键合二苯甲酮的蓖麻油基UV减黏胶的制备及性能

doi:10.16085/j.issn.1000-6613.2024-1256

摘要/Abstract

摘要：

随着半导体晶圆制造过程对缩小尺寸和引入全尺寸3D集成需求的高涨，对紫外光（UV）减黏胶固化后的残胶量和减黏性提出了更高要求。本文通过4-丙烯酰氧基二苯甲酮（ABP）与常规丙烯酸酯单体溶液共聚制备了键合二苯甲酮（BP）光引发剂的丙烯酸酯共聚物主胶（ABP-PSA）。结果表明，ABP的引入可提高丙烯酸酯共聚物的分子量，降低其玻璃化转变温度，使得其内聚强度和剥离力随ABP含量的增加呈先提高后降低的趋势。当ABP的质量分数为3%时，ABP-PSA的常态剥离强度最高（9.9N/25mm），明显高于不含ABP的共聚物（6.2N/25mm）。UV照射时，BP基团夺取侧链中叔碳氢原子，使聚合物链自交联，剥离强度降低至3.8N/25mm，减黏率超过60%。本文采用ABP-PSA与具有热/光双固化功能的蓖麻油基聚氨酯丙烯酸酯预聚物（CO-PUB-PETA）反应制备了UV减黏胶。借助CO-PUB-PETA中异氰酸酯基与ABP-PSA中羟基的热固化反应形成的网状结构，使得该减黏胶UV照射前的180°剥离强度可超过25N/25mm，同时赋予主胶光聚合功能。UV照射时，键合在主胶链上的BP，引发主胶与活性稀释剂光聚合的同时发生自交联，形成致密的全交联结构胶膜，180°剥离强度降至0.12N/25mm，减黏率超过99.5%，并显著降低了残胶量。

关键词: 紫外光减黏胶, 蓖麻油基聚氨酯丙烯酸酯, 二苯甲酮, 自交联, 残胶

Abstract:

With the increasing demand for decreasing the size and introducing full-scale 3D integration in the semiconductor wafer manufacturing process, higher requirements are put forward for the residual adhesive and the adhesion-reducing performance of UV adhesion-reducing adhesive. In this paper, an acrylic copolymer (ABP-PSA) bonded with benzophenone (BP) photoinitiator was prepared by copolymerization of 4-acryloyloxy benzophenone (ABP) with conventional acrylate monomers. The results showed that the introduction of ABP increased the molecular weight of acrylate copolymer and reduced its glass transition temperature. Thus, its cohesion strength and peeling force increased firstly and then decreased with the increase of ABP content. When the weight content of ABP was 3%, the normal peel strength of ABP-PSA was the highest (9.9N/25mm), which was significantly higher than that of the ABP-free copolymer (6.2N/25mm). During UV irradiation, the BP group seized the tertiary hydrocarbon atom in the polymer side chain, which made the polymer chain self-crosslinked and the peeling strength was reduced to 3.8N/25mm. The adhesion-reducing rate was over 60%. A new UV adhesion-reducing adhesive was prepared by ABP-PSA and castor oil-based polyurethane acrylate prepolymer (CO-PUB-PETA) with heat/light dual curing functions. With the help of the network structure formed by the thermal curing reaction of the NCO group in CO-PUB-PETA and the hydroxyl group in ABP-PSA, the 180° peel strength of the UV adhesion-reducing adhesive before UV curing exceeded 25N/25mm and the photopolymerization function was endowed to the acrylic copolymer adhesive. After UV irradiation, the BP groups bonded to the copolymer chains initiated the photopolymerization of the acrylic copolymer and the reactive diluent, and self-crosslinking for polymer chains occurred, forming a dense fully cross-linked structured adhesive film. The 180° peel strength was reduced to 0.12N/25mm and the adhesion-reducing rate was over 99.5%. Furthermore, the amounts of residual adhesives were significantly reduced.

Key words: UV adhesion-reducing adhesive, castor oil-based polyurethane acrylate, benzophenone, self-crosslinking, residual adhesives

中图分类号:

TQ436⁺.3

崔宗晖, 申洪刚, 韦敬旗, 伊松龄, 孙玉娟, 刘少杰, 赵松. 键合二苯甲酮的蓖麻油基UV减黏胶的制备及性能[J]. 化工进展, 2025, 44(9): 5292-5300.

CUI Zonghui, SHEN Honggang, WEI Jingqi, YI Songling, SUN Yujuan, LIU Shaojie, ZHAO Song. Preparation and properties of castor oil-based UV adhesion-reducing adhesive bonded with dibenenone photoinitiator[J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5292-5300.

图/表 10

参考文献 23

[1]	VITALE Alessandra, TRUSIANO Giuseppe, BONGIOVANNI Roberta. UV-curing of adhesives: A critical review[J]. Progress in Adhesion and Adhesives, 2018, 3: 101-154.
[2]	BANDL Christine, KERN Wolfgang, Sandra SCHLÖGL. Adhesives for “debonding-on-demand”: Triggered release mechanisms and typical applications[J]. International Journal of Adhesion and Adhesives, 2020, 99: 102585.
[3]	MULCAHY Kira R, KILPATRICK Alexander F R, HARPER Gavin D J, et al. Debondable adhesives and their use in recycling[J]. Green Chemistry, 2022, 24(1): 36-61.
[4]	GUO Chan, PAN Zhangxu, LI Changhao, et al. Large-scale programmable assembly of functional micro-components for advanced electronics via light-regulated adhesion and polymer growth[J]. NPJ Flexible Electronics, 2022, 6: 44.
[5]	YAO Yin, LI Lu, JIANG Jiaxi, et al. Reversible bonding for microfluidic devices with UV release tape[J]. Microfluidics and Nanofluidics, 2022, 26(3): 23.
[6]	KIM Sang-Woo, JU Yun Hee, HAN Sangmoon, et al. A UV-responsive pressure sensitive adhesive for damage-free fabrication of an ultrathin imperceptible mechanical sensor with ultrahigh optical transparency[J]. Journal of Materials Chemistry A, 2019, 7(39): 22588-22595.
[7]	贺贝贝, 解一军. 紫外光本体聚合制备丙烯酸酯压敏胶[J]. 化工进展, 2017, 36(12): 4508-4512.
	HE Beibei, XIE Yijun. Preparation of acrylate pressure sensitive adhesive by UV bulk polymerization[J]. Chemical Industry and Engineering Progress, 2017, 36(12): 4508-4512.
[8]	HAO Panpan, ZHAO Ting, WANG Lili, et al. IPN structured UV-induced peelable adhesive tape prepared by isocyanate terminated urethane oligomer crosslinked acrylic copolymer and photo-crosslinkable trifunctional acrylic monomer[J]. Progress in Organic Coatings, 2019, 137: 105281.
[9]	HAO Panpan, SUN Bingyan, CHU Xiaomeng, et al. Effect of castor oil based urethane oligomer on properties of UV-curable pressure sensitive adhesive for peelable wafer dicing tape[J]. Journal of Adhesion Science and Technology, 2020, 34(23): 2499-2509.
[10]	焦珊珊, 任凤梅, 武星, 等. 基于端羟基聚丁二烯聚氨酯型UV减粘胶的合成与性能[J]. 高分子材料科学与工程, 2022, 38(7): 1-6.
	JIAO Shanshan, REN Fengmei, WU Xing, et al. Synthesis and characterization of UV adhesion-reducing adhesives based on hydroxy-terminated polybutadiene polyurethane[J]. Polymer Materials Science & Engineering, 2022, 38(7): 1-6.
[11]	HAN Jinshi, ZHOU Yawei, BAI Guanghang, et al. Preparation of photo-crosslinkable acrylic copolymer and its debonding property on silicon wafer[J]. Journal of Adhesion Science and Technology, 2022, 36(4): 424-436.
[12]	CHEN Jiahui, CUI Yanyan, DING Zhu, et al. A novel CO₂ based UV-induced peelable adhesive for wafer dicing[J]. Progress in Organic Coatings, 2023, 184: 107824.
[13]	WANG Juan, DONG Zhikai, CHEN Jingwen, et al. Preparation of UV debonding acrylate adhesives by a postgrafting reaction[J]. Materials, 2023, 16(17): 5911.
[14]	WANG Juan, SHI Weihe, XIANG Shanglin, et al. Bonding and UV debonding behaviors of acrylate pressure-sensitive adhesives by rheological methods[J]. Polymer Bulletin, 2024, 81(8): 6935-6955.
[15]	HWANG Chiwon, BACK Jong-Ho, Dowon AHN, et al. A facile post-modification strategy for carboxylic acid-functionalized UV-responsive pressure-sensitive adhesives[J]. Polymer Chemistry, 2022, 13(2): 193-200.
[16]	PARK Hee-Woong, SEO Hyun-Su, KWON Kiok, et al. Preparation of UV-curable PSAs by grafting isocyanate-terminated photoreactive monomers and the effect of the functionality of grafted monomers on the debonding properties on Si wafers[J]. RSC Advances, 2023, 13(17): 11874-11882.
[17]	LIU Ziwei, CHEN Shan, WAN Ye, et al. Efficient utilization of peach gum to prepare UV-responsive peelable pressure-sensitive adhesives for non-destructive fabrication of ultrathin electronics[J]. Applied Surface Science, 2023, 612: 155748.
[18]	WU Xing, REN Fengmei, MA Haihong, et al. The effect of surface morphology on the peel performance of UV-induced adhesion-reducing adhesives[J]. Materials Research Express, 2022, 9(2): 025302.
[19]	WANG Gang, ZHOU Zhengxiang, CHEN Mengyu, et al. UV-curable polyurethane acrylate pressure-sensitive adhesives with high optical clarity for full lamination of TFT-LCD[J]. ACS Applied Polymer Materials, 2023, 5(3): 2051-2061.
[20]	LI Meng, REN Fengmei, MA Haihong, et al. Effect of double bond position and density on properties of UV-induced bio-based polyurethane adhesion-reducing adhesives[J]. International Journal of Adhesion and Adhesives, 2023, 124: 103381.
[21]	Goseong BOK, LEE Chan-Jae, LEE Hyounji, et al. Fabrication of flexible electrodes using peelable pressure-sensitive adhesives containing methacrylic-modified cyclic siloxanes[J]. Reactive and Functional Polymers, 2021, 165: 104940.
[22]	CZECH Zbigniew, BARTKOWIAK Marcin, MOZELEWSKA Karolina. Influence of unsaturated photoinitiators on acrylic pressure-sensitive adhesive properties[J]. International Journal of Adhesion and Adhesives, 2021, 107: 102846.
[23]	MOZELEWSKA Karolina, CZECH Zbigniew, BARTKOWIAK Marcin, et al. Preparation and characterization of acrylic pressure-sensitive adhesives crosslinked with UV radiation-influence of monomer composition on adhesive properties[J]. Materials, 2021, 15(1): 246.

共聚物	ABP质量分数/%	分子量	T_g/℃	初黏力/钢球号	持黏力/h	180°剥离强度/N·25mm^-1		UV减黏率/%
共聚物	ABP质量分数/%	分子量	T_g/℃	初黏力/钢球号	持黏力/h	UV照射前	UV照射后	UV减黏率/%
PSA	0	60598	-43.20	15	0.5	6.2	6.1	—
ABP-PSA-1	1	61843	-44.71	14	0.6	8.2	5.2	36.6
ABP-PSA-2	2	71544	-45.79	13	0.8	8.9	4.7	47.2
ABP-PSA-3	3	91482	-46.98	13	1.1	9.9	3.8	61.6
ABP-PSA-4	4	111760	-47.66	10	0.9	9.1	3.5	61.5
ABP-PSA-5	5	127074	-49.94	7	0..6	8.1	3.1	61.7

共聚物	ABP质量分数/%	分子量	T_g/℃	初黏力/钢球号	持黏力/h	180°剥离强度/N·25mm^-1		UV减黏率/%
共聚物	ABP质量分数/%	分子量	T_g/℃	初黏力/钢球号	持黏力/h	UV照射前	UV照射后	UV减黏率/%
PSA	0	60598	-43.20	15	0.5	6.2	6.1	—
ABP-PSA-1	1	61843	-44.71	14	0.6	8.2	5.2	36.6
ABP-PSA-2	2	71544	-45.79	13	0.8	8.9	4.7	47.2
ABP-PSA-3	3	91482	-46.98	13	1.1	9.9	3.8	61.6
ABP-PSA-4	4	111760	-47.66	10	0.9	9.1	3.5	61.5
ABP-PSA-5	5	127074	-49.94	7	0..6	8.1	3.1	61.7

UV减黏胶	主胶	预聚物	—NCO含量/mmol·g^-1		180°剥离强度/N·25mm^-1		UV减黏性/%	凝胶质量分数/%
UV减黏胶	主胶	预聚物	热固化前	热固化后	UV照射前	UV照射后	UV减黏性/%	凝胶质量分数/%
UV-PSA-1	ABP-PSA-3	CO-PUB-PETA	0.4269	0.1074	25.09	0.12	99.5	95.26
UV-PSA-2	PSA	CO-PUB-PETA	0.4260	0.1074	22.61	0.35	98.5	93.96
UV-PSA-3	ABP-PSA-3	CO-PU	0.6405	0.3324	16.65	0.80	95.2	85.53
UV-PSA-4	ABP-PSA-3	CO-PUA-PETA	0	0	15.86	0.57	96.4	93.61

UV减黏胶	主胶	预聚物	—NCO含量/mmol·g^-1		180°剥离强度/N·25mm^-1		UV减黏性/%	凝胶质量分数/%
UV减黏胶	主胶	预聚物	热固化前	热固化后	UV照射前	UV照射后	UV减黏性/%	凝胶质量分数/%
UV-PSA-1	ABP-PSA-3	CO-PUB-PETA	0.4269	0.1074	25.09	0.12	99.5	95.26
UV-PSA-2	PSA	CO-PUB-PETA	0.4260	0.1074	22.61	0.35	98.5	93.96
UV-PSA-3	ABP-PSA-3	CO-PU	0.6405	0.3324	16.65	0.80	95.2	85.53
UV-PSA-4	ABP-PSA-3	CO-PUA-PETA	0	0	15.86	0.57	96.4	93.61