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Article(id=1210601627829014604, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210601623135581115, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.10.014, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1718294400000, receivedDateStr=2024-06-14, revisedDate=1721836800000, revisedDateStr=2024-07-25, acceptedDate=null, acceptedDateStr=null, onlineDate=1766559519965, onlineDateStr=2025-12-24, pubDate=1729353600000, pubDateStr=2024-10-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766559519965, onlineIssueDateStr=2025-12-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766559519965, creator=13701087609, updateTime=1766559519965, updator=13701087609, issue=Issue{id=1210601623135581115, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='10', pageStart='1', pageEnd='141', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766559518846, creator=13701087609, updateTime=1766564021205, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210620507448275814, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210601623135581115, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210620507448275815, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210601623135581115, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=106, endPage=113, ext={EN=ArticleExt(id=1210601628114227278, articleId=1210601627829014604, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Patent analysis of photosensitive polyimide applied by Toray in China, columnId=1203281640207393262, journalTitle=Insulating Materials, columnName=Special Issue on High Performance Polyimide Materials, runingTitle=null, highlight=null, articleAbstract=

Photosensitive polyimide (PSPI) is widely used in electronics, microelectronics, optical display, and other fields. Foreign companies attach great importance to the patent protection of PSPI material formulas and applications. In this paper, the PSPI patents applied by Toray Industries Inc. in China were taken into research, and the changes in the number of patent applications, legal status, technical subject distribution, and other key information were analyzed in detail. Through combining with Toray's representative PSPI products and their applications, the technical development, patent protection strategy, key points of patent technology of Toray were clarified. Based on the above analysis, the technology development trends and application direction of PSPI materials were explored and presented.

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光敏聚酰亚胺（PSPI）广泛应用于电子、微电子及光学显示等领域，国外企业高度重视有关PSPI材料配方及应用的专利技术保护。本文以日本东丽公司在中国申请的PSPI专利为研究对象，详细分析了专利的申请数量变化、法律状态、技术主题分布等信息，并结合东丽公司代表性的PSPI产品与应用情况，明确了其发展历程、专利保护策略、专利技术构成，以此探讨PSPI材料的技术发展趋势与应用方向。

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翟磊（1985-），男（汉族），山东潍坊人，副研究员，主要从事高性能聚酰亚胺材料的基础与应用研究。
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苑伟康（1982-），女（汉族），河北衡水人，三级调研员，主要从事材料领域专利的复审无效审理；

徐建锋（1982-），男（汉族），河北石家庄人，三级调研员，主要从事材料领域专利的复审无效审理。

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苑伟康（1982-），女（汉族），河北衡水人，三级调研员，主要从事材料领域专利的复审无效审理；

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苑伟康（1982-），女（汉族），河北衡水人，三级调研员，主要从事材料领域专利的复审无效审理；

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徐建锋（1982-），男（汉族），河北石家庄人，三级调研员，主要从事材料领域专利的复审无效审理。

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徐建锋（1982-），男（汉族），河北石家庄人，三级调研员，主要从事材料领域专利的复审无效审理。

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label=Fig.7, caption=Technical subjects of PSPI patents applied in China from Toray Industries Inc., figureFileSmall=Qs7Ibva7sX5Piixjhq2tzA==, figureFileBig=sxbp8S5rX0yALfaXi9GFWQ==, tableContent=null), ArticleFig(id=1218837318400660384, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601627829014604, language=CN, label=图7, caption=东丽公司PSPI中国专利的技术主题分布, figureFileSmall=Qs7Ibva7sX5Piixjhq2tzA==, figureFileBig=sxbp8S5rX0yALfaXi9GFWQ==, tableContent=null), ArticleFig(id=1218837318501323682, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601627829014604, language=EN, label=Fig.8, caption=Representative compound structures of PSPI patents applied in China from Toray Industries Inc., figureFileSmall=oE65923GaTNIKG7Lp0SMFg==, figureFileBig=IqcnSt4gui2fwEmHEbzGtQ==, tableContent=null), ArticleFig(id=1218837318622958501, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601627829014604, language=CN, label=图8, caption=东丽公司PSPI中国专利中代表性化合物结构, figureFileSmall=oE65923GaTNIKG7Lp0SMFg==, figureFileBig=IqcnSt4gui2fwEmHEbzGtQ==, tableContent=null), ArticleFig(id=1218837318711038885, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601627829014604, language=EN, label=Fig.9, caption=Change trends in the number of PSPI patents about two types of technical subjects applied in China from Toray Industries Inc., figureFileSmall=hwD+OUDi2GFJyAybPZVR8A==, figureFileBig=jfjYZdKA5ZY9M82ju6JVmg==, tableContent=null), ArticleFig(id=1218837318815896487, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601627829014604, language=CN, label=图9, caption=东丽公司两大主题PSPI中国专利的申请数量变化, figureFileSmall=hwD+OUDi2GFJyAybPZVR8A==, figureFileBig=jfjYZdKA5ZY9M82ju6JVmg==, tableContent=null), ArticleFig(id=1218837318912365481, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601627829014604, language=EN, label=Table 1, caption=Key performance data of three types of PSPI products from Toray Industries Inc., figureFileSmall=null, figureFileBig=null, tableContent=
性能PW系列LT系列PN系列
固化温度(1h)/℃320～350170～250200～350
抗拉强度/MPa≥150≥120≥110
弹性伸长率/%≥20≥60≥20
弹性模量/GPa3.8～4.01.7～2.53.3～3.9
热膨胀系数/(×10-6℃-1)35～4055～6060～65
玻璃化转变温度/℃≥300≥270≥312
5%热失重温度/℃≥450≥340≥382
), ArticleFig(id=1218837318987862954, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210601627829014604, language=CN, label=表1, caption=

东丽公司三类PSPI产品的主要性能数据

, figureFileSmall=null, figureFileBig=null, tableContent=
性能PW系列LT系列PN系列
固化温度(1h)/℃320～350170～250200～350
抗拉强度/MPa≥150≥120≥110
弹性伸长率/%≥20≥60≥20
弹性模量/GPa3.8～4.01.7～2.53.3～3.9
热膨胀系数/(×10-6℃-1)35～4055～6060～65
玻璃化转变温度/℃≥300≥270≥312
5%热失重温度/℃≥450≥340≥382
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东丽公司光敏聚酰亚胺中国专利分析
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苑伟康 1 , 徐建锋 1 , 杨斐 1 , 郭彦 1 , 黄颖 1 , 赵锴 1 , 翟磊 2 , 范琳 2
绝缘材料 | 高性能聚酰亚胺材料专题 2024,57(10): 106-113
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绝缘材料 | 高性能聚酰亚胺材料专题 2024, 57(10): 106-113
东丽公司光敏聚酰亚胺中国专利分析
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苑伟康1, 徐建锋1, 杨斐1, 郭彦1, 黄颖1, 赵锴1, 翟磊2, 范琳2
作者信息
  • 1国家知识产权局，北京 100081
  • 2中国科学院化学研究所，北京 100190

    • 苑伟康（1982-），女（汉族），河北衡水人，三级调研员，主要从事材料领域专利的复审无效审理；

    徐建锋（1982-），男（汉族），河北石家庄人，三级调研员，主要从事材料领域专利的复审无效审理。

通讯作者:

翟磊（1985-），男（汉族），山东潍坊人，副研究员，主要从事高性能聚酰亚胺材料的基础与应用研究。
Patent analysis of photosensitive polyimide applied by Toray in China
Weikang YUAN1, Jianfeng XU1, Fei YANG1, Yan GUO1, Ying HUANG1, Kai ZHAO1, Lei ZHAI2, Lin FAN2
Affiliations
  • 1China National Intellectual Property Administration, Beijing 100081, China
  • 2Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
出版时间: 2024-10-20 doi: 10.16790/j.cnki.1009-9239.im.2024.10.014
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摘要
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光敏聚酰亚胺（PSPI）广泛应用于电子、微电子及光学显示等领域，国外企业高度重视有关PSPI材料配方及应用的专利技术保护。本文以日本东丽公司在中国申请的PSPI专利为研究对象，详细分析了专利的申请数量变化、法律状态、技术主题分布等信息，并结合东丽公司代表性的PSPI产品与应用情况，明确了其发展历程、专利保护策略、专利技术构成，以此探讨PSPI材料的技术发展趋势与应用方向。

光敏聚酰亚胺  /  中国专利  /  东丽公司  /  技术主题  /  发展趋势

Photosensitive polyimide (PSPI) is widely used in electronics, microelectronics, optical display, and other fields. Foreign companies attach great importance to the patent protection of PSPI material formulas and applications. In this paper, the PSPI patents applied by Toray Industries Inc. in China were taken into research, and the changes in the number of patent applications, legal status, technical subject distribution, and other key information were analyzed in detail. Through combining with Toray's representative PSPI products and their applications, the technical development, patent protection strategy, key points of patent technology of Toray were clarified. Based on the above analysis, the technology development trends and application direction of PSPI materials were explored and presented.

PSPI  /  patents applied in China  /  Toray  /  technical subject  /  development trend
苑伟康, 徐建锋, 杨斐, 郭彦, 黄颖, 赵锴, 翟磊, 范琳. 东丽公司光敏聚酰亚胺中国专利分析. 绝缘材料, 2024 , 57 (10) : 106 -113 . DOI: 10.16790/j.cnki.1009-9239.im.2024.10.014
Weikang YUAN, Jianfeng XU, Fei YANG, Yan GUO, Ying HUANG, Kai ZHAO, Lei ZHAI, Lin FAN. Patent analysis of photosensitive polyimide applied by Toray in China[J]. Insulating Materials, 2024 , 57 (10) : 106 -113 . DOI: 10.16790/j.cnki.1009-9239.im.2024.10.014
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0 引言
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随着电子产品朝着超薄化、轻量化、高集成化和多功能化方向发展，电子及微电子用高分子材料面临愈发苛刻的性能要求。聚酰亚胺因其优异的耐热、力学、绝缘、介电性能以及化学稳定性等特性，作为层间介质材料、再布线封装材料、屏蔽/钝化/缓冲/保护层、基板材料等广泛用于集成电路制造领域[1-5]。在众多聚酰亚胺材料中，分子结构中同时含有酰亚胺与光敏功能基团的光敏聚酰亚胺（PSPI）是一类重要的半导体或显示器件封装材料，其对紫外光、X射线、电子束或离子束有良好的感光性，可以利用光刻工艺技术直接实现图形化，有效解决了传统光刻胶繁琐复杂的多步工艺流程，极大提升了微电子器件的制备效率，因而一直受到人们的关注[6-8]。
根据感光化学机理或图形显影方式的不同，PSPI材料可分为负性PSPI和正性PSPI两大类。负性PSPI的特点是曝光区发生光交联反应导致溶解性能下降，而非曝光区的分子结构没有变化，依然保持良好的溶解性，选用适当的有机溶剂作显影液将其溶解除去，可使曝光部分保留下来成为光刻图案[9-10]。关于负性PSPI的研究最早报道于1971年，美国贝尔电话实验室开发了由聚酰胺酸溶液与重铬酸钾组成的负性光敏抗蚀剂体系[11]，其基本原理是二者在紫外光照射下可发生光化学交联反应，之后通过显影液除去未曝光部分，从而形成清晰的光刻图案。之后在1973年，德国西门子公司申请了第一件关于负性PSPI材料的发明专利（DE 2308830A），将烯丙基酯基团引入到聚酰胺酸的分子结构中制备得到对紫外光敏感的聚酰胺酯，该方法也成为后续PSPI合成的基础路线之一[12-13]。
与此相反，正性PSPI的特点是曝光区的分子结构发生光化学反应而使溶解性增大，在显影时被溶解除去，而非曝光区因不溶于碱水稀溶液或其他显影液，因而得以保留下来形成光刻图案[14-15]。关于正性PSPI的研究最早公开报道于1975年，美国GAF公司申请了首件关于正性PSPI材料的发明专利（US4093461A），开发了一种由聚酰胺酸、邻醌类或萘醌类二叠氮化合物等组成的光敏体系，曝光后采用碱性溶液显影，获得了良好的光刻图形。与负性PSPI相比，正性PSPI具有诸多应用优势，例如采用碱性水溶液作为显影剂，不仅环境相容性好，而且避免了负性体系采用的有机显影液对光刻图案的侵蚀，从而可获得更高的图形分辨率。因此，正性PSPI材料日益成为研发与应用的重点[16-18]。
鉴于PSPI材料在微电子领域的重要作用，日本和美国的企业与科研机构很早便围绕PSPI材料开展系统性研究与大规模商品化开发，涌现出一大批代表性的材料生产企业，包括日本东丽、富士胶片、旭化成、日立杜邦微系统等[19-21]。在推出大量不同系列PSPI商品化产品的同时，国外公司高度重视PSPI材料相关的专利技术保护，在中国地区申请了大量高价值、高技术壁垒的PSPI配方与应用专利。已有工作证明，通过对国外专利信息的挖掘以及技术内容和专利布局的分析，有助于深入了解该领域的发展趋势和产品技术特点，对国内科研机构、生产或应用企业有着重要指导意义[22-26]。
目前，国内在高端PSPI材料开发方面与国外产品仍存在明显差距，面临着诸多技术挑战，同时新申请的PSPI核心专利也亟需突破国外已有的专利保护布局。为此，本文选取国外最具代表性的PSPI材料研发公司之一的日本东丽公司（Toray Industries Inc.）为分析对象，通过对东丽公司在中国（不含港澳台）所申请PSPI专利的数量变化、法律状态、技术主题等进行深入研究，梳理PSPI的技术发展趋势与特点，为国内PSPI材料的研发与应用，以及针对性开展PSPI材料的技术保护和专利布局提供参考。
1 日本公司PSPI中国专利的总体分析
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本文专利样本来源于国家知识产权局专利检索系统和incoPat专利数据库，分别以光敏（性）聚酰亚胺、感光（性）聚酰亚胺、聚酰亚胺光刻胶等为关键词，通过国际专利分类号、申请人等为入口进行检索。检索日期自1985年1月1日至2024年4月6日，即在此时间范围内已公开并录入检索系统和数据库的专利申请。对检索结果进行同族合并，每个同族计为一项。同时，分析的专利样本经人工核实后，已剔除掉无关噪音专利。
根据申请人在中国（不含港澳台）提出的PSPI专利申请检索结果，以排名在前的8家日本公司为代表，包括东丽株式会社、富士胶片株式会社、旭化成株式会社、日立化成杜邦微系统股份有限公司、日产化学工业株式会社、JSR株式会社、住友电木株式会社、信越化学工业株式会社，分析了日本在PSPI材料与应用领域的整体状况。上述公司在国内申请的PSPI专利数量如图1所示。
日本是国外申请人在华申请PSPI专利最多的国家，据统计，日本申请的PSIP专利数量约占国外专利数量的近60%，反映出其在该领域的优势地位以及相关公司对专利技术保护的重视。从图1可以看出，上述8家代表性日本公司的专利申请数量总计为319件，其中，东丽作为PSPI研发和应用领域最为活跃的日本公司，其专利申请数量最多，达到104件，约占8家日本公司专利申请总量的1/3；其次为富士胶片，专利申请数量为58件，旭化成以53件专利申请量紧随其后；其余5家的PSPI专利申请数量相差不大，基本在18～24件。
2 东丽公司PSPI中国专利的申请数量
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针对东丽公司在不同年份所申请的PSPI中国专利数量进行了统计，并同时给出了8家代表性日本公司的整体申请数量变化情况，如图2所示。从图2可以看出，东丽公司PSPI中国专利的申请数量变化与日本公司整体走势情况基本相同，表明东丽公司中国PSPI专利申请很大程度上影响了日本公司的总体变化趋势。
根据东丽公司在中国所申请PSPI专利的数量变化情况，其发展趋势可分为两个阶段：
第一阶段（1997—2014年）为起步及平稳期。东丽公司于1997年提出第一件与PSPI有关的中国专利申请（CN 1177751A），报道了一类树脂刻蚀溶液和刻蚀方法，利用该树脂刻蚀溶液可获得单面或双面形成光刻胶图案或金属层图案的聚酰亚胺膜。随后在1998年，东丽公司报道了一种室温下黏度时效稳定性与感光性能均优异的化学射线感应性聚合物组合物（CN1201061A），主组分包括光引发剂和/或光敏感剂，以及通过含有光交联性基团的胺化合物与聚酰胺酸的羧基相互作用进而获得的聚酰亚胺前体组合物。之后一直到2014年，东丽公司基本维持在每年3件及以下的PSPI相关专利申请数量。在该阶段，东丽公司并没有进行规模化和系统性的PSPI专利布局，这反映出国内PSPI领域在此时期未得到充分发展，行业应用成熟度不高、企业竞争不充分，尚没有引起国外优势公司在中国地区开展专利技术保护的重视。
第二阶段（2015—2024年）为快速发展期。自2015年期，东丽公司申请的PSPI中国专利数量有明显提升，且每年度均维持在较高的申请量水平。例如，2016年和2017年的专利申请量分别达到16和18件。该阶段的专利申请量占其申请总量的78%，反映出东丽公司开始加大对PSPI领域的研发投入和中国地区的专利技术保护。与此同时，日本其他几家代表性PSPI领域的企业申请人也在此阶段集中发力，相关专利申请量大幅增加，该阶段专利申请量占PSPI中国专利申请总量的72%。上述结果从侧面也表明国内的PSPI研发和应用领域已渐具竞争规模，国外公司积极开展专利布局以抢占市场。需要说明的是，图2中给出的2023与2024年度的专利申请量并未反映出当年的真实申请情况，主要是因专利申请公布（包含PCT申请的国家公布和部分发明公布）以及公布数据录入数据库均存在时间滞后性，导致部分专利申请尚未正式公开，因而并未纳入实际统计范围。
3 东丽公司PSPI中国专利的法律状态
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经统计发现，东丽公司所申请的PSPI中国专利均为发明专利，进一步针对该公司PSPI中国专利的法律状态进行了分析。专利的法律状态主要包括授权有效、实质审查和失效3类状态，其中失效状态可分为撤回、驳回、放弃、期限届满和未缴年费4种情形。“期限届满”是专利获得授权后由于保护期限届满而失效，“未缴年费”和“放弃”是专利获得授权后专利权人主动放弃而失效。
东丽公司PSPI中国专利的整体法律状态如图3所示。
从图3可以看出，处于“授权有效”状态的专利数量为57件，占总申请量的54.8%，“实质审查”状态的专利数量为28件，而“失效”专利有19件。针对处于“失效”状态的专利进行分析，其中因“期限届满”而失效的专利数量为5件，“未缴年费”和“放弃”的专利分别为6件和1件。综合以上3种失效情况，合并现有“授权有效”专利数量，东丽公司总计获得授权的专利数量为69件，占其申请总量的66.3%，占审结量的90.8%。此外，在处于“失效”状态的专利中，被动“驳回”的专利数量仅为1件，仅占申请总量的不足1%。综合来看，东丽公司PSPI中国专利的授权率远高于我国发明专利申请的平均授权率，驳回率远低于发明专利申请的平均驳回率，反映出该公司在本领域巨大的技术优势，以及高的专利技术复杂度与良好的专利撰写水平。
按照申请年份对东丽公司PSPI中国专利的法律状态进行了统计，结果如图4所示。从图4可以看出，在2014年之前的第一阶段，东丽公司所申请PSPI中国专利的授权率为100%，主要可能归因于早期该领域的研发处于空白期，现有技术数量较少。在2015年之后的第二阶段，出现了驳回以及专利权人主动撤回的情况，说明随着专利申请量的增加，该领域研究逐渐充分，技术密度越来越大，获得专利授权的难度有所增高。另一方面，也可能是由于东丽公司围绕核心技术有意构建密集的专利保护池，导致部分专利申请与先前专利申请的区分度不够，因此对部分专利申请采取撤回处理，也间接反映了该公司对PSPI中国专利布局的主动性。
授权专利的维持时间是该项专利技术含金量的体现之一。对东丽公司授权专利的维持时间进行统计，结果如图5所示。从图5可以看出，其总授权专利为69件，目前还处于有效状态的有57件，维持时间在6～9年的专利数量占比最多。考虑发明专利的保护期限为20年，对申请日在2005年之前的专利申请进行分析才能够准确反映其维持情况。申请日在2005年之前的专利申请总量为12件且均获得授权，目前达到19～20年保护期的专利为7件，其余5件专利授权后由于专利权人主动放弃而失效。
东丽公司主动放弃而失效的专利主要发生在早期阶段，表明其后续研发方向以及在华的专利布局策略进行了较大的调整。值得注意的是，维持时间为6～9年的专利占东丽公司已授权专利的一半以上，这些专利仍有10年及以上的保护期，同时含有大量的在审专利，国内相关企业需要重点关注。
图6为东丽公司PSPI中国专利自申请日至公开日的历时时长情况。从图6可以看出，历时时长在20个月左右的专利申请数量最多，18个月以上的专利数量占总申请量的91.3%，而申请提前公开的只占8.7%。这体现了东丽公司针对PSPI中国专利的布局策略，即充分利用我国发明专利公开滞后的规则，对专利技术的研发方向和市场布局意图进行特意保护，同时也反映了该领域竞争的激烈性。
4 东丽公司PSPI中国专利的技术主题
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针对东丽公司PSPI中国专利的技术主题分布情况进行了统计，根据国际专利IPC分类号，对所涉及的技术领域进行分类，并以关键词作为技术主题归类的补充依据。由于同一件专利往往会涵盖多个技术主题，不可避免存在同一件专利被多个技术主题重复统计的现象。图7给出了东丽公司PSPI中国专利涉及的最主要的技术主题分布情况。
从图7可以看出，东丽公司的PSPI专利主要集中在三大领域：PSPI配方设计与制备（包括树脂、聚合物、组合物、固化膜等）、显示装置、半导体元件及封装，特别是位于产业最上游的PSPI配方设计与制备是其最主要的申请方向。东丽公司PSPI中国专利涉及的应用领域主要是显示和半导体领域，包括有机场致发光元件、半导体元件及其封装、光学元件、印刷电路等。此外，针对PSPI配方设计与制备，东丽公司所申请的PSPI中国专利中大量采用含酰胺基团的二酐或二胺化合物。例如，CN109563353A、CN108779251A等多篇专利均给出了图8所示的二酐与二胺结构示意。
针对东丽公司聚焦的主要应用领域，即半导体元件及封装、显示装置两大主题，进一步分析了各自主题下PSPI中国专利的申请量随年份的变化情况，如图9所示。从图9可以看出，东丽公司在这两类主题下的PSPI专利申请数量变化趋势基本相同，均在2015年以后出现快速增长；显示装置主题的专利申请量稍高于半导体元件及封装主题领域。2015年以后两类技术主题下的专利申请量差值有所扩大，说明东丽公司更重视在我国布局显示装置领域，并有意加强了此方面的专利布局。需要说明的是，最近几年东丽公司的PSPI专利数量有所下降，特别是2023和2024两年出现了专利申请量为零的现象，这极有可能与相关专利尚未公开导致未能统计有关，这符合前面针对东丽公司专利自申请至公开的时长分析。
此外，通过人工阅读专利的权利要求书及全文，根据专利内容对东丽公司所申请全部PSPI中国专利涉及的技术主题进行了更为准确地分类统计。其中，根据材料类型分为“正性PSPI”和“负性PSPI”两大类；根据材料应用领域大致分为“半导体封装”（含电子器件）与“显示装置”（含光学元件）两大领域。由于同一件专利会同时涉及一种或正、负两种类型PSPI，应用领域也会出现类似情况，同一件专利会被重复统计。结果表明，东丽公司的PSPI中国专利中涉及“正性PSPI”的专利数量为40件，而涉及“负性PSPI”的专利数量高达73件；涉及“半导体封装”领域的专利数量为37件，而涉及“显示装置”领域的专利数量达到60件。可以看出，东丽公司在中国更加重视对负性PSPI材料及显示装置应用领域的专利技术保护，这不仅体现了该公司的PSPI产品研发与应用特点，更与国内显示领域飞速发展带来的旺盛需求有着重要关系。
5 东丽公司的代表性PSPI产品特点
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为更好地理解专利技术内容与实际产品技术的关联，进一步对东丽公司代表性PSPI产品的特点与应用情况进行了分析。东丽公司商品化的PSPI材料产品牌号为PHOTONEECE™，主要包括正性的PW系列和LT系列，以及负性的PN系列等，主要性能数据如表1所示（来源于公司官网），已广泛应用于半导体/电子元件的保护膜或缓冲膜、晶圆级/面板级封装再布线层、电子元件层间绝缘材料等。
其中，PW-1000牌号是PW系列正性PSPI产品中的早期标准型产品[27]，之后推出了耐热性更高、化学稳定性更好、感度更高的其他牌号产品，包括厚膜型PW-1200、耐溶剂型PW-1500及PW-1500s、高感度PW-2100等。此外，东丽公司针对图像传感器领域推出了CS系列正性PSPI产品，该类产品具有高透明性、高折射率、高感光度及良好的化学稳定性等特点；针对显示器件领域还推出了DL系列和SL系列正性PSPI产品，其特点是较低固化温度、高分辨率、良好的粘附性与化学稳定性。
LT系列是东丽公司针对下一代半导体制造应用需求，开发出的固化温度低和残留应力低的高端正性PSPI产品。随着半导体芯片愈发薄型化，绝缘层高温固化后的高残余应力会导致晶圆出现翘曲变形等问题，亟需具有低残余应力和高分辨率的可低温固化正性PSPI保护涂层[28]。2012年1月，东丽公司推出了首款可在170℃低温固化、残余应力低至13 MPa或更低的正性PSPI产品。除高的耐热性和耐化学性外，该产品的残余应力仅为传统低温固化PSPI和PBO材料的一半，同时还具有出色的分辨率，可使用更为环保的碱性水系显影剂进行显影。据报道，除了赋予其新的预亚胺化聚合物分子结构外，东丽公司还在该类正性PSPI中使用了专有的交联设计，以防止材料在图案加工过程中120℃加热下发生反应，但可在170℃时发生充分反应，以此提高其耐热性到260～280℃。同时，东丽公司还开发了与可溶性预亚胺化聚合物具有纳米层级良好相容性的正性光活性化合物。使用该类光敏化合物的正性PSPI产品，通过使用普通碱性显影剂TMAH即可表现出良好的分辨率。与传统250℃固化的产品相比，LT系列产品在170℃低温固化可获得更加优良的光刻效果，在5 μm膜层厚度下可获得图案宽度为3 μm的高分辨率图案。
针对负性PSPI材料，东丽公司推出了可低温固化的PN系列产品，该类负性PSPI的固化温度低、收缩率低、热稳定性高。传统负性PSPI材料往往具有较低的透光率，当厚度超过50 μm时光敏性会变差，导致无法进行精细加工，同时材料在固化后往往出现高的热应力和明显翘曲，严重影响加工过程中的可靠性。2022年1月，东丽公司对外公布了一种针对高速通信技术而开发的低热膨胀、低介电常数与介质损耗的全新负性PSPI材料，该产品通过提高透光率和控制光反应技术实现了100 μm的高厚度，并可制造直径为10 μm的通孔。通过控制树脂在曝光过程中的光反应交联密度和降低固化收缩率，该产品可将热应力降低到普通材料一半以下，显著减少翘曲等问题，从而实现高速通信电子元件和半导体封装布线的小型化，并大幅提高可靠性。
综合对比东丽公司开发的正性与负性系列PSPI产品，该公司的正性产品已广泛应用于微电子封装领域，是全球正性PSPI产品市场化最成功的企业之一。然而，前面针对东丽公司PSPI中国专利的分析结果却表明，涉及“正性PSPI”的专利数量远少于涉及“负性PSPI”的专利数量，这与该公司在正性产品方面的技术优势并不完全相符。值得注意的是，东丽公司所申请PSPI中国专利偏向于显示领域的明显更多，据此推测东丽公司在我国的专利布局或申请策略可能不仅以PSPI技术先进性或优势来主导，而且更与国内显示领域对PSPI产品的巨大需求有直接关联。此外，随着欧洲国家和美国因环保问题逐渐限制有机溶剂N-甲基-2-吡咯烷酮（NMP）的使用，东丽公司还于2022年12月推出了不含NMP溶剂的PSPI产品，以降低对环境的潜在影响，并可应用于特高电压领域的半导体器件。该类PSPI产品通过应用增强光透明度技术可实现高厚度膜层制备，厚度为同类产品的两倍多即超过15 μm，也能实现与传统产品相同的高分辨率图案加工，同时与硅、铜或其他基材均有良好的高粘合性。
6 结论
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（1）日本东丽公司PSPI中国专利的申请数量经历了较长的起步及平稳期，自2015年以后进入到快速发展期，反映出该公司对PSPI材料专利技术保护日益重视。
（2）东丽公司PSPI中国专利的授权率远高于我国发明专利申请的平均授权率，而驳回率远低于国内平均水平，反映出该公司在本领域巨大的技术优势；专利自申请至公开的时长在18个月以上的数量占比高达91.3%，表明其专利布局策略为利用发明专利公开滞后的规则，对专利技术的研发方向和市场布局意图进行特意保护。
（3）专利技术主题分析结果表明，PSPI配方设计与制备是其最主要的申请方向，而涉及的应用领域主要集中在显示装置和半导体封装。进一步根据专利内容分析可知，涉及负性PSPI材料以及显示应用的专利数量明显更多。
基金
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  • 国家重点研发计划项目资助(2022YFB3603105)
文献
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2024年第57卷第10期
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doi: 10.16790/j.cnki.1009-9239.im.2024.10.014
  • 接收时间：2024-06-14
  • 首发时间：2025-12-24
  • 出版时间：2024-10-20
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  • 收稿日期：2024-06-14
  • 修回日期：2024-07-25
基金
国家重点研发计划项目资助(2022YFB3603105)
作者信息
    1国家知识产权局，北京 100081
    2中国科学院化学研究所，北京 100190

通讯作者:

翟磊（1985-），男（汉族），山东潍坊人，副研究员，主要从事高性能聚酰亚胺材料的基础与应用研究。
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2种不同金属材料的力学参数
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Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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