WO2021057847A1 - 一种冷关型粘合剂及其制备方法和一种粘合带的制备方法 - Google Patents

一种冷关型粘合剂及其制备方法和一种粘合带的制备方法 Download PDF

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WO2021057847A1
WO2021057847A1 PCT/CN2020/117468 CN2020117468W WO2021057847A1 WO 2021057847 A1 WO2021057847 A1 WO 2021057847A1 CN 2020117468 W CN2020117468 W CN 2020117468W WO 2021057847 A1 WO2021057847 A1 WO 2021057847A1
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meth
acrylate
cold
adhesive
carbon atoms
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PCT/CN2020/117468
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English (en)
French (fr)
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董村东
赵朋
陈坤
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南京清尚新材料科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2475/00—Presence of polyurethane

Definitions

  • the invention relates to a temperature-sensitive adhesive, in particular to a cold-seal adhesive and a preparation method thereof and a preparation method of an adhesive tape.
  • the main feature of the cold-close adhesive is that when the temperature is lower than the melting point of the side chain crystalline polymer, it crystallizes and exhibits low viscosity; when the temperature is higher than the melting point, a phase change occurs to show fluidity and adhesion. Power recovery.
  • This adhesive can be reused according to temperature changes. In the fields of electronic components, semiconductor wafers, and liquid crystals, it has important applications for temporarily fixing components.
  • patent CN201210376120.2 Adhesive Composition and Adhesive With “in the presence of polyurethane (meth) acrylate, UV irradiation of monomer mixture containing (meth) acrylate and (meth) acrylamide compounds, to form a certain cross-linking system in the system, Improve cohesion and heat resistance. UV curing is a transient reaction. It is easy to cause uneven monomer concentration during cross-linking, resulting in uneven surface adhesion of the adhesive tape.
  • the object of the present invention is to provide an adhesive with good heat resistance, high cohesion and uniform viscosity, and to provide a method for preparing an adhesive tape containing the adhesive.
  • a cold-closing adhesive including the following mass parts of raw materials:
  • linear alkyl (meth)acrylate with 14 or more carbon atoms is tetradecyl (meth)acrylate, cetyl (meth)acrylate, (meth) One or more of octadecyl acrylate, eicosyl (meth)acrylate and behenyl (meth)acrylate.
  • linear alkyl (meth)acrylate with carbon atoms number of 1-6 is methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate (Base) One or more of hexyl acrylate.
  • the polar monomers are (meth)acrylic acid, crotonic acid, maleic acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, olefin One or more of propanol, dimethylaminoethyl (meth)acrylate, and glycidyl (meth)acrylate.
  • the initiator for copolymerization is one or more of benzoyl peroxide, dimethyl ethyl ketone peroxide, 2,2-azobisisobutyronitrile, and azobisisoheptonitrile .
  • the bifunctional polymer is a hydroxyl-containing polyurethane acrylic resin with a hydroxyl value of 15-80 mg KOH/g, preferably, the hydroxyl value is 20-65 mg KOH/g; more preferably, the hydroxyl value is 20-65 mg KOH/g; It is 20-50 mg KOH/g.
  • the molecular weight of the bifunctional polymer is 1000-10000, preferably, the molecular weight is 1000-5000.
  • the isocyanate crosslinking agent is isophorone diisocyanate polymer, (hydrogenated) toluene diisocyanate polymer, hexamethylene diisocyanate polymer, naphthalene diisocyanate polymer and ( (Hydrogenated) one or more of xylylene diisocyanate polymers, or a commercially available isocyanate compound.
  • a method for preparing a cold-closed adhesive includes the following steps:
  • Step 1 Add linear alkyl (meth)acrylate with 14 or more carbon atoms, alkyl (meth)acrylate with 1-6 carbon atoms and polar monomers to toluene, and add it to the N2 drum Stir uniformly in the bubble and add the initiator for copolymerization to obtain a crystalline prepolymer with side chains;
  • Step 2 Add bifunctional polymer and isocyanate crosslinking agent to the crystalline prepolymer with side chains prepared in Step 1, and stir thoroughly, and after stirring evenly, the cold-closing adhesive is obtained .
  • a method for preparing an adhesive tape made of a cold-closed adhesive including the following steps: adding a photoinitiator to the adhesive, mixing uniformly and coating it on the base film, drying to remove the solvent and heating Solid treatment, and then ultraviolet ray irradiation to produce an adhesive tape.
  • the photoinitiator is ⁇ -hydroxyalkyl phenone, thiopropoxythioxanthone, alkyl iodonium salt, cumene ferrocene hexafluorophosphate, 2,2-diethyl Oxybenzophenone, 4-methylbenzophenone, 2-chloroanthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and iso One or more of propyl thioxanthone, or commercially available photoinitiators, such as TPO and 819.
  • the substrate film is one of polyethylene film, polyvinyl chloride film, polypropylene film, polycarbonate film, and polyethylene terephthalate film.
  • the heat treatment time is 2.5-4 minutes
  • the drying temperature is 100-150°C
  • the ultraviolet irradiation time is 30s.
  • the thickness of the fabricated adhesive tape is set to 50um.
  • the heat resistance of the adhesive is effectively improved; the tensile strength of the adhesive tape is significantly improved; the high-temperature adhesive force of the adhesive tape is significantly improved; the viscosity distribution and thickness of the adhesive tape are uniform.
  • a cold-closing adhesive including the following mass parts of raw materials:
  • Methyl methacrylate 40 servings
  • a method for preparing a cold-closed adhesive includes the following steps:
  • Step 1 Add 20 parts of behenyl methacrylate, 40 parts of methyl methacrylate and 3 parts of methacrylic acid to 20 parts of toluene, and stir evenly in N2 bubbling, and add 0.1 part of initiator. Oxidize benzoyl to obtain a crystalline prepolymer with side chains;
  • Step 2 Add 8 parts of bifunctional polymer and 2 parts of hexamethylene diisocyanate curing agent to the crystalline prepolymer with side chains prepared in Step 1. mixture.
  • the bifunctional polymer has a hydroxyl value of 35mg KOH/g and a molecular weight of less than 5000.
  • An adhesive tape made of a cold-closed adhesive which is made by the following method: add 1 part of 2,2-diethoxybenzophenone to the adhesive to avoid light, and mix it evenly. Coated on polyethylene terephthalate film, 3min Drying at 150°C to remove the solvent and thermosetting treatment, and irradiate with ultraviolet rays to form an adhesive tape of 50um thickness.
  • a cold-closing adhesive including the following parts by mass of raw materials:
  • Methyl methacrylate 40 servings
  • a method for preparing a cold-closed adhesive includes the following steps:
  • Step 1 Add 30 parts of octadecyl methacrylate, 40 parts of methyl methacrylate and 5 parts of (meth)-2-2 hydroxypropyl (meth)acrylate to 20 parts of toluene, and stir under N2 bubbling Evenly, add 0.1 part of initiator azobisisobutyronitrile to obtain a crystalline prepolymer with side chains;
  • Step 2 Add 10 parts of bifunctional polymer and 2.5 parts of toluene diisocyanate curing agent to the crystalline prepolymer with side chains prepared in Step 1, and stir thoroughly to obtain a cold-closing adhesive.
  • the bifunctional polymer has a hydroxyl value of 30 mg KOH/g and a molecular weight of less than 5000.
  • An adhesive tape made of a cold-closed adhesive which is made by the following method: add 0.2 parts of photoinitiator TPO and 0.1 part of photoinitiator 819 to the adhesive, and mix them evenly. Coated on a polyethylene terephthalate film, dried at 100°C for 3 minutes to remove the solvent, heat-cured, and irradiated with ultraviolet rays to form an adhesive tape with a thickness of 50um.
  • a cold-closing adhesive including the following parts by mass of raw materials:
  • a method for preparing a cold-closed adhesive includes the following steps:
  • Step 1 Add 30 parts of tetradecyl methacrylate, 60 parts of ethyl methacrylate and 5 parts of (meth)-2-2 hydroxypropyl (meth)acrylate to 20 parts of toluene, and stir under N2 bubbling Evenly, add 0.15 parts of initiator azobisisobutyronitrile to obtain a crystalline prepolymer with side chains;
  • Step 2 Add 8 parts of bifunctional polymer and 8 parts of toluene diisocyanate curing agent to the crystalline prepolymer with side chains prepared in Step 1, and stir thoroughly to obtain a cold-closed adhesive.
  • the bifunctional polymer has a hydroxyl value of 35mg KOH/g and a molecular weight of less than 5000.
  • An adhesive tape made of cold-closed adhesive which is made by the following method: add 0.15 parts of photoinitiator TPO to the adhesive to avoid light, mix well and coat it on polyterephthalic acid On the glycol ester film, dry it at 100°C for 3 minutes to remove the solvent and heat-set it, and irradiate it with ultraviolet rays to form an adhesive tape with a thickness of 50um.
  • a cold-closing adhesive including the following mass parts of raw materials:
  • Methyl methacrylate 60 servings
  • Toluene diisocyanate curing agent 0.5 part.
  • a method for preparing a cold-closed adhesive includes the following steps:
  • Step 1 Add 30 parts of eicosanyl methacrylate, 60 parts of methyl methacrylate and 5 parts of (meth)-2-hydroxypropyl acrylate to 20 parts of toluene, and stir under N2 bubbling Evenly, add 0.15 parts of initiator azobisisobutyronitrile to obtain a crystalline prepolymer with side chains;
  • Step 2 Add 2 parts of bifunctional polymer and 0.5 part of toluene diisocyanate curing agent to the crystalline prepolymer with side chains prepared in Step 1, and stir thoroughly to obtain a cold-closing adhesive.
  • the bifunctional polymer has a hydroxyl value of 30 mg KOH/g and a molecular weight of less than 5000.
  • An adhesive tape made of a cold-closed adhesive which is made by the following method: add 0.03 parts of photoinitiator TPO and 0.01 parts of photoinitiator 819 to the adhesive to avoid light, and mix them evenly. Coated on a polyethylene terephthalate film, dried at 100°C for 3 minutes to remove the solvent, heat-cured, and irradiated with ultraviolet rays to form an adhesive tape with a thickness of 50um.
  • a cold-closing adhesive including the following mass parts of raw materials:
  • a method for preparing a cold-closed adhesive includes the following steps:
  • Step 1 Add 25 parts of eicosyl methacrylate, 50 parts of hexyl methacrylate and 4 parts of (meth)acrylic acid to 20 parts of toluene, stir evenly in N2 bubbling, and add 0.12 parts of initiator Azobisisobutyronitrile to obtain a crystalline prepolymer with side chains;
  • Step 2 Add 2 parts of bifunctional polymer and 0.5 part of toluene diisocyanate curing agent to the crystalline prepolymer with side chains prepared in Step 1, and stir thoroughly to obtain a cold-closing adhesive.
  • the bifunctional polymer has a hydroxyl value of 50 mg KOH/g and a molecular weight of less than 5000.
  • An adhesive tape made of a cold-closed adhesive which is made by the following method: add 0.03 parts of photoinitiator TPO and 0.01 parts of photoinitiator 819 to the adhesive to avoid light, and mix them evenly. Coated on a polyethylene terephthalate film, dried at 100°C for 3 minutes to remove the solvent, heat-cured, and irradiated with ultraviolet rays to form an adhesive tape with a thickness of 50um.
  • the test results show that: the heat resistance of the adhesive is effectively improved; the tensile strength of the adhesive tape is significantly improved; the high-temperature adhesive force of the adhesive tape is significantly improved; the viscosity distribution and thickness of the adhesive tape are uniform.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明涉及一种冷关型粘合剂及其制备方法和一种粘合带的制备方法，包括碳原子数14以上的直链状烷基（甲基）丙烯酸酯、碳原子数1-6的烷基（甲基）丙烯酸酯、极性单体、共聚用引发剂、双功能型聚合物及异氰酸酯类交联剂。由粘合剂制成的粘合带由以下方法制备：在甲苯中加入碳原子数14以上的直链状烷基（甲基）丙烯酸酯、碳原子数1-6的烷基（甲基）丙烯酸酯、极性单体，并N2鼓泡中搅拌均匀，加入共聚用引发剂，得到带侧链结晶性预聚物，在上述体系中加入双功能型聚合物和异氰酸酯类交联剂，搅拌均匀，得到粘合剂。避阳光加入光引发剂，混合均匀后涂布到基膜上，烘干并热固处理后，紫外线照射，制作成粘合带。本发明具有耐热性好、粘合力强等优点。

Description

一种冷关型粘合剂及其制备方法和一种粘合带的制备方法 技术领域
本发明涉及一种温敏型粘合剂，具体涉及一种冷关型粘合剂及其制备方法和一种粘合带的制备方法。
 背景技术
冷关型粘合剂的主要特征在于当温度低于侧链结晶性聚合物的熔点时，发生结晶化，表现出低粘性；温度高于熔点时，发生相变而显示出流动性，粘合力恢复。这种粘合剂可以根据温度变化而重复利用。在电子部件、半导体晶圆、液晶等领域中，用于暂时固定部件具有重要的应用。
目前，冷关型粘合剂的技术主要掌握在日本手里，并在中国申请了诸多相关专利，比如中国专利CN201080007840.0《感温性粘合剂及感温性粘合带》，利用金属螯合物与侧链结晶性聚合物形成配位键，从而提高粘合剂的耐热性，该篇专利仅靠配位键作用效果有限；专利CN201210376120.2《粘合剂组合物和粘合带》，利用在聚氨酯（甲基）丙烯酸酯存在下，对含有（甲基）丙烯酸酯和（甲基）丙烯酰胺类化合物单体混合液进行UV照射，在体系内形成一定的交联体系，提高凝聚力，从而提高耐热性，UV固化是一种瞬时性反应，交联时容易使单体浓度不均，从而造成粘合带表面粘性不一。
 技术问题
本发明的目的在于提供一种耐热性好，高凝聚力且粘性均匀的粘合剂，另外提供包含这种粘合剂的粘合带的制备方法。
 技术解决方案
一种冷关型粘合剂，包括以下质量份数的原料：
碳原子数14以上的直链状烷基（甲基）丙烯酸酯      20-50份
碳原子数1-6的烷基（甲基）丙烯酸酯               20-70份
极性单体                                         1-10份
共聚用引发剂                                     0.05-0.5份
双功能型聚合物                                   1-20份
异氰酸酯类交联剂                                 0.1-5份。
进一步地，所述的碳原子数14以上的直链状烷基（甲基）丙烯酸酯为（甲基）丙烯酸十四烷基酯、（甲基）丙烯酸十六烷基酯、（甲基）丙烯酸十八烷基酯、（甲基）丙烯酸二十烷基酯和（甲基）丙烯酸二十二烷基酯中的一种或多种。
进一步地，所述的碳原子数1-6的直链烷基（甲基）丙烯酸酯为（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸己酯中的一种或多种。
进一步地，所述的极性单体为（甲基）丙烯酸、巴豆酸、马来酸、（甲基）丙烯酸-2-羟基乙酯、（甲基）丙烯酸-2-2羟基丙酯、烯丙醇、（甲基）丙烯酸二甲氨基乙酯以及（甲基）丙烯酸缩水甘油酯中的一种或多种。
进一步地，所述的共聚用引发剂为过氧化苯甲酰、过氧化二甲基乙基酮、2,2-偶氮双异丁腈、偶氮二异庚腈中的一种或多种。
进一步地，所述的双功能型聚合物为含羟基的聚氨酯丙烯酸树脂，羟值为15-80 mg KOH/g，优选地，羟值为20-65 mg KOH/g；更优选地，羟值为20-50 mg KOH/g。
进一步地，所述的双功能型聚合物的分子量为1000-10000，优选地，分子量为1000-5000。
进一步地，所述的异氰酸酯类交联剂为异佛尔酮二异氰酸酯多聚体、（氢化）甲苯二异氰酸酯多聚体、六亚甲基二异氰酸酯多聚体、萘二异氰酸酯多聚体以及（氢化）苯二亚甲基二异氰酸酯多聚体中的一种或多种，或者采用市售的异氰酸酯化合物。
一种冷关型粘合剂的制备方法，包括以下步骤：
步骤一，向甲苯中加入碳原子数14以上的直链状烷基（甲基）丙烯酸酯、碳原子数1-6的烷基（甲基）丙烯酸酯和极性单体，并在N2鼓泡中搅拌均匀，加入共聚用引发剂，得到带侧链结晶性预聚物；
步骤二，向步骤一制备得到的带侧链结晶性预聚物中加入双功能型聚合物和异氰酸酯类交联剂，充分搅拌均匀后，搅拌均匀后，得到所述的冷关型粘合剂。
一种由冷关型粘合剂的制成的粘合带的制备方法，包括如下步骤：向粘合剂中加入光引发剂，混合均匀后涂布到基膜上，烘干除去溶剂并热固处理，然后紫外线照射，制作形成粘合带。
进一步地，所述的光引发剂为α-羟烷基苯酮、硫代丙氧基硫杂蒽酮、烷基碘鎓盐、异丙苯茂铁六氟磷酸盐、2,2-二乙氧基二苯甲酮、4-甲基二苯甲酮、2-氯蒽醌、1-羟基环己基苯基酮、2-羟基-2-甲基-1-苯基-1-丙酮和异丙基噻吨酮中的一种或多种，或者采用市售的光引发剂，比如：TPO和819等。
进一步地，所述的基材膜为聚乙烯膜、聚氯乙烯膜、聚丙烯膜、聚碳酸酯膜、聚对苯二甲酸乙二醇酯膜中的一种。
进一步地，热处理时间为2.5-4分钟，烘干温度为100-150℃，紫外线照射时间为30s。
进一步地，制作形成粘合带的厚度设置为50um。
 有益效果
粘合剂的耐热性得到有效提高；粘合带的拉伸强度明显提升；粘合带的高温粘合力明显提升；粘合带粘性分布及厚度均匀。
 本发明的实施方式
下面结合具体实施例对本发明作进一步说明。
实施例1
一种冷关型粘合剂，包括以下质量份数的原料：
甲基丙烯酸二十二烷基酯          20份
甲基丙烯酸甲酯                  40份
甲基丙烯酸                      3份
过氧化苯甲酰                    0.1份
双功能型聚合物                   8份
六亚甲基二异氰酸酯类固化剂       2份。
一种冷关型粘合剂的制备方法，包括以下的步骤：
步骤一，20份甲苯中加入20份甲基丙烯酸二十二烷基酯、40份的甲基丙烯酸甲酯和3份的甲基丙烯酸，并N2鼓泡中搅拌均匀，加入0.1份引发剂过氧化苯甲酰，得到带侧链结晶性预聚物；
步骤二，向步骤一制备得到的带侧链结晶性预聚物中加入双功能型聚合物8份和六亚甲基二异氰酸酯类固化剂 2份，充分搅拌均匀后，得到的冷关型粘合剂。
双功能型聚合物的羟值35mg KOH/g，分子量5000以下。
一种由冷关型粘合剂制成的粘合带，由下述方法制成：向粘合剂中避光加入1份的2,2-二乙氧基二苯甲酮，混合均匀后涂布到聚对苯二甲酸乙二醇酯膜上，3min 150℃烘干除去溶剂并热固处理，并用紫外线照射，制作形成50um厚度的粘合带。
实施例2
一种冷关型粘合剂，包括以下质量份数的原料：
甲基丙烯酸十八烷基酯           30份
甲基丙烯酸甲酯                 40份
（甲基）丙烯酸-2-2羟基丙酯      5份
偶氮二异丁腈                    0.1份
双功能型聚合物                  10份
甲苯二异氰酸酯类固化剂         2.5份。
一种冷关型粘合剂的制备方法，包括以下的步骤：
步骤一，20份甲苯中加入30份甲基丙烯酸十八烷基酯、40份的甲基丙烯酸甲酯和5份的（甲基）丙烯酸-2-2羟基丙酯，并N2鼓泡中搅拌均匀，加入0.1份引发剂偶氮二异丁腈，得到带侧链结晶性预聚物；
步骤二，向步骤一制备得到的带侧链结晶性预聚物中加入双功能型聚合物 10份和甲苯二异氰酸酯类固化剂 2.5份，充分搅拌均匀后，得到的冷关型粘合剂。
双功能型聚合物的羟值30mg KOH/g，分子量5000以下。
一种由冷关型粘合剂制成的粘合带，由下述方法制成：向粘合剂中避光加入0.2份的光引发剂TPO和0.1份的光引发剂819，混合均匀后涂布到聚对苯二甲酸乙二醇酯膜上，3min 100℃烘干除去溶剂并热固处理，并用紫外线照射，制作形成50um厚度的粘合带。
实施例3
一种冷关型粘合剂，包括以下质量份数的原料：
甲基丙烯酸十四烷基酯          30份
甲基丙烯酸乙酯                 60份
（甲基）丙烯酸-2-2羟基丙酯      5份
偶氮二异丁腈                    0.15份
双功能型聚合物                  8份
甲苯二异氰酸酯类固化剂          8份。
一种冷关型粘合剂的制备方法，包括以下的步骤：
步骤一，20份甲苯中加入30份甲基丙烯酸十四烷基酯、60份的甲基丙烯酸乙酯和5份的（甲基）丙烯酸-2-2羟基丙酯，并N2鼓泡中搅拌均匀，加入0.15份引发剂偶氮二异丁腈，得到带侧链结晶性预聚物；
步骤二，向步骤一制备得到的带侧链结晶性预聚物中加入双功能型聚合物 8份和甲苯二异氰酸酯类固化剂 8份，充分搅拌均匀后，得到的冷关型粘合剂。
双功能型聚合物的羟值35mg KOH/g，分子量5000以下。
一种由冷关型粘合剂制成的粘合带，由下述方法制成：向粘合剂中避光加入0.15份的光引发剂TPO，混合均匀后涂布到聚对苯二甲酸乙二醇酯膜上，3min 100℃烘干除去溶剂并热固处理，并用紫外线照射，制作形成50um厚度的粘合带。
实施例4
一种冷关型粘合剂，包括以下质量份数的原料：
甲基丙烯酸二十烷基酯          30份
甲基丙烯酸甲酯                60份
（甲基）丙烯酸-2-2羟基丙酯      5份
偶氮二异丁腈                    0.15份
双功能型聚合物                  2份
甲苯二异氰酸酯类固化剂          0.5份。
一种冷关型粘合剂的制备方法，包括以下的步骤：
步骤一，20份甲苯中加入30份甲基丙烯酸二十烷基酯、60份的甲基丙烯酸甲酯和5份的（甲基）丙烯酸-2-2羟基丙酯，并N2鼓泡中搅拌均匀，加入0.15份引发剂偶氮二异丁腈，得到带侧链结晶性预聚物；
步骤二，向步骤一制备得到的带侧链结晶性预聚物中加入双功能型聚合物 2份和甲苯二异氰酸酯类固化剂 0.5份，充分搅拌均匀后，得到的冷关型粘合剂。
双功能型聚合物的羟值30mg KOH/g，分子量5000以下。
一种由冷关型粘合剂制成的粘合带，由下述方法制成：向粘合剂中避光加入0.03份的光引发剂TPO和0.01份的光引发剂819，混合均匀后涂布到聚对苯二甲酸乙二醇酯膜上，3min 100℃烘干除去溶剂并热固处理，并用紫外线照射，制作形成50um厚度的粘合带。
实施例5
一种冷关型粘合剂，包括以下质量份数的原料：
甲基丙烯酸二十烷基酯            25份
甲基丙烯酸己酯                  50份
（甲基）丙烯酸                  4份
偶氮二异丁腈                    0.12份
双功能型聚合物                  10份
（氢化）甲苯二异氰酸酯多聚体      2.5份。
一种冷关型粘合剂的制备方法，包括以下的步骤：
步骤一，20份甲苯中加入25份甲基丙烯酸二十烷基酯、50份的甲基丙烯酸己酯和4份的（甲基）丙烯酸，并N2鼓泡中搅拌均匀，加入0.12份引发剂偶氮二异丁腈，得到带侧链结晶性预聚物；
步骤二，向步骤一制备得到的带侧链结晶性预聚物中加入双功能型聚合物 2份和甲苯二异氰酸酯类固化剂 0.5份，充分搅拌均匀后，得到的冷关型粘合剂。
双功能型聚合物的羟值50mg KOH/g，分子量5000以下。
一种由冷关型粘合剂制成的粘合带，由下述方法制成：向粘合剂中避光加入0.03份的光引发剂TPO和0.01份的光引发剂819，混合均匀后涂布到聚对苯二甲酸乙二醇酯膜上，3min 100℃烘干除去溶剂并热固处理，并用紫外线照射，制作形成50um厚度的粘合带。
对实施例1-5制备得到的粘合带进行性能测试，具体测试结果如表1所示：
实施例号熔点（℃）     20℃粘合力（N/25mm）       80℃温度粘合力（N/25mm）拉伸强度（MPa）
1       52     0.02 5.6   20
2       55     0.01 5.3   27
3       50     0.01 5.0   23
4       51     0.02 5.1   16
5       57     0.01 4.9   31
注：针对所得的冷关型粘合带测试180°与不锈钢板在不同温度下的剥离强度。
测试结果表明：粘合剂的耐热性得到有效提高；粘合带的拉伸强度明显提升；粘合带的高温粘合力明显提升；粘合带粘性分布及厚度均匀。
以上内容仅为本发明的较佳实施例，对于本领域的普通技术人员，依据本发明的思想，在具体实施方式及应用范围上可以作出许多变化，只要这些变化未脱离本发明的构思，均属于本发明的保护范围。

Claims (11)

  1. 一种冷关型粘合剂，其特征在于，包括以下质量份数的原料：
    碳原子数14以上的直链状烷基（甲基）丙烯酸酯      20-50份
    碳原子数1-6的烷基（甲基）丙烯酸酯               20-70份
    极性单体                                         1-10份
    共聚用引发剂                                     0.05-0.5份
    双功能型聚合物                                   1-20份
    异氰酸酯类交联剂                                 0.1-5份。
  2. 根据权利要求1所述的冷关型粘合剂，其特征在于，所述的碳原子数14以上的直链状烷基（甲基）丙烯酸酯为（甲基）丙烯酸十四烷基酯、（甲基）丙烯酸十六烷基酯、（甲基）丙烯酸十八烷基酯、（甲基）丙烯酸二十烷基酯和（甲基）丙烯酸二十二烷基酯中的一种或多种。
  3. 根据权利要求1所述的冷关型粘合剂，其特征在于，所述的碳原子数1-6的直链烷基（甲基）丙烯酸酯为（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸己酯中的一种或多种。
  4. 根据权利要求1所述的冷关型粘合剂，其特征在于，所述的极性单体为（甲基）丙烯酸、巴豆酸、马来酸、（甲基）丙烯酸-2-羟基乙酯、（甲基）丙烯酸-2-2羟基丙酯、烯丙醇、（甲基）丙烯酸二甲氨基乙酯以及（甲基）丙烯酸缩水甘油酯中的一种或多种。
  5. 根据权利要求1所述的冷关型粘合剂，其特征在于，所述的共聚用引发剂为过氧化苯甲酰、过氧化二甲基乙基酮、2,2-偶氮双异丁腈、偶氮二异庚腈中的一种或多种。
  6. 根据权利要求1所述的冷关型粘合剂，其特征在于，所述的双功能型聚合物为含羟基的聚氨酯丙烯酸树脂，羟值为15-80 mg KOH/g。
  7. 根据权利要求1所述的冷关型粘合剂，其特征在于，所述的双功能型聚合物的羟值为20-65 mg KOH/g或20-50 mg KOH/g。
  8. 根据权利要求1所述的冷关型粘合剂，其特征在于，所述的双功能型聚合物的分子量为1000-10000或1000-5000。
  9. 根据权利要求1所述的冷关型粘合剂，其特征在于，所述的异氰酸酯类交联剂为异佛尔酮二异氰酸酯多聚体、（氢化）甲苯二异氰酸酯多聚体、六亚甲基二异氰酸酯多聚体、萘二异氰酸酯多聚体以及（氢化）苯二亚甲基二异氰酸酯多聚体中的一种或多种。
  10. 一种由权利要求1至9任意一项所述的冷关型粘合剂的制备方法，其特征在于，包括以下步骤：
    步骤一，向甲苯中加入碳原子数14以上的直链状烷基（甲基）丙烯酸酯、碳原子数1-6的烷基（甲基）丙烯酸酯和极性单体，并在N2鼓泡中搅拌均匀，加入共聚用引发剂，得到带侧链结晶性预聚物；
    步骤二，向步骤一制备得到的带侧链结晶性预聚物中加入双功能型聚合物和异氰酸酯类交联剂，充分搅拌均匀后，得到所述的冷关型粘合剂。
  11. 一种由权利要求1-9任意一项所述的冷关型粘合剂制成的粘合带的制备方法，其特征在于，包括如下步骤：向粘合剂中加入光引发剂，混合均匀后涂布到基膜上，烘干除去溶剂并热固处理，然后紫外线照射，制作形成粘合带。
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