WO2023226568A1 - 一种具有延迟固化功能的紫外光固化胶及其制备方法 - Google Patents

一种具有延迟固化功能的紫外光固化胶及其制备方法 Download PDF

Info

Publication number
WO2023226568A1
WO2023226568A1 PCT/CN2023/083241 CN2023083241W WO2023226568A1 WO 2023226568 A1 WO2023226568 A1 WO 2023226568A1 CN 2023083241 W CN2023083241 W CN 2023083241W WO 2023226568 A1 WO2023226568 A1 WO 2023226568A1
Authority
WO
WIPO (PCT)
Prior art keywords
rosin
resin
modified
borate
aziridine
Prior art date
Application number
PCT/CN2023/083241
Other languages
English (en)
French (fr)
Inventor
潘光君
王建斌
陈田安
解海华
Original Assignee
烟台德邦科技股份有限公司
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 烟台德邦科技股份有限公司 filed Critical 烟台德邦科技股份有限公司
Publication of WO2023226568A1 publication Critical patent/WO2023226568A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives

Definitions

  • the invention belongs to the field of light-curing materials and relates to an ultraviolet curing glue with delayed curing function and a preparation method thereof.
  • UV curing adhesives have been widely studied due to their many outstanding advantages, such as fast curing speed, environmental friendliness, low energy consumption, and no solvent evaporation, and have been rapidly promoted in various industries.
  • UV curing adhesives also have their own limitations.
  • Conventional UV curing adhesives can only be used in bonding applications with light-transmitting materials.
  • UV-curing adhesives are not transparent because the materials are opaque.
  • the glue cannot be cured, which has obvious limitations in practical applications; the UV-curable glue of the present invention has the function of delayed curing and can be used in opaque application scenarios, solving the problem of conventional UV glue that is limited by the light transmittance of the material. problem.
  • the present invention provides a UV-curable adhesive with a delay function and a preparation method thereof, so that the cured product of the UV-curable adhesive has a delay function. Curing function can be used in bonding opaque materials.
  • a UV-curable adhesive with delayed curing function consisting of the following raw materials in weight percentages: rosin-modified aziridine resin 40-70%, acrylate monomer 15-35%, rosin-modified propylene Acid ester resin 10-30%, free radical photoinitiator 0.3-6%, photo-acid generator 0.1-5%, stabilizer 0.01-1%.
  • the present invention can also make the following improvements.
  • the rosin-modified aziridine resin refers to a rosin-modified aziridine resin containing an aziridine reactive group synthesized using rosin diol, diisocyanate and hydroxyaziridine.
  • Alcohol refers to a glycol containing two hydroxyl groups and having a basic structure of rosin acid.
  • the diisocyanates include: toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate ( MDI) or hexamethylene diisocyanate (HDI), or any mixture thereof.
  • hydroxyaziridine refers to a compound containing both hydroxyl and aziridine groups, such as 1-hydroxyethyl aziridine (cas: 1072-52-2). Rosin-modified aziridine resin, its structural formula is represented by the following general formula (I):
  • Synthesis method Add 200g of rosin diol, 11.6g of toluene diisocyanate, and 0.01g of catalyst dibutyltin dilaurate into a three-necked flask with a thermometer, raise the temperature to 65 degrees, control the temperature at 70-75 degrees, and react 2- 3h; then add 3.2g of 1-hydroxyethylaziridine (1072-52-2), control the temperature at 70-75 degrees, and react for 2-3h; use an infrared spectrometer to analyze the NCO group until the NCO peak completely disappears. , stop the heating reaction, and obtain rosin-modified aziridine resin.
  • the reaction formula is as follows:
  • the acrylate monomer is a monofunctional or two-functional or above-functional acrylate monomer, including tetrahydrofuran acrylate (THFA), isooctyl methacrylate (ISOA), and lauryl methacrylate (LA). , one or any mixture of isobornyl methacrylate (IBOA), N,N-dimethylacrylamide (DMAA), 1,6 hexanediol diacrylate (HDDA).
  • THFA tetrahydrofuran acrylate
  • ISOA isooctyl methacrylate
  • LA lauryl methacrylate
  • IBOA isobornyl methacrylate
  • DMAA N,N-dimethylacrylamide
  • HDDA 1,6 hexanediol diacrylate
  • the free radical photoinitiators are brands 1173 (2-hydroxy-2-methyl-1-phenyl acetone), 184 (1-hydroxycyclohexyl benzophenone), 907 (2-methyl-1- (4-methylmercaptophenyl)-2-morpholine-1-propanone), 369 (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone), 819 (bis(2,4,6-trimethylbenzoyl)phenyl phosphorus oxide), 651 ( ⁇ , ⁇ '-dimethylbenzoyl ketal), ITX (isopropylthiaxantrone), One or a mixture of any of BP (benzophenone), OMBB (methyl o-benzoate), TPO (2,4,6-trimethylbenzoyldiphenylphosphorus oxide) .
  • the photoacid generator includes cationic photoinitiators such as sulfonium salts and iodonium salts.
  • cationic photoinitiators can generate super strong protonic acid when exposed to UV light.
  • IRGACURE 250 of BASF Company WPI-113, WPI-116 and WPI-124 of Japanese Fujifilm Company.
  • the stabilizer in the synthesis method is one or a mixture of one or more of borate esters, aluminum chelates and organic acids, including trimethyl borate, triethyl borate, tri-n-propyl borate, Triisopropyl borate, (dodecyl) borate, tri(cetyl) borate, tri(octadecyl) borate, tri-o-creyl borate, tri-m-creyl borate, triethanolamine Boric acid esters, barbituric acid, etc.
  • the preparation method of a UV-curable adhesive with delayed curing function includes: weighing 40% to 70% of rosin-modified aziridine resin, 15% to 35% of acrylate monomer, and rosin-modified propylene. Acid ester resin 10-30%, free radical photoinitiator 0.3-6%, photo-acid generator 0.1-5%, stabilizer 0.01-1%, add them to the mixer in sequence, and evacuate until the vacuum degree is -0.08 ⁇ - 0.05MPa, stir at 500-1000 rpm for 0.5-2 hours, stir evenly, let it naturally cool to room temperature, and then seal and package.
  • the ultraviolet curable adhesive prepared by the present invention utilizes the reaction mechanism of aziridine under the catalysis of acid.
  • the photoacid generator in the formula is irradiated by UV, super strong protons are generated Acid, super protonic acid then catalyzes the polymerization of aziridine.
  • the polymerization of acid-catalyzed aziridine does not occur instantaneously, so the formula has the reaction characteristics of UV delayed curing.
  • the present invention also introduces aziridine groups into the macromolecular chain of rosin ester through molecular structure design to synthesize rosin-modified aziridine resin.
  • the resin containing rosin structure has better adhesion to the substrate;
  • the ultraviolet curable glue obtained by the present invention not only has the function of delayed curing and can meet the needs of bonding opaque materials, but also has the advantages of high adhesion to the base material, excellent cured product performance, and high bonding reliability. Widely used in high-end electronic packaging industry.
  • the synthesis method of rosin-modified aziridine resin is: add 200g of rosin diol, 11.6g of toluene diisocyanate, and 0.01g of catalyst dibutyltin dilaurate into a three-necked flask with a thermometer, raise the temperature to 65 degrees, and control the temperature At 70-75 degrees, react for 2-3 hours; then add 3.2g of hydroxyaziridine (1072-52-2), control the temperature at 70-75 degrees, and react for 2-3 hours; use an infrared spectrometer to analyze the NCO group, wait When the NCO peak disappears completely, stop the heating reaction and obtain rosin-modified aziridine resin.
  • the performance of the ultraviolet curable glue with delayed curing function of the present invention is tested through the following test.
  • Laminating time test Dispens glue on the black base material, activate it with UV light, let it stand for different times, and then laminate the aluminum sheet. If the cohesive strength of the glue is too high, it will not fit. We tested that it can fit. The maximum time is the laminating time.
  • UV activated curing conditions light intensity 50mW/cm 2 , illumination time 10s;
  • the UV-curing adhesive with delayed curing function of the present invention has a delayed curing function, has good adhesion to the base material, and has a greater Elongation, better drop performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明制备的一种具有延迟固化功能的紫外光固化胶，由以下重量百分比的原料组成：松香改性氮丙啶树脂40～70％、丙烯酸酯单体15～35％、松香改性丙烯酸酯树脂10-30％、自由基型光引发剂0.3～6％、光产酸剂0.1～5％、稳定剂0.01～1％。本发明的紫外光固化胶具有延迟固化的功能，可以在不透光的应用场景中使用，解决了常规UV胶受材料透光性限制的难题，且固化物性能优良，粘接可靠性高，适用范围广泛。

Description

一种具有延迟固化功能的紫外光固化胶及其制备方法 技术领域
本发明属于光固化材料领域，涉及一种具有延迟固化功能的紫外光固化胶及其制备方法。
背景技术
光固化材料由于其固化速度快、环境友好、能源消耗量少、无溶剂挥发等众多突出优点而得到广泛研究，并且在各行各业中迅速推广。但是紫外光固化胶也有其本身的局限,常规的紫外光固化胶只能在透光材料的粘接应用中使用，而不透光材料粘接场合中，因材料不透光，紫外光固化胶胶无法固化，所在实际的应用中有明显的局限；本发明的紫外光固化胶具有延迟固化的功能，可以在不透光的应用场景中使用，解决了常规UV胶受材料透光性限制的难题。
发明内容
为了解决现有技术中紫外光固化胶在不透光材料中无法固化的难题，本发明提供了一种具有延迟功能的紫外光固化胶及其制备方法，以达到紫外光固化胶固化物具有延迟固化功能，能应用在不透光的材料粘接中。
本发明解决上述技术问题的技术方案如下：
一种具有延迟固化功能的紫外光固化胶，由以下重量百分比的原料组成：松香改性氮丙啶树脂40～70％、丙烯酸酯单体15～35％、松香改性丙烯 酸酯树脂10-30％、自由基型光引发剂0.3～6％、光产酸剂0.1～5％、稳定剂0.01～1％。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述的松香改性氮丙啶树脂，是指用松香二醇、二异氰酸酯和羟基氮丙啶合成的含有氮丙啶反应基团的松香改性氮丙啶树脂，所述的松香二醇是指含有两个羟基，并具有松香酸基本结构的二元醇，所述的二异氰酸酯包括：甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、二苯基甲烷二异氰酸酯(MDI)或六亚甲基二异氰酸酯(HDI)等中的一种和任意几种的混合物。所述的羟基氮丙啶是指同时含有羟基和氮丙啶基团的化合物，比如1-羟乙基氮丙啶(cas：1072-52-2)。松香改性氮丙啶树脂，其结构式由下述通式(Ⅰ)表示：
合成方法：将松香二醇200g、甲苯二异氰酸酯11.6g、催化剂二月桂酸二丁基锡0.01g加入到带有温度计的三口烧瓶中，升温至65度，将温度控制在70-75度，反应2-3h；再加入1-羟乙基氮丙啶(1072-52-2)3.2g，将温度控制在70-75度，反应2-3h；用红外光谱仪分析NCO基团，待NCO峰完全消失时，停止加热反应，可得到松香改性氮丙啶树脂。反应式如下：
进一步，所述丙烯酸酯单体为单官能度或者两官能及以上官能团的丙烯酸酯单体，包括四氢呋喃丙烯酸酯(THFA)、甲基丙烯酸异辛酯(ISOA)、甲基丙烯酸月桂酯(LA)、甲基丙烯酸异冰片酯(IBOA)、N，N-二甲基丙烯酰胺(DMAA)、1，6己二醇二丙烯酸酯(HDDA)中的一种或任意几种的混合物。
进一步，所述松香改性丙烯酸酯树脂，分子结构式如下：
进一步，所述自由基光引发剂为牌号1173(2-羟基-2-甲基-1-苯基丙酮)、184(1-羟基环己基苯甲酮)、907(2-甲基-1-(4-甲巯基苯基)-2-吗啉-1-丙酮)、369(2-苄基-2-二甲氨基-1-(4-吗啉苯基)-1-丁酮)、819(双(2，4，6-三甲基苯甲酰基)苯基氧化磷)、651(α,α’-二甲基苯偶酰缩酮)、ITX(异丙基硫杂蒽酮)、BP(二苯甲酮)、OMBB(邻苯甲酰基苯甲酸甲酯)、TPO(2,4,6-三甲基苯甲酰基二苯基氧化磷)中的一种或任意几种的混合物。
进一步，所述光产酸剂，包括硫鎓盐和碘鎓盐类阳离子光引发剂，此类阳离子光引发剂在UV光照时可产生超强质子酸。例如：BASF公司的IRGACURE 250，日本Fujifilm公司WPI-113、WPI-116和WPI-124。
进一步地，所述合成方法中的稳定剂为硼酸酯、铝螯合物及有机酸中的一种或几种的混合物，包括硼酸三甲酯、硼酸三乙酯、硼酸三正丙酯、硼酸三异丙酯、硼酸(十二烷基)酯、硼酸三(十六烷基)酯、硼酸三(十八烷基)酯、、硼酸三邻甲苯酯、硼酸三间甲苯酯、三乙醇胺硼酸酯、巴比妥酸等。
本发明所述的一种具有延迟固化功能的紫外光固化胶的制备方法包括：称取松香改性氮丙啶树脂40～70％、丙烯酸酯单体15～35％、松香改性丙烯 酸酯树脂10-30％、自由基型光引发剂0.3～6％、光产酸剂0.1～5％，稳定剂0.01～1％，依次加入搅拌机内，抽真空至真空度为-0.08～-0.05MPa，于500～1000转/分搅拌0.5～2小时，搅拌均匀，自然晾置至室温，密封包装即可。
本发明的有益效果是：本发明制备的紫外光固化胶，利用了氮丙啶在酸的催化作用下发生反应的机理，当配方中的光产酸剂经UV照射后，产生了超强质子酸，超强质子酸再催化氮丙啶进行聚合反应，与丙烯酸酯的自由基聚合的瞬时反应不同，酸催化氮丙啶的聚合反应不是瞬时发生的，所以配方具有了UV延迟固化的反应特点；本发明还通过分子结构设计，把氮丙啶基团引入到松香酯的大分子链中，合成出松香改性氮丙啶树脂，含松香结构的树脂对基材具有更好的附着力；本发明得到的紫外光固化胶不仅具有延迟固化的功能，能满足不透光材料粘接的场合，而且还具有对基材附着力高，固化物性能优良，粘接可靠性高的优点，可广泛应用在高端电子封装行业。
具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
合成实施例
松香改性氮丙啶树脂的合成方法是：将松香二醇200g、甲苯二异氰酸酯11.6g、催化剂二月桂酸二丁基锡0.01g加入到带有温度计的三口烧瓶中，升温至65度，将温度控制在70-75度，反应2-3h；再加入羟基氮丙啶(1072-52-2)3.2g，将温度控制在70-75度，反应2-3h；用红外光谱仪分析NCO基团，待NCO峰完全消失时，停止加热反应，可得到松香改性氮丙啶树脂。
实施例1
准确称取如下原料，松香改性氮丙啶树脂55g、THFA 20g、松香改性丙烯酸酯树脂21g、光引发剂184 2g、光引发剂TPO 0.5g、光产酸剂IRGACURE 250 2g，硼酸三乙酯0.6g；将上述各组分依次加入双行星动力混合搅拌机内，抽真空至真空度为-0.08MPa，于500转/分搅拌2小时，搅拌均匀，自然晾置至室温，得到紫外光固化胶，密封包装即可。
实施例2
准确称取如下原料，松香改性氮丙啶树脂45g、IBOA 30g、松香改性丙烯酸酯树脂26g、光引发剂184 3g、光引发剂TPO 1.1g、光产酸剂IRGACURE 250 1.5g，巴比妥酸0.3g；将上述各组分依次加入双行星动力混合搅拌机内，抽真空至真空度为-0.05MPa，于750转/分搅拌1小时，搅拌均匀，自然晾置至室温，得到紫外光固化胶，密封包装即可。
实施例3
准确称取如下原料，松香改性氮丙啶树脂67g、IBOA 15g、松香改性丙烯酸酯树脂14g、光引发剂651 3g、光引发剂TPO 1.1g、光产酸剂WPI-116 5g，巴比妥酸0.06g；将上述各组分依次加入双行星动力混合搅拌机内，抽真空至真空度为-0.06MPa，于700转/分搅拌1.5小时，搅拌均匀，自然晾置至室温，得到紫外光固化胶，密封包装即可。
实施例4
准确称取如下原料，松香改性氮丙啶树脂58g、LA 29g、松香改性丙烯酸酯树脂11g、光引发剂1842g、光引发剂TPO 1.5g、光产酸剂IRGACURE 250 1.9g，巴比妥酸0.16g；将上述各组分依次加入双行星动力混合搅拌机内，抽真空至真空度为-0.07MPa，于800转/分搅拌1小时，搅拌均匀，自然晾置至室温，得到紫外光固化胶，密封包装即可。
实施例5
准确称取如下原料，松香改性氮丙啶树脂65g、THFA 10g、IBOA 13g、 松香改性丙烯酸酯树脂21g、光引发剂6512g、光引发剂TPO 0.5g、光产酸剂WPI-124 2.3g，硼酸三间甲苯酯0.29g；将上述各组分依次加入双行星动力混合搅拌机内，抽真空至真空度为-0.08MPa，于1000转/分搅拌0.5小时，搅拌均匀，自然晾置至室温，得到紫外光固化胶，密封包装即可。
比较例1
准确称取如下原料，沙多玛公司的CN966J75，55g；LA，48g；光引发剂1173，2g；光引发剂TPO，1g；将上述各组分依次加入双行星动力混合搅拌机内，抽真空至真空度为-0.08MPa，于500转/分搅拌2小时，搅拌均匀，自然晾置至室温，得到紫外光固化胶，密封包装即可。
比较例2
准确称取如下原料，长兴化学的6127，42g；IBOA，51g；光引发剂651，3g；光引发剂TPO，1g；将上述各组分依次加入双行星动力混合搅拌机内，抽真空至真空度为-0.05MPa，于750转/分搅拌1小时，搅拌均匀，自然晾置至室温，得到紫外光固化胶，密封包装即可。
比较例3
准确称取如下原料，双酚A型环氧树脂60g，聚己内酯多元醇5g，阳离子固化剂1g，1173光引发剂1g，丁二醇缩水甘油醚2g，异丙基噻吨酮0.01g，聚乙烯亚胺改性氧化石墨烯0.1g，气相硅触变剂1g；将上述各组分依次加入双行星动力混合搅拌机内，抽真空至真空度为-0.05MPa，于750转/分搅拌1小时，搅拌均匀，自然晾置至室温，得到紫外光固化胶，密封包装即可。
比较例4
准确称取如下原料，光产碱剂0.2g和双酚A型环氧树脂(E51)7.73g混合，并于110℃下搅拌至澄清透明，冷却至室温；再向上述体系中加入双酚A环氧丙烯酸酯(EA)4.23g、二丙烯酸1,6-己二醇酯(HDDA)1.94g、季戊四醇四-3-巯基丙酸酯(SH4)8.2g、光敏剂2-异丙基硫杂蒽酮(ITX)0.1g、自由 基抑制剂2,2,6,6-四甲基哌啶-1-氧基自由基(TEMPO)0.1g，；将上述各组分依次加入双行星动力混合搅拌机内，抽真空至真空度为-0.05MPa，于750转/分搅拌1小时，搅拌均匀，自然晾置至室温，得到紫外光固化胶，密封包装即可。
通过下面的试验测试本发明的一种具有延迟固化功能的紫外光固化胶的性能。
试验实施例性能测试
可贴合时间测试：在黑色基材上点胶，UV光进行激活，静置不同的时间，再贴合铝片，如果胶的内聚强度太高，则贴合不了，我们测试可以贴合的最长时间即为可贴合时间。
UV激活固化条件：光强50mW/cm2,光照时间10s；
剪切强度：基材黑色PC+铝。
跌落性能测试：高度1.8m，跌落50次，判断是否开裂。
测试结果如表1所示：
表1实施例1-5制得的样品与普通紫外光固化胶性能对比测试结果

从上述结果可以看出，本发明的一种具有延迟固化功能的紫外光固化胶与现有的普通光固化胶粘剂相比，具有延迟固化功能，而且对基材的附着力好，具有更大的伸长率，更好的跌落性能。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种具有延迟固化功能的紫外光固化胶，由以下重量百分比的原料组成：松香改性氮丙啶树脂40～70％、丙烯酸酯单体15～35％、松香改性丙烯酸酯树脂10-30％、自由基型光引发剂0.3～6％、光产酸剂0.1～5％、稳定剂0.01～1％。
  2. 根据权利要求1所述的一种具有延迟固化功能的紫外光固化胶，其特征在于，所述松香改性氮丙啶树脂为松香二醇、二异氰酸酯和羟基氮丙啶合成的含有氮丙啶反应基团的松香改性氮丙啶树脂。
  3. 根据权利要求2所述的一种具有延迟固化功能的紫外光固化胶，其特征在于，所述的松香二醇是指含有两个羟基，并具有松香酸基本结构的二元醇；所述的二异氰酸酯包括甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯等中的一种和任意几种的混合物；所述的羟基氮丙啶是指同时含有羟基和氮丙啶基团的化合物。
  4. 根据权利要求3所述的一种具有延迟固化功能的紫外光固化胶，其特征在于，所述松香改性氮丙啶树脂结构式由下述通式(Ⅰ)表示：
  5. 根据权利要求4所述的一种具有延迟固化功能的紫外光固化胶，其特征在于，所述松香改性氮丙啶树脂的合成方法为：将松香二醇200份、甲苯二异氰酸酯11.6份、催化剂二月桂酸二丁基锡0.01份加入到带有温度计的三口烧瓶中，升温至65℃，将温度控制在70-75℃，反应2-3h；再加入1-羟乙基氮丙啶3.2份，将温度控制在70-75℃，反应2-3h；用红外光谱仪分析NCO基团，待NCO峰完全消失时，停止加热反应，可得到松香改性氮丙啶树脂。
  6. 根据权利要求1所述的一种具有延迟固化功能的紫外光固化胶，其特征在 于，所述丙烯酸酯单体为四氢呋喃丙烯酸酯、甲基丙烯酸异辛酯、甲基丙烯酸月桂酯、甲基丙烯酸异冰片酯、N，N-二甲基丙烯酰胺、1，6己二醇二丙烯酸酯中的一种或任意几种的混合物。
  7. 根据权利要求1所述的一种具有延迟固化功能的紫外光固化胶，其特征在于，所述松香改性丙烯酸酯树脂的分子结构式如下：
  8. 根据权利要求1所述的一种具有延迟固化功能的紫外光固化胶，其特征在于，所述自由基光引发剂为2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯甲酮、2-甲基-1-(4-甲巯基苯基)-2-吗啉-1-丙酮、2-苄基-2-二甲氨基-1-(4-吗啉苯基)-1-丁酮、双(2，4，6-三甲基苯甲酰基)苯基氧化磷、α,α’-二甲基苯偶酰缩酮、异丙基硫杂蒽酮、二苯甲酮、邻苯甲酰基苯甲酸甲酯、2,4,6-三甲基苯甲酰基二苯基氧化磷中的一种或任意几种的混合物。
  9. 根据权利要求1所述的一种具有延迟固化功能的紫外光固化胶，其特征在于，所述光产酸剂，包括硫鎓盐和碘鎓盐类阳离子光引发剂；所述稳定剂为硼酸三甲酯、硼酸三乙酯、硼酸三正丙酯、硼酸三异丙酯、硼酸(十二烷基)酯、硼酸三(十六烷基)酯、硼酸三(十八烷基)酯、、硼酸三邻甲苯酯、硼酸三间甲苯酯、三乙醇胺硼酸酯、巴比妥酸等中的一种或几种的混合物。
  10. 一种如权利要求1-9任一项所述的一种具有延迟固化功能的紫外光固化胶的制备方法，其特征在于，包括以下步骤：称取松香改性氮丙啶树脂40～70％、丙烯酸酯单体15～35％、松香改性丙烯酸酯树脂10-30％、自由基型光引发剂0.3～6％、光产酸剂0.1～5％，稳定剂0.01～1％，依次加入搅拌机内， 抽真空至真空度为-0.08～-0.05MPa，于500～1000转/分搅拌0.5～2小时，搅拌均匀，自然晾置至室温，密封包装即可。
PCT/CN2023/083241 2022-05-25 2023-03-23 一种具有延迟固化功能的紫外光固化胶及其制备方法 WO2023226568A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210572953.X 2022-05-25
CN202210572953.XA CN114958209A (zh) 2022-05-25 2022-05-25 一种具有延迟固化功能的紫外光固化胶及其制备方法

Publications (1)

Publication Number Publication Date
WO2023226568A1 true WO2023226568A1 (zh) 2023-11-30

Family

ID=82956737

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/083241 WO2023226568A1 (zh) 2022-05-25 2023-03-23 一种具有延迟固化功能的紫外光固化胶及其制备方法

Country Status (2)

Country Link
CN (1) CN114958209A (zh)
WO (1) WO2023226568A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114958209A (zh) * 2022-05-25 2022-08-30 烟台德邦科技股份有限公司 一种具有延迟固化功能的紫外光固化胶及其制备方法

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10330722A (ja) * 1997-06-05 1998-12-15 Sekisui Chem Co Ltd アクリル系粘着剤組成物
TW200636032A (en) * 2005-04-13 2006-10-16 Lg Chemical Ltd Acrylic adhesive composition having excellent impact resistance, optical film using the adhesive composition, and liquid crystal display comprising the optical film
CN101945902A (zh) * 2008-02-14 2011-01-12 3M创新有限公司 具有氮丙啶交联剂的丙烯酸类压敏粘合剂
CN102127183A (zh) * 2010-01-20 2011-07-20 3M创新有限公司 可交联的丙烯酸酯粘合剂聚合物组合物
CN105153407A (zh) * 2015-10-20 2015-12-16 山东科技大学 一种热固性松香基树脂组合物及其制备方法
CN105733493A (zh) * 2016-05-11 2016-07-06 烟台德邦科技有限公司 一种具有低挥发物含量的紫外光固化胶
CN105829468A (zh) * 2013-12-18 2016-08-03 3M创新有限公司 可后固化压敏粘合剂
KR101649760B1 (ko) * 2015-04-29 2016-08-19 한국신발피혁연구원 내수 및 내열 특성이 우수한 1액형 수성 접착제 조성물의 제조방법 및 이 방법에 의해 제조된 1액형 수성 접착제 조성물
CN108291127A (zh) * 2015-11-17 2018-07-17 3M创新有限公司 基于丙烯酸类的压敏粘合剂的可后固化前体
CN112225878A (zh) * 2020-09-01 2021-01-15 华南理工大学 一种高耐碱水性双组分异氰酸酯固化剂及其制备方法
CN113528065A (zh) * 2020-04-16 2021-10-22 3M创新有限公司 丙烯酸系压敏胶组合物、其制品及相关制备方法
CN114958209A (zh) * 2022-05-25 2022-08-30 烟台德邦科技股份有限公司 一种具有延迟固化功能的紫外光固化胶及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003277669A (ja) * 2002-03-25 2003-10-02 Toyo Ink Mfg Co Ltd 印刷インキ用バインダー組成物
JP6950150B2 (ja) * 2016-06-09 2021-10-13 横浜ゴム株式会社 ２液硬化型ウレタン接着剤組成物
CN108003802B (zh) * 2017-12-07 2021-03-30 烟台德邦科技股份有限公司 一种基于逐步聚合机理热致自愈合紫外光固化胶黏剂

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10330722A (ja) * 1997-06-05 1998-12-15 Sekisui Chem Co Ltd アクリル系粘着剤組成物
TW200636032A (en) * 2005-04-13 2006-10-16 Lg Chemical Ltd Acrylic adhesive composition having excellent impact resistance, optical film using the adhesive composition, and liquid crystal display comprising the optical film
CN101945902A (zh) * 2008-02-14 2011-01-12 3M创新有限公司 具有氮丙啶交联剂的丙烯酸类压敏粘合剂
CN102127183A (zh) * 2010-01-20 2011-07-20 3M创新有限公司 可交联的丙烯酸酯粘合剂聚合物组合物
CN105829468A (zh) * 2013-12-18 2016-08-03 3M创新有限公司 可后固化压敏粘合剂
KR101649760B1 (ko) * 2015-04-29 2016-08-19 한국신발피혁연구원 내수 및 내열 특성이 우수한 1액형 수성 접착제 조성물의 제조방법 및 이 방법에 의해 제조된 1액형 수성 접착제 조성물
CN105153407A (zh) * 2015-10-20 2015-12-16 山东科技大学 一种热固性松香基树脂组合物及其制备方法
CN108291127A (zh) * 2015-11-17 2018-07-17 3M创新有限公司 基于丙烯酸类的压敏粘合剂的可后固化前体
CN105733493A (zh) * 2016-05-11 2016-07-06 烟台德邦科技有限公司 一种具有低挥发物含量的紫外光固化胶
CN113528065A (zh) * 2020-04-16 2021-10-22 3M创新有限公司 丙烯酸系压敏胶组合物、其制品及相关制备方法
CN112225878A (zh) * 2020-09-01 2021-01-15 华南理工大学 一种高耐碱水性双组分异氰酸酯固化剂及其制备方法
CN114958209A (zh) * 2022-05-25 2022-08-30 烟台德邦科技股份有限公司 一种具有延迟固化功能的紫外光固化胶及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHAO CHIH-HAO, TA-ZEN WANG, GUAN-NAN CHEN, KWEI-JU CHEN, JEN-TAUT YEH & KAN-NAN CHEN: "Aqueous-Based Polyurethane with Dual-Functional Curing Agent", JOURNAL OF POLYMER RESEARCH, vol. 7, no. 1, 1 March 2020 (2020-03-01), pages 41 - 49, XP093111242 *

Also Published As

Publication number Publication date
CN114958209A (zh) 2022-08-30

Similar Documents

Publication Publication Date Title
CN101649171B (zh) 一种聚乙烯保护膜用无溶剂型紫外光固化压敏胶及其制备方法
US11370944B2 (en) UV curable epoxy/acrylate adhesive composition
CN110776855B (zh) 一种uv光固化高透光率光学胶及其制备方法
CN102337099B (zh) 单组分可光热双重固化的胶粘剂及其制备方法
CN110467890A (zh) 压敏胶带及其制备方法、用于制备压敏胶带的树脂组合物
CN110396370B (zh) 一种uv-led固化改性丙烯酸酯压敏胶及其制备方法
WO2023226568A1 (zh) 一种具有延迟固化功能的紫外光固化胶及其制备方法
CN111205810B (zh) 一种可光热双固化的胶粘剂及其制备方法
CN105916899B (zh) 液体光学粘合剂组合物
CN105860916B (zh) 一种耐高温紫外光固化胶及其制备方法
CN108003802B (zh) 一种基于逐步聚合机理热致自愈合紫外光固化胶黏剂
JP2015108099A (ja) 活性エネルギー線重合性樹脂組成物及び積層体
EP3645650A1 (en) Printable curable mixtures and cured compositions
CN112646537A (zh) 一种用于硅晶片切割工艺的蓖麻油基全交联uv光致可剥离胶的制备方法
CN106753183A (zh) 一种可低能量快速固化的紫外光固化胶及其制备方法
CN113493654B (zh) 一种可光热双固化的胶粘剂及其制备方法
CN111139020A (zh) 一种热固化兼uv固化复合胶及其制备方法
JP4333100B2 (ja) 活性エネルギー線硬化型粘着剤及び粘着シート
CN104031591A (zh) 一种led封装用紫外光固化组合物
CN113861854B (zh) 一种图像显示装置用粘着胶膜及图像显示装置
Wang et al. Preparation and properties of UV cation-initiated self-crosslinking acrylate pressure-sensitive adhesive without reactive diluent
CN114561174B (zh) 一种uv固化压敏胶及其制备方法
CN113980582B (zh) 一种可光、热、湿气固化的胶黏剂及其制备方法
CN115260948B (zh) 一种阻燃uv固化胶黏剂及其制备方法和应用
JPS61145268A (ja) 湿気硬化型粘着剤組成物

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: 23810643

Country of ref document: EP

Kind code of ref document: A1