段与硬段的重量百分比为：65％～95％∶5％～35％。
与现有技术相比，本发明具有以下优点：压敏胶聚合物分子链由聚丙烯酸酯软段和聚苯乙烯硬段构成的嵌段结构，该结构中聚丙烯酸酯链段玻璃化温度低，浸润性好，提供粘附性能，聚苯乙烯链段硬且凭借链段间作用力，提供物理交联点，为压敏胶提供内聚力和持粘力。此压敏胶成本低廉，兼具良好初粘力、持粘力和剥离强度，综合性能突出，耐曲面性佳，可以在曲面标签领域有广泛应用。
具体实施方式
实施例1
步骤(1)称取30份去离子水、0.3份乳化剂SE-10、0.25份乳化剂TX-4SA加入到预乳化釜中，开启搅拌，加入80份丙烯酸丁酯、10份丙烯酸异辛酯，搅拌30min得到丙烯酸酯单体预乳化液；称取6份去离子水、0.12份乳化剂SE-10加入到另一预乳化釜中，开启搅拌，加入10份苯乙烯，搅拌30min得到苯乙烯单体预乳化液；
步骤(2)反应釜中加入40份去离子水、0.02份AS-801，升温至65-70℃开启冷凝回流装置，搅拌升温至80℃，加入2.5％丙烯酸酯单体预乳化液，再将0.12份过硫酸铵溶解在3份水中并一次性加入反应釜中，反应30min；
步骤(3)滴加38％丙烯酸酯单体预乳化液，将第二引发剂0.24份过硫酸铵溶解在18份水中，与单体预乳化液同时滴加到反应釜中；滴加完成后保温15min；再滴加全部苯乙烯单体预乳化液，滴加时间3-5h，滴加完成后保温15min，最后滴加剩余59.5％丙烯酯单体乳化液，步骤(4)滴加完成保温1h，降温至45℃，加入氨水调节pH至7，出料得到嵌段型丙烯酸酯压敏胶乳液。
实施例2
步骤(1)称取30份去离子水，0.36份DNS-86、0.24份乳化剂SN-10加入到预乳化釜中，开启搅拌，加入70份丙烯酸丁酯、16份丙烯酸异辛酯、2份甲基丙烯酸，搅拌30min得到丙烯酸酯单体预乳化液；称取6份去离子水、0.12份乳化剂SE-10加入到另一预乳化釜中，开启搅拌，加入12份苯乙烯，搅拌30min得到苯乙烯单体预乳化液；
步骤(2)反应釜中加入36份去离子水、0.012份乳化剂AES-4，升温至65-70℃开启冷凝回流装置，搅拌升温至80℃，加入3.5％丙烯酸酯单体预乳化液，再将0.09份过硫酸铵溶解在3份水中并一次性加入反应釜中，反应30min；
步骤(3)滴加26％丙烯酸酯单体预乳化液，将第二引发剂0.27份过硫酸铵溶解在18份水中，与单体预乳化液同时滴加到反应釜中；滴加完成后保温15min；再滴加全部苯乙烯单体预乳化液，滴加时间3-5h，滴加完成后保温20min，最后滴加剩余70.5％丙烯酸酯单体预乳化液，
步骤(4)滴加完成保温1h，降温至45℃，加入氨水调节pH至7，出料得到嵌段型丙烯酸酯压敏胶乳液。
实施例3
步骤(1)称取30份去离子水、0.3份乳化剂SE-10、0.45份乳化剂AMPS加入到预乳化釜中，开启搅拌，加入70份丙烯酸丁酯、18份丙烯酸异辛酯、2份甲基丙烯酸羟乙酯、2份甲基丙烯酸缩水甘油酯，搅拌30min得到丙烯酸酯单体预乳化液；称取6份去离子水、0.09份乳化剂SE-10加入到另一预乳化釜中，开启搅拌，加入8份苯乙烯，搅拌30min得到苯乙烯单体预乳化液；
步骤(2)反应釜中加入45份去离子水、0.018份NPES-4，升温至65-70℃开启冷凝回流装置，搅拌升温至80℃，加入2.5％丙烯酸酯单体预乳化液，再将0.12份过硫酸铵溶解在3份水中并一次性加入反应釜中，反应30min；
步骤(3)滴加50％丙烯酸酯单体预乳化液，将第二引发剂0.24份g过硫酸铵溶解在18份水中，与单体预乳化液同时滴加到反应釜中；滴加完成后保温20min；再滴加全部苯乙烯单体预乳化液，滴加时间3-5h，滴加完成后保温20min，最后滴加剩余47.5％丙烯酸酯单体预乳化液，
步骤(4)滴加完成保温1h，降温至45℃，加入氨水调节pH至7，出料得到嵌段型丙烯酸酯压敏胶乳液。
实施例4
步骤(1)称取27份去离子水、0.24份乳化剂SE-10、0.24份乳化剂SN-10加入到预乳化釜中，开启搅拌，加入42份丙烯酸丁酯、40份丙烯酸异辛酯、1份丙烯酸、2份甲基丙烯酸脲基酯，搅拌30min得到丙烯酸酯单体预乳化液；称取9份去离子水、0.15份乳化剂SE-10加入到另一预乳化釜中，开启搅拌，加入15份苯乙烯，搅拌30min得到苯乙烯单体预乳化液；
步骤(2)反应釜中加入40份去离子水、0.012份乳化剂AS-801，升温至65-70℃开启冷凝回流装置，搅拌升温至80℃，加入3％丙烯酸酯单体预乳化液，再将0.12份过硫酸铵溶解在3份水中并一次性加入反应釜中，反应30min；
步骤(3)滴加32％丙烯酸酯单体预乳化液，将第二引发剂0.3份过硫酸铵溶解在18份水中，与单体预乳化液同时滴加到反应釜中；滴加完成后保温15min；再滴加全部苯乙烯单体预乳化液，滴加时间3-5h,滴加完成后保温20min，最后滴加剩余65％丙烯酸酯单体预乳化液，
步骤(4)滴加完成保温1h，降温至45℃，加入氨水调节pH至7，出料得到嵌段型丙烯酸酯压敏胶乳液。
效果实施例
下面对实施例制备的压敏胶进行相关性能测试。
其中压敏胶性能测试方法如下：
(1)初粘力：按照GB/T4852～2002进行测试，以球号表示初粘性大小。
(2)持粘力：按照GB/T4851～1998进行测试，以胶带破坏重物掉落的时间计算。
(3)180°剥离强度：用电脑式按照试验机按照GB/T2792～1998进行测试。
(4)90°剥离持粘力：采用企业制定的检测方法进行测试。制备用酒精棉球将不锈钢板表面擦拭干净，停放干燥约10分钟。粘贴上标签并压平，使标签和不锈钢之间粘贴牢固，无间隙、无气泡，用2公斤垂直压力压20分钟并放置30分钟。然后在标签纵向的一段加规定重量的砝码，对标签垂直向下进行剥离。直至规定长度全部剥离脱开，并记下剥离脱开过程所用的时间。
表1嵌段结构丙烯酸酯压敏胶性能测试结果
Figure PCTCN2018086236-appb-000002
本发明制备的嵌段结构丙烯酸酯压敏胶综合性能优异，尤其90°剥离持粘力佳，特别适用于对耐曲面性能要求较高的领域，如碱性干电池标签等。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效结构或等效流程变换，或直接或间接运用在其它的相关技术领域，均同理包括在本发明的专利保护范围内。

Claims (10)

  1. 一种嵌段结构的丙烯酸酯压敏胶乳液的制备方法，其特征在于包括以下制备步骤：
    (1)将丙烯酸酯单体和苯乙烯单体分别与去离子水、乳化剂混合均匀，充分搅拌乳化分别得到丙烯酸酯单体预乳化液和苯乙烯单体预乳化液；
    (2)将去离子水和打底乳化剂搅拌混合均匀，升温至65～70℃，冷凝回流；加入占步骤(1)丙烯酸酯单体预乳液重量0.5～5％丙烯酸酯单体预乳化液，再加入第一引发剂，升温至78～84℃，反应20～40min；
    (3)向步骤(2)的乳液中滴加部分丙烯酸酯单体预乳化液，以及第二引发剂，丙烯酸酯单体预乳化液滴完后保温10～30min，然后滴加全部苯乙烯单体预乳化液，滴完后保温10～30min，最后滴加剩余丙烯酸酯单体预乳化液，全部单体预乳化液滴加时间为3～5h；
    (4)全部滴完后保温1～2h，然后降温至50℃以下，调节乳液pH值至7～8，出料得到嵌段结构丙烯酸酯压敏胶乳液。
  2. 根据权利要求1所述的一种嵌段结构的丙烯酸压敏胶乳液的制备方法，其特征在于所述的步骤(1)中按重量比为
    Figure PCTCN2018086236-appb-100001
  3. 根据权利要求2所述的一种嵌段结构的丙烯酸压敏胶乳液的制备方法，其特征在于所述的步骤(1)得到的丙烯酸酯单体预乳化液中丙烯酸酯单体重量百分比为65～80％，苯乙烯单体预乳化液苯乙烯单体重量百分比为55～70％。
  4. 根据权利要求1所述的一种嵌段结构的丙烯酸压敏胶乳液的制备方法，其特征在于步骤(2)的第一引发剂占单体重量0.08～0.2％，步骤(3)第二引发剂占单体重量的0.15～0.5％。
  5. 根据权利要求1所述的一种嵌段结构的丙烯酸压敏胶乳液的制备方法，其特征在于所述丙烯酸酸酯单体为丙烯酸丁酯、丙烯酸酸异辛酯、丙烯酸、甲基丙烯酸、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、羟甲基丙烯酰胺、羟乙基丙烯酰胺、甲基丙烯酸缩水甘油酯、甲基丙烯酸酸异冰片酯、甲基丙烯酸脲基酯中的一种或多 种；所述乳化剂为2-丙烯酰胺基-2-甲基丙磺酸钠、1-烯丙氧基-3-(4-壬基苯酚)-2-聚氧乙烯醚硫酸铵、烯丙氧基壬基苯氧基丙醇聚氧乙烯醚、烯丙氧基壬基苯氧基丙醇聚氧乙烯醚硫酸铵、壬基酚聚氧乙烯醚硫酸铵中一种或多种；步骤(2)所述打底乳化剂为烷基醇烷氧基化硫酸钠、壬基酚乙氧基硫酸铵、C12烷基醇乙氧基化硫酸钠盐中一种或多种。
  6. 根据权利要求1所述的一种嵌段结构的丙烯酸压敏胶乳液的制备方法，其特征在于步骤(2)所述的打底乳化剂量占乳化剂总量的0.6～6％。
  7. 根据权利要求4所述的一种嵌段结构的丙烯酸压敏胶乳液的制备方法，其特征在于所述的第一引发剂为过硫酸铵、过硫酸钾中一种；第二引发剂为过硫酸铵、过硫酸钾中的一种。
  8. 根据权利要求1所述的一种嵌段结构的丙烯酸压敏胶乳液的制备方法，其特征在于所述的步骤(3)中部分丙烯酸酯单体预乳化液占总丙烯酸酯单体预乳液重量的30～60％，剩余丙烯酸酯单体预乳化液占总丙烯酸酯单体预乳化液重量的40％～70％。
  9. 根据权利要求1所述的一种嵌段结构的丙烯酸压敏胶乳液的制备方法，其特征在于：所述的步骤(4)用氨水调节PH值至7-8。
  10. 根据权利要求1或2所述的一种嵌段结构的丙烯酸压敏胶乳液的制备方法制得的压敏胶乳液，其特征在于所述的乳液由聚丙烯酸酯软段和聚苯乙烯硬段构成的嵌段结构，软段与硬段的重量百分比为65％～95％∶5％～35％。
PCT/CN2018/086236 2017-09-15 2018-05-10 一种嵌段结构的丙烯酸压敏胶乳液的制备方法 WO2019052203A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710829722.1 2017-09-15
CN201710829722.1A CN107573469A (zh) 2017-09-15 2017-09-15 一种嵌段结构的丙烯酸酯压敏胶乳液的制备方法

Publications (1)

Publication Number Publication Date
WO2019052203A1 true WO2019052203A1 (zh) 2019-03-21

Family

ID=61032960

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/086236 WO2019052203A1 (zh) 2017-09-15 2018-05-10 一种嵌段结构的丙烯酸压敏胶乳液的制备方法

Country Status (2)

Country Link
CN (1) CN107573469A (zh)
WO (1) WO2019052203A1 (zh)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112778916A (zh) * 2020-12-30 2021-05-11 四川轻化工大学 一种特种含氟压敏胶及其制备方法
CN113429917A (zh) * 2021-07-21 2021-09-24 江苏斯迪克新材料科技股份有限公司 一种丙烯酸乳液压敏胶及其制备方法
CN113755120A (zh) * 2021-08-13 2021-12-07 江苏斯迪克新材料科技股份有限公司 一种丙烯酸酯胶黏剂及制备方法
CN114177941A (zh) * 2021-12-16 2022-03-15 太仓运通新材料科技有限公司 一种酯化催化剂及其制备方法
CN114891464A (zh) * 2022-05-30 2022-08-12 山东新华医疗器械股份有限公司 一种高初粘耐高温水性丙烯酸酯压敏胶及其制备方法
CN115322285A (zh) * 2022-08-10 2022-11-11 上海金狮化工有限公司 一种应用于皮革效应层的通透型丙烯酸树脂及其制备方法
CN115403694A (zh) * 2022-09-28 2022-11-29 沧州冀春新材料有限公司 一种常温双重交联磷酸酯改性苯丙防腐乳液及其制备方法
CN116622314A (zh) * 2023-04-07 2023-08-22 北京领力网络科技有限公司 一种耐低温压敏胶的制备工艺
CN116769434A (zh) * 2023-08-25 2023-09-19 广东远东高分子科技有限公司 一种气排钉胶水及其加工工艺

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107573469A (zh) * 2017-09-15 2018-01-12 江苏景宏新材料科技有限公司 一种嵌段结构的丙烯酸酯压敏胶乳液的制备方法
CN108467698A (zh) * 2018-04-12 2018-08-31 广东晨戈新材料科技有限公司 一种耐水性粘结剂及其制备方法
JP7372544B2 (ja) * 2020-03-10 2023-11-01 藤倉化成株式会社 粘着剤組成物
CN111394023B (zh) * 2020-04-01 2022-04-08 上海保立佳新材料有限公司 一种耐水白丙烯酸酯压敏胶及其制备方法
CN114276504A (zh) * 2021-11-09 2022-04-05 杭州传化精细化工有限公司 一种无纺布用后整理乳液及其制备方法
CN114437654B (zh) * 2021-12-24 2023-06-13 英创新材料(绍兴)有限公司 一种水性快凝型胶粘剂及其制备方法
CN115287024B (zh) * 2022-07-07 2024-08-30 江苏景宏新材料科技股份有限公司 一种水性丙烯酸酯复合胶及其制备方法
CN115322712B (zh) * 2022-08-29 2023-10-13 湖北航天化学新材料科技有限公司 一种水性聚丙烯酸酯嵌段共聚物压敏胶及制备方法
CN115322706B (zh) * 2022-08-31 2023-08-15 福建华峰新材料有限公司 一种弹滑粘合剂及其制备方法
CN115491153B (zh) * 2022-10-26 2023-10-20 湖北航天化学技术研究所 一种交联型水性丙烯酸酯嵌段共聚物压敏胶及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928534A (zh) * 2010-08-24 2010-12-29 华南理工大学 纸塑复合用单组份低温自交联乳液胶黏剂及其制备方法
CN106010379A (zh) * 2015-08-18 2016-10-12 江苏景宏新材料科技有限公司 一种电池标签用水性丙烯酸酯压敏胶及其制备方法
CN107573469A (zh) * 2017-09-15 2018-01-12 江苏景宏新材料科技有限公司 一种嵌段结构的丙烯酸酯压敏胶乳液的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3523565B2 (ja) * 2000-05-10 2004-04-26 三菱レイヨン株式会社 積層用アクリル樹脂フィルム及びこれを用いたアクリル積層成形品
JP5781302B2 (ja) * 2010-12-28 2015-09-16 日東電工株式会社 放射線硬化型粘着剤組成物及び粘着シート
JP2012224733A (ja) * 2011-04-19 2012-11-15 Mitsui Chemicals Inc 接着剤組成物、その製造方法、その硬化物、及びこれを用いた電子デバイス
CN103045113B (zh) * 2012-08-31 2014-07-02 江苏创基新材料有限公司 自交联互穿网络型有机硅-丙烯酸酯共聚乳液压敏胶粘剂的制备方法
CN103408691B (zh) * 2013-08-06 2016-03-16 中科院广州化学有限公司 一种丙烯酸酯压敏胶乳液及其制备方法与应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928534A (zh) * 2010-08-24 2010-12-29 华南理工大学 纸塑复合用单组份低温自交联乳液胶黏剂及其制备方法
CN106010379A (zh) * 2015-08-18 2016-10-12 江苏景宏新材料科技有限公司 一种电池标签用水性丙烯酸酯压敏胶及其制备方法
CN107573469A (zh) * 2017-09-15 2018-01-12 江苏景宏新材料科技有限公司 一种嵌段结构的丙烯酸酯压敏胶乳液的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FENG, XIUE ET AL.: "Synthesis and Characterization of ABAType Block Copolymer", JOURNAL OF TAIYUAN UNIVERSITY OF TECHNOLOGY, vol. 34, no. 2, 20 March 2003 (2003-03-20), pages 212 - 215 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112778916B (zh) * 2020-12-30 2023-04-18 四川轻化工大学 一种特种含氟压敏胶及其制备方法
CN112778916A (zh) * 2020-12-30 2021-05-11 四川轻化工大学 一种特种含氟压敏胶及其制备方法
CN113429917A (zh) * 2021-07-21 2021-09-24 江苏斯迪克新材料科技股份有限公司 一种丙烯酸乳液压敏胶及其制备方法
CN113755120A (zh) * 2021-08-13 2021-12-07 江苏斯迪克新材料科技股份有限公司 一种丙烯酸酯胶黏剂及制备方法
CN114177941A (zh) * 2021-12-16 2022-03-15 太仓运通新材料科技有限公司 一种酯化催化剂及其制备方法
CN114891464A (zh) * 2022-05-30 2022-08-12 山东新华医疗器械股份有限公司 一种高初粘耐高温水性丙烯酸酯压敏胶及其制备方法
CN114891464B (zh) * 2022-05-30 2023-11-21 山东新华医疗器械股份有限公司 一种高初粘耐高温水性丙烯酸酯压敏胶及其制备方法
CN115322285B (zh) * 2022-08-10 2023-09-12 上海金狮化工有限公司 一种应用于皮革效应层的通透型丙烯酸树脂及其制备方法
CN115322285A (zh) * 2022-08-10 2022-11-11 上海金狮化工有限公司 一种应用于皮革效应层的通透型丙烯酸树脂及其制备方法
CN115403694A (zh) * 2022-09-28 2022-11-29 沧州冀春新材料有限公司 一种常温双重交联磷酸酯改性苯丙防腐乳液及其制备方法
CN116622314A (zh) * 2023-04-07 2023-08-22 北京领力网络科技有限公司 一种耐低温压敏胶的制备工艺
CN116622314B (zh) * 2023-04-07 2024-01-12 深圳国兴祥胶粘材料有限公司 一种耐低温压敏胶的制备工艺
CN116769434A (zh) * 2023-08-25 2023-09-19 广东远东高分子科技有限公司 一种气排钉胶水及其加工工艺
CN116769434B (zh) * 2023-08-25 2023-10-31 广东远东高分子科技有限公司 一种气排钉胶水及其加工工艺

Also Published As

Publication number Publication date
CN107573469A (zh) 2018-01-12

Similar Documents

Publication Publication Date Title
WO2019052203A1 (zh) 一种嵌段结构的丙烯酸压敏胶乳液的制备方法
CN101974299B (zh) 一种耐高温聚丙烯酸酯压敏胶乳液及其制法和应用
CN104004477B (zh) 一种室温自交联聚丙烯酸酯压敏胶及其制备方法与应用
CN106432586B (zh) 硅氟改性丙烯酸酯压敏胶及其制备方法
CN100489047C (zh) 橡胶用丙烯酸乳液胶粘剂的制备方法
CN109762097A (zh) 一种聚丙烯酸酯、压敏胶及制备方法
CN111187586B (zh) 一种特高粘丙烯酸酯乳液压敏胶及其制备方法
CN103952105B (zh) 一种聚乙烯保护膜用氟硅改性水性压敏胶及其制备方法
JP4422239B2 (ja) アクリルエマルジョン型感圧接着剤およびこれを用いた感圧接着剤製品
CN111363503B (zh) 一种高固含量低粘度压敏胶乳液
CN113999632A (zh) 一种水性丙烯酸酯压敏胶及其制备方法
CN109897574B (zh) 一种压敏胶水及其制备方法、不干胶标签及其制备方法
CN102977823B (zh) 一种墙纸用环保胶水及其制备方法
CN112250789A (zh) 一种乳液型丙烯酸酯压敏胶，其制备方法及双面胶带
CN110387199B (zh) 一种卫浴钢化玻璃安全膜用丙烯酸酯压敏胶的制备方法及其应用
CN105408437B (zh) 由多阶段乳液聚合制备用于保护膜的压敏胶粘剂分散体
CN104497201A (zh) 松香衍生物/聚丙烯酸酯复合细乳液压敏胶及其制备方法
CN107868639A (zh) 一种丙烯酸酯压敏胶、压敏胶带及丙烯酸酯压敏胶的制备方法
JP2020506271A (ja) 感圧粘着剤組成物およびこれを調製する方法
CN106811159B (zh) 一种双组份改性氯丁胶的制备方法
CN111849364A (zh) 一种丙烯酸酯乳液压敏胶的制备方法
CN104449457B (zh) 用于惰性材料粘接的底胶促进剂及其制备方法
JP4422240B2 (ja) アクリルエマルジョン型感圧接着剤およびこれを用いた感圧接着剤製品
CN109438617B (zh) 具有松香基粘性单体的高初粘乳液型丙烯酸酯压敏胶及其制备方法
CN111073558A (zh) 一种高抗剪切的丙烯酸酯压敏胶、压敏胶带及其制备方法

Legal Events

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

Ref document number: 18857273

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18857273

Country of ref document: EP

Kind code of ref document: A1