CN101189124B - 粘接剂图案形成用组合物、使用其获得的层压结构物及其制造方法 - Google Patents

粘接剂图案形成用组合物、使用其获得的层压结构物及其制造方法 Download PDF

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CN101189124B
CN101189124B CN2006800192880A CN200680019288A CN101189124B CN 101189124 B CN101189124 B CN 101189124B CN 2006800192880 A CN2006800192880 A CN 2006800192880A CN 200680019288 A CN200680019288 A CN 200680019288A CN 101189124 B CN101189124 B CN 101189124B
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adhesive pattern
adhesive
composition
pattern
light
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CN101189124A (zh
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宇敷滋
槙田昇平
日马征智
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13Integrated optical circuits characterised by the manufacturing method
    • G02B6/138Integrated optical circuits characterised by the manufacturing method by using polymerisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284Application of adhesive
    • B32B37/1292Application of adhesive selectively, e.g. in stripes, in patterns
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    • C09J133/00Adhesives 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
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    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
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    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
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    • C09J7/385Acrylic polymers
    • HELECTRICITY
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    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
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    • B29C65/1403Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the type of electromagnetic or particle radiation
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
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    • B29C65/4845Radiation curing adhesives, e.g. UV light curing adhesives
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4865Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4865Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives
    • B29C65/487Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives characterised by their shape, e.g. being fibres or being spherical
    • B29C65/4875Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives characterised by their shape, e.g. being fibres or being spherical being spherical, e.g. particles or powders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/52Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/40General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
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    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • GPHYSICS
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    • G03F7/004Photosensitive materials
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Abstract

本发明在作为被粘接构件的基板(1)的表面,涂布含有(A)1分子中同时具有羧基和烯属不饱和键且具有酸值30~160mgKOH/g的含羧基感光性预聚物、(B)环氧树脂及(C)光聚合引发剂作为必须成分的光固化型热固化型粘接剂,通过光掩模(3)用活性能量射线进行选择性图案曝光后,以碱水溶液进行显影除去未曝光部分,从而形成粘接剂图案(4)。接着,将作为应接合的粘接构件的薄片构件5压接在上述粘接剂图案上,并将上述粘接剂图案热固化,得到层压结构物。

Description

粘接剂图案形成用组合物、使用其获得的层压结构物及其制造方法
技术领域
本发明涉及一种粘接剂图案形成用组合物、使用该组合物获得的层压结构物及其制造方法,更详细而言,涉及一种由光固化型热固化型粘接剂所构成的粘接剂图案形成用组合物,其形成的粘接剂图案具有粘接功能的同时,还具有作为隔板等结构构件的功能;层压结构物,其由构件之间通过该组合物所形成的粘接剂图案的固化物进行接合而形成;及该层压结构物的制造方法。本发明的光固化型热固化型粘接剂,适用于形成各种显示装置中的多层结构,该显示装置需要作为精细图案的结构支撑部(称为隔板、肋或隔壁)的粘接剂图案,另外,在要求精细的图案的情况下,还适于形成将各种基板上所形成的微细布线图案与其它的布线图案或各种电子零件的电极进行导电连接的层压结构、背光装置(背面照明装置)的光反射部等。
背景技术
目前,通常使用热固化型的粘接剂作为用于形成这种层压结构的粘接剂图案。例如,如下形成目前的背光装置中的光反射部:通常,在作为粘合剂的透明树脂清漆中混入氧化钛等反射材料,将用有机溶剂稀释成适于印刷的粘度的油墨,用丝网印刷等在导光板的背面涂布成点状等特定的图案,或者如日本特开平6-194527号公报记载,使用含反射材料的油墨在白色的塑料片(反射材料薄片)的单面印刷反射图案,利用该反射图案本身的粘接性而粘接到透明压克力板(导光板(light guideplate))。
但是,热固化型的粘接剂的情况下,必须通过印刷形成特定的图案形状,因此很难形成精细的粘接剂图案。
为解决该问题,近年开发出通过光刻法形成粘接剂图案的方法,并用于形成各种层压结构的粘接剂图案(例如,参考日本特开平3-185086号公报)。但是,感光性树脂组合物用于形成光固化型的粘接剂图案时,其通常由(甲基)丙烯酸酯系化合物-光聚合引发剂的组成所构成,因此仍存在着对基板和所层叠的薄片构件的粘接性不充分的问题。另外,所形成的粘接剂图案的固化物的硬度、耐热性、化学药品耐受性等特性方面仍存在改善的余地。
发明内容
发明要解决的技术问题
本发明鉴于前述的现有技术的问题点而提出,其目的在于解决前述的通过光刻法形成精细的粘接剂图案时的问题,并提供一种组合物,其形成的粘接剂图案的固化物对于各种构件例如各种基板或其表面所层叠的各种薄片构件的粘接性优异,同时硬度、耐热性、化学药品性耐受性等特性优异;一种层压结构物,其由构件之间通过该组合物所形成的粘接剂图案的固化物进行接合而形成;及该层压结构物的制造方法。
解决技术问题的方案
为实现前述目的,本发明提供一种组合物,其是用于构件之间通过以碱显影型光刻法所形成的粘接剂图案的固化物接合的组合物,其特征在于:该组合物由含有(A)1分子中同时具有羧基和烯属不饱和键,且具有酸值30~160mgKOH/g的含羧基感光性预聚物、(B)环氧树脂及(C)光聚合引发剂作为必须成分的光固化型热固化型粘接剂所构成。
进一步,本发明提供一种层压结构物的制造方法,其特征在于:将上述粘接剂图案形成用组合物涂布于被粘接构件表面,用活性能量射线进行选择性图案曝光后,通过显影除去未曝光部分,由此形成粘接剂图案,然后,将应接合的粘接构件压接于上述粘接剂图案,并将上述粘接剂图案热固化。
进一步,本发明还提供一种层压结构物,其特征在于:其由构件之间通过上述粘接剂图案形成用组合物所形成的粘接剂图案的固化物进行接合而形成。
另外,在本说明书中,“层压结构物”是指:通过本发明的光固化型热固化型粘接剂所形成的粘接剂图案的固化物,在被粘接构件上接合粘接构件而形成的结构体。根据用途,前述被粘接构件及粘接构件可以使用各种绝缘性构件、各种导电性构件、各种透明或半透明构件或着色构件等任意性质的构件。另外,被粘接构件及粘接构件可以使用玻璃、陶瓷、金属、塑料、纸等各种材料制成的成形品、板状成型品、薄片等,根据希望的用途可以使用各种构件。
发明效果
本发明的用于形成层压结构物的粘接剂图案的前述光固化型热固化型粘接剂,含有(A)含羧基感光性预聚物、(B)环氧树脂及(C)光聚合引发剂作为必须成分,因此通过用活性能量射线进行选择性图案曝光、显影,可以形成高精细的粘接剂图案,且具有粘接功能的同时,还具有隔壁等结构构件的功能,因此可以得到构件之间通过上述粘接剂图案的固化物牢固地接合的层压结构物。另外,将构件之间接合的粘接剂图案的固化物,硬度、耐热性、化学药品耐受性等特性也优异,因而有用于制造各种用途的层压结构物。
附图说明
图1是用于说明使用本发明的光固化型热固化型粘接剂,通过光刻法形成层压结构物的工序的简要部分剖面图。
符号说明
1:基板(被粘接构件)
2:光固化型热固化型粘接剂的涂膜
3:光掩模
4:粘接剂图案
5:薄片构件(粘接构件)
具体实施方式
本发明人为解决前述课题,进行了深入研究,结果发现将前述含有(A)含羧基感光性预聚物、(B)环氧树脂及(C)光聚合引发剂作为必须成分的光固化型热固化型粘接剂用于形成层压结构物的粘接剂图案时,发现通过碱显影型光刻法可以在被粘接构件表面形成精细的粘接剂图案,同时惊讶地发现,曝光、显影后,将应接合的粘接构件压接于上述粘接剂图案,并将其热固化,则构件之间通过粘接剂图案的固化物极牢固地接合,直至完成本发明。以下,参照附图进行说明。
图1示出使用本发明的光固化型热固化型粘接剂,通过光刻法形成粘接剂图案的方法的一个例子。首先,如图1(A)所示,在被粘接构件例如基板1的表面形成光固化型热固化型粘接剂的涂膜2。涂膜形成过程如下:根据需要,在光固化型热固化型粘接剂中添加稀释剂(作为反应性稀释剂的后述光聚合性单体、有机溶剂),调整粘度后,通过丝网印刷法、帘涂法、辊涂法、浸渍涂布法、及旋涂法等适当的涂布方法,将其涂布在期望的基板上,在例如约60℃~120℃的温度下暂时干燥,以此除去组合物中含有的有机溶剂,形成涂膜。
然后,将如上形成的光固化型热固化型粘接剂的涂膜进行图案曝光。图案曝光如下进行:如图1(B)所示,在该涂膜2上,重叠形成有特定曝光图案的光掩模3(接触或非接触任一方式均可,但通常采用接触方式),选择性地照射活性能量射线而曝光。或者,通过激光光线等按照图案直接描绘而曝光。
上述活性能量射线的照射光源适宜为低压汞灯、中压汞灯、高压汞灯、超高压汞灯、氙灯、金属卤化物灯和各种激光光线等。此外,还可以利用电子束、α射线、β射线、γ射线、X射线、中子束等。
然后,除去光掩模3后(或者,通过激光光线等直接描绘而进行曝光的情况下,则保持原状),通过以例如稀碱水溶液将未曝光部分进行显影,如图1(C)概略地所示,可以得到特定的粘接剂图案4。另外,也可以重复涂布、曝光、显影各个工序,形成期望高度的粘接剂图案。根据期望的用途,粘接剂图案可以间隔任意的距离配置组成点、线、面等花纹的要素,使其成为例如条状、斑点状、网格状等各种花纹。
上述显影中使用的碱水溶液可以使用氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、硅酸钠、氨、有机胺、四甲基氢氧化铵等的水溶液。显影液中的碱浓度可以为约0.1~5wt%。显影方式可以使用浸渍显影、桨式显影、喷雾显影等公知的方法。
然后,如图1(D)所示,将应接合的粘接构件例如薄片构件5压接在粘接剂图案4上,加热至例如约140~200℃的温度,优选为约150℃左右,进行热固化。由此,在光固化型热固化型粘接剂中的热固化性成分的固化反应的基础上,通过促进光固化性树脂成分的聚合以及其与热固化性成分的共聚,可以提高所得的粘接剂图案的固化物的耐热性、溶剂耐受性、耐酸性、密合性、电特性、硬度等各种特性。
另外,压接的压力只要为不破坏所形成的粘接剂图案的程度的压力即可,可以根据曝光、显影后的粘接剂图案的硬度任意地设定。
前述被粘接构件及粘接构件可以使用由玻璃、陶瓷、金属、塑料、纸等各种材料制成的成形品、板状成形品、薄片等,可以根据期望的用途使用各种构件。
特别是,被粘接构件可以适当地使用玻璃板、玻璃-环氧基板、陶瓷基板、金属板、塑料板、这些的复合板或与其它材料的复合板等各种基板,根据期望的用途,可以使用各种材料。另外,应接合的粘接构件,可以适当地使用合成树脂膜、金属膜、玻璃片、纸、纸-合成树脂复合膜、纸-金属箔-合成树脂复合膜等薄片构件,根据期望的用途,可以使用各种材料。这些被粘接构件和/或粘接构件还可以进行开孔加工等机械加工。
另外,这些被粘接构件和粘接构件应为可以耐受热固化处理温度的构件。
下面,对本发明的粘接剂图案形成所用的光固化型热固化型粘接剂进一步进行详细说明。
首先,本发明中所用的含羧基感光性预聚物(A)可以适当地使用如下形成的含羧基感光性预聚物(A-1):使1分子中具有至少2个环氧基的多官能环氧化合物(a)的环氧基与不饱和单羧酸(b)的羧基进行酯化反应(完全酯化或部分酯化,优选完全酯化),使所生成的仲羟基进一步与饱和或不饱和的多元酸酐(c)发生加成反应而得到。
这样的含羧基感光性预聚物(A-1),其主链聚合物的例链带有多个游离的羧基,因此含有该感光性预聚物的光固化型热固化型粘接剂可以通过稀碱水溶液显影,通过将其涂布在基板上,选择性曝光后,用碱水溶液显影,可以形成特定的图案。
前述多官能环氧化合物(a)可以使用所有的环氧树脂,但其代表性的例子可以列举双酚A型、氢化双酚A型、双酚F型、双酚S型、苯酚酚醛清漆型、甲酚酚醛清漆型、双酚A的酚醛清漆型、联苯二酚型、联二甲苯酚型、N-缩水甘油基型等公知常用的多官能环氧化合物。这些多官能环氧化合物(a),可以单独或组合2种以上而使用。
另一方面,不饱和单羧酸(b)的具体例子可以列举丙烯酸、甲基丙烯酸、巴豆酸、马来酸、富马酸、衣康酸、肉桂酸、α-氰基肉桂酸、β-苯乙烯基丙烯酸、β-糠基丙烯酸等。这些不饱和单羧酸(b)可以单独或组合2种以上而使用。
另外,饱和或不饱合多元酸酐(c)的具体例子可以列举琥珀酸酐、马来酸酐、衣康酸酐、己二酸酐、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、衣康酸酐、甲基桥亚甲基四氢邻苯二甲酸酐、偏苯三酸酐、均苯四酸酐等。进一步可以列举均苯四酸酐与(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯等(甲基)丙烯酸羟烷基酯类等具有羟基的不饱和化合物的部分反应生成物等。这些多元酸酐(c)可以单独或组合2种以上而使用。
进一步,其它的含羧基感光性预聚物(A)可以列举:
(1)含羧基感光性预聚物:使侧链具有环氧基的寡聚物或聚合物与(甲基)丙烯酸等不饱和单羧酸反应,使所生成的仲羟基进一步与饱和或不饱和的多元酸酐进行部分加成反应而得到;所述侧链具有环氧基的寡聚物或聚合物为例如由(甲基)丙烯酸烷基酯等具有不饱和双键的化合物与(甲基)丙烯酸缩水甘油酯等1分子中具有不饱和双键和环氧基的不饱和化合物形成的共聚物;
(2)含羧基感光性预聚物:使具有羟基和环氧基的寡聚物或聚合物与(甲基)丙烯酸等不饱和单羧酸反应后,进一步与饱和或不饱和多元酸酐进行部分加成反应而得到;所述具有羟基与环氧基的寡聚物或聚合物为例如(甲基)丙烯酸羟烷基酯、(甲基)丙烯酸烷基酯和(甲基)丙烯酸缩水甘油酯的共聚物;
(3)含羧基感光性预聚物:使具有羧基的寡聚物或聚合物与1分子中具有不饱和双键和环氧基的不饱和化合物例如(甲基)丙烯酸缩水甘油酯进行部分反应而得到;所述具有羧基的寡聚物或聚合物为例如(甲基)丙烯酸烷基酯与(甲基)丙烯酸的共聚物;
(4)含羧基感光性预聚物:使含羟基的聚合物与饱和或不饱和多元酸酐进行加成反应,进一步使得到的反应生成物的部分羧基与1分子中具有不饱和双键和环氧基的不饱和化合物反应而得到;
(5)含羧基感光性预聚物:使马来酸酐等不饱和多元酸酐与苯乙烯、异丁烯等具有乙烯基的芳香族烃或脂肪族烃的共聚物,与(甲基)丙烯酸羟烷基酯等含羟基(甲基)丙烯酸酯反应而得到;
等含羧基感光性预聚物(A-2)。这些含羧基感光性预聚物(A-2)可以单独使用,但从所形成的粘接剂图案对被粘接构件及粘接构件的粘接性的观点出发,优选与前述含羧基的感光性预聚物(A-1)并用。这些含羧基感光性预聚物(A-2)的量的比例,优选为含羧基感光性预聚物总量的50质量%以下。
这样的含羧基感光性预聚物(A),其酸值的适宜范围因其种类而不同,但应在30~160mgKOH/g的范围内,优选的范围为45~120mgKOH/g。酸值小于30mgKOH/g时,对碱水溶液的溶解性变差,相反,酸值大于160mgKOH/g时,由于亲水性变得过高,显影时容易产生皮膜的密合性恶化和光固化部(曝光部分)的溶解,故不优选。
前述环氧树脂(B)可以使用目前公知的所有多官能环氧树脂,可以列举例如JAPAN EPOXY RESIN(株)生产的Epikote828、Epikote 834、Epikote 1001、Epikote 1004、Dainippon Ink& Chemicals,Inc生产的Epichlon 840、Epichlon850、Epichlon1050、Epichlon2055、东都化成(株)生产的Epotote YD-011、YD-013、YD-127、YD-128、住友化学工业(株)生产的Sumi-Epoxy ESA-011、ESA-014、ELA-115、ELA-128(均为商品名)等双酚A型环氧树脂;JAPAN EPOXYRESIN(株)生产的E pikote YL903、Dainippon Ink & Chemicals,Inc生产的Epichlon152、Epichlon165、东都化成(株)生产的Epotote YDB-400、YDB-500、住友化学工业(株)生产的Sumi-Epoxy ESB-400、ESB-700(均为商品名)等溴化环氧树脂;JAPAN EPOXY RESIN(株)生产的Epikote 152、Epikote154、Dainippon Ink & Chemicals,Inc生产的Epichlon N-730、EpichlonN-770、EpichlonN-865、东都化成(株)生产的EpototeYDCN-701、YDCN-704、日本化药(株)生产的EPPN-201、EOCN-1025、EOCN-1020、EOCN-104S、RE-306、住友化学工业(株)生产的Sumi-Epoxy ESCN-195X、ESCN-220(均为商品名)等的酚醛清漆型环氧树脂;Dainippon Ink &Chemicals,Inc生产的Epichlon 830、JAPAN EPOXY RESIN(株)生产的Epikote 807、东都化成(株)生产的Epotote YDF-170、YDF-175、YDF-2004(均为商品名)等双酚F型环氧树脂;东都化成(株)生产的Epotote ST-2004、ST-2007、ST-3000(均为商品名)等氢化双酚A型环氧树脂;JAPAN EPOXYRESIN(株)生产的Epikote 604、东都化成(株)生产的EpototeYH-434、住友化学工业(株)生产的Sumi-Epoxy ELM-120(均为商品名)等缩水甘油基胺型环氧树脂;Daicel化学工业(株)生产的Ceroxide 2021(商品名)等脂环式环氧树脂;JAPANEPOXY RESIN(株)生产的YL-933、日本化药(株)生产的EPPN-501、EPPN-502(均为商品名)等三羟苯基甲烷型环氧树脂;JAPAN EPOXY RESIN(株)生产的YL-6056、YX-4000、YL-6121(均为商品名)等联二甲苯酚型或联苯二酚型环氧树脂或这些的混合物;日本化药(株)生产的EBPS-200、旭电化工业(株)生产的EPX-30、Dainippon Ink & Chemicals,Inc生产的EXA-1514(均为商品名)等双酚S型环氧树脂;JAPAN EPOXY RESIN(株)生产的Epikote 157S(商品名)等双酚A酚醛清漆型环氧树脂;JAPAN EPOXY RESIN(株)生产的Epikote YL-931(商品名)等四苯酚基乙烷型环氧树脂;日产化学(株)生产的TEPIC、TEPIC-H(商品名)等杂环式环氧树脂;日本油脂(株)生产的Blemmer DGT(商品名)等邻苯二甲酸二缩水甘油酯树脂;东都化成(株)生产的ZX-1063(商品名)等四缩水甘油基二甲苯酚乙烷树脂;新日铁化学(株)生产的ESN-190、ESN-360、Dainippon Ink & Chemicals,Inc生产的HP-4032、EXA-4750、EXA-4700(均为商品名)等含萘基环氧树脂;Dainippon Ink & Chemicals,Inc生产的HP-7200、HP-7200H(均为商品名)等具有二环戊二烯骨架的环氧树脂;日本油脂(株)生产的CP-50S、CP-50M(均为商品名)等甲基丙烯酸缩水甘油酯共聚系环氧树脂;进一步,在环己基马来酰亚胺与甲基丙烯酸缩水甘油酯共聚系环氧树脂等一分子中具有2个以上环氧基的化合物等。这些可以分别单独使用或组合2种以上而使用。
上述热固化性成分即环氧树脂(B)的配合量,相对于前述含羧基感光性预聚物(A)的1当量羧基,环氧基为0.6~2.0当量,优选为0.8~1.6当量的比例。环氧基的配合量不足0.6当量时,羧基残留,耐碱性和电绝缘性将降低,故不优选。另一方面,环氧基的配合量超过2.0当量时,过量的环氧树脂作为增塑剂而起作用,涂膜强度降低,故不优选。
另外,作为这些环氧树脂(B)与前述含羧基感光性预聚物(A)的反应促进剂,可以并用胺类、双氰胺、尿素衍生物、三聚氰胺、均三嗪化合物、三聚氰二胺化合物、2-乙基-4-甲基咪唑等咪唑化合物及其衍生物等公知的环氧固化促进剂。通过并用这些并进行热固化,可以提高固化涂膜的耐热性、化学药品耐受性、密合性、铅笔硬度等各种特性。
前述光聚合引发剂(C)的具体例子,可以列举例如苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻异丙醚等苯偶姻和苯偶姻烷基醚类;乙酰苯、2,2-二甲氧基-2-苯基乙酰苯、2,2-二乙氧基-2-苯基乙酰苯、1,1-二氯乙酰苯等乙酰苯类;2-甲基-1-〔4-(甲基硫)苯基〕-2-吗啉丙烷-1-酮、2-苯甲基-2-二甲基氨基-1-(4-吗啉苯基)-1-丁酮等氨基乙酰苯类;2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、1-氯蒽醌等蒽醌类;2,4-二甲基噻吨酮、2,4-二乙基噻吨酮、2-氯噻吨酮、2,4-二异丙基噻吨酮等噻吨酮类;乙酰苯二甲基缩酮、苯偶酰二甲基缩酮等缩酮类;二苯甲酮等二苯甲酮类;或氧杂蒽酮类;(2,6-二甲氧基苯甲酰基)-2,4,4-戊基氧化膦、双(2,4,6-三甲基苯甲酰基)-苯基氧化膦、2,4,6-三甲基苯甲酰基二苯基氧化膦、乙基2,4,6-三甲基苯甲酰基苯基亚磷酸酯等氧化膦类;各种过氧化物类等,可以单独或组合2种以上而使用这些公知常用的光聚合引发剂。这些光聚合引发剂的配合比例以常用量的比例即足够,每100重量份前述感光性预聚合物(A)中的配合量适宜为1~20重量份。
另外,如上所述的光聚合引发剂可以与N,N-二甲基氨基安息香酸乙酯、N,N-二甲基氨基安息香酸异戊酯、4-二甲基氨基苯甲酸戊酯、三乙胺、三乙醇胺等叔胺类、无色染料等这样的1种或2种以上光敏剂组合使用。
进一步,要求更深的光固化深度时,根据需要可以组合使用在可见光区引发自由基聚合的固化助剂如Ciba SpecialtyChemical公司生产的CG1784等二茂钛系光聚合引发剂等。
另外,为了提高光固化性等,可以根据需要在本发明所用的光固化型热固化型粘接剂中配合光聚合性单体。
光聚合性单体的代表例子,可以列举(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯等(甲基)丙烯酸羟烷基酯类;乙二醇、甲氧基四乙二醇、聚乙二醇等甘醇的单(甲基)丙烯酸酯或二(甲基)丙烯酸酯类;N,N-二甲基(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺等(甲基)丙烯酰胺类;(甲基)丙烯酸N,N-二甲基氨基乙酯等(甲基)丙烯酸氨基烷基酯类;己二醇、三羟甲基丙烷、季戊四醇、双三羟甲基丙烷、二季戊四醇、三聚异氰酸三羟乙酯等多元醇或其环氧乙烷或环氧丙烷加成物的多元(甲基)丙烯酸酯类;(甲基)丙烯酸苯氧基乙酯、双酚A的聚乙氧化二(甲基)丙烯酸酯等酚类的环氧乙烷或环氧丙烷加成物的(甲基)丙烯酸酯类;甘油二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、三聚异氰酸三缩水甘油酯等缩水甘油醚的(甲基)丙烯酸酯类;及三聚氰胺(甲基)丙烯酸酯类等。进一步,可以列举含羟基(甲基)丙烯酸酯与多元羧酸化合物的酸酐的反应产物。这些光聚合性单体与如前所述的感光性预聚物混合使用时,不仅作为稀释剂发挥作用,也有助于促进组合物的光固化性及提高显影性。
另外,相对于100质量份前述含羧基的感光性预聚物(A),光聚合性单体的配合量期待以60质量份以下的比例来使用,比60质量份多时,指触干燥性变差,故不优选。
另外,根据需要,可以在本发明所用的光固化型热固化型粘接剂中添加各种颜料、导电性颗粒。根据期望的用途,可以单独或组合2种以上目前公知的任意颜料,作为颜料例如酞菁绿等绿色颜料,酞菁蓝等蓝色颜料,单偶氮颜料、双偶氮颜料等黄色颜料,钼红、氧化铁红等红色颜料,炭黑、灯黑、骨黑、石墨、铁黑、铜铬系黑、铜铁锰系黑、钴铁铬系黑、四氧化三钴等氧化钴、氧化钌等黑色颜料,喹吖啶酮紫、二噁嗪紫等紫色颜料,氧化钛(二氧化钛颜料或钛白)、氧化锌等白色颜料等。导电性颗粒可以列举铜、银、镍、铝、锡、铂、钨、金、钯、焊料等金属颗粒及覆盖有上述金属层的树脂颗粒等。
从析像度的观点出发,期望这样的颜料、导电性颗粒的平均粒径为20μm以下,更优选为5μm以下。另外,只要无损本发明的效果,这些物质的配合比例可以根据期望的用途而采用任意的比例。
为了进一步提高涂膜的密合性、硬度等特性,或者根据期望的用途,本发明所用的光固化型热固化型粘接剂还可以含有玻璃粉,氧化铝、堇青石、锆石等的陶瓷微粒,硫酸钡、滑石、氧化硅、氧化钛、氧化铝、碳酸钙等填充剂成分。另外,为了防止颜料、导电性颗粒、填充剂成分的二次聚集、提高分散性,可以使用预先用发挥稳定化剂作用的有机酸、无机酸或磷酸化合物(无机磷酸、有机磷酸)、硅烷偶联剂、钛酸酯系偶联剂、铝系偶联剂等进行表面处理的上述物质,或在调制组合物时,添加少量上述处理剂。
进一步根据需要,可以在本发明所用的光固化型热固化型粘接剂中添加稀释剂,以调整粘度。稀释剂可以使用如前所述的液状单官能的光聚合性单体等反应性稀释剂、此外还可以使用有机溶剂。有机溶剂可以使用甲乙酮、环己酮等酮类;甲苯、二甲苯、四甲基苯等芳香族烃类;溶纤剂、甲基溶纤剂、丁基溶纤剂、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇单甲醚、二丙二醇单甲醚、二丙二醇二乙醚、三丙二醇单甲醚等二醇醚类;醋酸乙酯、醋酸丁酯、乳酸丁酯、醋酸溶纤剂、丁基溶纤剂醋酸酯、卡必醇醋酸酯、丁基卡必醇醋酸酯、丙二醇单甲醚乙酸酯、二丙二醇单甲醚乙酸酯、碳酸丙二酯等酯类;辛烷、癸烷等脂肪族烃类;石油醚、石脑油、溶剂石脑油等石油系溶剂等公知常用的有机溶剂。这些有机溶剂可以单独或组合2种以上而使用。
进一步,为了形成稳定的糊剂,根据需要可以在本发明所用的光固化型热固化型粘接剂中添加与颜料、导电性颗粒、填充剂成分相适应的分散剂,或以不损害本发明的效果的量的比例添加公知常用的热阻聚剂、增稠剂、增塑剂、流动性赋予剂、稳定剂、消泡剂、流平剂、防结块剂等。分散剂可以使用具有羧基、羟基、酸酯等与颜料、填充剂成分有亲和性的极性基的化合物或高分子化合物,例如磷酸酯类等含酸化合物、含酸基的共聚物、含羟基的聚羧酸酯、聚硅氧烷、长链聚氨基酰胺与酸酯的盐等。市售的分散剂中特别适宜使用的可以列举Disperbyk(注册商标)-101、-103、-110、-111、-160、及-300(均为BYK Chemie公司制)。
实施例
以下示出实施例及比较例对本发明进行更具体的说明,当然本发明并不限于下述实施例。另外,以下的“份”只要无特别声明,全部为质量基准。
实施例1~4
按表1所示的比例配合各成分,搅拌后,用3辊辊磨机进行分散,得到光固化型热固化型粘接剂。
〔表1〕
组成(质量份)     实施例No.
    1     2     3     4
含羧基感光性预聚物的清漆     156     156     156     156
环氧树脂  Epikote828     18     -     -     -
 Epikote1001的清漆     60     -     -     -
 DEN483的清漆     -     75     -     -
 Epikote YX-4000     -     -     75     -
 TEPIC-H     -     -     -     40
 Aronix M6200     35     35     35     35
 Irgacure-907     12     12     12     12
 硅酮系消泡剂     1     1     1     1
备注 含羧基感光性预聚物的清漆:对甲酚酚醛清漆型环氧树脂的1环氧当量加成0.95~1.05摩尔丙烯酸,然后,再加成0.6摩尔四氢邻苯二甲酸酐得到含羧基感光性预聚物,该含羧基感光性预聚物的含35%卡必醇醋酸酯的清漆Epikote 828:Japan Epoxy Resin(株)生产的双酚A型环氧树脂Epikote 1001的清漆:Japan Epoxy Resin(株)生产的双酚A型环氧树脂的含25%卡必醇醋酸酯的清漆Den483的清漆:Dow Chemical(株)生产的酚醛清漆型环氧树脂的含10%卡必醇醋酸酯的清漆TEPIC-H:三(2,3-环氧丙基)三聚异氰酸酯(日产化学工业(株)生产)Epikote YX-4000:Japan Epoxy Resin(株)生产的联苯型环氧树脂Aronix M6200:东亚合成化学(株)生产的两末端丙烯酸酯聚酯寡聚物Irgacure-907:2-甲基-1-〔4-(甲基硫)苯基〕-2-吗啉丙烷-1-酮(Ciba Speciality Chemicals公司生产)硅酮系消泡剂:信越化学工业(株)生产的KS-66
将如上调制的各光固化型热固化型粘接剂,用丝网印刷涂布于1.6mm厚玻璃环氧基材(FR-4)整面上,使膜厚度为40μm,并用热风循环式干燥炉在80℃下干燥30分钟。然后,粘附线和间隙为200μm的负型光掩模,用金属卤化物灯的光源在累积光量为400mJ/cm2的条件下进行曝光,然后用30℃的1%碳酸钠水溶液显影,水洗、干燥,从而在基材上形成粘接剂图案。
接着,将表2所示的各原材料粘附到上述粘接剂图案上,以50g/cm2的压力固定而压接,用热风循环式干燥炉在150℃下热固化60分钟,得到层压结构物。此时,粘接剂图案的形状具有膜厚度均为约20μm、线和间隙为200μm的结构,可以确认其作为粘接剂发挥作用的同时,还作为高精细的结构构件发挥作用。
将这样得到的各个层压结构物的粘接性评估结果示于表2中。
〔表2〕
薄片构件   实施例No.
  1   2   3   4
FR-4基材(厚度1.6mm)   ○   ○   ○   ○
聚酰亚胺膜(厚度100μm)   ○   ○   ○   ○
薄片构件   实施例No.
  1   2   3   4
纸-酚醛复合基材(厚度1.6mm)   ○   ○   ○   ○
BT基材<sup>1)</sup>(厚度1.6mm)   ○   ○   ○   ○
无卤基材<sup>2)</sup>(厚度1.6mm)   ○   ○   ○   ○
玻璃板(厚度1mm)   ○   ○   ○   ○
铜板(厚度0.8mm)   △   △   △   △
不锈钢板(厚度0.8mm)   △   △   △   △
纸(上纸)   ○   ○   ○   ○
PET膜(厚度125μm)   △   △   △   △
备注 ○:牢固地粘接,剥离时原材料破坏△:粘接,但很干净地剥离<sup>*1)</sup>BT基材:双马来酰亚胺·三嗪树脂基材<sup>*2)</sup>无卤基材:日立化成工业(株)生产MCL-RO-67G(MCL为注册商标)
从表2所示的结果可以明确地确认其与各种粘接构件(结构构件)的粘接性也良好。
产业上的可利用性
本发明的光固化型热固化型粘接剂,适用于形成各种显示装置中的多层结构,该显示装置需要作为精细图案的结构支撑部(称为隔板、肋或隔壁)的粘接剂图案,另外,还适于形成将各种基板上所形成的微细布线图案与其它的布线图案或各种电子零件的电极进行导电连接的层压结构、背光装置(背面照明装置)的光反射部等。

Claims (7)

1.一种层压结构物的粘接剂图案形成用组合物,所述组合物用于通过该组合物的固化物而接合构件之间,所述固化物是由碱显影型光刻法形成的粘接剂图案的固化物,其特征在于,该组合物由含有以(A)1分子中同时具有羧基和烯属不饱和键且具有酸值30~160mgKOH/g的含羧基感光性预聚物、(B)环氧树脂及(C)光聚合引发剂作为必须成分的光固化型热固化型粘接剂所构成。
2.根据权利要求1所述的粘接剂图案形成用组合物,其特征在于,所述含羧基感光性预聚物(A)如下形成:使1分子中至少具有2个环氧基的多官能环氧化合物(a)的环氧基与不饱和单羧酸(b)的羧基进行酯化反应,使所生成的仲羟基进一步与饱和或不饱和的多元酸酐(c)进行加成而得到。
3.根据权利要求1所述的粘接剂图案形成用组合物,其特征在于,所述光固化型热固化型粘接剂进一步包含有机溶剂和/或光聚合性单体作为稀释剂。
4.根据权利要求1~3任一项所述的粘接剂图案形成用组合物,其中所述光固化型热固化型粘接剂还包含选自颜料、导电性颗粒、填充剂、分散剂、热阻聚剂、增稠剂、增塑剂、流动性赋予剂、稳定剂、消泡剂、流平剂、及防结块剂中的至少一种添加剂。
5.根据权利要求1~3任一项所述的粘接剂图案形成用组合物,其中所述光固化型热固化型粘接剂还包含陶瓷微粒。
6.一种层压结构物的制造方法,其特征在于,将所述权利要求1~5任一项所述的粘接剂图案形成用组合物涂布于被粘接构件表面,用活性能量射线进行选择性图案曝光后,通过显影除去未曝光部分,由此形成粘接剂图案,接着,将应接合的粘接构件压接于所述粘接剂图案上,并将上述粘接剂图案热固化。
7.一种层压结构物,其特征在于,构件之间通过所述权利要求1~5任一项所述的粘接剂图案形成用组合物所形成的粘接剂图案的固化物进行接合。
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