TW201937287A - Photosensitive composition and use thereof - Google Patents
Photosensitive composition and use thereof Download PDFInfo
- Publication number
- TW201937287A TW201937287A TW108102793A TW108102793A TW201937287A TW 201937287 A TW201937287 A TW 201937287A TW 108102793 A TW108102793 A TW 108102793A TW 108102793 A TW108102793 A TW 108102793A TW 201937287 A TW201937287 A TW 201937287A
- Authority
- TW
- Taiwan
- Prior art keywords
- photosensitive composition
- mass
- composition according
- conductive
- photopolymerization initiator
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/0285—Silver salts, e.g. a latent silver salt image
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
本發明是有關於一種感光性組成物及其應用。The present invention relates to a photosensitive composition and its application.
先前,已知有使用包含光聚合性化合物與光聚合起始劑的感光性組成物並藉由光硬化而於基材上形成導電層或樹脂絕緣層的方法(參照專利文獻1~專利文獻6)。例如於專利文獻1中揭示出,藉由包含膜狀體的成形步驟、曝光步驟、顯影步驟、及煅燒步驟的光刻法而於基板上形成配線圖案。該方法中,首先,於膜狀體的成形步驟中,利用印刷法等將感光性組成物賦予至基材上並使其乾燥,從而將膜狀體成形。繼而,於曝光步驟中,於所述成形的膜狀體上覆蓋具有規定的開口圖案的光罩後,介隔光罩對膜狀體進行曝光。藉此,使膜狀體的曝光部分光硬化。繼而,於顯影步驟中,利用鹼性的蝕刻液對由光罩遮光的未曝光部分進行腐蝕並將其去除。然後,於煅燒步驟中,對成為所需顯影圖案的膜狀體進行煅燒。根據所述方法,與先前的各種印刷法相比,可形成高精細圖案的導電層。
[現有技術文獻]
[專利文獻]Conventionally, a method is known in which a conductive layer or a resin insulating layer is formed on a substrate by photocuring using a photosensitive composition containing a photopolymerizable compound and a photopolymerization initiator (see Patent Documents 1 to 6). ). For example, Patent Document 1 discloses that a wiring pattern is formed on a substrate by a photolithography method including a film-like body forming step, an exposure step, a developing step, and a firing step. In this method, first, in a step of forming a film-like body, a photosensitive composition is applied to a substrate by a printing method or the like and dried to form the film-like body. Then, in the exposure step, the formed film-shaped body is covered with a photomask having a predetermined opening pattern, and then the film-shaped body is exposed through the photomask. Thereby, the exposed part of a film-shaped body is light-hardened. Then, in the developing step, the unexposed portion shielded by the photomask is etched with an alkaline etchant and removed. Then, in the calcination step, the film-like body that becomes a desired development pattern is calcined. According to the method, a high-definition patterned conductive layer can be formed compared to various previous printing methods.
[Prior Art Literature]
[Patent Literature]
[專利文獻1]日本專利第4437603號
[專利文獻2]日本專利第4095163號
[專利文獻3]日本專利申請公開2003-183401號公報
[專利文獻4]日本專利申請公開2015-110745號公報
[專利文獻5]日本專利申請公開2015-184631號公報
[專利文獻6]日本專利第5393402號[Patent Document 1] Japanese Patent No. 4437603
[Patent Document 2] Japanese Patent No. 4095163
[Patent Document 3] Japanese Patent Application Publication No. 2003-183401
[Patent Document 4] Japanese Patent Application Publication No. 2015-110745
[Patent Document 5] Japanese Patent Application Publication No. 2015-184631
[Patent Document 6] Japanese Patent No. 5933402
然而近年來,各種電子機器的小型化或高性能化快速發展,亦對安裝於電子機器中的電子零件要求進一步的小型化或高密度化。伴隨與此,當製造電子零件時,要求導電層的低電阻化與細線化(狹小化)。例如,要求形成包含線寬度(line width)為30 μm以下的細線狀的配線(以下,有時稱作「細實線(fine line)」)的導電層。However, in recent years, the miniaturization or high performance of various electronic devices has been rapidly developed, and further miniaturization or high density of electronic components mounted in electronic devices is required. Along with this, when manufacturing electronic parts, it is required to reduce the resistance of the conductive layer and reduce the thickness (narrowing) of the conductive layer. For example, it is required to form a conductive layer including a thin line-shaped wiring (hereinafter, sometimes referred to as a “fine line”) having a line width of 30 μm or less.
但是,根據本發明者等人的研究,若使用如所述專利文獻中記載般的先前的感光性組成物,則難以穩定地形成細實線。例如,有時於顯影步驟中未能將未曝光部分完全去除,從而相鄰的配線彼此相連並發生短路不良。另外,若為了抑制此種短路不良的發生而將顯影步驟的時間設定得較長,則有時曝光部分變細,且顯影圖案中發生剝離或斷線等。However, according to a study by the present inventors, it is difficult to form a thin solid line stably by using a conventional photosensitive composition as described in the aforementioned patent document. For example, the unexposed portion may not be completely removed in the developing step, so that adjacent wirings are connected to each other and short-circuit failure occurs. In addition, if the time of the development step is set to be long in order to suppress the occurrence of such a short-circuit failure, the exposed portion may become thinner, and peeling or disconnection may occur in the development pattern.
認為所述問題產生的一個原因是顯影裕度短。此處,所謂「顯影裕度」,表示於顯影步驟中,自完全去除未曝光部分的點(斷點(breakpoint,B.P.))至構成顯影圖案的曝光部分中發生剝離或斷線等不良情況的時間的長度。即,若未充分確保顯影裕度,則去除未曝光部分之後,立刻於曝光部分發生變細或消失。因此,尤其是於形成細實線的情況下,難以判明使顯影步驟結束的時機(timing)。因而,於步驟管理方面,要求一種可較長地(例如10秒以上)確保顯影裕度並再現性良好地形成細實線的技術。It is considered that one cause of the problem is a short development margin. Here, the "developing margin" means that in the developing step, from the point (breakpoint (BP)) of the unexposed portion is completely removed to the occurrence of defects such as peeling or disconnection in the exposed portion constituting the developing pattern. The length of time. That is, if the development margin is not sufficiently ensured, the unexposed portion is thinned or disappeared immediately after the unexposed portion is removed. Therefore, especially in the case of forming a thin solid line, it is difficult to discern the timing of ending the development step. Therefore, in terms of step management, there is a need for a technology that can ensure a long development margin (for example, 10 seconds or more) and form a thin solid line with good reproducibility.
本發明是鑒於所述方面而成,其目的在於提供一種顯影裕度長、可穩定地形成細實線的感光性組成物。另外,相關的另一目的是提供一種具備包含所述感光性組成物的乾燥體的導電膜的複合體。另外,相關的又一目的是提供一種具備包含所述感光性組成物的煅燒體的導電層的電子零件、及其製造方法。The present invention has been made in view of the above-mentioned aspects, and an object thereof is to provide a photosensitive composition that has a long development margin and can form a thin solid line stably. Another related object is to provide a composite including a conductive film including a dried body of the photosensitive composition. Another related object is to provide an electronic component including a conductive layer including a fired body of the photosensitive composition, and a method for manufacturing the electronic component.
根據本發明,提供一種用於製作包含線寬為30 μm以下的配線的導電層的感光性組成物。所述感光性組成物包含:導電性粉末、光聚合性化合物、及光聚合起始劑。所述光聚合起始劑至少包含以下兩種成分:(1)2,4,6-三甲基苯甲醯基-二苯基-氧化膦;(2)α-胺基烷基苯酮類,當將所述光聚合起始劑的整體設為100質量%時,所述(1)2,4,6-三甲基苯甲醯基-二苯基-氧化膦佔50質量%以上。According to the present invention, there is provided a photosensitive composition for producing a conductive layer including a wiring having a line width of 30 μm or less. The photosensitive composition includes a conductive powder, a photopolymerizable compound, and a photopolymerization initiator. The photopolymerization initiator includes at least the following two components: (1) 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide; (2) α-amino alkyl phenones When the entire photopolymerization initiator is set to 100% by mass, the (1) 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide accounts for 50% by mass or more.
所述感光性組成物中,作為光聚合起始劑,至少包含所述(1)、(2)兩種成分。藉此,於顯影步驟中可較長地確保顯影裕度的時間,並且可提升曝光部分的細線形成性。其結果,即便是線寬為30 μm以下的細實線,亦可再現性良好地形成。另外,可抑制短路不良、剝離、斷線等不良情況的發生,從而提升良率。The photosensitive composition contains, as a photopolymerization initiator, at least the two components (1) and (2). Thereby, the development margin time can be ensured for a long time in the development step, and the fine line formability of the exposed portion can be improved. As a result, even a thin solid line with a line width of 30 μm or less can be formed with good reproducibility. In addition, it is possible to suppress the occurrence of defects such as short circuit failure, peeling, and disconnection, thereby improving the yield.
此處所揭示的較佳的一態樣中,所述(1)2,4,6-三甲基苯甲醯基-二苯基-氧化膦與所述(2)α-胺基苯乙酮類的質量比率為50:50~90:10。藉此,可更良好地提升細線形成性,並以更高的水準發揮此處所揭示的技術的效果。例如,即便為進一步推進了細實線化的導電層,亦可精度良好地形成。In a preferred aspect disclosed herein, the (1) 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and the (2) α-aminoacetophenone The mass ratio of the class is 50:50 to 90:10. Thereby, the formation of fine lines can be improved better, and the effect of the technology disclosed herein can be exerted at a higher level. For example, the conductive layer can be formed with high accuracy even if the conductive layer is further thinned.
此處所揭示的較佳的一態樣中,所述(1)2,4,6-三甲基苯甲醯基-二苯基-氧化膦與所述(2)α-胺基苯乙酮類的質量比率為50:50~85:15。藉此,可更良好地提升曝光部分的耐蝕刻性,並以更高的水準抑制導電層的剝離。In a preferred aspect disclosed herein, the (1) 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and the (2) α-aminoacetophenone The mass ratio of the class is 50:50 to 85:15. Thereby, it is possible to better improve the etching resistance of the exposed portion, and to suppress the peeling of the conductive layer at a higher level.
此處所揭示的較佳的一態樣中,當將所述感光性組成物的整體設為100質量%時,所述光聚合起始劑的比例為2質量%以下。藉此,發揮更長地確保顯影裕度的時間的效果、以及更良好地提升細線形成性的效果中的至少一個效果。In a preferred aspect disclosed herein, when the entire photosensitive composition is 100% by mass, the proportion of the photopolymerization initiator is 2% by mass or less. Thereby, at least one of the effect of securing the development time for a longer period of time and the effect of improving the fine line formability is exhibited.
此處所揭示的較佳的一態樣中,所述光聚合性化合物包含具有胺基甲酸酯鍵的光聚合性化合物。藉此,可使包含感光性組成物的乾燥體的導電膜成為柔軟性或伸縮性優異者。另外,可更良好地提升曝光部分的耐蝕刻性。其結果,可提升基材與導電層的密接性,並以更高的水準抑制剝離等不良情況的發生。In a preferred aspect disclosed herein, the photopolymerizable compound includes a photopolymerizable compound having a urethane bond. Thereby, the conductive film containing the dried body of the photosensitive composition can be made excellent in flexibility or stretchability. In addition, it is possible to further improve the etching resistance of the exposed portion. As a result, it is possible to improve the adhesion between the substrate and the conductive layer, and to suppress the occurrence of defects such as peeling at a higher level.
此處所揭示的較佳的一態樣中,所述導電性粉末包含銀系粒子。藉此,可實現成本與低電阻的平衡優異的導電層。In a preferred aspect disclosed herein, the conductive powder includes silver-based particles. Thereby, a conductive layer excellent in balance between cost and low resistance can be realized.
此處所揭示的較佳的一態樣中,所述導電性粉末包含核殼粒子,所述核殼粒子具有:包含金屬材料的核部、以及將所述核部的表面的至少一部分被覆且包含陶瓷材料的被覆部。藉此,可更良好地提升曝光部分的耐蝕刻性,並且更良好地提高細線形成性。此外,於製造在陶瓷製的基材(陶瓷基材)上具備導電層的陶瓷電子零件的用途中,可提高陶瓷基材與導電層的一體性,並提升陶瓷電子零件的耐久性。In a preferred aspect disclosed herein, the conductive powder includes core-shell particles, and the core-shell particles include a core portion including a metallic material, and at least a portion of a surface of the core portion is covered and includes Covered part of ceramic material. Thereby, the etching resistance of an exposed part can be improved more, and the fine-line formation property can be improved more. In addition, in the application for manufacturing a ceramic electronic component having a conductive layer on a ceramic substrate (ceramic substrate), the integration of the ceramic substrate and the conductive layer can be improved, and the durability of the ceramic electronic component can be improved.
此處所揭示的較佳的一態樣中,於基於日本工業標準(Japanese Industrial Standards,JIS)JIS Z 8781:2013年的L*a*b*表色系中,所述導電性粉末的明度L*為50以上。藉此,於曝光步驟中,光穩定地到達曝光部分的深部,亦能夠穩定地實現厚膜狀的導電層。In a preferred aspect disclosed herein, in the L * a * b * color system based on Japanese Industrial Standards (JIS) JIS Z 8781: 2013, the brightness L of the conductive powder is * It is 50 or more. Thereby, in the exposure step, light reaches the deep part of the exposed part stably, and a thick film-like conductive layer can also be stably realized.
此處所揭示的較佳的一態樣中,於感光性組成物中進而包含沸點為150℃以上且250℃以下的有機溶劑。藉此,可提升感光性組成物的保存穩定性或導電膜形成時的操作性,並且將印刷後的乾燥溫度抑制得低。In a preferable aspect disclosed herein, the photosensitive composition further contains an organic solvent having a boiling point of 150 ° C or higher and 250 ° C or lower. Thereby, the storage stability of the photosensitive composition and the operability at the time of formation of a conductive film can be improved, and the drying temperature after printing can be suppressed low.
另外,根據本發明,提供一種複合體,其包括:生片(green sheet);以及導電膜,所述導電膜配置於所述生片上,且包含所述感光性組成物的乾燥體。In addition, according to the present invention, there is provided a composite including: a green sheet; and a conductive film, the conductive film being disposed on the green sheet and including a dried body of the photosensitive composition.
另外,根據本發明,提供一種電子零件,其包括導電層,所述導電層包含所述感光性組成物的煅燒體。根據所述感光性組成物,可穩定地實現細實線。因此,可較佳地實現具備小型及/或高密度的導電層的電子零件。In addition, according to the present invention, there is provided an electronic component including a conductive layer including a fired body of the photosensitive composition. According to the photosensitive composition, a fine solid line can be stably realized. Therefore, an electronic component having a small and / or high-density conductive layer can be preferably realized.
另外,根據本發明,提供一種電子零件的製造方法,其包括如下步驟:將所述感光性組成物賦予至基材上,於曝光、顯影後進行煅燒,形成包含所述感光性組成物的煅燒體的導電層。所述感光性組成物的顯影裕度得到較長地確保。因此,根據此種製造方法,可穩定地製造具備小型及/或高密度的導電層的電子零件,從而可提升良率。In addition, according to the present invention, there is provided a method for manufacturing an electronic component, which includes the steps of: applying the photosensitive composition to a substrate, and calcining after exposure and development to form a calcination including the photosensitive composition. Body's conductive layer. The development margin of the photosensitive composition is ensured for a long time. Therefore, according to this manufacturing method, an electronic component having a small and / or high-density conductive layer can be stably manufactured, and the yield can be improved.
以下,對本發明的較佳的實施形態進行說明。再者,於本說明書中特別提及的事項(例如,感光性組成物中所包含的光聚合起始劑)以外的事情且為本發明的實施中所需的事情(例如,感光性組成物的製備方法、導電膜或導電層的形成方法、電子零件的製造方法等)可基於由本說明書所指點的技術內容及該領域中的從業人員的一般的技術常識來理解。本發明可基於本說明書中所揭示的內容與該領域中的技術常識來實施。Hereinafter, preferred embodiments of the present invention will be described. Furthermore, matters other than those specifically mentioned in this specification (for example, a photopolymerization initiator contained in a photosensitive composition) are matters required for the implementation of the present invention (for example, a photosensitive composition (Manufacturing method, forming method of conductive film or conductive layer, manufacturing method of electronic parts, etc.) can be understood based on the technical content pointed out in this specification and the general technical knowledge of practitioners in the field. The present invention can be implemented based on the contents disclosed in this specification and technical common sense in the field.
再者,以下說明中,將使感光性組成物於光聚合性化合物及光聚合起始劑的沸點以下的溫度、具體而言為大概200℃以下,例如100℃以下乾燥而成的膜狀體(乾燥物)稱作「導電膜」。導電膜包含未煅燒(煅燒前)的膜狀體全部。導電膜可為光硬化前的未硬化物,亦可為光硬化後的硬化物。另外,以下說明中,將使感光性組成物於導電性粉末的燒結溫度以上煅燒而成的燒結體(煅燒物)稱作「導電層」。導電層包含配線(線狀體)與配線圖案。
另外,本說明書中表示範圍的「A~B」的表述是指A以上且B以下。In addition, in the following description, a film-like body obtained by drying the photosensitive composition at a temperature below the boiling point of the photopolymerizable compound and the photopolymerization initiator, specifically about 200 ° C or lower, for example, 100 ° C or lower (Dry matter) is called "conductive film". The conductive film includes all the film-like bodies that have not been calcined (before calcination). The conductive film may be an uncured material before light curing or a cured material after light curing. In the following description, a sintered body (fired product) obtained by firing a photosensitive composition at a temperature higher than the sintering temperature of the conductive powder is referred to as a "conductive layer". The conductive layer includes a wiring (linear body) and a wiring pattern.
In addition, the expression "A to B" which shows a range in this specification means A or more and B or less.
《感光性組成物》
此處所揭示的感光性組成物是用於製作包含煅燒後的線寬(線寬度)為30 μm以下的細實線的配線的導電層。例如較佳地用於形成包含線寬(線寬度)為30 μm以下的部分的導電膜。此處所揭示的感光性組成物包含導電性粉末、光聚合性化合物、及光聚合起始劑作為必需的成分。以下,對各構成成分依次進行說明。`` Photosensitive composition ''
The photosensitive composition disclosed here is a conductive layer for producing a wiring including a thin solid line having a line width (line width) of 30 μm or less after firing. For example, it is preferably used to form a conductive film including a portion having a line width (line width) of 30 μm or less. The photosensitive composition disclosed here contains a conductive powder, a photopolymerizable compound, and a photopolymerization initiator as essential components. Hereinafter, each component will be described in order.
<導電性粉末>
導電性粉末是對將感光性組成物煅燒所得的導電層賦予電傳導性的成分。作為導電性粉末,並無特別限定,可自先前公知者中例如根據用途等適當選擇一種或兩種以上來使用。作為導電性粉末的一較佳例,可列舉:金(Au)、銀(Ag)、銅(Cu)、鉑(Pt)、鈀(Pd)、鋁(Al)、鎳(Ni)、釕(Ru)、銠(Rh)、鎢(W)、銥(Ir)、鋨(Os)等金屬單體、以及該些金屬單體的混合物或合金等。作為合金,例如可列舉:銀-鈀(Ag-Pd)、銀-鉑(Ag-Pt)、銀-銅(Ag-Cu)等銀合金。< Conductive powder >
The conductive powder is a component that imparts electrical conductivity to a conductive layer obtained by firing a photosensitive composition. There are no particular limitations on the conductive powder, and one or two or more of them can be appropriately selected from known ones, for example, depending on the application and the like. Preferred examples of the conductive powder include gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), aluminum (Al), nickel (Ni), and ruthenium ( Ru), rhodium (Rh), tungsten (W), iridium (Ir), osmium (Os) and other metal monomers, and mixtures or alloys of these metal monomers. Examples of the alloy include silver alloys such as silver-palladium (Ag-Pd), silver-platinum (Ag-Pt), and silver-copper (Ag-Cu).
於較佳的一態樣中,導電性粉末包含銀系粒子。銀的成本比較低廉,且電導度高。因此,藉由導電性粉末包含銀系粒子,可實現成本與低電阻的平衡優異的導電層。再者,本說明書中,所謂「銀系粒子」,包含全部含有銀成分者。作為銀系粒子的一例,可列舉:將銀的單體、所述銀合金、銀系粒子作為核的核殼粒子等。In a preferred aspect, the conductive powder includes silver-based particles. Silver is relatively inexpensive and highly conductive. Therefore, when the conductive powder contains silver-based particles, a conductive layer excellent in balance between cost and low resistance can be realized. It should be noted that the term "silver-based particles" as used in this specification includes those that all contain a silver component. Examples of the silver-based particles include core-shell particles using a monomer of silver, the silver alloy, and silver-based particles as a core.
於另一較佳的態樣中,導電性粉末包含金屬-陶瓷的核殼粒子。金屬-陶瓷的核殼粒子具有:包含金屬材料的核部;以及被覆部,所述被覆部將核部的表面的至少一部分被覆且包含陶瓷材料。陶瓷材料的化學穩定性或耐熱性、耐久性優異。因此,藉由採用金屬-陶瓷的核殼粒子的形態,可更良好地提升感光性組成物中的導電性粉末的穩定性,另外,可更良好地提高細線形成性。此外,於製造陶瓷電子零件的用途中,可提高陶瓷基材與導電層的一體性,並提升陶瓷電子零件的耐久性。In another preferred aspect, the conductive powder includes metal-ceramic core-shell particles. The metal-ceramic core-shell particle includes a core portion including a metal material, and a coating portion that covers at least a part of a surface of the core portion and includes a ceramic material. Ceramic materials are excellent in chemical stability, heat resistance, and durability. Therefore, by adopting the form of the core-shell particles of the metal-ceramic, the stability of the conductive powder in the photosensitive composition can be further improved, and the fine-line forming property can be further improved. In addition, in applications for manufacturing ceramic electronic parts, the integrity of the ceramic substrate and the conductive layer can be improved, and the durability of the ceramic electronic parts can be improved.
於金屬-陶瓷的核殼粒子中,作為構成核部的金屬材料,例如可列舉所述金屬的單體、以及該些金屬單體的混合物或合金。其中,就所述原因而言,較佳為銀系粒子。換言之,較佳為導電性粉末包含銀-陶瓷的核殼粒子。Among the metal-ceramic core-shell particles, examples of the metal material constituting the core portion include a monomer of the metal and a mixture or alloy of the metal monomers. Among these, silver-based particles are preferred. In other words, the conductive powder preferably contains silver-ceramic core-shell particles.
作為構成被覆部的陶瓷材料,並無特別限定,例如可列舉:氧化鋯(zirconia)、氧化鎂(magnesia)、氧化鋁(alumina)、氧化矽(silica)、氧化鈦(titania)、氧化鈰(ceria)、氧化釔(yttria)、鈦酸鋇等氧化物系材料;堇青石(cordierite)、富鋁紅柱石(mullite)、鎂橄欖石(forsterite)、塊滑石(steatite)、矽鋁氮氧化物(Sialon)、鋯石(zircon)、肥粒鐵(ferrite)等複合氧化物系材料;氮化矽(silicon nitride)、氮化鋁(aluminum nitride)等氮化物系材料;碳化矽(silicon carbide)等碳化物系材料;羥磷灰石(hydroxyapatite)等氫氧化物系材料;等。例如於陶瓷基材上形成導電層來製造陶瓷電子零件的用途中,較佳為與陶瓷基材為相同種類或者親和性優異的種類的陶瓷材料。The ceramic material constituting the coating portion is not particularly limited, and examples thereof include zirconia, magnesia, alumina, silica, titanium oxide, and cerium oxide ( ceria), yttria, barium titanate and other oxide-based materials; cordierite, mullite, forsterite, steasite, silico-aluminum oxynitride (Sialon), zircon (zircon), ferrite, and other composite oxide-based materials; silicon nitride (silicon nitride), aluminum nitride (aluminum nitride) and other nitride-based materials; silicon carbide (silicon carbide) And other carbide-based materials; hydroxyapatite (hydroxyapatite) and other hydroxide-based materials; etc. For example, in the application in which a conductive layer is formed on a ceramic substrate to produce a ceramic electronic component, a ceramic material of the same type or an excellent affinity as the ceramic substrate is preferred.
雖無特別限定,但金屬-陶瓷的核殼粒子中的陶瓷材料的含有比率相對於核部的金屬材料100質量份,例如亦可為0.01質量份~5.0質量份。再者,金屬-陶瓷的核殼粒子可藉由現有公知的方法來製作。例如,可藉由如本案申請人的在先申請案即日本專利第5075222號的段落0025~段落0028中所記載般,使金屬材料與具有目標金屬元素的有機系金屬化合物(例如金屬烷醇鹽或螯合化合物)或氧化物溶膠反應來製作。Although not particularly limited, the content ratio of the ceramic material in the metal-ceramic core-shell particles may be, for example, 0.01 to 5.0 parts by mass relative to 100 parts by mass of the metal material in the core portion. The metal-ceramic core-shell particles can be produced by a conventionally known method. For example, as described in paragraphs 0025 to 0028 of Japanese Patent No. 5075222, which was the applicant's earlier application, the metallic material and the organic metal compound (for example, a metal alkoxide) having a target metal element can be used Or chelating compounds) or oxide sol.
雖無特別限定,但就與曝光步驟中的曝光性能的平衡而言,導電性粉末的D50
粒徑可為大概1.0 μm~5.0 μm。藉由將D50
粒徑設為所述範圍,可提升曝光部分的曝光性能,並更加穩定地形成細實線。再者,本說明書中所謂「D50
粒徑」,是指於基於雷射繞射·散射法的體積基準的粒度分佈中,相當於自粒徑小的一側起累計值50%的粒徑。
就抑制感光性組成物中的凝聚並提升穩定性的觀點而言,導電性粉末的D50
粒徑例如亦可為1.5 μm以上、2.0 μm以上、2.5 μm以上。另外,就提升細線形成性、或者推進導電層的緻密化或低電阻化的觀點而言,導電性粉末的D50
粒徑例如亦可為4.5 μm以下、4.0 μm以下。Although not particularly limited, the D 50 particle diameter of the conductive powder may be about 1.0 μm to 5.0 μm in terms of balance with the exposure performance in the exposure step. By setting the D 50 particle diameter to the above range, the exposure performance of the exposed portion can be improved, and a fine solid line can be formed more stably. The “D 50 particle size” in this specification refers to a particle size distribution corresponding to 50% of the cumulative value from the side with a smaller particle size in the particle size distribution based on the volume basis of the laser diffraction and scattering method. .
From the viewpoint of suppressing aggregation in the photosensitive composition and improving stability, the D 50 particle diameter of the conductive powder may be, for example, 1.5 μm or more, 2.0 μm or more, and 2.5 μm or more. The D 50 particle diameter of the conductive powder may be, for example, 4.5 μm or less and 4.0 μm or less from the viewpoint of improving the formation of fine wires or promoting the densification or reduction of the electrical resistance of the conductive layer.
雖無特別限定,但導電性粉末整體的粒度分佈可具有多峰性。換言之,可包含D50 粒徑不同的第1導電性粉末與第2導電性粉末。藉此,跟第1導電性粉末與第2導電性粉末的D50 粒徑之差小的情況相比,可提升導電層的緻密性或填充性,並且適當地減少電阻。第1導電性粉末與第2導電性粉末的D50 粒徑可相差至少0.5 μm、典型而言為0.5 μm~3.0 μm、例如1.0 μm~2.0 μm左右。於一具體例中,第1導電性粉末的D50 粒徑可處於大概3 μm~5 μm、例如3.5 μm~4.5 μm的範圍,第2導電性粉末的D50 粒徑可處於大概1 μm~3.5 μm、例如1.5 μm~3 μm的範圍。Although not particularly limited, the particle size distribution of the entire conductive powder may have multimodality. In other words, the first conductive powder and the second conductive powder having different D 50 particle diameters may be included. Whereby, as compared with the difference between the diameter 50 of the first conductive powder and the second conductive powder D is small, can improve compactness or filling conductive layer, and suitably reduce the resistance. The D 50 particle size of the first conductive powder and the second conductive powder may differ by at least 0.5 μm, typically 0.5 μm to 3.0 μm, for example, about 1.0 μm to 2.0 μm. In a specific example, the D 50 particle size of the first conductive powder may be in a range of approximately 3 μm to 5 μm, for example, 3.5 μm to 4.5 μm, and the D 50 particle size of the second conductive powder may be in a range of approximately 1 μm to 3.5 μm, for example, in a range of 1.5 μm to 3 μm.
雖無特別限定,但構成導電性粉末的導電性粒子的形狀典型而言為平均縱橫比(長徑/短徑比)為大概1~2的大致球狀,較佳為1~1.5、例如1~1.2的球狀。藉此,可更穩定地實現曝光性能。導電性粉末的平均縱橫比可處於所述範圍。再者,本說明書中所謂「平均縱橫比」,是指利用電子顯微鏡觀察多個導電性粒子,並根據所獲得的觀察圖像而算出的縱橫比的算出平均值。另外,本說明書中所謂「球狀」,表示為整體上大概可看作球體(球)的形態,為可包含橢圓狀、多面體狀、圓盤球狀等的用語。Although not particularly limited, the shape of the conductive particles constituting the conductive powder is typically a substantially spherical shape having an average aspect ratio (longer diameter / shorter diameter ratio) of about 1 to 2, preferably 1 to 1.5, for example 1 Spherical to ~ 1.2. This makes it possible to achieve more stable exposure performance. The average aspect ratio of the conductive powder may be in the range. In addition, the "average aspect ratio" as used in this specification means the calculated average value of the aspect ratio calculated from the observation image obtained by observing a several electroconductive particle with an electron microscope. The term "spherical shape" as used in this specification refers to a form that can be roughly regarded as a sphere (ball) as a whole, and is a term that can include ellipses, polyhedrons, disks, and the like.
雖無特別限定,但導電性粉末整體於基於日本工業標準JIS Z 8781:2013年的L*a*b*表色系中,明度L*可為50以上。藉此,於曝光步驟中,照射光穩定地到達曝光部分的深部,例如亦能夠穩定地實現膜厚為5 μm以上、進而為10 μm以上般的較厚的導電層。就所述觀點而言,導電性粉末的明度L*亦可為大概55以上、例如60以上。明度L*例如可藉由所述導電性粉末的種類或D50 粒徑來調整。再者,明度L*的測定例如可利用依據日本工業標準JIS Z 8722:2009年的分光測色計來進行。Although not particularly limited, the entire conductive powder is in the L * a * b * color system based on Japanese Industrial Standard JIS Z 8781: 2013, and the lightness L * may be 50 or more. Thereby, in the exposure step, the irradiation light stably reaches the deep part of the exposed portion, and for example, a thick conductive layer having a film thickness of 5 μm or more and further 10 μm or more can be stably realized. From this viewpoint, the lightness L * of the conductive powder may be about 55 or more, for example, 60 or more. The lightness L * can be adjusted by, for example, the type of the conductive powder or the D 50 particle size. The measurement of the lightness L * can be performed using, for example, a spectrophotometer based on Japanese Industrial Standard JIS Z 8722: 2009.
再者,導電性粉末亦可於其表面上附著有機表面處理劑。有機表面處理劑可出於例如提升感光性組成物中的導電性粉末的分散性、提高與其他含有成分的親和性、防止構成導電性粉末的金屬的表面氧化、中的至少一個目的而使用。作為有機表面處理劑,例如可列舉:羧酸等脂肪酸、苯并***系化合物等。Furthermore, an organic surface treatment agent may be adhered to the surface of the conductive powder. The organic surface treatment agent can be used, for example, for at least one of the purpose of improving the dispersibility of the conductive powder in the photosensitive composition, improving the affinity with other contained components, preventing the surface oxidation of the metal constituting the conductive powder, and the like. Examples of the organic surface treatment agent include fatty acids such as carboxylic acids, and benzotriazole-based compounds.
雖無特別限定,但導電性粉末於感光性組成物整體中所佔的比例可為大概50質量%以上、典型而言為60質量%~95質量%、例如70質量%~90質量%。藉由滿足所述範圍,可較佳地形成緻密性或電傳導性優異的導電層。另外,可提升感光性組成物的操作性、或將導電膜成形時的作業性。Although not particularly limited, the proportion of the conductive powder in the entire photosensitive composition may be about 50% by mass or more, typically 60% to 95% by mass, for example, 70% to 90% by mass. By satisfying the above range, it is possible to form a conductive layer excellent in denseness or electrical conductivity. In addition, it is possible to improve the operability of the photosensitive composition or the workability when the conductive film is molded.
<光聚合性化合物>
光聚合性化合物是藉由因後述光聚合起始劑的分解而產生的活性種進行聚合並硬化的成分。聚合反應可為加成聚合,亦可為開環聚合。典型而言,光聚合性化合物具有一個以上的不飽和鍵及/或環狀結構。光聚合性化合物包含單體、聚合物、寡聚物。其中,較佳為單體。作為光聚合性化合物,並無特別限定,可自現有公知者中例如根據用途或基材的種類等適當選擇一種或兩種以上來使用。作為光聚合性化合物的一較佳例,可列舉具有一個以上的(甲基)丙烯醯基或乙烯基之類的不飽和鍵的自由基聚合性的單體、或具有環氧基之類的環狀結構的陽離子聚合性的單體。<Photopolymerizable compound>
A photopolymerizable compound is a component which polymerizes and hardens by the active species which generate | occur | produce the decomposition | disassembly of the photopolymerization initiator mentioned later. The polymerization reaction may be addition polymerization or ring-opening polymerization. Typically, a photopolymerizable compound has one or more unsaturated bonds and / or a cyclic structure. The photopolymerizable compound includes a monomer, a polymer, and an oligomer. Among these, a monomer is preferable. The photopolymerizable compound is not particularly limited, and one or two or more kinds can be appropriately selected and used from conventionally known ones, for example, depending on the application, the type of the substrate, and the like. As a preferable example of the photopolymerizable compound, a radically polymerizable monomer having one or more unsaturated bonds such as a (meth) acrylfluorenyl group or a vinyl group, or an epoxy group or the like Cationic polymerizable monomer having a cyclic structure.
於較佳的一態樣中,光聚合性化合物包含具有(甲基)丙烯醯基的(甲基)丙烯酸酯單體。藉由包含(甲基)丙烯酸酯單體,可提升導電層的柔軟性或對基材的追隨性。其結果,能夠以更高的水準抑制剝離或斷線等不良情況的發生。再者,本說明書中,所謂「(甲基)丙烯醯基」,為包含「甲基丙烯醯基」及「丙烯醯基」的用語,所謂「(甲基)丙烯酸酯」,為包含「甲基丙烯酸酯」及「丙烯酸酯」的用語。另外,(甲基)丙烯酸酯單體包含:每一分子具有一個官能基的單官能(甲基)丙烯酸酯;每一分子具有兩個以上的官能基的多官能(甲基)丙烯酸酯;以及該等的改質物。In a preferred aspect, the photopolymerizable compound includes a (meth) acrylic acid ester monomer having a (meth) acrylfluorenyl group. By including a (meth) acrylic acid ester monomer, the flexibility of a conductive layer or the followability to a base material can be improved. As a result, it is possible to suppress the occurrence of defects such as peeling or disconnection at a higher level. In addition, in the present specification, the term "(meth) acrylfluorenyl" includes terms such as "methacrylfluorenyl" and "acrylfluorenyl", and the term "(meth) acrylic acid ester" includes "formyl "Acrylate" and "acrylate". In addition, the (meth) acrylate monomer includes: a monofunctional (meth) acrylate having one functional group per molecule; a polyfunctional (meth) acrylate having two or more functional groups per molecule; and Such modifications.
作為(甲基)丙烯酸酯單體的一較佳例,可列舉:三乙二醇單丙烯酸酯、三乙二醇單甲基丙烯酸酯、四乙二醇單丙烯酸酯、四乙二醇單甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、三季戊四醇七丙烯酸酯、三季戊四醇八丙烯酸酯、四季戊四醇九丙烯酸酯、四季戊四醇十丙烯酸酯等多官能(甲基)丙烯酸酯。其中,就提高光硬化性的觀點而言,較佳為每一分子具有五個以上的(甲基)丙烯醯基的單體。As a preferable example of the (meth) acrylate monomer, triethylene glycol monoacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monoacrylate, and tetraethylene glycol monomethyl Acrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nine acrylate, tetrapentaerythritol ten acrylic Polyfunctional (meth) acrylates such as esters. Among these, a monomer having five or more (meth) acrylfluorenyl groups per molecule is preferred from the viewpoint of improving photocurability.
於較佳的另一態樣中,光聚合性化合物包含具有胺基甲酸酯鍵(-NH-C(=O)-O-)的光聚合性化合物(含胺基甲酸酯鍵的化合物)。藉此,可更良好地提升曝光部分的耐蝕刻性,並且實現柔軟性或伸縮性優異的導電層。因而,可提升基材與導電層的密接性,並以更高的水準抑制剝離或斷線等不良情況的發生。作為含胺基甲酸酯鍵的化合物的一較佳例,可列舉:胺基甲酸酯改質(甲基)丙烯酸酯、或胺基甲酸酯改質環氧等。含胺基甲酸酯鍵的化合物於光聚合性化合物整體中所佔的比例以質量基準計更佳為大概30質量%以上,典型而言為50質量%以上,例如亦可為95質量%以上、實質上為100質量%。In another preferable aspect, the photopolymerizable compound includes a photopolymerizable compound (a urethane bond-containing compound) having a urethane bond (-NH-C (= O) -O-). ). Thereby, it is possible to better improve the etching resistance of the exposed portion, and to realize a conductive layer excellent in flexibility or stretchability. Therefore, it is possible to improve the adhesion between the substrate and the conductive layer, and to suppress the occurrence of defects such as peeling or disconnection at a higher level. As a preferable example of a urethane bond containing compound, a urethane modified (meth) acrylate, a urethane modified epoxy, etc. are mentioned. The proportion of the urethane bond-containing compound in the entire photopolymerizable compound is more preferably about 30% by mass or more, typically 50% by mass or more, and for example, 95% by mass or more It is substantially 100% by mass.
雖無特別限定,但光聚合性化合物的重量平均分子量可為大概100~10000、典型而言為200~5000、例如300~2000。再者,本說明書中所謂「重量平均分子量」,是指藉由凝膠層析法(凝膠滲透層析法(Gel Permeation Chromatography:GPC))測定,並使用標準聚苯乙烯校準曲線換算而成的重量基準的平均分子量。於光聚合性化合物為單體的情況下,與分子量為相同含義。Although not particularly limited, the weight-average molecular weight of the photopolymerizable compound may be approximately 100 to 10,000, typically 200 to 5,000, and for example 300 to 2,000. The "weight-average molecular weight" as used in this specification refers to a measurement by gel chromatography (Gel Permeation Chromatography (GPC)) and conversion using a standard polystyrene calibration curve Weight average molecular weight. When a photopolymerizable compound is a monomer, it has the same meaning as molecular weight.
雖無特別限定,但光聚合性化合物於感光性組成物整體中所佔的比例可為大概0.1質量%~20質量%、典型而言為0.5質量%~10質量%、例如2質量%~8質量%、進而為3質量%~6質量%。藉由滿足所述範圍,可充分發揮感光性組成物的光硬化性,並以更高的水準穩定地形成導電層。Although not particularly limited, the proportion of the photopolymerizable compound in the entire photosensitive composition may be approximately 0.1% to 20% by mass, typically 0.5% to 10% by mass, for example, 2% to 8% by mass The mass% is further 3 mass% to 6 mass%. By satisfying the above range, the photocurability of the photosensitive composition can be fully exhibited, and the conductive layer can be stably formed at a higher level.
<光聚合起始劑>
光聚合起始劑是藉由紫外線等的光能的照射而分解並產生自由基或陽離子等活性種,從而使光聚合性化合物的聚合反應開始的成分。於此處所揭示的感光性組成物中,光聚合起始劑必須至少包含以下兩種成分:(1)2,4,6-三甲基苯甲醯基-二苯基-氧化膦;(2)α-胺基烷基苯酮類。<Photopolymerization initiator>
A photopolymerization initiator is a component which decomposes by irradiation of light energy, such as an ultraviolet-ray, and generates active species, such as a radical and a cation, and starts a polymerization reaction of a photopolymerizable compound. In the photosensitive composition disclosed herein, the photopolymerization initiator must contain at least the following two components: (1) 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide; (2) ) Α-Aminoalkylphenones.
典型而言,所述(1)、(2)的光聚合起始劑的吸收波長互不相同。因此,藉由併用該些光聚合起始劑,與單獨使用一種光聚合起始劑的情況相比,吸收波長區域擴展,且能夠以高效率產生活性種。另外,藉由所述(1)、(2)的光聚合起始劑的合併效果,於顯影步驟中,例如至斷點(B.P.)為止的時間如先前般,可較長地確保顯影裕度的時間。以上效果相互結合,於此處所揭示的技術中,可提升細線形成性,且即便是線寬為30 μm以下的細實線,亦可再現性良好地形成。以下,對(1)、(2)的光聚合起始劑進行說明。Typically, the absorption wavelengths of the photopolymerization initiators (1) and (2) are different from each other. Therefore, by using these photopolymerization initiators in combination, the absorption wavelength region is expanded compared to the case where a single photopolymerization initiator is used alone, and active species can be generated with high efficiency. In addition, due to the combined effect of the photopolymerization initiators of (1) and (2), in the development step, for example, the time to the break point (BP) is as before, and the development margin can be ensured for a long time. time. The above effects are combined with each other. In the technology disclosed herein, the formation of fine lines can be improved, and even a thin solid line with a line width of 30 μm or less can be formed with good reproducibility. Hereinafter, the photopolymerization initiators (1) and (2) will be described.
(1)2,4,6-三甲基苯甲醯基-二苯基-氧化膦為單醯基氧化膦(monoacylphosphine oxide,MAPO)。作為市售品,可列舉:達羅卡(DAROCUR)(商標)TPO、豔佳固(IRGACURE)(商標)TPO(均為巴斯夫日本(BASF JAPAN)股份有限公司製造)等。醯基氧化膦系的光聚合起始劑與光聚合性化合物或有機系分散介質的相容性優異。因此,對於提升感光性組成物的保存穩定性而言是有效的。(1) 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide is monoacylphosphine oxide (MAPO). Examples of commercially available products include DAROCUR (trademark) TPO, IRGACURE (trademark) TPO (all manufactured by BASF Japan). The fluorenyl phosphine oxide-based photopolymerization initiator is excellent in compatibility with a photopolymerizable compound or an organic dispersion medium. Therefore, it is effective for improving the storage stability of a photosensitive composition.
再者,作為被分類為與所述(1)相同的醯基氧化膦系的光聚合起始劑,可列舉:雙醯基氧化膦(bisacylphosphine oxide,BAPO)、例如雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦。但是,如後述試驗例所示般,於代替所述(1)而使用雙醯基氧化膦的情況下,並未發揮如上所述的此處所揭示的技術的效果。即,可以說,併用所述(1)、(2)的光聚合起始劑這一情形存在特異性。Furthermore, as the photopolymerization initiator classified into the same fluorenylphosphine oxide based on (1), bisacylphosphine oxide (BAPO), for example, bis (2,4,6) -Trimethylbenzyl) -phenylphosphine oxide. However, as shown in a test example described later, when the bisfluorenylphosphine oxide is used instead of the above-mentioned (1), the effects of the technique disclosed herein as described above are not exerted. That is, it can be said that there is specificity when the photopolymerization initiators (1) and (2) are used in combination.
於此處所揭示的技術中,所述(1)成為光聚合起始劑的主體。換言之,當將光聚合起始劑的整體設為100質量%時,所述(1)的比例佔50質量%以上。藉此,可提升細線形成性,並較佳地形成細實線。就所述觀點而言,所述(1)的比例亦可為例如75質量%以上、較佳為80質量%以上、更佳為85質量%以上。另外,就更良好地發揮與所述(2)的合併效果的觀點、或者提升基材與導電層的密接性的觀點而言,所述(1)的比例亦可為大概90質量%以下、較佳為85質量%以下。In the technology disclosed herein, (1) becomes the main body of the photopolymerization initiator. In other words, when the entire photopolymerization initiator is set to 100% by mass, the proportion of (1) described above accounts for 50% by mass or more. Thereby, the fine line forming property can be improved, and a fine solid line can be formed better. From the viewpoint, the ratio (1) may be, for example, 75% by mass or more, preferably 80% by mass or more, and more preferably 85% by mass or more. In addition, from the viewpoint of better exhibiting the combined effect with the above (2), or the viewpoint of improving the adhesion between the substrate and the conductive layer, the ratio of the (1) may be about 90% by mass or less, It is preferably 85% by mass or less.
作為(2)α-胺基烷基苯酮類,只要為具有α-胺基烷基苯酮骨架的化合物即可,可自現有公知者中適當選擇一種或兩種以上來使用。α-胺基烷基苯酮骨架可作為例如具有分子內裂解型的光聚合起始能力的官能基來把握。烷基部位可為直鏈狀亦可為分支狀。烷基部位亦可具有取代基。作為α-胺基烷基苯酮類的一較佳例,可列舉分子量為大概1000以下、典型而言為200~500、例如250~400的化合物。作為另一較佳例,可列舉具有α-胺基苯乙酮骨架的化合物。作為具有α-胺基苯乙酮骨架的化合物的一較佳例,可列舉具有下述(A)的結構部分的化合物。(2) The α-aminoalkyl phenones may be compounds having an α-amino alkyl phenone skeleton, and one or two or more of them may be appropriately selected from conventionally known ones and used. The α-aminoalkylbenzophenone skeleton can be grasped as a functional group having an intramolecular cleavage-type photopolymerization initiation ability, for example. The alkyl moiety may be linear or branched. The alkyl moiety may have a substituent. A preferable example of the α-aminoalkyl phenones includes compounds having a molecular weight of about 1,000 or less, typically 200 to 500, for example, 250 to 400. As another preferred example, a compound having an α-aminoacetophenone skeleton may be mentioned. As a preferable example of the compound which has an α-aminoacetophenone skeleton, the compound which has a structural part of the following (A) is mentioned.
[化1]
[Chemical 1]
所述(A)中,R1 、R2 分別獨立地選自碳原子數1~18的烴基。R1 、R2 可相同,亦可不同。R1 例如為碳原子數1~18的烷基。R1 的碳原子數較佳為1~8,典型而言為1~4,例如1、2或3。R2 例如為碳原子數1~18的烷基、芳基或芳基烷基。R2 的碳原子數較佳為1~8。另外,R3 、R4 分別獨立地選自氫原子、或碳原子數1~18的烴基。R3 、R4 可相同,亦可不同。R3 、R4 例如分別獨立地為碳原子數1~18的烷基、芳基、芳基烷基、或者R3 與R4 鍵結而成的環狀烷基醚基。R3 與R4 的碳原子數的合計較佳為1~8,典型而言為1~6,例如2~4。In the (A), R 1 and R 2 are each independently selected from a hydrocarbon group having 1 to 18 carbon atoms. R 1 and R 2 may be the same or different. R 1 is, for example, an alkyl group having 1 to 18 carbon atoms. The number of carbon atoms of R 1 is preferably 1 to 8, typically 1 to 4, such as 1, 2 or 3. R 2 is, for example, an alkyl group, an aryl group, or an arylalkyl group having 1 to 18 carbon atoms. The number of carbon atoms in R 2 is preferably 1 to 8. R 3 and R 4 are each independently selected from a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. R 3 and R 4 may be the same or different. R 3 and R 4 are each independently an alkyl group having 1 to 18 carbon atoms, an aryl group, an arylalkyl group, or a cyclic alkyl ether group in which R 3 and R 4 are bonded. The total number of carbon atoms of R 3 and R 4 is preferably 1 to 8, typically 1 to 6, such as 2 to 4.
作為所述(2)的具體例,可列舉:2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)丁酮-1、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮、N,N-二甲基胺基苯乙酮等。作為市售品,可列舉:豔佳固(IRGACURE)(商標)369、豔佳固(IRGACURE)(商標)379、豔佳固(IRGACURE)(商標)907(均為巴斯夫日本(BASF JAPAN)股份有限公司製造)等。Specific examples of the above (2) include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2- (dimethylamino) ) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methyl Thio) phenyl] -2-morpholinopropane-1-one, N, N-dimethylaminoacetophenone, and the like. Examples of commercially available products include: IRGACURE (trademark) 369, IRGACURE (trademark) 379, IRGACURE (trademark) 907 (all BASF JAPAN shares) Co., Ltd.) and so on.
雖無特別限定,但就以高水準發揮此處所揭示的技術的效果的觀點而言,當將光聚合起始劑的整體設為100質量%時,所述(2)的比例亦可為大概10質量%以上。另外,就提升基材與導電層的密接性的觀點而言,所述(2)的比例亦可為15質量%以上。另外,就更良好地提升細線形成性的觀點而言,所述(2)的比例亦可為例如25質量%以下、較佳為20質量%以下、更佳為15質量%以下。Although not particularly limited, from the viewpoint of exerting the effects of the technology disclosed herein at a high level, when the entire photopolymerization initiator is set to 100% by mass, the ratio of (2) may be approximately 10% by mass or more. In addition, from the viewpoint of improving the adhesion between the substrate and the conductive layer, the ratio (2) may be 15% by mass or more. In addition, from the viewpoint of further improving the fine line formability, the ratio (2) may be, for example, 25% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.
雖無特別限定,但就以高水準發揮此處所揭示的技術的效果的觀點而言,當將光聚合起始劑的整體設為100質量%時,所述(1)、(2)的合計比例亦可為大概80質量%以上、較佳為90質量%以上、更佳為95質量%以上,例如100質量%。Although not particularly limited, from the viewpoint of exerting the effects of the technology disclosed herein at a high level, when the entire photopolymerization initiator is set to 100% by mass, the total of (1) and (2) described above The ratio may also be approximately 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more, such as 100% by mass.
雖無特別限定,但所述(1)、(2)的質量比率可為大概50:50~95:5。藉此,可提升細線形成性,並以更高的水準發揮此處所揭示的技術的效果。例如,即便為進一步推進了細實線化的導電層,亦可精度良好地形成。另外,就更良好地提升曝光部分的耐蝕刻性並抑制導電層的剝離的觀點而言,所述(1)、(2)的質量比率可較佳為50:50~90:10、更佳為50:50~85:15。Although not particularly limited, the mass ratios of (1) and (2) may be approximately 50:50 to 95: 5. Thereby, the formation of fine lines can be improved, and the effects of the technology disclosed herein can be exerted at a higher level. For example, the conductive layer can be formed with high accuracy even if the conductive layer is further thinned. In addition, from the viewpoint of better improving the etching resistance of the exposed portion and suppressing the peeling of the conductive layer, the mass ratio of (1) and (2) may be preferably 50:50 to 90:10, more preferably It is 50:50 to 85:15.
雖無特別限定,但光聚合起始劑於感光性組成物整體中所佔的比例可為大概0.01質量%以上、典型而言為0.04質量%以上、例如0.05質量%以上。藉此,可充分發揮感光性組成物的光硬化性,並穩定地形成導電層。另外,光聚合起始劑於感光性組成物整體中所佔的比例可為大概0.5質量%以下、典型而言為0.3質量%以下、較佳為0.2質量%以下、例如0.1質量%以下。藉此,於顯影步驟中,能夠以更高的水準使相反的耐蝕刻性與剝離性平衡。因此,可更長地確保顯影裕度的時間,且更良好地提高細線形成性。Although not particularly limited, the proportion of the photopolymerization initiator in the entire photosensitive composition may be approximately 0.01% by mass or more, typically 0.04% by mass or more, for example, 0.05% by mass or more. Thereby, the photocurability of the photosensitive composition can be fully utilized, and the conductive layer can be formed stably. The proportion of the photopolymerization initiator in the entire photosensitive composition may be about 0.5% by mass or less, typically 0.3% by mass or less, preferably 0.2% by mass or less, for example, 0.1% by mass or less. Thereby, in the developing step, the opposite etching resistance and peelability can be balanced at a higher level. Therefore, it is possible to secure the development margin for a longer period of time, and to improve the fine line formability better.
雖無特別限定,但光聚合起始劑的含有比率相對於導電性粉末100質量份,亦可為大概0.01質量份~1質量份、典型而言為0.02質量份~0.2質量份、例如0.05質量份~0.1質量份。另外,光聚合起始劑的含有比率相對於光聚合性化合物100質量份,亦可為大概0.1質量份~25質量份、典型而言為0.2質量份~5質量份、例如0.5質量份~3質量份、進而為1質量份~2質量份。Although not particularly limited, the content ratio of the photopolymerization initiator relative to 100 parts by mass of the conductive powder may be about 0.01 to 1 part by mass, typically 0.02 to 0.2 part by mass, for example, 0.05 part by mass Parts to 0.1 parts by mass. The content ratio of the photopolymerization initiator may be about 0.1 to 25 parts by mass, typically 0.2 to 5 parts by mass, for example, 0.5 to 3 parts by mass, based on 100 parts by mass of the photopolymerizable compound. 1 part by mass to 2 parts by mass.
<有機黏合劑>
感光性組成物除了所述必需的成分之外,亦可含有有機黏合劑。有機黏合劑是提高基材與未硬化的導電膜的接著性的成分。作為有機黏合劑,可自現有公知者中例如根據基材的種類或光聚合性化合物、光聚合起始劑的種類等適當選擇一種或兩種以上來使用。作為有機黏合劑,較佳為於顯影步驟中能夠利用蝕刻液容易地去除者。例如,於顯影步驟中使用鹼性的蝕刻液的情況下,較佳為具有羥基(-OH)、羧基(-C(=O)OH)、酯鍵(-C(=O)O-)、磺基(-SO3
H)等顯示酸性的結構部分的化合物。藉此,未曝光部分不易殘存殘渣,例如可穩定地確保細實線之間的空間。< Organic Adhesives >
The photosensitive composition may contain an organic binder in addition to the essential components. An organic binder is a component which improves the adhesiveness of a base material and an unhardened conductive film. As the organic binder, one or two or more kinds can be appropriately selected and used from conventionally known ones according to, for example, the type of the substrate, the type of the photopolymerizable compound, the type of the photopolymerization initiator, and the like. The organic binder is preferably one that can be easily removed with an etchant in the developing step. For example, when an alkaline etching solution is used in the developing step, it is preferable to have a hydroxyl group (-OH), a carboxyl group (-C (= O) OH), an ester bond (-C (= O) O-), A compound having an acidic structural moiety such as sulfo (-SO 3 H). Thereby, residues are not easily left in the unexposed portion, and for example, the space between the thin solid lines can be stably secured.
作為有機黏合劑的一較佳例,可列舉:甲基纖維素、乙基纖維素、羧甲基纖維素、羥甲基纖維素等纖維素系高分子,丙烯酸樹脂,酚樹脂,醇酸樹脂,聚乙烯醇,聚乙烯丁醛(polyvinyl butyral)等。其中,就於顯影步驟中容易去除的觀點而言,較佳為親水性的有機黏合劑,例如纖維素系高分子或丙烯酸樹脂等。A preferable example of the organic binder includes cellulose-based polymers such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and hydroxymethyl cellulose, acrylic resins, phenol resins, and alkyd resins. , Polyvinyl alcohol, polyvinyl butyral, etc. Among these, from the viewpoint of easy removal in the developing step, a hydrophilic organic binder such as a cellulose polymer or an acrylic resin is preferred.
於感光性組成物中包含有機黏合劑的情況下,並無特別限定,有機黏合劑於感光性組成物整體中所佔的比例亦可為大概0.1質量%~20質量%、典型而言為0.5質量%~10質量%、例如1質量%~5質量%。另外,雖無特別限定,但光聚合性化合物與有機黏合劑的含有比例可大概相等(兩者的含有比例之差為大概1質量%以下、例如0.5質量%以下)。藉此,於顯影步驟中,能夠以更高的水準使相反的耐蝕刻性(密接性)與剝離性平衡。When an organic binder is contained in the photosensitive composition, it is not particularly limited, and the proportion of the organic binder in the entire photosensitive composition may also be about 0.1% to 20% by mass, typically 0.5. Mass% to 10% by mass, for example, 1% to 5% by mass. In addition, although not particularly limited, the content ratio of the photopolymerizable compound and the organic binder may be approximately equal (the difference between the content ratios of the two is approximately 1% by mass or less, for example, 0.5% by mass or less). Accordingly, in the developing step, the opposite etching resistance (adhesiveness) and peelability can be balanced at a higher level.
<有機系分散介質>
感光性組成物除了所述必需的成分之外,亦可含有使該等分散的有機系分散介質。有機系分散介質是對感光性組成物賦予適度的黏性或流動性,並提升感光性組成物的操作性、或者提升將導電膜成形時的作業性的成分。作為有機系分散介質,可自現有公知者中例如根據光聚合性化合物或光聚合起始劑的種類等適當選擇一種或兩種以上來使用。< Organic Dispersion Medium >
The photosensitive composition may contain, in addition to the above-mentioned essential components, an organic dispersion medium for dispersing these. An organic dispersion medium is a component which imparts moderate viscosity or fluidity to a photosensitive composition, improves the handleability of a photosensitive composition, or improves the workability at the time of shaping a conductive film. As the organic dispersion medium, one or two or more kinds can be appropriately selected and used from conventionally known ones, for example, depending on the type of the photopolymerizable compound or the photopolymerization initiator.
作為有機系分散介質的一較佳例,可列舉:萜品醇(terpineol)、二氫萜品醇(薄荷腦(menthanol))、酯醇(texanol)、3-甲基-3-甲氧基丁醇、苄醇等醇系溶劑;乙二醇、丙二醇、二乙二醇等二醇系溶劑;二丙二醇甲醚、甲基溶纖劑(乙二醇單甲醚)、溶纖劑(乙二醇單***)、丁基卡必醇(二乙二醇單丁醚)等醚系溶劑;二乙二醇單丁醚乙酸酯、二丙二醇甲醚乙酸酯、丁基乙二醇乙酸酯(butyl glycol acetate)、丁基二甘醇乙酸酯(butyldiglycol acetate)、丁基溶纖劑乙酸酯、丁基卡必醇乙酸酯(二乙二醇單丁醚乙酸酯)、乙酸異冰片酯等酯系溶劑;甲苯、二甲苯、石油腦(naphtha)、石油系烴等烴系溶劑;礦油精(mineral spirit);等有機溶劑。A preferred example of the organic dispersion medium includes terpineol, dihydroterpineol (menthanol), texanol, and 3-methyl-3-methoxy. Alcohol solvents such as butanol and benzyl alcohol; glycol solvents such as ethylene glycol, propylene glycol, and diethylene glycol; dipropylene glycol methyl ether, methyl cellosolve (ethylene glycol monomethyl ether), and cellosolve (B Ether solvents such as glycol monoethyl ether), butylcarbitol (diethylene glycol monobutyl ether); diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, butyl ethylene glycol (Butyl glycol acetate), butyldiglycol acetate, butyl cellosolve acetate, butylcarbitol acetate (diethylene glycol monobutyl ether acetate), acetic acid Esters such as isobornyl esters; hydrocarbon solvents such as toluene, xylene, naphtha, petroleum hydrocarbons; mineral spirit; and other organic solvents.
其中,就提升感光性組成物的保存穩定性或導電膜形成時的操作性的觀點而言,較佳為沸點為150℃以上的有機溶劑、進而為170℃以上的有機溶劑。另外,作為另一較佳例,就將印刷導電膜後的乾燥溫度抑制得低的觀點而言,較佳為沸點為250℃以下的有機溶劑、進而為沸點為220℃以下的有機溶劑。藉此,可提升生產性,並且減少生產成本。Among them, an organic solvent having a boiling point of 150 ° C. or higher, and further an organic solvent of 170 ° C. or higher is preferred from the viewpoint of improving the storage stability of the photosensitive composition or the operability during formation of the conductive film. In addition, as another preferable example, an organic solvent having a boiling point of 250 ° C. or lower, and an organic solvent having a boiling point of 220 ° C. or lower are preferred from the viewpoint of suppressing the drying temperature after printing the conductive film to a low level. This can improve productivity and reduce production costs.
另外,例如於陶瓷基材上形成導電層來製造陶瓷電子零件的用途中,較佳為對陶瓷生片(ceramic green sheet)的滲透性低的有機溶劑。作為對陶瓷生片的滲透性低的有機溶劑,例如可列舉:如環己基或第三丁基等般具有立體大體積結構的有機溶劑、或分子量比較大的有機溶劑。進而,例如亦較佳為將如上所述的對陶瓷生片的滲透性低的有機溶劑、與可較佳地溶解感光性組成物中所含有的成分(例如光聚合性物質及/或光聚合起始劑)的有機溶劑以任意比例混合,並用作有機系分散介質。In addition, for example, in the application for forming a ceramic electronic component by forming a conductive layer on a ceramic substrate, an organic solvent having low permeability to a ceramic green sheet is preferred. Examples of the organic solvent having low permeability to the ceramic green sheet include an organic solvent having a three-dimensional bulk structure such as a cyclohexyl group or a third butyl group, or an organic solvent having a relatively large molecular weight. Furthermore, for example, it is also preferable that the organic solvent having low permeability to the ceramic green sheet as described above and the component (for example, a photopolymerizable substance and / or photopolymerization) contained in the photosensitive composition can be better dissolved. The organic solvent of the initiator) is mixed in an arbitrary ratio and used as an organic dispersion medium.
作為具有如上所述的性狀(沸點及對陶瓷生片的滲透性)的市售的有機溶劑,例如可列舉:達瓦諾(Dowanol)DPM(商標)(沸點:190℃,陶氏化學公司(Dow Chemical Company)製造)、達瓦諾(Dowanol)DPMA(商標)(沸點:209℃,陶氏化學公司(Dow Chemical Company)製造)、薄荷腦(沸點:207℃)、薄荷腦P(沸點:216℃)、艾索帕(Isopar)H(沸點:176℃,關東燃料股份有限公司製造)、SW-1800(沸點:198℃,丸善石油股份有限公司製造)等。Examples of commercially available organic solvents having such properties (boiling point and permeability to ceramic green sheets) include Dowanol DPM (trademark) (boiling point: 190 ° C, Dow Chemical Co., Ltd. ( (Manufactured by Dow Chemical Company), Dowanol DPMA (trademark) (boiling point: 209 ° C, manufactured by Dow Chemical Company), menthol (boiling point: 207 ° C), menthol P (boiling point: 216 ° C), Isopar H (boiling point: 176 ° C, manufactured by Kanto Fuel Co., Ltd.), SW-1800 (boiling point: 198 ° C, manufactured by Maruzan Petroleum Co., Ltd.), etc.
於感光性組成物中包含有機系分散介質的情況下,並無特別限定,但有機系分散介質於感光性組成物整體中所佔的比例亦可為大概1質量%~50質量%、典型而言為3質量%~30質量%、例如5質量%~20質量%。When an organic dispersion medium is contained in the photosensitive composition, it is not particularly limited, but the proportion of the organic dispersion medium in the entire photosensitive composition may also be approximately 1% to 50% by mass. It is 3 to 30% by mass, for example, 5 to 20% by mass.
<其他成分>
感光性組成物只要不明顯損害此處所揭示的技術的效果,則除了所述成分以外,進而視需要可含有各種添加成分。作為添加成分,可自現有公知者中適當選擇一種或兩種以上來使用。作為添加成分的一例,例如可列舉:無機填料、光增感劑、聚合抑制劑、自由基捕捉劑、抗氧化劑、紫外線吸收劑、塑化劑、界面活性劑、調平劑、增稠劑、分散劑、消泡劑、防凝膠化劑、穩定劑、防腐劑、顏料等。雖無特別限定,但添加成分於感光性組成物整體中所佔的比例可設為大概5質量%以下、例如3質量%以下。< Other ingredients >
As long as the photosensitive composition does not significantly impair the effect of the technology disclosed herein, it may contain various additional components in addition to the components described above, as necessary. As the additive component, one kind or two or more kinds can be appropriately selected from conventionally known ones and used. Examples of the additive component include inorganic fillers, photosensitizers, polymerization inhibitors, radical scavengers, antioxidants, ultraviolet absorbers, plasticizers, surfactants, leveling agents, thickeners, Dispersant, defoamer, anti-gelling agent, stabilizer, preservative, pigment, etc. Although not particularly limited, the proportion of the additive component in the entire photosensitive composition may be about 5 mass% or less, for example, 3 mass% or less.
如上所述,此處所揭示的感光性組成物中,作為光聚合起始劑,同時含有所述(1)、(2)兩種成分。而且,當將光聚合起始劑的整體設為100質量%時,所述(1)的比例佔50質量%以上。藉此,於顯影步驟中,能夠以更高的水準使耐蝕刻性(密接性)與剝離性平衡。即,可提高曝光部分的耐蝕刻性,且可較長地確保顯影裕度的時間。其結果,可於顯影步驟之後使曝光部分適當留於基材上,且可抑制剝離或斷線等不良情況的發生。另外,可提升導電膜的剝離性,適當去除未曝光部分,並且抑制曝光部分變得過粗。換言之,可提升曝光部分的細線形成性。其結果,可於相鄰的配線間穩定地確保空間,且可抑制短路不良的發生。此外,根據此處所揭示的技術,該些效果相互結合,即便是線寬為30 μm以下的細實線,亦可再現性良好地形成。另外,可提升良率。As described above, the photosensitive composition disclosed herein contains both the components (1) and (2) as a photopolymerization initiator. When the entire photopolymerization initiator is 100% by mass, the ratio of (1) is 50% by mass or more. Thereby, the etching resistance (adhesion) and the peelability can be balanced at a higher level in the developing step. That is, it is possible to improve the etching resistance of the exposed portion and to secure a long development time. As a result, the exposed portion can be appropriately left on the substrate after the development step, and occurrence of defects such as peeling or disconnection can be suppressed. In addition, the peelability of the conductive film can be improved, the unexposed portions can be appropriately removed, and the exposed portions can be prevented from becoming too thick. In other words, the fine line formability of the exposed portion can be improved. As a result, it is possible to stably secure a space between adjacent wirings, and it is possible to suppress occurrence of short-circuit failure. In addition, according to the technology disclosed here, these effects are combined with each other, and even a thin solid line with a line width of 30 μm or less can be formed with good reproducibility. In addition, yield can be improved.
<感光性組成物的用途>
根據此處所揭示的感光性組成物,能夠以高解析度穩定地形成線寬度較30 μm更微細的細實線。另外,可減少導電層的剝離或斷線等,並且抑制短路不良的發生。因此,此處所揭示的感光性組成物例如可較佳地用於電感(inductance)零件或電容器零件、多層電路基板等各種電子零件中的導電層的形成。< Application of photosensitive composition >
According to the photosensitive composition disclosed herein, it is possible to stably form a fine solid line with a finer line width than 30 μm at a high resolution. In addition, peeling or disconnection of the conductive layer can be reduced, and occurrence of short-circuit failure can be suppressed. Therefore, the photosensitive composition disclosed herein can be preferably used, for example, to form conductive layers in various electronic components such as inductance components, capacitor components, and multilayer circuit boards.
電子零件可為表面安裝類型或通孔(through hole)安裝類型等各種安裝形態的電子零件。電子零件可為積層型,或者可為繞組型,亦可為薄膜型。作為電感零件的典型例,可列舉:高頻濾波器、共模濾波器(common mode filter)、高頻電路用電感器(線圈)、普通電路用電感器(線圈)、高頻濾波器、抗流線圈(choking coil)、變壓器(transformer)等。The electronic parts can be electronic parts of various mounting forms such as a surface mounting type or a through hole mounting type. The electronic component may be a laminated type, or may be a winding type, or may be a thin film type. Typical examples of inductive components include high-frequency filters, common mode filters, inductors (coils) for high-frequency circuits, inductors (coils) for general circuits, high-frequency filters, and Choking coil, transformer, etc.
另外,導電性粉末包含金屬-陶瓷的核殼粒子的感光性組成物可較佳地用於陶瓷電子零件的導電層的形成。再者,本說明書中,所謂「陶瓷電子零件」,包含具有非晶質的陶瓷基材(玻璃陶瓷基材)或結晶質(即,非玻璃)的陶瓷基材的電子零件全部。作為典型例,可列舉:具有陶瓷基材的高頻濾波器、陶瓷電感器(線圈)、陶瓷電容器、低溫煅燒積層陶瓷基材(低溫共燒陶瓷基材(Low Temperature Co-fired Ceramics Substrate:LTCC基材))、高溫煅燒積層陶瓷基材(高溫共燒陶瓷基材(High Temperature Co-fired Ceramics Substrate:HTCC基材))等。In addition, the photosensitive composition in which the conductive powder contains metal-ceramic core-shell particles can be preferably used for forming a conductive layer of a ceramic electronic component. In addition, in this specification, a "ceramic electronic component" includes all the electronic components which have an amorphous ceramic substrate (glass ceramic substrate) or a crystalline (that is, non-glass) ceramic substrate. Typical examples include high-frequency filters with ceramic substrates, ceramic inductors (coils), ceramic capacitors, low-temperature calcined laminated ceramic substrates (Low Temperature Co-fired Ceramics Substrate: LTCC) Substrate)), high-temperature calcined laminated ceramic substrate (High Temperature Co-fired Ceramics Substrate: HTCC substrate), etc.
圖1是示意性地表示積層晶片電感器1的結構的剖面圖。再者,圖1中的尺寸關係(長度、寬度、厚度等)未必反映實際的尺寸關係。另外,圖式中的符號X、符號Y分別表示左右方向、上下方向。但是,其僅為說明上方便的方向。FIG. 1 is a cross-sectional view schematically showing the structure of a multilayer chip inductor 1. Moreover, the dimensional relationship (length, width, thickness, etc.) in FIG. 1 does not necessarily reflect the actual dimensional relationship. The symbols X and Y in the drawings indicate the left-right direction and the up-down direction, respectively. However, this is only a convenient direction for explanation.
積層晶片電感器1包括:本體部10;以及設置於本體部10的左右方向X的兩側面部分的外部電極20。積層晶片電感器1例如為1608形狀(1.6 mm×0.8 mm)、2520形狀(2.5 mm×2.0 mm)等尺寸。The multilayer chip inductor 1 includes a main body portion 10 and external electrodes 20 provided on both side portions of the main body portion 10 in the left-right direction X. The multilayer chip inductor 1 has dimensions such as a 1608 shape (1.6 mm × 0.8 mm) and a 2520 shape (2.5 mm × 2.0 mm).
本體部10具有將陶瓷層(電介質層)12與內部電極層14一體化而成的結構。陶瓷層12例如作為可構成導電性粉末的被覆部者而由如上所述的陶瓷材料構成。於上下方向Y上,於陶瓷層12之間配置有內部電極層14。內部電極層14是使用所述感光性組成物而形成。隔著陶瓷層12而於上下方向Y上相鄰的內部電極層14通過設置於陶瓷層12中的通路(via)16而被導通。藉此,內部電極層14構成為三維的旋渦形狀(螺旋狀)。內部電極層14的兩端分別與外部電極20連接。The main body portion 10 has a structure in which a ceramic layer (dielectric layer) 12 and an internal electrode layer 14 are integrated. The ceramic layer 12 is made of a ceramic material as described above, for example, as a coating part that can constitute a conductive powder. In the vertical direction Y, an internal electrode layer 14 is disposed between the ceramic layers 12. The internal electrode layer 14 is formed using the photosensitive composition. The internal electrode layers 14 adjacent to each other in the vertical direction Y with the ceramic layer 12 interposed therebetween are conducted through a via 16 provided in the ceramic layer 12. Thereby, the internal electrode layer 14 is formed into a three-dimensional spiral shape (spiral shape). Both ends of the internal electrode layer 14 are connected to the external electrode 20, respectively.
此種積層晶片電感器1例如可按照以下順序來製造。
即,首先製備包含成為原料的陶瓷材料與黏合劑樹脂及有機溶劑的糊(paste),並將其供給至載片(carrier sheet)上,從而形成陶瓷生片。繼而,對該陶瓷生片進行軋製後,將其切割為所需尺寸,從而獲得多個陶瓷層形成用生片。繼而,使用穿孔機等在多個陶瓷層形成用生片的規定位置上適當形成通路孔(via hole)。Such a multilayer chip inductor 1 can be manufactured in the following procedure, for example.
That is, first, a paste including a ceramic material as a raw material, a binder resin, and an organic solvent is prepared and supplied to a carrier sheet to form a ceramic green sheet. Next, after rolling the ceramic green sheet, the ceramic green sheet is cut into a desired size to obtain a plurality of green sheets for forming a ceramic layer. Then, a via hole is appropriately formed at a predetermined position of the plurality of green sheets for forming ceramic layers using a punch or the like.
繼而,使用所述感光性組成物於多個陶瓷層形成用生片的規定位置上形成規定的線圈圖案的導電膜。作為一例,可藉由包含以下步驟的製造方法來形成未煅燒狀態的導電膜:(步驟S1:膜狀體的成形步驟)將感光性組成物賦予至陶瓷層形成用生片上並加以乾燥,藉此將包含感光性組成物的乾燥體的導電膜成形的步驟;(步驟S2:曝光步驟)於導電膜上覆蓋規定的開口圖案的光罩,並介隔光罩進行曝光,從而使導電膜局部光硬化的步驟;(步驟S3:顯影步驟)對光硬化後的導電膜進行蝕刻並將未曝光部分去除的步驟。Next, a conductive film having a predetermined coil pattern is formed at a predetermined position on a plurality of green sheets for forming a ceramic layer using the photosensitive composition. As an example, a non-calcined conductive film can be formed by a manufacturing method including the following steps: (Step S1: Step of forming a film-like body) A photosensitive composition is applied to a green sheet for forming a ceramic layer, and is dried. This step is a step of forming a conductive film including a dried body of the photosensitive composition; (Step S2: exposure step) covering the conductive film with a photomask having a predetermined opening pattern, and exposing through the photomask to partially make the conductive film. Photo-hardening step; (Step S3: developing step) a step of etching the photo-cured conductive film and removing unexposed portions.
再者,當使用所述感光性組成物形成導電膜時,可適當使用現有公知的方法。例如,於(步驟S1)中,感光性組成物的賦予可使用網版印刷等各種印刷法、或棒塗機等來進行。感光性組成物的乾燥可於光聚合性化合物及光聚合起始劑的沸點以下的溫度、典型而言為50℃~100℃下進行。於(步驟S2)中,曝光時可使用例如發出10 nm~500 nm的波長範圍的光線的曝光機,例如高壓水銀燈、金屬鹵化物燈、氙燈等紫外線照射燈。於(步驟S3)中,蝕刻時,典型而言可使用鹼性的蝕刻液。例如可使用包含氫氧化鈉或碳酸鈉等的水溶液。鹼性的水溶液的濃度例如可調整為0.01質量%~0.5質量%。When a conductive film is formed using the photosensitive composition, a conventionally known method can be appropriately used. For example, in (step S1), application of a photosensitive composition can be performed using various printing methods, such as screen printing, or a bar coater. The photosensitive composition can be dried at a temperature below the boiling point of the photopolymerizable compound and the photopolymerization initiator, typically at 50 ° C to 100 ° C. In (Step S2), an exposure machine that emits light in a wavelength range of 10 nm to 500 nm, such as a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like, can be used for the exposure. In (step S3), during etching, an alkaline etchant is typically used. For example, an aqueous solution containing sodium hydroxide, sodium carbonate, or the like can be used. The concentration of the alkaline aqueous solution can be adjusted, for example, from 0.01% by mass to 0.5% by mass.
繼而,(步驟S4:煅燒步驟)將多片形成有未煅燒狀態的導電膜的陶瓷層形成用生片積層並進行壓接。藉此,製作未煅燒的陶瓷生片的積層體。繼而,例如於600℃~1000℃下對陶瓷生片的積層體進行煅燒。藉此,將陶瓷生片一體地燒結,從而形成具備陶瓷層12與包含感光性組成物的煅燒體的內部電極層14的本體部10。然後,對本體部10的兩端部賦予適當的外部電極形成用糊,並進行煅燒,藉此形成外部電極20。
以所述方式可製造積層晶片電感器1。Next, (step S4: firing step) a plurality of green sheets for forming a ceramic layer on which a conductive film in an unfired state is formed are laminated and pressure-bonded. Thereby, a laminated body of a ceramic green sheet which is not calcined is produced. Then, the laminated body of a ceramic green sheet is fired at 600 to 1000 ° C, for example. Thereby, the ceramic green sheet is integrally sintered to form a main body portion 10 including a ceramic layer 12 and an internal electrode layer 14 containing a fired body of a photosensitive composition. Then, an appropriate external electrode forming paste is applied to both end portions of the main body portion 10 and then fired to form the external electrode 20.
In this way, a multilayer chip inductor 1 can be manufactured.
以下,對與本發明有關的若干實施例進行說明,但並非意在將本發明限定於所述實施例所示者。Hereinafter, several embodiments related to the present invention will be described, but it is not intended to limit the present invention to those shown in the embodiments.
(銀粉末的準備)
首先,準備D50
粒徑不同的市售的兩種銀粉末(銀粉末a、銀粉末b)。再者,銀粉末a的D50
粒徑為3.9 μm,銀粉末b的D50
粒徑為2.8 μm。另外,銀粉末a、銀粉末b均於基於日本工業標準JIS Z 8781:2013年的L*a*b*表色系中,明度L*為50~80。(Preparation of silver powder)
First, two commercially available silver powders (silver powder a, silver powder b) having different D 50 particle sizes were prepared. The D 50 particle diameter of the silver powder a was 3.9 μm, and the D 50 particle diameter of the silver powder b was 2.8 μm. In addition, both the silver powder a and the silver powder b are in the L * a * b * color system based on Japanese Industrial Standard JIS Z 8781: 2013, and the lightness L * is 50 to 80.
另外,使用銀粉末a來準備銀粉末c。具體而言,首先向甲醇中添加丁氧基鋯,從而製備塗佈液。繼而,向該塗佈液中添加銀粉末a並攪拌1小時。繼而,自塗佈液中回收固體成分,並於100℃下進行乾燥。藉此,獲得利用相對於銀粉末100質量份,以氧化鋯(ZrO2 )換算計成為0.5質量份的量的丁氧基鋯進行了表面塗佈的銀粉末(銀-氧化鋯的核殼粒子)。如此,準備了銀粉末c。The silver powder a is used to prepare the silver powder c. Specifically, zirconyl butoxyl was first added to methanol to prepare a coating liquid. Then, silver powder a was added to this coating liquid, and it stirred for 1 hour. Then, the solid content was recovered from the coating liquid and dried at 100 ° C. Thereby, a silver powder (silver-zirconia core-shell particles) was obtained by surface coating with zirconium oxide (ZrO 2 ) conversion in an amount of 0.5 parts by mass based on 100 parts by mass of silver powder. ). In this way, silver powder c was prepared.
(光聚合起始劑的準備)
繼而,準備下述所示的市售的4種光聚合起始劑(起始劑a~起始劑d)。再者,起始劑a、起始劑b為α-胺基烷基苯酮系的光聚合起始劑,起始劑c、起始劑d為醯基氧化膦系的光聚合起始劑。
·起始劑a:2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁酮-1
·起始劑b:2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮
·起始劑c:2,4,6-三甲基苯甲醯基-二苯基-氧化膦
·起始劑d:雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(Preparation of photopolymerization initiator)
Then, four commercially available photopolymerization initiators (initiator a to initiator d) shown below were prepared. In addition, the initiator a and the initiator b are α-aminoalkyl phenone-based photopolymerization initiators, and the initiator c and the initiator d are fluorenylphosphine oxide-based photopolymerization initiators. .
· Initiator a: 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone-1
· Starter b: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-but Ketone · Initiator c: 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide · Initiator d: bis (2,4,6-trimethylbenzylidene)- Phenylphosphine oxide
(感光性組成物的製備)
首先,以成為表1所示的含有比例的方式秤量作為光聚合性化合物的胺基甲酸酯丙烯酸酯單體、有機黏合劑、及所述光聚合起始劑,並使其溶解於有機系分散介質中,從而製備載色劑(vehicle)。然後,將所述準備的銀粉末與所述製備的載色劑以77:23的質量比混合,藉此製備感光性組成物(例1~例7、比較例1~比較例6)。再者,表1所示的質量比是將感光性組成物的整體設為100質量%時的質量比,且是指於表1所示的質量比的合計不滿100質量%的情況下,包含微量的其他添加成分(例如,聚合抑制劑、增感劑、防凝膠化劑、紫外線吸收劑)。(Preparation of photosensitive composition)
First, a urethane acrylate monomer as a photopolymerizable compound, an organic binder, and the photopolymerization initiator are weighed so as to have a content ratio shown in Table 1, and dissolved in an organic system. The dispersion medium is used to prepare a vehicle. Then, the prepared silver powder was mixed with the prepared vehicle at a mass ratio of 77:23 to prepare a photosensitive composition (Examples 1 to 7, and Comparative Examples 1 to 6). In addition, the mass ratio shown in Table 1 is a mass ratio when the entire photosensitive composition is 100% by mass, and when the total mass ratio shown in Table 1 is less than 100% by mass, it includes Trace amounts of other added ingredients (for example, polymerization inhibitors, sensitizers, anti-gelling agents, UV absorbers).
(配線圖案的製作)
首先,使用不鏽鋼製的網版,將所述製備的感光性組成物分別塗佈於市售的陶瓷生片上。繼而,使其於60℃下乾燥15分鐘,從而於生片上成形導電膜(膜狀體的成形步驟)。繼而,自導電膜的上方覆蓋光罩。此時,作為光罩,使用配線的線寬度為25 μm、相鄰的線的間隔部分(空間)為25 μm(L/S=25 μm/25 μm)的螺旋圖案(spiral pattern)的光罩。於覆蓋有該光罩的狀態下,藉由曝光機以2500 mJ/cm2
的強度來照射光,從而使曝光部分硬化(曝光步驟)。曝光後,於陶瓷生生片的表面噴附0.1質量%的鹼性Na2
CO3
水溶液,直至到達斷點(B.P.)(顯影步驟)。此處,作為B.P.,設為利用0.1質量%的鹼性蝕刻液對未曝光部分進行顯影,直至能夠以目視確認到未曝光部分消失為止的時間。以此種方式將未曝光部分去除後,利用純水進行清洗,並於室溫下使其乾燥。然後,於700℃下對其進行煅燒(煅燒步驟)。如此,於陶瓷生片上形成配置有旋渦狀的配線的配線圖案的導電層。(Production of wiring pattern)
First, using a stainless steel screen, the prepared photosensitive composition was coated on a commercially available ceramic green sheet, respectively. Then, it was made to dry at 60 degreeC for 15 minutes, and the electroconductive film was shape | molded on the green sheet (forming process of a film-like body). Then, a photomask is covered from above the conductive film. At this time, as the mask, a spiral pattern with a line width of 25 μm and a space pattern (space) between adjacent lines of 25 μm (L / S = 25 μm / 25 μm) was used. . In a state covered with the photomask, the exposure part is irradiated with light at an intensity of 2500 mJ / cm 2 to harden the exposed portion (exposure step). After the exposure, a 0.1% by mass alkaline Na 2 CO 3 aqueous solution was sprayed on the surface of the ceramic green sheet until the break point (BP) was reached (development step). Here, as BP, the time until the unexposed part was developed with 0.1% by mass of an alkaline etching solution until the unexposed part disappeared visually was confirmed. After the unexposed portion is removed in this manner, it is washed with pure water, and dried at room temperature. Then, it was calcined at 700 ° C (calcination step). In this manner, a conductive layer having a wiring pattern in which spiral-shaped wirings are arranged is formed on the ceramic green sheet.
(配線圖案的評價)
針對所述製作的配線圖案來評價剝離、線寬、顯影裕度,並基於該些評價來進行綜合評價。(Evaluation of wiring pattern)
The produced wiring pattern was evaluated for peeling, line width, and development margin, and comprehensive evaluation was performed based on these evaluations.
·剝離的評價:
利用電子顯微鏡來觀察配線圖案,並進行剝離的評價。再者,觀察圖像是以倍率200倍進行拍攝。然後,於所獲得的觀察圖像中確認剝離與斷線的有無。將結果示於表1的「剝離的評價」一欄。該欄的表述如下所述。
「○」:無剝離
「△」:有局部剝離(無斷線)
「×」:有剝離、斷線Evaluation of peeling:
The wiring pattern was observed with an electron microscope, and peeling was evaluated. Furthermore, the observation image was taken at a magnification of 200 times. Then, the presence or absence of peeling and disconnection was confirmed in the obtained observation image. The results are shown in the "Evaluation of peeling" column in Table 1. The expressions in this column are as follows.
"○": No peeling "△": Partial peeling (no disconnection)
"×": peeling or disconnection
·線寬的評價:
根據所述觀察圖像來測量配線圖案的線寬。再者,線寬的測量是針對多個視場來進行,將其算術平均值設為線寬(μm)。將結果示於表1的「線寬」一欄。另外,評價一欄的表述如下所述。
「○」:20 μm~30 μm(目標值的範圍內)
「×」:30 μm以上
另外,圖2中針對比較例1~比較例3、例1~例4的評價結果,表示起始劑c的含有比例與配線圖案的線寬之間的關係。· Evaluation of line width:
The line width of the wiring pattern is measured based on the observation image. In addition, the measurement of the line width is performed for a plurality of fields of view, and the arithmetic mean thereof is set to the line width (μm). The results are shown in the "line width" column of Table 1. The expression in the evaluation column is as follows.
"○": 20 μm to 30 μm (within the range of the target value)
“×”: 30 μm or more In addition, the evaluation results of Comparative Examples 1 to 3 and Examples 1 to 4 in FIG. 2 show the relationship between the content ratio of the initiator c and the line width of the wiring pattern.
·顯影裕度的評價:
於所述曝光步驟中,超過斷點再噴附10秒鐘(B.P.+10秒鐘)鹼性的蝕刻液。然後,與所述同樣地利用電子顯微鏡來觀察曝光步驟後的導電膜,根據所獲得的觀察圖像來進行顯影裕度的評價。將結果示於表1的「顯影裕度的評價」一欄。該欄的表述如下所述。
「○」:導電膜的形狀得到保持
「×」:導電膜的形狀未得到保持Evaluation of development margin:
In the exposure step, an alkaline etchant is sprayed for 10 seconds (BP + 10 seconds) after the break point. Then, the conductive film after the exposure step was observed with an electron microscope in the same manner as described above, and the development margin was evaluated based on the obtained observation image. The results are shown in the "Evaluation of development margin" column in Table 1. The expressions in this column are as follows.
"○": The shape of the conductive film is maintained "×": The shape of the conductive film is not maintained
·綜合評價:
「○」:於所述剝離、線寬、顯影裕度的各評價中,一個△及×亦不存在(全部為○)
「△」:於所述剝離、線寬、顯影裕度的各評價中,△為一個,其餘為○
「×」:於所述剝離、線寬、顯影裕度的各評價中,存在一個以上的×·Overview:
"○": In each evaluation of the peeling, line width, and development margin, neither △ nor × existed (all ○)
"△": In each evaluation of the peeling, line width, and development margin, △ is one, and the rest are ○
"×": In each evaluation of the peeling, line width, and development margin, there is one or more ×
[表1]
比較例1、比較例2是僅使用了起始劑a的試驗例。如表1所示般,比較例1中,顯影裕度可確保10秒鐘以上,但導電圖案中線寬的偏差大,於各處確認到線寬變粗。其結果,線寬較目標值而變得過大,難以穩定地形成細實線。另外,相較於比較例1而減少了起始劑a的含有比例的比較例2中,未能充分確保顯影裕度。比較例4是僅使用了起始劑c的試驗例。如表1所示般,比較例4中,導電圖案確認到剝離或斷線,細實線的形成本身已經困難。Comparative Examples 1 and 2 are test examples using only the initiator a. As shown in Table 1, in Comparative Example 1, the development margin was secured for 10 seconds or more, but the line width in the conductive pattern had a large deviation, and it was confirmed that the line width became thick everywhere. As a result, the line width becomes too large compared with the target value, and it is difficult to form a thin solid line stably. In addition, in Comparative Example 2 in which the content ratio of the initiator a was reduced compared to Comparative Example 1, the development margin was not sufficiently secured. Comparative Example 4 is a test example using only the initiator c. As shown in Table 1, in Comparative Example 4, peeling or disconnection of the conductive pattern was confirmed, and formation of a thin solid line itself was already difficult.
比較例3、例1~例4是併用了起始劑a、起始劑c的試驗例。如表1及圖2所示般,起始劑c的含有比例少的比較例3中,未充分表現出起始劑c的添加效果,與比較例1同樣地,難以穩定地形成細實線。相對於此,將起始劑c的含有比例設為光聚合起始劑整體的50質量%以上的例1~例4中,充分確保顯影裕度,且穩定地形成了所需線寬的細實線。另外,藉由提高起始劑c的含有比例,細線形成性進一步提升。尤其是於將起始劑c:起始劑a的質量比設為50:50~85:15的例1~例3中,曝光部分的耐蝕刻性提升,更良好地抑制了導電層的剝離。Comparative Examples 3 and 1 to 4 are test examples in which the initiator a and the initiator c are used in combination. As shown in Table 1 and FIG. 2, in Comparative Example 3 in which the content ratio of the initiator c was small, the effect of the addition of the initiator c was not sufficiently exhibited. As in Comparative Example 1, it was difficult to form a thin solid line stably. . On the other hand, in Examples 1 to 4, in which the content ratio of the initiator c was 50% by mass or more of the entire photopolymerization initiator, the development margin was sufficiently ensured, and the fine line width required was stably formed. solid line. In addition, by increasing the content ratio of the initiator c, the fine-line forming property is further improved. In particular, in Examples 1 to 3 in which the mass ratio of the initiator c: the initiator a is 50:50 to 85:15, the etching resistance of the exposed portion is improved, and the peeling of the conductive layer is more effectively suppressed. .
例5是代替起始劑a而使用了作為相同的α-胺基烷基苯酮類的起始劑b的試驗例。如表1所示般,例5中,亦與例1~例4同樣地,充分確保顯影裕度,且實現了細實線的穩定形成。換言之,於代替起始劑a而使用了起始劑b的情況下,亦發揮了此處所揭示的技術的效果。Example 5 is a test example using the same α-aminoalkylbenzophenone-based initiator b instead of the initiator a. As shown in Table 1, in Example 5, as in Examples 1 to 4, the development margin was sufficiently secured, and stable formation of a thin solid line was achieved. In other words, when the initiator b is used instead of the initiator a, the effect of the technique disclosed herein is also exerted.
比較例5、比較例6是代替起始劑c而使用了相同的醯基氧化膦系的起始劑d的試驗例。如表1所示般,比較例5、比較例6中,與例1~例4不同,顯影裕度並不充分,以及/或者難以穩定地形成細實線。換言之,於代替起始劑c而使用了起始劑d的情況下,並未發揮此處所揭示的技術的效果。Comparative Examples 5 and 6 are test examples in which the same fluorenylphosphine oxide-based initiator d was used instead of the initiator c. As shown in Table 1, in Comparative Examples 5 and 6, unlike Examples 1 to 4, the development margin was insufficient, and / or it was difficult to form a thin solid line stably. In other words, when the initiator d is used instead of the initiator c, the effect of the technique disclosed here is not exerted.
例6、例7是代替銀粉末a、銀粉末b而使用了銀粉末c的試驗例。如表1所示般,例6、例7中,亦與例1~例4同樣地,充分確保顯影裕度,且實現了細實線的穩定形成。進而,與使用銀粉末a、銀粉末b的情況相比,以更高的水準發揮此處所揭示的技術的效果,且細線形成性進一步提升。Examples 6 and 7 are test examples using silver powder c instead of silver powder a and silver powder b. As shown in Table 1, in Examples 6 and 7, as in Examples 1 to 4, the development margin was sufficiently ensured, and stable formation of a thin solid line was achieved. Furthermore, compared with the case where the silver powder a and the silver powder b are used, the effect of the technique disclosed here is exhibited at a higher level, and the fine line formability is further improved.
如上所述,作為光聚合起始劑,併用2,4,6-三甲基苯甲醯基-二苯基-氧化膦(起始劑c)與α-胺基烷基苯酮類(起始劑a、起始劑b),且以光聚合起始劑整體的50質量%以上的比例包含2,4,6-三甲基苯甲醯基-二苯基-氧化膦,藉此,於顯影步驟中,可較長地確保顯影裕度的時間。另外,可提升曝光部分的細線形成性。藉此,即便是線寬為30 μm以下的細實線,亦可再現性良好地形成。此外,可抑制短路不良、剝離、斷線等不良情況的發生,並提升良率。該些結果表示此處所揭示的技術的意義。As described above, as the photopolymerization initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide (starter c) and α-aminoalkyl phenones (from The initiator a, the initiator b), and including 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide in a proportion of 50% by mass or more of the entire photopolymerization initiator, In the developing step, it is possible to ensure a long development margin time. In addition, the fine line formability of the exposed portion can be improved. Thereby, even a thin solid line with a line width of 30 μm or less can be formed with good reproducibility. In addition, it can suppress the occurrence of short-circuit failure, peeling, and disconnection, and improve the yield. These results indicate the significance of the techniques disclosed herein.
以上對本發明進行了詳細說明,但該等僅為例示,本發明可於不偏離其主旨的範圍內加以各種變更。The present invention has been described in detail above, but these are merely examples, and the present invention can be modified in various ways without departing from the spirit thereof.
1‧‧‧積層晶片電感器1‧‧‧Multilayer Chip Inductor
10‧‧‧本體部 10‧‧‧Body
12‧‧‧陶瓷層(電介質層) 12‧‧‧Ceramic layer (dielectric layer)
14‧‧‧內部電極層 14‧‧‧Internal electrode layer
16‧‧‧通路 16‧‧‧ access
20‧‧‧外部電極 20‧‧‧External electrode
X‧‧‧左右方向 X‧‧‧ Left and right direction
Y‧‧‧上下方向 Y‧‧‧ Up and down direction
圖1是示意性地表示一實施形態的積層晶片電感器(inductor)的結構的剖面圖。FIG. 1 is a cross-sectional view schematically showing a structure of a multilayer chip inductor according to an embodiment.
圖2是表示起始劑c的含有比例與配線圖案的線寬之間的關係的圖表。 FIG. 2 is a graph showing the relationship between the content ratio of the initiator c and the line width of the wiring pattern.
Claims (12)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018-021134 | 2018-02-08 | ||
JP2018021134A JP6637087B2 (en) | 2018-02-08 | 2018-02-08 | Photosensitive composition and its use |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201937287A true TW201937287A (en) | 2019-09-16 |
TWI796424B TWI796424B (en) | 2023-03-21 |
Family
ID=67547946
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW108102793A TWI796424B (en) | 2018-02-08 | 2019-01-24 | Photosensitive composition, complex, electronic part and manufacturing method thereof |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6637087B2 (en) |
KR (1) | KR102658648B1 (en) |
CN (1) | CN111699436A (en) |
TW (1) | TWI796424B (en) |
WO (1) | WO2019155819A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6717439B1 (en) * | 2018-11-30 | 2020-07-01 | 東レ株式会社 | Laminated material |
WO2022030382A1 (en) * | 2020-08-07 | 2022-02-10 | 東レ株式会社 | Photosensitive conductive paste, cured article, sintered body, electronic component, method for producing circuit pattern-equipped insulative ceramic layer, method for producing electronic component, method for producing circuit pattern-equipped substrate and method for producing inductor |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5393402U (en) | 1976-12-29 | 1978-07-29 | ||
JP4437603B2 (en) * | 2000-09-06 | 2010-03-24 | 京都エレックス株式会社 | Alkali development type photosensitive paste composition |
JP2003183401A (en) | 2001-12-20 | 2003-07-03 | Showa Denko Kk | Curable resin composition and cured product thereof |
JP4151363B2 (en) * | 2002-09-27 | 2008-09-17 | Jsr株式会社 | Photosensitive resin composition and method for producing inorganic shaped article using the same |
JP3779260B2 (en) * | 2002-11-26 | 2006-05-24 | 京都エレックス株式会社 | Alkali development type photosensitive resin composition |
JP4389202B2 (en) * | 2003-11-21 | 2009-12-24 | 昭栄化学工業株式会社 | Photosensitive conductive paste |
US7618766B2 (en) * | 2005-12-21 | 2009-11-17 | E. I. Du Pont De Nemours And Company | Flame retardant photoimagable coverlay compositions and methods relating thereto |
JP5043516B2 (en) * | 2007-06-04 | 2012-10-10 | 太陽ホールディングス株式会社 | Photocurable / thermosetting resin composition and printed wiring obtained using the same |
JP2010138251A (en) * | 2008-12-10 | 2010-06-24 | Fujifilm Corp | Dispersion composition, polymerizable composition, light shielding color filter, solid-state image sensor, and liquid crystal display device |
JP5315441B1 (en) * | 2012-03-30 | 2013-10-16 | 太陽インキ製造株式会社 | Photocurable resin composition, dry film, cured product and printed wiring board |
JP5463498B1 (en) * | 2012-12-28 | 2014-04-09 | 東洋インキScホールディングス株式会社 | Photosensitive conductive ink and cured product thereof |
JP5828851B2 (en) * | 2013-03-01 | 2015-12-09 | 株式会社ノリタケカンパニーリミテド | Photosensitive paste |
JP2015110745A (en) | 2013-11-01 | 2015-06-18 | セメダイン株式会社 | Photocurable conductive composition |
JP2015184631A (en) | 2014-03-26 | 2015-10-22 | 太陽インキ製造株式会社 | Photosensitive resin composition, two-layer electrode structure, method for manufacturing the same, and plasma display panel |
JP2016071173A (en) * | 2014-09-30 | 2016-05-09 | 東洋紡株式会社 | Photosensitive conductive paste, conductive thin film, electric circuit and touch panel |
JP2017182901A (en) * | 2016-03-28 | 2017-10-05 | 東レ株式会社 | Photosensitive conductive paste and manufacturing method of electronic component using the same |
-
2018
- 2018-02-08 JP JP2018021134A patent/JP6637087B2/en active Active
-
2019
- 2019-01-11 KR KR1020207025548A patent/KR102658648B1/en active IP Right Grant
- 2019-01-11 CN CN201980012121.9A patent/CN111699436A/en active Pending
- 2019-01-11 WO PCT/JP2019/000675 patent/WO2019155819A1/en active Application Filing
- 2019-01-24 TW TW108102793A patent/TWI796424B/en active
Also Published As
Publication number | Publication date |
---|---|
WO2019155819A1 (en) | 2019-08-15 |
KR102658648B1 (en) | 2024-04-19 |
TWI796424B (en) | 2023-03-21 |
JP6637087B2 (en) | 2020-01-29 |
CN111699436A (en) | 2020-09-22 |
KR20200118135A (en) | 2020-10-14 |
JP2019139014A (en) | 2019-08-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI812688B (en) | Photosensitive composition, complex, electronic part, and method for producing electronic part | |
JP5828851B2 (en) | Photosensitive paste | |
JP6614355B2 (en) | Photosensitive conductive paste, method for manufacturing multilayer electronic component, and multilayer electronic component | |
TWI796424B (en) | Photosensitive composition, complex, electronic part and manufacturing method thereof | |
JP6814237B2 (en) | Photosensitive compositions and their use | |
JP7446355B2 (en) | Photosensitive composition and its use | |
JP7113779B2 (en) | Photosensitive composition and its use | |
TWI780277B (en) | Photosensitive composition, composite, electronic component, and method for producing electronic component | |
JP7108778B1 (en) | Photosensitive composition and its use | |
TW202244068A (en) | Photosensitive composition and use thereof |