TWI830712B - Printed wiring board manufacturing method, resin sheet and hardened product - Google Patents
Printed wiring board manufacturing method, resin sheet and hardened product Download PDFInfo
- Publication number
- TWI830712B TWI830712B TW107145155A TW107145155A TWI830712B TW I830712 B TWI830712 B TW I830712B TW 107145155 A TW107145155 A TW 107145155A TW 107145155 A TW107145155 A TW 107145155A TW I830712 B TWI830712 B TW I830712B
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- Prior art keywords
- resin composition
- photosensitive resin
- composition layer
- support
- meth
- Prior art date
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- 238000011161 development Methods 0.000 claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 44
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- VNTPGSZQKARKHG-UHFFFAOYSA-N trimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C[Si](C)(C)CCCOCC1CO1 VNTPGSZQKARKHG-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- 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
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
提供一種能夠形成密著性及配線的遮蔽性為優異、且孔洞形狀為良好的硬化物之樹脂薄片等。 To provide a resin sheet and the like capable of forming a cured product having excellent adhesion and wiring shielding properties and a good hole shape.
印刷配線板之製造方法,其係包含下述步驟:(1)準備具有支撐體與設置在該支撐體上的包含感光性樹脂組成物的感光性樹脂組成物層的樹脂薄片之步驟、(2)在基板上層合樹脂薄片之步驟、(3)將感光性樹脂組成物層進行曝光之步驟及(4)藉由顯影來形成圖型感光性樹脂組成物層之步驟,支撐體的霧度為20%以下,於(4)步驟後的圖型感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|)為500nm以上,感光性樹脂組成物滿足指定的條件(I)或(II)。 A method for manufacturing a printed wiring board, which includes the following steps: (1) preparing a resin sheet having a support and a photosensitive resin composition layer including a photosensitive resin composition provided on the support; (2) ) the step of laminating the resin sheet on the substrate, (3) the step of exposing the photosensitive resin composition layer and (4) the step of forming the patterned photosensitive resin composition layer by development, the haze of the support is 20% or less, and the absolute value (|Rv|) of the maximum valley depth on the support side of the patterned photosensitive resin composition layer after step (4) is 500 nm or more, the photosensitive resin composition meets the specified Condition (I) or (II).
Description
本發明為關於樹脂薄片、使用上述樹脂薄片之印刷配線板之製造方法及硬化物。 The present invention relates to a resin sheet, a method of manufacturing a printed wiring board using the resin sheet, and a cured product.
在印刷配線板上設置的阻焊劑(solder resist),其係作為用來抑制焊料附著到不需要錫焊的部分,同時抑制電路基板的腐蝕之永久保護膜。對於阻焊劑要求著與密封材或底部填充材的密著性,例如,專利文獻1中揭示著一種感光性元件,其係具備支撐薄膜與設置在該支撐薄膜上的由感光性樹脂組成物所形成的感光層,且前述支撐薄膜與感光層相接的面的表面粗糙度Ra為200~4000nm。 A solder resist provided on a printed wiring board serves as a permanent protective film to prevent solder from adhering to parts that do not require soldering and to prevent corrosion of the circuit board. The solder resist requires adhesion to a sealing material or an underfill material. For example, Patent Document 1 discloses a photosensitive element including a support film and a photosensitive resin composition provided on the support film. The photosensitive layer is formed, and the surface roughness Ra of the surface connecting the supporting film and the photosensitive layer is 200 to 4000 nm.
[專利文獻1]國際公開第2015/163455號 [Patent Document 1] International Publication No. 2015/163455
近年,因應於印刷配線板的高密度化,而對阻焊劑亦要求著作業性或更一步的高性能化。於印刷配線板的高密度化時,安裝各種的半導體晶片後利用密封材將半導體晶片予以密封時,由於密封材與阻焊劑的接觸面會減少,為了提高密封性能,而要求阻焊劑為更高的密著力。進而,藉由電路設計來將印刷配線板進行高密度化時,經由阻焊劑來遮蔽配線、並防止設計被模仿,此點亦為重要的。 In recent years, in response to the increase in density of printed wiring boards, solder resists are required to have better workability or higher performance. As the density of printed wiring boards increases, when various semiconductor chips are mounted and the semiconductor chips are sealed using a sealing material, the contact surface between the sealing material and the solder resist will be reduced. In order to improve the sealing performance, the solder resist is required to be higher. of tight adhesion. Furthermore, when densifying a printed wiring board through circuit design, it is also important to shield the wiring with a solder resist and prevent the design from being imitated.
為了提高阻焊劑的密著力,如專利文獻1般,認為是以使用具有表面凹凸的支撐體,來將該表面凹凸轉印在感光性樹脂組成物層上。但如同後述般,該方法係由於曝光時的光散射,而具有產生孔洞形狀扭曲等的缺點之情形。 In order to improve the adhesion of the solder resist, as in Patent Document 1, it is considered that a support having surface unevenness is used to transfer the surface unevenness to the photosensitive resin composition layer. However, as will be described later, this method has disadvantages such as distortion of the hole shape due to light scattering during exposure.
本發明之課題係提供一種能夠形成密著性及配線的遮蔽性為優異、且孔洞形狀為良好的硬化物之樹脂薄片;使用該樹脂薄片的印刷配線板之製造方法;及硬化物。 An object of the present invention is to provide a resin sheet that can form a cured product that is excellent in adhesion and wiring shielding properties and has a good hole shape; a method for manufacturing a printed wiring board using the resin sheet; and a cured product.
本發明入等為了解決上述課題經深入研究之結果發現,藉由下述構成可解決上述課題,進而完成本發明。 As a result of intensive research in order to solve the above-mentioned problems, the present invention found that the above-mentioned problems can be solved by the following configuration, and further completed the present invention.
即,本發明係包含以下之內容。 That is, the present invention includes the following contents.
[1].一種印刷配線板之製造方法,其係包含下述步驟: (1)準備具有支撐體與設置在該支撐體上的包含感光性樹脂組成物的感光性樹脂組成物層的樹脂薄片之步驟、 (2)在基板上層合樹脂薄片之步驟、 (3)將感光性樹脂組成物層進行曝光之步驟及 (4)藉由顯影來形成圖型感光性樹脂組成物層之步驟, 其特徵為, 支撐體的霧度為20%以下, (4)步驟後的圖型感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|)為500nm以上, 感光性樹脂組成物滿足以下之條件(I)或(II), (I)感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材,若將感光性樹脂組成物的不揮發成分設為100質量%時,(a)成分的含有量為60質量%以上; (II)感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材、(b)包含乙烯性不飽和基及羧基的樹脂、(c)環氧樹脂及(d)光聚合起始劑。 [2].如[1]之印刷配線板之製造方法,其中,進而包含(5)將圖型感光性樹脂組成物層進行硬化之步驟。 [3].如[2]之印刷配線板之製造方法,其中,圖型感光性樹脂組成物層的硬化物為阻焊劑。 [4].如[1]~[3]中任一項之印刷配線板之製造方法,其中,感光性樹脂組成物為負型感光性樹脂組成物。 [5].如[1]~[4]中任一項之印刷配線板之製造方法,其中,若將於(3)步驟後(4)步驟前的感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|)設為A1 (nm),並將於(4)步驟後的圖型感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|)設為A2(nm)時,滿足3<A2/A1<100的關係。 [6].如[1]~[5]中任一項之印刷配線板之製造方法,其中,進而包含(6)剝離支撐體之步驟。 [7].如[6]之印刷配線板之製造方法,其中,(6)步驟係於(2)步驟後(3)步驟前來進行。 [8].一種樹脂薄片,其具有支撐體與設置在該支撐體上的包含感光性樹脂組成物的感光性樹脂組成物層, 其特徵為, 支撐體的霧度為20%以下, 於顯影後的圖型感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|)為500nm以上, 感光性樹脂組成物滿足以下之條件(I)或(II), (I)感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材,若將感光性樹脂組成物的不揮發成分設為100質量%時,(a)成分的含有量為60質量%以上; (II)感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材、(b)包含乙烯性不飽和基及羧基的樹脂、(c)環氧樹脂及(d)光聚合起始劑。 [9].如[8]之樹脂薄片,其中,(b)成分含有玻璃轉移溫度為-20℃以下的(甲基)丙烯酸聚合物。 [10].如[8]或[9]之樹脂薄片,其中,感光性樹脂組成物層係阻焊劑形成用。 [11].如[8]~[10]中任一項之樹脂薄片,其中,若將於曝光後顯影前的感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|)設為A1(nm),並將於顯影後的圖型感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|)設為A2(nm)時,滿足3<A2/A1<100的關係。 [12].一種硬化物,其係使[8]~[11]中任一項之樹脂薄片的感光性樹脂組成物層硬化而成。[1]. A method of manufacturing a printed wiring board, which includes the following steps: (1) The step of preparing a resin sheet having a support and a photosensitive resin composition layer including a photosensitive resin composition provided on the support, (2) Steps of laminating resin sheets on the substrate, (3) The steps of exposing the photosensitive resin composition layer and (4) The step of forming a patterned photosensitive resin composition layer by development, Its characteristics are: The haze of the support is below 20%. (4) The absolute value of the maximum valley depth (|Rv|) of the support-side surface of the patterned photosensitive resin composition layer after the step is 500 nm or more, The photosensitive resin composition satisfies the following conditions (I) or (II), (I) The photosensitive resin composition contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more. When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of component (a) is 60 Mass% or more; (II) The photosensitive resin composition contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) a photopolymerizable resin. starter. [2]. The manufacturing method of a printed wiring board according to [1], further comprising (5) the step of hardening the patterned photosensitive resin composition layer. [3]. The manufacturing method of a printed wiring board according to [2], wherein the hardened material of the patterned photosensitive resin composition layer is a solder resist. [4]. The method for manufacturing a printed wiring board according to any one of [1] to [3], wherein the photosensitive resin composition is a negative photosensitive resin composition. [5]. The method for manufacturing a printed wiring board according to any one of [1] to [4], wherein, if the photosensitive resin composition layer after the step (3) and before the step (4) is placed on the support side The absolute value (|Rv|) of the maximum valley depth on the surface is set to A1 (nm), and the maximum valley depth on the support side of the patterned photosensitive resin composition layer after step (4) is When the absolute value (|Rv|) is set to A2 (nm), the relationship of 3<A2/A1<100 is satisfied. [6]. The method for manufacturing a printed wiring board according to any one of [1] to [5], further comprising (6) the step of peeling off the support. [7]. The manufacturing method of a printed wiring board according to [6], wherein step (6) is performed after step (2) and before step (3). [8]. A resin sheet having a support body and a photosensitive resin composition layer including a photosensitive resin composition provided on the support body, Its characteristics are: The haze of the support is below 20%. The absolute value of the maximum valley depth (|Rv|) on the surface of the support side of the patterned photosensitive resin composition layer after development is 500 nm or more, The photosensitive resin composition satisfies the following conditions (I) or (II), (I) The photosensitive resin composition contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more. When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of component (a) is 60 Mass% or more; (II) The photosensitive resin composition contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) a photopolymerizable resin. starter. [9]. The resin sheet according to [8], wherein the component (b) contains a (meth)acrylic polymer having a glass transition temperature of -20°C or lower. [10]. The resin sheet according to [8] or [9], wherein the photosensitive resin composition layer is used for solder resist formation. [11]. The resin sheet according to any one of [8] to [10], wherein the absolute value of the maximum valley depth on the support side surface of the photosensitive resin composition layer after exposure and before development (|Rv|) is set to A1 (nm), and the absolute value (|Rv|) of the maximum valley depth on the support side surface of the patterned photosensitive resin composition layer after development is set to A2 (nm ), the relationship of 3<A2/A1<100 is satisfied. [12]. A cured product obtained by curing the photosensitive resin composition layer of the resin sheet according to any one of [8] to [11].
依據本發明,可提供一種能夠形成密著性及配線的遮蔽性為優異、且孔洞形狀為良好的硬化物之樹脂薄片;使用該樹脂薄片的印刷配線板之製造方法;及硬化物。According to the present invention, it is possible to provide a resin sheet capable of forming a cured product that is excellent in adhesion and wiring shielding properties and has a good hole shape; a method of manufacturing a printed wiring board using the resin sheet; and a cured product.
[實施發明之最佳形態][The best way to implement the invention]
如圖4所表示般,以往的樹脂薄片11具有支撐體111與設置在該支撐體111上的感光性樹脂組成物層112。支撐體111的感光性樹脂組成物層112側之面111a,其具有表面凹凸,且該面的算術平均粗糙度Ra係一般為200~4000nm,支撐體111的霧度係一般為60%以上。感光性樹脂組成物層112的支撐體111側之面112a,其轉印有上述之面111a的表面凹凸,該面112a的算術平均粗糙度Ra,係與面111a具有相同的算術平均粗糙度Ra。As shown in FIG. 4 , the conventional resin sheet 11 has a support 111 and a photosensitive resin composition layer 112 provided on the support 111 . The surface 111a of the support 111 on the side of the photosensitive resin composition layer 112 has surface irregularities, and the arithmetic mean roughness Ra of this surface is generally 200~4000 nm, and the haze of the support 111 is generally more than 60%. The surface 112a of the photosensitive resin composition layer 112 on the support 111 side has the above-mentioned surface irregularities of the surface 111a transferred thereto, and the arithmetic mean roughness Ra of the surface 112a is the same as the arithmetic mean roughness Ra of the surface 111a. .
使用以往的樹脂薄片11來製造印刷配線板時,如圖5所表般,首先將以往的樹脂薄片11層合在基板113上。層合後,通過遮罩圖型(未圖示)對感光性樹脂組成物層112的指定部分照射活性光線hν,來使感光性樹脂組成物層112的照射部光硬化,即,進行感光性樹脂組成物層112的曝光。於感光性樹脂組成物層112的曝光後,如圖6所表示般,於剝離支撐體111後,來進行顯影。之後,使已顯影的感光性樹脂組成物層112b硬化,在其上形成未圖示的導體層。與已顯影的感光性樹脂組成物層112b的基板113之面為相反側之面112c,其具有起因於支撐體111的表面凹凸,因此與未圖示的導體層的密著性將為提升。When the conventional resin sheet 11 is used to manufacture a printed wiring board, as shown in FIG. 5 , the conventional resin sheet 11 is first laminated on the substrate 113 . After lamination, a designated portion of the photosensitive resin composition layer 112 is irradiated with active light hν through a mask pattern (not shown), so that the irradiated portion of the photosensitive resin composition layer 112 is photocured, that is, photosensitized Exposure of the resin composition layer 112 . After the photosensitive resin composition layer 112 is exposed, as shown in FIG. 6 , the support 111 is peeled off and then developed. Thereafter, the developed photosensitive resin composition layer 112b is hardened, and a conductor layer (not shown) is formed thereon. The surface 112c opposite to the surface of the substrate 113 of the developed photosensitive resin composition layer 112b has surface irregularities caused by the support 111, so the adhesion to the conductor layer (not shown) is improved.
本發明人發現,如前述般使用以往的樹脂薄片11來進行曝光時,因面111a、及面112a的表面凹凸而導致活性光線hν產生散射,其結果,使得孔洞形狀扭曲。The inventor found that when the conventional resin sheet 11 was used for exposure as described above, the active light hν was scattered due to the surface irregularities of the surfaces 111a and 112a, resulting in distortion of the hole shape.
相較於此,本發明中製造的印刷配線板,其所使用的樹脂薄片具有支撐體與設置在該支撐體上的包含感光性樹脂組成物的感光性樹脂組成物層,且該樹脂薄片滿足下述之條件(A)及(B)。 (A)支撐體的霧度為20%以下。 (B)於顯影後的圖型感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|)為500nm以上。In contrast, the printed wiring board manufactured in the present invention uses a resin sheet having a support and a photosensitive resin composition layer including a photosensitive resin composition provided on the support, and the resin sheet satisfies The following conditions (A) and (B). (A) The haze of the support is 20% or less. (B) The absolute value of the maximum valley depth (|Rv|) on the surface of the support side of the patterned photosensitive resin composition layer after development is 500 nm or more.
本發明人係於製造印刷配線板時,藉由使用滿足上述特定的條件(A)及(B)的樹脂薄片來形成絕緣層,因而達成能夠形成密著性及配線的遮蔽性為優異、且具有良好的孔洞形狀的通孔洞。尚,所謂的感光性樹脂組成物層的「支撐體側之面」係表示於支撐體的剝離後,與感光性樹脂組成物層的支撐體為對向之面,一般而言係表示與基板(其係與樹脂薄片層合者)為相反側的感光性樹脂組成物層之面。The inventors of the present invention formed an insulating layer using a resin sheet that satisfies the above-mentioned specific conditions (A) and (B) when manufacturing a printed wiring board, thereby achieving excellent adhesion and shielding properties for wiring, and Via hole with good hole shape. Furthermore, the so-called "support side surface" of the photosensitive resin composition layer refers to the surface facing the support of the photosensitive resin composition layer after the support is peeled off. Generally speaking, it refers to the surface facing the substrate. It is the surface of the photosensitive resin composition layer on the opposite side (which is laminated with the resin sheet).
<條件(A)> 條件(A)係關於支撐體的霧度為20%以下。本發明人發現,藉由曝光顯影來形成絕緣層時,支撐體的霧度係對於密著性、配線的遮蔽性、及孔洞形狀具有很大的影響。<Condition (A)> The condition (A) is that the haze of the support is 20% or less. The inventor found that when the insulating layer is formed by exposure and development, the haze of the support has a great influence on the adhesion, the shielding property of the wiring, and the hole shape.
如圖1所表示之一例,本發明之樹脂薄片10,其具有支撐體101與設置在該支撐體101上的包含感光性樹脂組成物的感光性樹脂組成物層102,支撐體101的霧度為20%以下。一般而言,霧度與支撐體的感光性樹脂組成物層102側之面101a的算術平均粗糙度Ra為具有關連性,若降低霧度值的話,則算術平均粗糙度Ra值會變低。由於支撐體101的霧度為20%以下,故與以往的樹脂薄片11中之面111a為不同,支撐體的感光性樹脂組成物層102側之面101a的表面凹凸為小而呈平滑面。感光性樹脂組成物層102的支撐體101側之面102a,其轉印有面101a的表面凹凸,因此該面102a的表面形狀亦與面101a為相同地,表面凹凸為小而呈平滑面。As shown in FIG. 1 , the resin sheet 10 of the present invention has a support 101 and a photosensitive resin composition layer 102 including a photosensitive resin composition provided on the support 101. The haze of the support 101 is is less than 20%. Generally speaking, haze is correlated with the arithmetic mean roughness Ra of the surface 101a of the support on the photosensitive resin composition layer 102 side. If the haze value is reduced, the arithmetic mean roughness Ra value will become lower. Since the haze of the support 101 is 20% or less, unlike the surface 111a of the conventional resin sheet 11, the surface 101a of the support on the side of the photosensitive resin composition layer 102 has small unevenness and is smooth. The surface 102a of the photosensitive resin composition layer 102 on the support 101 side has the surface irregularities of the surface 101a transferred to it, so the surface shape of the surface 102a is also the same as the surface 101a, with the surface irregularities being small and smooth.
使用樹脂薄片10來製造印刷配線板時,如圖2所表示之一例般,將樹脂薄片10層合在基板103上。於層合後進行曝光。曝光之一實施形態係通過遮罩圖型(未圖示),對感光性樹脂組成物層102的指定部分照射活性光線hν,來使感光性樹脂組成物層102的照射部光硬化。面101a及面102a的表面凹凸皆為小而呈平滑面,因此於曝光時照射活性光線hν之際,將能夠抑制活性光線hν的散射。其結果,可抑制孔洞形狀扭曲,進而可抑制活性光線hν的散射,因而可使顯影性得到提升。又,即使是剝離支撐體101後才進行曝光之情形時,由於與面101a為相同地,面102a的表面凹凸為小而呈平滑面,因此可發揮與不用剝離支撐體101而進行曝光之情形為相同之效果。When manufacturing a printed wiring board using the resin sheet 10, as shown in FIG. 2, the resin sheet 10 is laminated|stacked on the board|substrate 103, for example. Exposure is performed after lamination. One embodiment of the exposure is to irradiate a designated portion of the photosensitive resin composition layer 102 with active light hν through a mask pattern (not shown), thereby photocuring the irradiated portion of the photosensitive resin composition layer 102 . The surface irregularities of the surface 101a and the surface 102a are both small and smooth. Therefore, when the active light hν is irradiated during exposure, the scattering of the active light hν can be suppressed. As a result, the distortion of the hole shape can be suppressed, and the scattering of the active light hν can be suppressed, thereby improving the developability. In addition, even when the support 101 is peeled off and then exposed, the surface unevenness of the surface 102a is small and smooth like the surface 101a. Therefore, it is possible to perform the exposure without peeling off the support 101. For the same effect.
支撐體101的霧度,就使孔洞形狀及顯影性提升之觀點而言為20%以下,較佳為15%以下,又較佳為10%。下限係例如能夠設為0.1%以上等。支撐體101的霧度係可使用例如Suga試驗機公司製的霧度計(HZ-V3)來進行測定。The haze of the support 101 is 20% or less, preferably 15% or less, and still more preferably 10%, from the viewpoint of improving hole shape and developability. The lower limit can be, for example, 0.1% or more. The haze of the support 101 can be measured using, for example, a haze meter (HZ-V3) manufactured by Suga Testing Machine Co., Ltd.
支撐體101之面101a的最大凹谷深度的絕對值(|Rv|),就使孔洞形狀及顯影性提升之觀點而言,較佳為未滿500nm,又較佳為400nm以下,更佳為300nm以下。下限係例如能夠設為0.1nm以上等。支撐體的最大凹谷深度的絕對值係可使用例如Bruker AXS公司製的白色光干擾型顯微鏡(Contoure GT-X series)來進行測定。From the viewpoint of improving the hole shape and developability, the absolute value (|Rv|) of the maximum valley depth of the surface 101a of the support 101 is preferably less than 500 nm, more preferably less than 400 nm, and more preferably Below 300nm. The lower limit can be, for example, 0.1 nm or more. The absolute value of the maximum valley depth of the support can be measured using, for example, a white light interference type microscope (Contoure GT-X series) manufactured by Bruker AXS.
支撐體101之面101a的算術平均粗糙度Ra,就使孔洞形狀及顯影性提升之觀點而言,較佳為未滿150nm,又較佳為100nm以下,更較佳為50nm以下、40nm以下、30nm以下、20nm以下。下限係例如能夠設為0.1nm以上等。算術平均粗糙度Ra係可使用例如AXS公司製的非接觸型干擾顯微鏡(WYKO Bruker)來進行測定。The arithmetic mean roughness Ra of the surface 101a of the support 101 is preferably less than 150 nm, more preferably less than 100 nm, more preferably less than 50 nm, and less than 40 nm, from the viewpoint of improving the hole shape and developability. Below 30nm, below 20nm. The lower limit can be, for example, 0.1 nm or more. The arithmetic mean roughness Ra can be measured using, for example, a non-contact interference microscope (WYKO Bruker) manufactured by AXS Corporation.
作為支撐體係以樹脂薄膜為較佳,可舉例如聚對苯二甲酸乙二醇酯薄膜、聚萘二甲酸乙二醇酯薄膜、聚丙烯薄膜、聚乙烯薄膜、聚乙烯醇薄膜、三乙醯乙酸酯薄膜等,特別是以聚對苯二甲酸乙二醇酯(PET)薄膜為較佳。As a supporting system, a resin film is preferred, and examples thereof include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, and triacetyl film. Acetate film, etc., especially polyethylene terephthalate (PET) film is preferred.
作為市售的支撐體,可舉例如王子製紙公司製的製品名「Arufun MA-410」、「E-200C」、信越薄膜公司製等的聚丙烯薄膜;Unitika公司製的製品名「S-25」、帝人公司製的製品名「PS-25」等的PS series等的聚對苯二甲酸乙二醇酯薄膜等。Examples of commercially available supports include polypropylene films, product names "Arufun MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd. and Shin-Etsu Film Co., Ltd.; product names "S-25" manufactured by Unitika Co., Ltd. ”, polyethylene terephthalate films such as the PS series manufactured by Teijin Corporation under the product name “PS-25”, etc.
該等的支撐體,可對於與樹脂組成物層接合之側之表面施予消光處理、電暈放電處理。又,作為支撐體,可使用與感光性樹脂組成物層接合之側之表面具有脫模層之「附帶脫模層的支撐體」。附帶脫模層的支撐體中,作為脫模層所使用的脫模劑,可舉例如選自由醇酸樹脂、烯烴樹脂、胺基甲酸酯樹脂、及聚矽氧樹脂所構成之群組之1種以上的脫模劑。作為脫模劑的市售品,可舉例如醇酸樹脂系脫模劑的Lintec公司製的「SK-1」、「AL-5」、「AL-7」等。附帶脫模層的支撐體,亦可藉由將脫模劑塗佈在支撐體上而來形成。The surface of these supports on the side bonded to the resin composition layer may be subjected to matting treatment or corona discharge treatment. Moreover, as a support body, the "support body with a release layer" which has a release layer on the surface of the side which joins a photosensitive resin composition layer can be used. In the support with a release layer, the release agent used as the release layer may be selected from the group consisting of alkyd resin, olefin resin, urethane resin, and polysiloxane resin. More than 1 type of release agent. Examples of commercially available mold release agents include "SK-1", "AL-5", and "AL-7" made by Lintec Corporation, which are alkyd resin-based mold release agents. The support body with a release layer can also be formed by coating a release agent on the support body.
支撐體的厚度係以5μm~50μm的範圍為較佳,以10μm~25μm的範圍為又較佳。藉由將厚度設為5μm以上,可抑制剝離支撐體時之支撐體破裂,藉由將厚度設為50μm以下,則可提升從支撐體上方來進行曝光時的解析度。又,以低魚眼(fisheye)的支撐體為較佳。於此,所謂的魚眼,係指將材料熱熔融並進行混練、擠出,藉由2軸延伸、澆鑄法等來製造薄膜時,材料的異物、未溶解物、氧化劣化物等進入薄膜中之涵義。The thickness of the support body is preferably in the range of 5 μm to 50 μm, and further preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, cracking of the support when peeling off the support can be suppressed. By setting the thickness to 50 μm or less, the resolution when exposing from above the support can be improved. In addition, a support with a low fisheye is preferred. Here, the so-called fisheye means that when the material is thermally melted, kneaded, extruded, and a film is produced by biaxial stretching, casting, etc., foreign matter, undissolved matter, oxidative deterioration, etc. of the material enter the film. its meaning.
如前述般,感光性樹脂組成物層102之面102a,其轉印有支撐體101之面101a的表面凹凸,因此與面101a之表面為相同地,表面凹凸為小而呈平滑面。As mentioned above, the surface unevenness of the surface 101a of the support 101 is transferred to the surface 102a of the photosensitive resin composition layer 102. Therefore, like the surface of the surface 101a, the surface unevenness is small and smooth.
於曝光後顯影前(後述之於(3)步驟後(4)步驟前)的感光性樹脂組成物層102之面102a的最大凹谷深度的絕對值(|Rv|),就提升顯影性並成為良好的孔洞形狀之觀點而言,較佳為未滿500nm,又較佳為400nm以下,更佳為300nm以下。下限係例如能夠設為1nm以上等。最大凹谷深度,可使用例如Bruker AXS公司製的白色光干擾型顯微鏡(Contoure GT-X series)來進行測定。尚,若感光性樹脂組成物為負型感光性樹脂組成物之情形時,該最大凹谷深度的絕對值係活性光線之照射部的感光性樹脂組成物層之面的最大凹谷深度的絕對值;若感光性樹脂組成物為正型感光性樹脂組成物之情形時,該最大凹谷深度的絕對值係活性光線之未照射部的感光性樹脂組成物層之面的最大凹谷深度的絕對值。The absolute value (|Rv|) of the maximum valley depth (|Rv|) on the surface 102a of the photosensitive resin composition layer 102 after exposure and before development (described later after (3) step (4) step) improves developability and From the viewpoint of obtaining a good hole shape, the hole diameter is preferably less than 500 nm, more preferably not more than 400 nm, and more preferably not more than 300 nm. The lower limit can be, for example, 1 nm or more. The maximum valley depth can be measured using, for example, a white light interference type microscope (Contoure GT-X series) manufactured by Bruker AXS. Furthermore, when the photosensitive resin composition is a negative photosensitive resin composition, the absolute value of the maximum valley depth is the absolute value of the maximum valley depth on the surface of the photosensitive resin composition layer in the irradiation part of the active light ray. value; if the photosensitive resin composition is a positive photosensitive resin composition, the absolute value of the maximum valley depth is the maximum valley depth on the surface of the photosensitive resin composition layer that is not irradiated with active light rays Absolute value.
作為於曝光後顯影前(後述之於(3)步驟後(4)步驟前)的感光性樹脂組成物層102之面102a的算術平均粗糙度Ra,就提升顯影性並成為良好的孔洞形狀之觀點而言,較佳為100nm以下,又較佳為80nm以下,更佳為50nm以下。下限係例如能夠設為1nm以上等。算術平均粗糙度Ra,可使用例如AXS公司製的非接觸型干擾顯微鏡(WYKO Bruker)來進行測定。尚,若感光性樹脂組成物為負型感光性樹脂組成物之情形時,該算術平均粗糙度Ra係活性光線之照射部的感光性樹脂組成物層之面的算術平均粗糙度;若感光性樹脂組成物為正型感光性樹脂組成物之情形時,該算術平均粗糙度Ra係活性光線之未照射部的感光性樹脂組成物層之面的算術平均粗糙度。As the arithmetic mean roughness Ra of the surface 102a of the photosensitive resin composition layer 102 after exposure and before development (to be described later after (3) step (4) step), it improves developability and achieves a good hole shape. From a viewpoint, the thickness is preferably 100 nm or less, more preferably 80 nm or less, and more preferably 50 nm or less. The lower limit can be, for example, 1 nm or more. The arithmetic mean roughness Ra can be measured using, for example, a non-contact interference microscope (WYKO Bruker) manufactured by AXS Corporation. However, if the photosensitive resin composition is a negative photosensitive resin composition, the arithmetic mean roughness Ra is the arithmetic mean roughness of the surface of the photosensitive resin composition layer in the irradiation part of the active light; if the photosensitive When the resin composition is a positive photosensitive resin composition, the arithmetic mean roughness Ra is the arithmetic mean roughness of the surface of the photosensitive resin composition layer in the portion not irradiated with active light.
曝光之條件係亦可藉由以往的曝光條件來進行,例如後述之實施例所記載般,具體而言係照射10mJ/cm2 以上1000mJ/cm2 以下的紫外線之方法。Exposure conditions can also be carried out according to conventional exposure conditions, such as those described in the examples described below. Specifically, the method is to irradiate ultraviolet rays of 10 mJ/cm 2 or more and 1000 mJ/cm 2 or less.
<條件(B)> 條件(B)係關於顯影後的圖型感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|)為500nm以上。本發明人發現,藉由進行曝光及顯影來形成絕緣層時,於顯影後(進行(4)步驟後)的圖型感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|),其對於密著性及配線的遮蔽性具有很大的影響。於此,顯影的條件係亦可藉由以往的顯影條件來進行,例如後述之實施例所記載般,具體而言係以噴霧壓0.2MPa,將30℃的1質量%碳酸鈉水溶液進行噴霧2分鐘之噴霧顯影。 所謂的圖型感光性樹脂組成物層,係指藉由將感光性樹脂組成物層進行曝光、顯影,而形成的圖型的感光性樹脂組成物層之涵義。<Condition(B)> Condition (B) is that the absolute value (|Rv|) of the maximum valley depth on the surface of the support side of the patterned photosensitive resin composition layer after development is 500 nm or more. The present inventors found that when an insulating layer is formed by exposure and development, the absolute maximum valley depth of the support-side surface of the patterned photosensitive resin composition layer after development (after step (4) is performed) value (|Rv|), which has a great impact on the adhesion and shielding of wiring. Here, the development conditions can also be carried out according to the conventional development conditions, for example, as described in the examples described below, specifically, a 1 mass % sodium carbonate aqueous solution at 30° C. is sprayed with a spray pressure of 0.2 MPa 2 Minute spray development. The so-called patterned photosensitive resin composition layer refers to a patterned photosensitive resin composition layer formed by exposing and developing the photosensitive resin composition layer.
如圖3所表示之一例般,進行曝光後感光性樹脂組成物層102的顯影。顯影之一實施形態係使用顯影液,去除感光性樹脂組成物層102之未曝光部,來形成顯影後的圖型感光性樹脂組成物層102b。進行感光性樹脂組成物層102的顯影前的支撐體側之面(與基板103側之面為相反側之面)102a,如前述般,表面凹凸為小而呈平滑面,但顯影後的圖型感光性樹脂組成物層102b,由於顯影中所使用的顯影液而使得感光性樹脂組成物之表面附近的一部分被去除,故圖型感光性樹脂組成物層102b的支撐體101側之面102c的最大凹谷深度的絕對值(|Rv|)成為500nm以上。面102c係具有指定的最大凹谷深度,故與未圖示的導體層的密著性會因為定錨效果而得到提升。As an example shown in FIG. 3 , the post-exposure photosensitive resin composition layer 102 is developed. One embodiment of development uses a developer to remove the unexposed portions of the photosensitive resin composition layer 102 to form the developed patterned photosensitive resin composition layer 102b. The surface on the support side (the surface opposite to the surface on the substrate 103 side) 102a before development of the photosensitive resin composition layer 102 has small surface irregularities and a smooth surface as described above. However, the image after development In the patterned photosensitive resin composition layer 102b, a part of the surface of the patterned photosensitive resin composition is removed due to the developer used in development, so that the surface 102c of the patterned photosensitive resin composition layer 102b on the support 101 side is removed. The absolute value of the maximum valley depth (|Rv|) becomes 500nm or more. Surface 102c has a specified maximum valley depth, so the adhesion to the conductor layer (not shown) will be improved due to the anchoring effect.
作為於顯影後的圖型感光性樹脂組成物層102b的支撐體101側之面102c的最大凹谷深度的絕對值(|Rv|),就使密著性及配線的遮蔽性提升之觀點而言為500nm以上,較佳為1000nm以上,又較佳為1500nm以上,上限係例如能夠設為10000nm以下等。特別是最大凹谷深度Rv,其與算術平均粗糙度Ra為不同,最大凹谷深度Rv係被認為是用來考量圖型感光性樹脂組成物層之表面的密著性及配線的遮蔽性之效果而言,為更佳的指標。As the absolute value (|Rv|) of the maximum valley depth on the support 101 side surface 102c of the patterned photosensitive resin composition layer 102b after development, from the viewpoint of improving the adhesion and wiring shielding properties It is said to be 500nm or more, preferably 1000nm or more, further preferably 1500nm or more, and the upper limit can be, for example, 10000nm or less. In particular, the maximum valley depth Rv is different from the arithmetic mean roughness Ra. The maximum valley depth Rv is considered to be used to consider the surface adhesion of the patterned photosensitive resin composition layer and the shielding property of the wiring. In terms of performance, it is a better indicator.
作為於顯影後的圖型感光性樹脂組成物層102b的支撐體101側之面102c的算術平均粗糙度Ra,就提升密著性之觀點而言,較佳為10nm以上,又較佳為30nm以上,更佳為50nm以上。上限係例如能夠設為1000nm以下等。The arithmetic mean roughness Ra of the surface 102c on the support 101 side of the patterned photosensitive resin composition layer 102b after development is preferably 10 nm or more, and further preferably 30 nm, from the viewpoint of improving adhesion. or above, more preferably 50nm or above. The upper limit can be, for example, 1000 nm or less.
若將於曝光後顯影前(於(3)步驟後(4)步驟前)的感光性樹脂組成物層102之面102a的最大凹谷深度的絕對值設為A1,並若將於顯影後(於(4)步驟後)的圖型感光性樹脂組成物層102b的支撐體101側之面102c的最大凹谷深度的絕對值設為A2時,就可顯著得到本發明之效果之觀點而言,A2/A1係較佳為超過3,又較佳為5以上,更佳為10以上,較佳為未滿100,又較佳為70以下,更較佳為40以下。If the absolute value of the maximum valley depth of the surface 102a of the photosensitive resin composition layer 102 after exposure and before development (after (3) step (4) step) is set to A1, and if after development ( When the absolute value of the maximum valley depth of the surface 102c of the patterned photosensitive resin composition layer 102b on the support 101 side is A2, the effect of the present invention can be significantly obtained. , the A2/A1 series is preferably more than 3, more preferably 5 or more, more preferably 10 or more, preferably less than 100, more preferably 70 or less, and more preferably 40 or less.
樹脂薄片10係要求顯影後的圖型感光性樹脂組成物層102b的支撐體101側之面102c的最大凹谷深度的絕對值為滿足上述範圍內。因此,形成感光性樹脂組成物層102的感光性樹脂組成物係要求:「藉由顯影((4)步驟)所使用的顯影液來去除感光性樹脂組成物中所包含的成分之一部分」。作為如此般的感光性樹脂組成物係可使用滿足下述條件(I)或(II)者。 (I)感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材,若將感光性樹脂組成物的不揮發成分設為100質量%時,該無機填充材的含有量為60質量%以上。 (II)感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材、(b)包含乙烯性不飽和基及羧基的樹脂、(c)環氧樹脂及(d)光聚合起始劑。The resin sheet 10 requires that the absolute value of the maximum valley depth of the surface 102c of the support 101 side of the patterned photosensitive resin composition layer 102b after development satisfies the above range. Therefore, the photosensitive resin composition forming the photosensitive resin composition layer 102 requires that "a part of the components contained in the photosensitive resin composition be removed by the developer used in development ((4) step)". As such a photosensitive resin composition, one that satisfies the following condition (I) or (II) can be used. (I) The photosensitive resin composition contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more. When the non-volatile content of the photosensitive resin composition is 100% by mass, the content of the inorganic filler is 60 Quality% or more. (II) The photosensitive resin composition contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) a photopolymerizable resin. starter.
-條件(I)- 條件(I)係感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材,若將感光性樹脂組成物的不揮發成分設為100質量%時,該無機填充材的含有量為60質量%以上。若無機填充材的平均粒徑為0.5μm以上時,無機填充材的一部分可藉由顯影液而容易被去除,故可提高感光性樹脂組成物層之表面的最大凹谷深度的絕對值。又,若將感光性樹脂組成物的不揮發成分設為100質量%時,藉由將該無機填充材的含有量設為60質量%以上,從而能夠在顯影後之面102c整體上形成均勻的表面凹凸。其結果,能夠將顯影後之面102c整體的最大凹谷深度的絕對值設為500nm以上。-Condition(I)- Condition (I) is that the photosensitive resin composition contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more. When the non-volatile content of the photosensitive resin composition is 100% by mass, the content of the inorganic filler It is more than 60 mass%. When the average particle diameter of the inorganic filler is 0.5 μm or more, part of the inorganic filler can be easily removed by the developer, so the absolute value of the maximum valley depth on the surface of the photosensitive resin composition layer can be increased. Furthermore, when the non-volatile component of the photosensitive resin composition is set to 100% by mass, by setting the content of the inorganic filler to 60% by mass or more, a uniform layer can be formed on the entire surface 102c after development. The surface is uneven. As a result, the absolute value of the maximum valley depth of the entire surface 102c after development can be set to 500 nm or more.
滿足條件(I)的感光性樹脂組成物,除(a)成分外另亦可進而包含任意的成分。作為任意的成分,能夠含有例如條件(II)的必須成分之(b)包含乙烯性不飽和基及羧基的樹脂、(c)環氧樹脂及(d)光聚合起始劑。又,作為進而的任意的成分,能夠含有條件(II)的任意的成分之(e)反應稀釋劑、(f)反應性稀釋劑、(g)有機溶劑、及(h)其他的添加劑。對於該等各成分於後述之。The photosensitive resin composition satisfying condition (I) may further contain optional components in addition to component (a). As optional components, for example, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) a photopolymerization initiator, which are essential components of condition (II), can be contained. Moreover, as further optional components, (e) reactive diluent, (f) reactive diluent, (g) organic solvent, and (h) other additives can be contained as any optional component of condition (II). Each of these components will be described later.
((a)平均粒徑0.5μm以上的無機填充材) 無機填充材的材料並無特別限定,但可舉例如矽石、氧化鋁、玻璃、堇青石、矽氧化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、水鋁礦、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、碳酸鍶、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、氧化鋯、鈦酸鋇、鈦酸鋯酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯、及鎢磷酸鋯等。該等之中係以矽石為特別適合。又作為矽石係以球形矽石為較佳。無機填充材係可使用單獨1種、或可組合2種以上來使用。((a) Inorganic filler with an average particle diameter of 0.5 μm or more) The material of the inorganic filler is not particularly limited, but examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and hydroaluminum. Mineral, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanium Bismuth acid, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungsten phosphate, etc. Among these, silica is particularly suitable. As for the silica system, spherical silica is preferred. The inorganic filler system can be used individually by 1 type, or can be used in combination of 2 or more types.
無機填充材的平均粒徑,就可得到顯影性為優異、且平均線熱膨脹率為低的硬化物之觀點而言為0.5μm以上,較佳為0.8μm以上,又較佳為1μm以上。該平均粒徑的上限,就可得到優異的解析性之觀點而言為2.5μm以下,較佳為2μm以下,又較佳為1.5μm以下,更佳為1.3μm以下。作為具有如此般的平均粒徑的無機填充材的市售品,可舉例如Admatechs公司製「SC2050」、「SC4050」、「ADMAFINE」、電氣化學工業公司製「SFP series」、Nippon Steel & Sumikin Materials公司製「SP(H) series」、堺化學工業公司製「Sciqas series」、日本觸媒公司製「Seahostar series」、Nippon Steel & Sumikin Materials公司製的「AZ series」、「AX series」、堺化學工業公司製的「B series」、「BF series」等。The average particle diameter of the inorganic filler is 0.5 μm or more, preferably 0.8 μm or more, and further preferably 1 μm or more, from the viewpoint of obtaining a cured product that is excellent in developability and has a low average linear thermal expansion coefficient. The upper limit of the average particle diameter is 2.5 μm or less, preferably 2 μm or less, more preferably 1.5 μm or less, and more preferably 1.3 μm or less from the viewpoint of obtaining excellent resolution. Examples of commercially available inorganic fillers having such an average particle diameter include "SC2050", "SC4050", "ADMAFINE" manufactured by Admatechs, "SFP series" manufactured by Denki Chemical Industry Co., Ltd., and Nippon Steel & Sumikin Materials "SP(H) series" made by the company, "Sciqas series" made by Sakai Chemical Industry Co., Ltd., "Seahostar series" made by Nippon Shokubai Co., Ltd., "AZ series" and "AX series" made by Nippon Steel & Sumikin Materials Co., Ltd., Sakai Chemical Industrial company-made "B series", "BF series", etc.
無機填充材的平均粒徑係可藉由基於米氏(Mie)散射理論之雷射繞射・散射法來進行測定。具體而言,藉由雷射繞射散射式粒徑分布測定裝置,利用體積基準來製作無機填充材的粒徑分布,並藉由將該中值粒徑(median diameter)設為平均粒徑從而來進行測定。測定樣品係可藉由超音波使無機填充材分散至水中者為較佳使用。作為雷射繞射散射式粒徑分布測定裝置係可使用堀場製作所公司製「LA-500」、島津製作所公司製「SALD-2200」等。The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, a laser diffraction scattering particle size distribution measuring device is used to prepare the particle size distribution of the inorganic filler using a volume basis, and the median diameter is set as the average particle diameter. to measure. It is better to use the test sample that can disperse the inorganic filler into water through ultrasonic waves. As a laser diffraction scattering particle size distribution measuring device, "LA-500" manufactured by Horiba Manufacturing Co., Ltd., "SALD-2200" manufactured by Shimadzu Corporation, etc. can be used.
無機填充材的比表面積,就可顯著得到本發明之效果之觀點而言,較佳為1m2 /g以上,又較佳為2m2 /g以上,特佳為5m2 /g以上。對於上限雖沒有特別的限制,較佳為60m2 /g以下,50m2 /g以下或40m2 /g以下。無機填充材的比表面積係可藉由BET法來進行測定。The specific surface area of the inorganic filler is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, and particularly preferably 5 m 2 /g or more, from the viewpoint of significantly obtaining the effects of the present invention. Although the upper limit is not particularly limited, it is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less. The specific surface area of the inorganic filler can be measured by the BET method.
就提高耐濕性及分散性之觀點而言,無機填充材係以利用表面處理劑來進行表面處理為較佳。作為表面處理劑,可舉例如胺基矽烷系偶合劑、環氧基矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、烷氧基矽烷化合物、有機矽氮烷化合物、鈦酸酯系偶合劑等。From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably surface-treated with a surface treatment agent. Examples of the surface treatment agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate ester compounds. Coupling agent, etc.
作為表面處理劑的市售品,可舉例如信越化學工業公司製「KBM22」(二甲基二甲氧基矽烷)、信越化學工業公司製「KBM403」(3-環氧丙氧基丙基三甲氧基矽烷)、信越化學工業公司製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業公司製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業公司製「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業公司製「KBM5783」(N-苯基-3-胺基辛基三甲氧基矽烷)、信越化學工業公司製「SZ-31」(六甲基二矽氮烷)、信越化學工業公司製「KBM103」(苯基三甲氧基矽烷)、信越化學工業公司製「KBM-4803」(長鏈環氧型矽烷偶合劑)等。表面處理劑係可使用單獨1種類、或以任意的比率組合2種類以上來使用。Examples of commercially available surface treatment agents include "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. and "KBM403" (3-glycidoxypropyltrimethylsilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Oxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., Shin-Etsu Chemical Industries "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by the company, "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., Shin-Etsu "SZ-31" (hexamethyldisilazane) made by Chemical Industry Co., Ltd., "KBM103" (phenyltrimethoxysilane) made by Shin-Etsu Chemical Industry Co., Ltd., "KBM-4803" (long chain ring) made by Shin-Etsu Chemical Industry Co., Ltd. Oxygen silane coupling agent), etc. The surface treatment agent can be used alone or in combination of two or more types at an arbitrary ratio.
藉由表面處理劑之表面處理的程度,可依(a)成分的每單位表面積的碳量來進行評估。(a)成分的每單位表面積的碳量,就提升(a)成分的分散性之觀點而言,較佳為0.02mg/m2 以上,又較佳為0.1mg/m2 以上,特佳為0.2mg/m2 以上。另一方面,就抑制感光性樹脂組成物的熔融黏度及在薄片形態下的熔融黏度的上昇之觀點而言,前述的碳量係較佳為1mg/m2 以下,又較佳為0.8mg/m2 以下,特佳為0.5mg/m2 以下。The degree of surface treatment by the surface treatment agent can be evaluated based on the amount of carbon per unit surface area of component (a). From the viewpoint of improving the dispersibility of component (a), the amount of carbon per unit surface area of component (a) is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and particularly preferably 0.2mg/ m2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the photosensitive resin composition and the melt viscosity in the sheet form, the carbon amount is preferably 1 mg/m 2 or less, and more preferably 0.8 mg/m 2 m 2 or less, preferably 0.5 mg/m 2 or less.
(a)成分的每單位表面積的碳量,可將經表面處理後的(a)成分藉由溶劑(例如甲基乙基酮(以下有簡稱為「MEK」之情形))予以洗淨處理後,來進行測定。具體而言,混合充分量的甲基乙基酮、與經表面處理劑進行表面處理後的(a)成分,並以25℃進行超音波洗淨5分鐘。之後,去除上清液並使固形分乾燥後,使用碳分析計可測定(a)成分的每單位表面積的碳量。作為碳分析計係可使用堀場製作所公司製「EMIA-320V」。The amount of carbon per unit surface area of component (a) can be determined by washing the surface-treated component (a) with a solvent (such as methyl ethyl ketone (hereinafter referred to as "MEK")). , for measurement. Specifically, a sufficient amount of methyl ethyl ketone and component (a) surface-treated with a surface treatment agent are mixed, and ultrasonic cleaning is performed at 25° C. for 5 minutes. Thereafter, the supernatant liquid is removed and the solid content is dried, and then the amount of carbon per unit surface area of the component (a) can be measured using a carbon analyzer. As a carbon analyzer system, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.
就可得到平均線熱膨脹率為低的硬化物之觀點而言,若將感光性樹脂組成物中之不揮發成分設為100質量%時,(a)成分的含有量為60質量%以上,較佳為65質量%以上,更較佳為70質量%以上。就提高顯影性之觀點而言,上限係較佳為95質量%以下,又較佳為80質量%以下,又較佳為75質量%以下。 尚,本發明中若無特別說明時,感光性樹脂組成物中之各成分的含有量係將感光性樹脂組成物中之不揮發成分設為100質量%時的值。From the viewpoint of obtaining a cured product with a low average linear thermal expansion coefficient, when the non-volatile components in the photosensitive resin composition are set to 100 mass %, the content of component (a) is 60 mass % or more, which is less than 60 mass %. Preferably, it is 65 mass % or more, and more preferably, it is 70 mass % or more. From the viewpoint of improving developability, the upper limit is preferably 95 mass% or less, more preferably 80 mass% or less, and still more preferably 75 mass% or less. Incidentally, unless otherwise specified in the present invention, the content of each component in the photosensitive resin composition is the value when the non-volatile component in the photosensitive resin composition is 100% by mass.
-條件(II)- 條件(II)係感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材、(b)包含乙烯性不飽和基及羧基的樹脂、(c)環氧樹脂及(d)光聚合起始劑。藉由組合並含有(a)~(d)成分,感光性樹脂組成物中之各成分的一部分可藉由顯影液而容易被去除,故可提高感光性樹脂組成物層之表面的最大凹谷深度的絕對值。-Condition(II)- Condition (II) is that the photosensitive resin composition contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) light Polymerization initiator. By combining and containing the components (a) to (d), part of each component in the photosensitive resin composition can be easily removed by the developer, so the maximum valley on the surface of the photosensitive resin composition layer can be increased. The absolute value of depth.
滿足條件(II)的感光性樹脂組成物,可進而包含任意的成分來與(a)~(d)成分組合。作為任意的成分係能夠包含例如(e)反應性稀釋劑、(f)有機溶劑、及(g)其他的添加劑。以下,對於感光性樹脂組成物中所包含的各成分進行詳細說明。The photosensitive resin composition that satisfies condition (II) may further contain optional components in combination with the components (a) to (d). The optional component system can include, for example, (e) reactive diluent, (f) organic solvent, and (g) other additives. Each component contained in the photosensitive resin composition will be described in detail below.
((a)平均粒徑0.5μm以上的無機填充材) 條件(II)的感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材。藉由含有(a)平均粒徑0.5μm以上的無機填充材,從而可得到平均線熱膨脹率為低的硬化物。((a) Inorganic filler with an average particle diameter of 0.5 μm or more) The photosensitive resin composition of condition (II) contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more. By containing (a) an inorganic filler with an average particle diameter of 0.5 μm or more, a hardened material with a low average linear thermal expansion rate can be obtained.
作為條件(II)中使用的(a)平均粒徑0.5μm以上的無機填充材,可舉例如在「-條件(I)-」所說明的無機填充材。Examples of the inorganic filler having an average particle diameter of (a) of 0.5 μm or more used in condition (II) include the inorganic filler described in “-Condition (I)-”.
無機填充材的平均粒徑係如同「-條件(I)-」中所說明般。The average particle diameter of the inorganic filler is as explained in "-Condition (I)-".
條件(II)中使用的(a)平均粒徑0.5μm以上的無機填充材,較佳為利用表面處理劑來進行處理。表面處理劑的種類及表面處理的程度係如同「-條件(I)-」中所說明般。The inorganic filler (a) with an average particle diameter of 0.5 μm or more used in condition (II) is preferably treated with a surface treatment agent. The type of surface treatment agent and the degree of surface treatment are as described in "-Condition (I)-".
就可得到平均線熱膨脹率為低的硬化物之觀點而言,若將感光性樹脂組成物中之不揮發成分設為100質量%時,條件(II)中使用的(a)成分的含有量為10質量%以上,較佳為20質量%以上,更佳為30質量%以上。就提高顯影性之觀點而言,上限係較佳為未滿60質量%,又較佳為55質量%以下,又較佳為50質量%以下。From the viewpoint of obtaining a cured product with a low average linear thermal expansion coefficient, if the non-volatile component in the photosensitive resin composition is 100% by mass, the content of component (a) used in condition (II) It is 10 mass % or more, preferably 20 mass % or more, more preferably 30 mass % or more. From the viewpoint of improving developability, the upper limit is preferably less than 60 mass %, more preferably 55 mass % or less, and still more preferably 50 mass % or less.
((b)包含乙烯性不飽和基及羧基的樹脂) 滿足條件(II)的感光性樹脂組成物含有(b)包含乙烯性不飽和基及羧基的樹脂。((b) Resin containing ethylenically unsaturated groups and carboxyl groups) The photosensitive resin composition satisfying condition (II) contains (b) a resin containing an ethylenically unsaturated group and a carboxyl group.
作為乙烯性不飽和基,可舉例如乙烯基、烯丙基、炔丙基、丁烯基、乙炔基、苯基乙炔基、馬來醯亞胺基、納迪醯亞胺基(nadimide group)、(甲基)丙烯醯基,就光自由基聚合的反應性之觀點而言,以(甲基)丙烯醯基為較佳。所謂的「(甲基)丙烯醯基」係指甲基丙烯醯基及丙烯醯基之涵義。Examples of the ethylenically unsaturated group include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide group, and nadimide group. , (meth)acrylyl group, from the viewpoint of reactivity in photoradical polymerization, (meth)acrylyl group is preferred. The so-called "(meth)acrylyl group" refers to the meaning of methacrylyl group and acrylyl group.
(b)成分係具有乙烯性不飽和基及羧基,可使用能夠光自由基聚合之同時能夠鹼顯影的任意的化合物,例如,以1分子中合併具有羧基與2個以上的乙烯性不飽和基的樹脂為較佳。The component (b) has an ethylenically unsaturated group and a carboxyl group, and can be any compound that can be photoradically polymerized and alkali developable at the same time. For example, a compound having a carboxyl group and two or more ethylenically unsaturated groups can be combined in one molecule. The resin is better.
作為含有乙烯性不飽和基及羧基的樹脂之一樣態,可舉出使環氧化合物與不飽和羧酸反應,進而再與酸酐反應的酸改性不飽和環氧酯樹脂等。詳細而言,可藉由使環氧化合物與不飽和羧酸反應而得到不飽和環氧酯樹脂,再使不飽和環氧酯樹脂與酸酐反應,從而得到酸改性不飽和環氧酯樹脂。 Examples of resins containing an ethylenically unsaturated group and a carboxyl group include an acid-modified unsaturated epoxy ester resin in which an epoxy compound is reacted with an unsaturated carboxylic acid and further reacted with an acid anhydride. Specifically, an unsaturated epoxy ester resin can be obtained by reacting an epoxy compound with an unsaturated carboxylic acid, and then the unsaturated epoxy ester resin can be reacted with an acid anhydride to obtain an acid-modified unsaturated epoxy ester resin.
作為環氧化合物,只要是分子內具有環氧基的化合物即能夠使用,可舉例如含有環氧基的共聚物、雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、雙酚F型環氧樹脂、氫化雙酚F型環氧樹脂、雙酚S型環氧樹脂、使雙酚F型環氧樹脂與環氧氯丙烷反應而得到改性成3官能以上的改性雙酚F型環氧樹脂等的雙酚型環氧樹脂;聯苯型環氧樹脂、四甲基聯苯型等的聯苯型環氧樹脂;苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A型酚醛清漆型環氧樹脂、烷基苯酚酚醛清漆型環氧樹脂等的酚醛清漆型環氧樹脂;雙酚AF型環氧樹脂、及全氟烷基型環氧樹脂等的含有氟的環氧樹脂;萘型環氧樹脂、二羥基萘型環氧樹脂、聚羥基聯萘型環氧樹脂、萘酚型環氧樹脂、聯萘酚型環氧樹脂、伸萘基醚型環氧樹脂萘酚酚醛清漆型環氧樹脂、藉由聚羥基萘與醛類的縮合反應而得到的萘型環氧樹脂等的具有萘骨架的環氧樹脂(含有萘骨架的環氧樹脂);聯二甲酚型環氧樹脂;二環戊二烯型環氧樹脂;三苯酚型環氧樹脂;tert-丁基-兒茶酚型環氧樹脂;含有蒽型環氧樹脂等的縮合環骨架的環氧樹脂;縮水甘油胺型環 氧樹脂;縮水甘油酯型環氧樹脂;聯苯型環氧樹脂;線狀脂肪族環氧樹脂;具有丁二烯構造的環氧樹脂;脂環式環氧樹脂;雜環式環氧樹脂;含有螺環的環氧樹脂;環己烷二甲醇型環氧樹脂;三羥甲基丙烷型環氧樹脂;四苯乙烷型環氧樹脂;聚(甲基)丙烯酸縮甘油酯、甲基丙烯酸縮水甘油酯與丙烯酸酯的共聚物等的含有縮水甘油基的丙烯酸樹脂;茀型環氧樹脂;鹵化環氧樹脂等。 As the epoxy compound, any compound having an epoxy group in the molecule can be used. Examples thereof include epoxy group-containing copolymers, bisphenol A-type epoxy resins, hydrogenated bisphenol A-type epoxy resins, and bisphenol F. type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, modified bisphenol F modified to have more than three functions by reacting bisphenol F type epoxy resin with epichlorohydrin Bisphenol-type epoxy resins such as bisphenol-type epoxy resin; biphenyl-type epoxy resins, tetramethylbiphenyl-type and other biphenyl-type epoxy resins; phenol novolak-type epoxy resin, cresol novolak-type epoxy Resins, novolak-type epoxy resins such as bisphenol A-type novolak-type epoxy resins, alkylphenol novolac-type epoxy resins, etc.; bisphenol AF-type epoxy resins, and perfluoroalkyl-type epoxy resins, etc. Fluorine-containing epoxy resin; naphthalene-type epoxy resin, dihydroxynaphthalene-type epoxy resin, polyhydroxybinaphthyl-type epoxy resin, naphthol-type epoxy resin, binaphthol-type epoxy resin, naphthyl ether type Epoxy resins include naphthol novolak-type epoxy resins, naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes, and other epoxy resins with a naphthalene skeleton (epoxy resins containing a naphthalene skeleton); Dixylenol type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; tert-butyl-catechol type epoxy resin; condensed ring skeleton containing anthracene type epoxy resin, etc. Epoxy resin; glycidyl amine type ring Oxygen resin; glycidyl ester type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; Epoxy resins containing spiro rings; cyclohexanedimethanol-type epoxy resins; trimethylolpropane-type epoxy resins; tetraphenylethane-type epoxy resins; polyglycidyl(meth)acrylate, methacrylic acid Acrylic resins containing glycidyl groups such as copolymers of glycidyl esters and acrylates; fluorine-type epoxy resins; halogenated epoxy resins, etc.
就使平均線熱膨脹率降低之觀點而言,環氧化合物較佳為含有環氧基的共聚物、含有芳香族骨架的環氧樹脂。於此,所謂的芳香族骨架,係指亦包含多環芳香族及芳香族雜環之概念。環氧化合物係以含有萘骨架的環氧樹脂、含有縮合環骨架的環氧樹脂、聯苯型環氧樹脂、雙酚F型環氧樹脂、雙酚A型環氧樹脂、甲酚酚醛清漆型環氧樹脂、縮水甘油酯型環氧樹脂為較佳。 From the viewpoint of reducing the average linear thermal expansion coefficient, the epoxy compound is preferably an epoxy group-containing copolymer or an epoxy resin containing an aromatic skeleton. Here, the so-called aromatic skeleton refers to a concept that also includes polycyclic aromatic and aromatic heterocyclic rings. Epoxy compounds include epoxy resins containing naphthalene skeletons, epoxy resins containing condensed ring skeletons, biphenyl-type epoxy resins, bisphenol F-type epoxy resins, bisphenol A-type epoxy resins, and cresol novolac-type epoxy resins. Epoxy resin and glycidyl ester type epoxy resin are preferred.
含有環氧基的共聚物,可藉由將含有環氧基的單體及因應所需的任意的單體進行聚合來得到。做為含有環氧基的單體,可舉例如(甲基)丙烯酸縮甘油酯、(甲基)丙烯酸3,4-環氧基丁酯、(甲基)丙烯酸2-甲基-3,4-環氧基環己酯、烯丙基縮水甘油醚等的含有環氧基的(甲基)丙烯酸酯單體,以(甲基)丙烯酸縮甘油酯為較佳。含有環氧基的單體係可單獨使用、亦可混合2種以上來使用。 The epoxy group-containing copolymer can be obtained by polymerizing an epoxy group-containing monomer and any desired monomer. Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 2-methyl-3,4 (meth)acrylate. - Epoxy group-containing (meth)acrylate monomers such as epoxycyclohexyl and allyl glycidyl ether, with glycidyl (meth)acrylate being preferred. The epoxy group-containing monosystem can be used alone, or two or more types can be mixed and used.
作為任意的單體,可舉例如苯乙烯、(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸n-丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸n-丁 酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸t-丁酯、(甲基)丙烯酸n-戊酯、(甲基)丙烯酸n-己酯、(甲基)丙烯酸n-庚酯、(甲基)丙烯酸n-辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十二烷基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸4-tert-丁基環己酯、(甲基)丙烯酸異莰基酯、(甲基)丙烯酸雙環戊二烯酯、(甲基)丙烯酸苄酯、丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、(甲基)丙烯腈、3-(甲基)丙烯醯基丙基三甲氧基矽烷、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸縮甘油酯、苯乙烯、α-甲基苯乙烯、p-甲基苯乙烯、p-甲氧基苯乙烯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基-n-丁酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基-n-丁酯、(甲基)丙烯酸3-羥基-n-丁酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、鄰苯二甲酸2-(甲基)丙烯醯基-2-羥基乙酯、末端具有羥基的內酯改性(甲基)丙烯酸酯、(甲基)丙烯酸1-金剛烷酯等,以(甲基)丙烯酸n-丁酯為較佳。任意的單體係可單獨使用、亦可混合2種以上來使用。 Examples of the optional monomer include styrene, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and iso(meth)acrylate. Propyl ester, n-butyl (meth)acrylate Ester, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate , n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, Tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, benzyl (meth)acrylate, acrylamide, N, N-dimethyl(meth)acrylamide, (meth)acrylonitrile, 3-(meth)acrylylpropyltrimethoxysilane, (meth)acrylic acid N,N-dimethylamino Ethyl ester, glycidyl (meth)acrylate, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, 2-hydroxyethyl (meth)acrylate, (meth)acrylate 3-hydroxypropyl acrylate, 4-hydroxy-n-butyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-n-butyl (meth)acrylate, (meth)acrylate base) 3-hydroxy-n-butyl acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, Polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acrylyl-2-hydroxyethyl phthalate, terminal hydroxyl group Lactone-modified (meth)acrylate, 1-adamantyl (meth)acrylate, etc., with n-butyl (meth)acrylate being preferred. Any single system can be used alone, or two or more types can be mixed and used.
作為含有萘骨架的環氧樹脂係以二羥基萘型環氧樹脂、聚羥基聯萘型環氧樹脂、藉由聚羥基萘與醛類 的縮合反應而得到的萘型環氧樹脂為較佳。作為二羥基萘型環氧樹脂,可舉例如1,3-二縮水甘油醚氧基萘、1,4-二縮水甘油醚氧基萘、1,5-二縮水甘油醚氧基萘、1,6-二縮水甘油醚氧基萘、2,3-二縮水甘油醚氧基萘、2,6-二縮水甘油醚氧基萘、2,7-二縮水甘油醚氧基萘等。作為聚羥基聯萘型環氧樹脂,可舉例如1,1’-聯-(2-縮水甘油醚氧基)萘基、1-(2,7-二縮水甘油醚氧基)-1’-(2’-縮水甘油醚氧基)聯萘基、1,1’-聯-(2,7-二縮水甘油醚氧基)萘基等。作為藉由聚羥基萘與醛類的縮合反應而得到的萘型環氧樹脂,可舉例如1,1’-雙(2,7-二縮水甘油醚氧基萘基)甲烷、1-(2,7-二縮水甘油醚氧基萘基)-1’-(2’-縮水甘油醚氧基萘基)甲烷、1,1’-雙(2-縮水甘油醚氧基萘基)甲烷。 As the epoxy resin containing naphthalene skeleton, dihydroxynaphthalene type epoxy resin, polyhydroxybinaphthyl type epoxy resin, polyhydroxynaphthalene and aldehydes are used. The naphthalene type epoxy resin obtained by the condensation reaction is preferred. Examples of the dihydroxynaphthalene type epoxy resin include 1,3-diglycidyl etheroxynaphthalene, 1,4-diglycidyl etheroxynaphthalene, 1,5-diglycidyl etheroxynaphthalene, 1, 6-diglycidyl etheroxynaphthalene, 2,3-diglycidyl etheroxynaphthalene, 2,6-diglycidyl etheroxynaphthalene, 2,7-diglycidyl etheroxynaphthalene, etc. Examples of the polyhydroxybinaphthyl epoxy resin include 1,1'-bis-(2-glycidyl etheroxy)naphthyl and 1-(2,7-diglycidyl etheroxy)-1'- (2'-glycidyl etheroxy)binaphthyl, 1,1'-bi-(2,7-diglycidyl etheroxy)naphthyl, etc. Examples of the naphthalene-type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2 ,7-diglycidyloxynaphthyl)-1'-(2'-glycidyloxynaphthyl)methane, 1,1'-bis(2-glycidyloxynaphthyl)methane.
作為不飽和羧酸,可舉例如丙烯酸、甲基丙烯酸、桂皮酸、巴豆酸等,該等係可使用單獨1種亦可併用2種以上。其中,就感光性樹脂組成物的光硬化性提升之觀點而言,以丙烯酸、甲基丙烯酸為較佳。尚,本說明書中將上述之環氧化合物與(甲基)丙烯酸的反應物之環氧酯樹脂,有記載為「環氧(甲基)丙烯酸酯」之情形,於此環氧化合物的環氧基,因與(甲基)丙烯酸的反應而導致實質上的消滅。所謂的「(甲基)丙烯酸酯」係指甲基丙烯酸酯及丙烯酸酯之涵義。有將丙烯酸與甲基丙烯酸統合稱為「(甲基)丙烯酸」之情形。 Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, and the like, and these may be used alone or in combination of two or more types. Among them, acrylic acid and methacrylic acid are preferred from the viewpoint of improving the photocurability of the photosensitive resin composition. Furthermore, in this specification, the epoxy ester resin that is the reaction product of the above-mentioned epoxy compound and (meth)acrylic acid is sometimes described as "epoxy (meth)acrylate". In this specification, the epoxy resin of the epoxy compound is group, resulting in substantial destruction due to reaction with (meth)acrylic acid. The so-called "(meth)acrylate" refers to both methacrylate and acrylate. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth)acrylic acid".
作為酸酐,可舉例如馬來酸酐、琥珀酸酐、伊康酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、二苯甲酮四羧酸二酐等,該等係可使用任何1種亦可併用2種以上。其中,就硬化物的解析性及絕緣可靠性提升之方面而言,以琥珀酸酐、四氫鄰苯二甲酸酐為較佳。Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. Benzophenone tetracarboxylic dianhydride, etc., any one type may be used, or two or more types may be used in combination. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred in terms of improving the resolution and insulation reliability of the hardened product.
在得到酸改性不飽和環氧酯樹脂時,因應所需亦可使用觸媒、溶劑及聚合抑制劑等。When obtaining acid-modified unsaturated epoxy ester resin, catalysts, solvents, polymerization inhibitors, etc. can also be used as needed.
作為酸改性不飽和環氧酯樹脂係以酸改性環氧(甲基)丙烯酸酯為較佳。酸改性不飽和環氧酯樹脂中,所謂的「環氧」係表示源自上述之環氧化合物的構造。例如,所謂的「酸改性雙酚型環氧(甲基)丙烯酸酯」係指作為環氧化合物使用雙酚型環氧樹脂,作為不飽和羧酸使用(甲基)丙烯酸而得到的酸改性不飽和環氧酯樹脂之涵義。As the acid-modified unsaturated epoxy ester resin, acid-modified epoxy (meth)acrylate is preferred. In the acid-modified unsaturated epoxy ester resin, "epoxy" means a structure derived from the above-mentioned epoxy compound. For example, "acid-modified bisphenol-type epoxy (meth)acrylate" refers to an acid-modified product obtained by using bisphenol-type epoxy resin as the epoxy compound and (meth)acrylic acid as the unsaturated carboxylic acid. The meaning of sexually unsaturated epoxy ester resin.
酸改性不飽和環氧酯樹脂係以玻璃轉移溫度為-20℃以下的(甲基)丙烯酸聚合物為較佳。玻璃轉移溫度為-20℃以下的(甲基)丙烯酸聚合物,其與(a)成分、(c)~(d)成分的相溶性,相較於其他的(b)成分為特別的低。因而,該(甲基)丙烯酸聚合物係在感光性樹脂組成物中容易相分離。因此,一般為將包含該(甲基)丙烯酸聚合物的區域(domain)分散、形成於感光性樹脂組成物層中。包含該(甲基)丙烯酸聚合物的區域係可容易利用顯影液來去除,因此於顯影後,在(甲基)丙烯酸聚合物被去除的部位會產生凹凸,故可增加於顯影後的圖型感光性樹脂組成物層表面的最大凹谷深度的絕對值。所謂的(甲基)丙烯酸聚合物,係指聚合物所包含的構造單位,其具有將(甲基)丙烯酸單體聚合而形成的構造。作為如此般的(甲基)丙烯酸聚合物,可舉出將(甲基)丙烯酸單體進行聚合而成的聚合物、或將(甲基)丙烯酸單體及能夠與該(甲基)丙烯酸單體共聚合的單體進行共聚合而成的聚合物。The acid-modified unsaturated epoxy ester resin is preferably a (meth)acrylic acid polymer with a glass transition temperature of -20°C or lower. The (meth)acrylic polymer with a glass transition temperature of -20°C or lower has particularly low compatibility with the component (a) and components (c) to (d) compared to the other components (b). Therefore, the (meth)acrylic polymer is easily phase-separated in the photosensitive resin composition. Therefore, domains containing the (meth)acrylic polymer are generally dispersed and formed in the photosensitive resin composition layer. The area containing the (meth)acrylic acid polymer can be easily removed using a developer. Therefore, after development, unevenness will be generated in the area where the (meth)acrylic acid polymer is removed, so it can be added to the pattern after development. The absolute value of the maximum valley depth on the surface of the photosensitive resin composition layer. A (meth)acrylic acid polymer refers to a structural unit contained in a polymer and has a structure formed by polymerizing a (meth)acrylic acid monomer. Examples of such a (meth)acrylic acid polymer include a polymer obtained by polymerizing a (meth)acrylic acid monomer, or a (meth)acrylic acid monomer and a polymer capable of being combined with the (meth)acrylic acid monomer. A polymer formed by the copolymerization of monomers.
作為玻璃轉移溫度為-20℃以下的(甲基)丙烯酸聚合物,可舉出將含有環氧基的共聚物與(甲基)丙烯酸反應,進而再與酸酐反應的酸改性不飽和環氧(甲基)丙烯酸共聚物等。詳細係藉由含有環氧基的共聚物與(甲基)丙烯酸反應而得到不飽和環氧(甲基)丙烯酸共聚物,再使不飽和環氧(甲基)丙烯酸共聚物與酸酐反應,從而可得到酸改性不飽和環氧(甲基)丙烯酸共聚物。Examples of (meth)acrylic polymers having a glass transition temperature of -20° C. or lower include acid-modified unsaturated epoxy in which an epoxy group-containing copolymer is reacted with (meth)acrylic acid and further reacted with an acid anhydride. (meth)acrylic acid copolymer, etc. In detail, an unsaturated epoxy (meth)acrylic acid copolymer is obtained by reacting a copolymer containing an epoxy group with (meth)acrylic acid, and then the unsaturated epoxy (meth)acrylic acid copolymer is reacted with an acid anhydride, thereby Acid-modified unsaturated epoxy (meth)acrylic acid copolymers can be obtained.
作為玻璃轉移溫度為-20℃以下的(甲基)丙烯酸聚合物的較佳樣態如下:一種化合物,其係將藉由含有環氧基的單體及任意的單體聚合而得到的含有環氧基的共聚物、與(甲基)丙烯酸以及酸酐進行反應而成的化合物,其中,含有環氧基的單體為甲基丙烯酸縮水甘油酯,任意的單體為丙烯酸丁酯,酸酐為四氫鄰苯二甲酸酐。A preferred aspect of the (meth)acrylic polymer having a glass transition temperature of -20°C or less is as follows: a compound containing a ring-containing compound obtained by polymerizing an epoxy group-containing monomer and an optional monomer. A copolymer of oxygen groups, a compound obtained by reacting with (meth)acrylic acid and an acid anhydride, in which the monomer containing an epoxy group is glycidyl methacrylate, an optional monomer is butyl acrylate, and the acid anhydride is tetramethacrylate. Hydrophthalic anhydride.
如此般的酸改性不飽和環氧酯樹脂係可使用市售品,作為具體例可舉出日本化藥公司製的「ZAR-2000」(雙酚A型環氧樹脂、丙烯酸、及琥珀酸酐的反應物)、「ZFR-1491H」、「ZFR-1533H」(雙酚F型環氧樹脂、丙烯酸、及四氫鄰苯二甲酸酐的反應物)、昭和電工公司製的「PR-300CP」(甲酚酚醛清漆型環氧樹脂、丙烯酸、及酸酐的反應物)等。該等係可使用單獨1種、或可組合2種以上來使用。Commercially available products can be used as such acid-modified unsaturated epoxy ester resins. Specific examples include "ZAR-2000" (bisphenol A type epoxy resin, acrylic acid, and succinic anhydride) manufactured by Nippon Kayaku Co., Ltd. Reactant), "ZFR-1491H", "ZFR-1533H" (reactant of bisphenol F epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), "PR-300CP" manufactured by Showa Denko Co., Ltd. (Reactant of cresol novolak type epoxy resin, acrylic acid, and acid anhydride), etc. These systems may be used individually by 1 type, or may be used in combination of 2 or more types.
作為含有乙烯性不飽和基及羧基的樹脂之其他的樣態,可舉出將(甲基)丙烯酸進行聚合而得到的構造單位中具有(甲基)丙烯酸樹脂,與含有乙烯性不飽和基的環氧化合物予以反應,來導入乙烯性不飽和基的不飽和改性(甲基)丙烯酸樹脂。含有乙烯性不飽和基的環氧化合物,可舉例如甲基丙烯酸縮水甘油酯、(甲基)丙烯酸4-羥基丁酯縮水甘油醚、(甲基)丙烯酸3,4-環氧基環己基甲酯等。進而亦可將酸酐、與在不飽和基導入時所產生的羥基進行反應。作為酸酐係可使用與上述之酸酐為相同者,較佳的範圍亦為相同。Other forms of the resin containing an ethylenically unsaturated group and a carboxyl group include a (meth)acrylic resin having a structural unit obtained by polymerizing (meth)acrylic acid, and an ethylenically unsaturated group-containing resin. The epoxy compound reacts to introduce an unsaturated modified (meth)acrylic resin with an ethylenically unsaturated group. Examples of epoxy compounds containing ethylenically unsaturated groups include glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Ester etc. Furthermore, an acid anhydride may be reacted with a hydroxyl group generated when an unsaturated group is introduced. As the acid anhydride, the same acid anhydrides as those mentioned above can be used, and the preferable ranges are also the same.
如此般的不飽和改性(甲基)丙烯酸樹脂係可使用市售品,作為具體例,可舉出昭和電工公司製的「SPC-1000」、「SPC-3000」、Daicel-allnex公司製「Cyclomer P(ACA)Z-250」、「Cyclomer P(ACA)Z-251」、「Cyclomer P(ACA)Z-254」、「Cyclomer P(ACA)Z-300」、「Cyclomer P(ACA)Z-320」等。Commercially available products can be used as such unsaturated modified (meth)acrylic resins. Specific examples include "SPC-1000" and "SPC-3000" manufactured by Showa Denko Co., Ltd., and "SPC-3000" manufactured by Daicel-allnex Co., Ltd. Cyclomer P(ACA)Z-250", "Cyclomer P(ACA)Z-251", "Cyclomer P(ACA)Z-254", "Cyclomer P(ACA)Z-300", "Cyclomer P(ACA)Z -320" etc.
就製膜性之觀點而言,作為(b)成分的重量平均分子量係以1000以上為較佳,以1500以上為又較佳,以2000以上為更佳。就顯影性之觀點而言,作為上限係以10000以下為較佳,以8000以下為又較佳,以7500以下為更佳。重量平均分子量係藉由凝膠滲透層析法(GPC)所測定之聚苯乙烯換算的重量平均分子量。From the viewpoint of film-forming properties, the weight average molecular weight of component (b) is preferably 1,000 or more, more preferably 1,500 or more, and more preferably 2,000 or more. From the viewpoint of developability, the upper limit is preferably 10,000 or less, more preferably 8,000 or less, and more preferably 7,500 or less. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
作為(b)成分的酸價,就使感光性樹脂組成物的鹼顯影性提升之觀點而言,以酸價為0.1mgKOH/g以上為較佳,以0.5mgKOH/g以上為又較佳,以1mgKOH/g以上為更佳。另一方面,就抑制硬化物的微細圖型因顯影而導致溶出、且使絕緣可靠性提升之觀點而言,以酸價為150mgKOH/g以下為較佳,以120mgKOH/g以下為又較佳,以100mgKOH/g以下為更佳。於此,所謂的酸價,係指(b)成分中存在的羧基的殘留酸價,酸價可藉由以下之方法來進行測定。首先,精確秤量測定樹脂溶液約1g後,在該樹脂溶液中添加丙酮30g,並均勻地來溶解樹脂溶液。接下來,將作為指示劑的酚酞適量添加在該溶液中,並使用0.1N的KOH水溶液來進行滴定。又,依據下述式來算出酸價。 式:A(b)=10×Vf×56.1/(Wp×I)As for the acid value of component (b), from the viewpoint of improving the alkali developability of the photosensitive resin composition, the acid value is preferably 0.1 mgKOH/g or more, and further preferably 0.5 mgKOH/g or more. More than 1 mgKOH/g is more preferable. On the other hand, from the viewpoint of suppressing the elution of the fine pattern of the hardened material due to development and improving the insulation reliability, the acid value is preferably 150 mgKOH/g or less, and is further preferably 120 mgKOH/g or less. , 100mgKOH/g or less is better. Here, the acid value refers to the residual acid value of the carboxyl group present in component (b), and the acid value can be measured by the following method. First, approximately 1 g of the resin solution is accurately weighed and then 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was performed using a 0.1N KOH aqueous solution. Moreover, the acid value was calculated based on the following formula. Formula: A(b)=10×Vf×56.1/(Wp×I)
尚,上述式中,A(b)係表示酸價(mgKOH/g),Vf係表示KOH的滴定量(mL),Wp係表示測定樹脂溶液質量(g),I係表示測定樹脂溶液的不揮發分的比例(質量%)。However, in the above formula, A(b) represents the acid value (mgKOH/g), Vf represents the titer of KOH (mL), Wp represents the measured mass of the resin solution (g), and I represents the measured mass of the resin solution. Proportion of volatile matter (mass %).
在(b)成分的製造中,就保存穩定性的提升之觀點而言,環氧樹脂的環氧基的莫耳數、及不飽和羧酸與酸酐所合計的羧基的莫耳數之比係以1:0.8~1.3的範圍為較佳,以1:0.9~1.2的範圍為又較佳。In the production of component (b), from the viewpoint of improvement of storage stability, the ratio of the molar number of the epoxy group of the epoxy resin and the molar number of the carboxyl group of the unsaturated carboxylic acid and the acid anhydride is The range of 1:0.8~1.3 is preferred, and the range of 1:0.9~1.2 is further preferred.
就使柔軟性提升之觀點而言,(b)成分的玻璃轉移溫度(Tg)係較佳為-300℃以上,又較佳為-200℃以上,更佳為-80℃以上,較佳為-20℃以下,又較佳為-23℃以下,更佳為-25℃以下。於此,所謂的(b)成分的玻璃轉移溫度,係指(b)成分的主鏈的理論上的玻璃轉移溫度,該理論上的玻璃轉移溫度係可藉由以下所表示之FOX公式來算出。藉由FOX公式而求得的玻璃轉移溫度,與藉由示差掃描熱量測定(TMA、DSC、DTA)所測定的玻璃轉移溫度大約為一致,因此亦可藉由示差掃描熱量測定來測定(b)成分的主鏈的玻璃轉移溫度。 1/Tg=(W1/Tg1)+(W2/Tg2)+・・・+(Wm/Tgm) W1+W2+・・・+Wm=1 Wm係表示構成(b)成分的各單體的含有量(質量%),Tgm係表示構成(b)成分的各單體的玻璃轉移溫度(K)。From the viewpoint of improving flexibility, the glass transition temperature (Tg) of component (b) is preferably -300°C or higher, more preferably -200°C or higher, more preferably -80°C or higher, and more preferably -20°C or lower, preferably -23°C or lower, more preferably -25°C or lower. Here, the glass transition temperature of component (b) refers to the theoretical glass transition temperature of the main chain of component (b). This theoretical glass transition temperature can be calculated by the FOX formula expressed below . The glass transition temperature obtained by the FOX formula is approximately consistent with the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), so (b) can also be measured by differential scanning calorimetry. The glass transition temperature of the component's backbone. 1/Tg=(W1/Tg1)+(W2/Tg2)+・・・+(Wm/Tgm) W1+W2+・・・+Wm=1 Wm represents the content (mass %) of each monomer constituting the component (b), and Tgm represents the glass transition temperature (K) of each monomer constituting the component (b).
就鹼顯影性的提升之觀點而言,若將感光性樹脂組成物的固形分整體設為100質量%時,(b)成分係以將該含有量設為20質量%以上為較佳,以設為25質量%以上為又較佳,以設為30質量%以上為更佳。就耐熱性或平均線膨脹率的提升之觀點而言,上限係以設為45質量%以下為較佳,以設為40質量%以下為又較佳,以設為35質量%以下為更佳。From the viewpoint of improving alkali developability, when the total solid content of the photosensitive resin composition is 100% by mass, the content of component (b) is preferably 20% by mass or more. It is more preferable that it is 25 mass % or more, and it is more preferable that it is 30 mass % or more. From the viewpoint of improving heat resistance or average linear expansion rate, the upper limit is preferably 45 mass% or less, more preferably 40 mass% or less, and more preferably 35 mass% or less. .
((c)環氧樹脂) 滿足條件(II)的感光性樹脂組成物含有(c)環氧樹脂。藉由含有(c)成分,從而可使絕緣可靠性提升。但,於此所謂的(c)成分,係不包括含有乙烯性不飽和基及羧基的環氧樹脂。((c) Epoxy resin) The photosensitive resin composition satisfying condition (II) contains (c) epoxy resin. By containing component (c), insulation reliability can be improved. However, the component (c) here does not include epoxy resins containing ethylenically unsaturated groups and carboxyl groups.
作為(c)成分,可舉例如雙酚AF型環氧樹脂、及全氟烷基型環氧樹脂等的含有氟的環氧樹脂;雙酚A型環氧樹脂;雙酚F型環氧樹脂;雙酚S型環氧樹脂;聯二甲酚型環氧樹脂;二環戊二烯型環氧樹脂;三苯酚型環氧樹脂;萘酚酚醛清漆型環氧樹脂;苯酚酚醛清漆型環氧樹脂;tert-丁基-兒茶酚型環氧樹脂;萘型環氧樹脂;萘酚型環氧樹脂;蒽型環氧樹脂;縮水甘油胺型環氧樹脂;縮水甘油酯型環氧樹脂;甲酚酚醛清漆型環氧樹脂;聯苯型環氧樹脂;聯苯芳烷基型環氧樹脂;線狀脂肪族環氧樹脂;具有丁二烯構造的環氧樹脂;脂環式環氧樹脂、具有酯骨架的脂環式環氧樹脂;雜環式環氧樹脂;含有螺環的環氧樹脂;環己烷二甲醇型環氧樹脂;伸萘基醚型環氧樹脂;三羥甲基丙烷型環氧樹脂;四苯乙烷型環氧樹脂、鹵化環氧樹脂等。環氧樹脂係可使用單獨1種、或可組合2種以上來使用。就使絕緣可靠性及密著性提升之觀點而言,(c)成分係以聯苯型環氧樹脂、聯苯芳烷基型環氧樹脂為較佳。Examples of the component (c) include fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin; bisphenol A type epoxy resin; and bisphenol F type epoxy resin. ; Bisphenol S type epoxy resin; Dixylenol type epoxy resin; Dicyclopentadiene type epoxy resin; Trisphenol type epoxy resin; Naphthol novolak type epoxy resin; Phenol novolac type epoxy Resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol type epoxy resin; anthracene type epoxy resin; glycidyl amine type epoxy resin; glycidyl ester type epoxy resin; Cresol novolak type epoxy resin; biphenyl type epoxy resin; biphenyl aralkyl type epoxy resin; linear aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin , alicyclic epoxy resin with ester skeleton; heterocyclic epoxy resin; epoxy resin containing spiro ring; cyclohexanedimethanol type epoxy resin; naphthyl ether type epoxy resin; trimethylol Propane type epoxy resin; tetraphenylethane type epoxy resin, halogenated epoxy resin, etc. The epoxy resin system can be used individually by 1 type, or can be used in combination of 2 or more types. From the viewpoint of improving insulation reliability and adhesion, biphenyl-type epoxy resin and biphenyl aralkyl-type epoxy resin are preferred as component (c).
(c)環氧樹脂係以1分子中具有2個以上的環氧基為較佳。若將環氧樹脂的不揮發成分設為100質量%時,1分子中具有2個以上的環氧基的環氧樹脂較佳為至少50質量%以上。環氧樹脂具有:在溫度20℃下呈液狀的環氧樹脂(以下有稱為「液狀環氧樹脂」之情形)與在溫度20℃下呈固體狀的環氧樹脂(有稱為「固體狀環氧樹脂」之情形)。感光性樹脂組成物係可僅包含液狀環氧樹脂、亦可僅包含固體狀環氧樹脂來作為(c)環氧樹脂,但就提高所得到的硬化物的絕緣可靠性之觀點而言,以固體狀環氧樹脂為較佳。(c) The epoxy resin preferably has two or more epoxy groups per molecule. When the non-volatile content of the epoxy resin is 100% by mass, the content of the epoxy resin having two or more epoxy groups per molecule is preferably at least 50% by mass. Epoxy resins include: epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") solid epoxy resin"). The photosensitive resin composition may contain only liquid epoxy resin or may contain only solid epoxy resin as (c) epoxy resin. However, from the viewpoint of improving the insulation reliability of the obtained cured product, Solid epoxy resin is preferred.
作為液狀環氧樹脂係以1分子中具有2個以上的環氧基的液狀環氧樹脂為較佳。As the liquid epoxy resin, one having two or more epoxy groups per molecule is preferred.
作為液狀環氧樹脂,可舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、萘型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、苯酚酚醛清漆型環氧樹脂、具有酯骨架的脂環式環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、縮水甘油胺型環氧樹脂、及具有丁二烯構造的環氧樹脂等。Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidyl ester type epoxy resin. Amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin , and epoxy resin with butadiene structure, etc.
作為液狀環氧樹脂的具體例,可舉出DIC公司製的「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂);Mitsubishi Chemical公司製的「828US」、「jER828EL」、「825」、「Epikote 828EL」(雙酚A型環氧樹脂);Mitsubishi Chemical公司製的「jER807」、「1750」(雙酚F型環氧樹脂);Mitsubishi Chemical公司製的「jER152」(苯酚酚醛清漆型環氧樹脂);Mitsubishi Chemical公司製的「630」、「630LSD」(縮水甘油胺型環氧樹脂);新日鐵住金化學公司製的「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂的混合品);Nagasechemtex公司製的「EX-721」(縮水甘油酯型環氧樹脂);Daicel公司製的「CELOXIDE 2021P」(具有酯骨架的脂環式環氧樹脂);Daicel公司製的「PB-3600」(具有丁二烯構造的環氧樹脂);新日鐵住金化學公司製的「ZX1658」、「ZX1658GS」(液狀1,4-縮水甘油基環己烷型環氧樹脂)等。該等係可使用單獨1種類、亦可組合2種類以上來使用。Specific examples of liquid epoxy resins include "HP4032", "HP4032D" and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL" and " 825", "Epikote 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "jER152" (phenol novolac Varnish type epoxy resin); "630" and "630LSD" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "ZX1059" (bisphenol A type epoxy resin and bisphenol A type epoxy resin) manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd. Mixed product of phenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) made by Nagasechemtex Co., Ltd.; "CELOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) made by Daicel Co., Ltd. ; "PB-3600" manufactured by Daicel Corporation (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation (liquid 1,4-glycidylcyclohexane type epoxy resin), etc. These systems may be used individually or in combination of two or more types.
作為固體狀環氧樹脂係以1分子中具有3個以上的環氧基的固體狀環氧樹脂為較佳,以1分子中具有3個以上的環氧基的芳香族系的固體狀環氧樹脂為又較佳。The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is preferred. Resin is better.
作為固體狀環氧樹脂係以聯二甲酚型環氧樹脂、萘型環氧樹脂、萘型4官能環氧樹脂、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三苯酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、聯苯芳烷基型環氧樹脂、伸萘基醚型環氧樹脂、蒽型環氧樹脂、雙酚A型環氧樹脂、雙酚AF型環氧樹脂、四苯乙烷型環氧樹脂為較佳,以聯苯型環氧樹脂、聯苯芳烷基型環氧樹脂為又較佳。Solid epoxy resins include dixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, Trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type Epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and biphenyl type epoxy resin and biphenyl aralkyl type epoxy resin are further preferred.
作為固體狀環氧樹脂的具體例,可舉出DIC公司製的「HP4032H」(萘型環氧樹脂);DIC公司製的「HP-4700」、「HP-4710」(萘型4官能環氧樹脂);DIC公司製的「N-690」(甲酚酚醛清漆型環氧樹脂);DIC公司製的「N-695」(甲酚酚醛清漆型環氧樹脂);DIC公司製的「HP-7200」、「HP-7200HH」、「HP-7200H」(二環戊二烯型環氧樹脂);DIC公司製的「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(伸萘基醚型環氧樹脂);日本化藥公司製的「EPPN-502H」(三苯酚型環氧樹脂);日本化藥公司製的「NC7000L」(萘酚酚醛清漆型環氧樹脂);日本化藥公司製的「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯型環氧樹脂(聯苯芳烷基型環氧樹脂));新日鐵住金化學公司製的「ESN475V」(萘型環氧樹脂);新日鐵住金化學公司製的「ESN485」(萘酚酚醛清漆型環氧樹脂);Mitsubishi Chemical公司製的「YX4000H」、「YX4000」、「YL6121」(聯苯型環氧樹脂);Mitsubishi Chemical公司製的「YX4000HK」(聯二甲酚型環氧樹脂);Mitsubishi Chemical公司製的「YX8800」(蒽型環氧樹脂);Osaka Gas Chemical公司製的「PG-100」、「CG-500」;Mitsubishi Chemical公司製的「YL7760」(雙酚AF型環氧樹脂);Mitsubishi Chemical公司製的「YL7800」(茀型環氧樹脂);Mitsubishi Chemical公司製的「jER1010」(固體狀雙酚A型環氧樹脂);Mitsubishi Chemical公司製的「jER1031S」(四苯乙烷型環氧樹脂)等。該等係可使用單獨1種類、亦可組合2種類以上來使用。Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation Resin); "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP- 7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" made by DIC Corporation ", "EXA-7311-G4S", "HP6000" (alkylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; manufactured by Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl aralkyl type epoxy resin (biphenyl aralkyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Oxygen resin)); "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Company; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Company; manufactured by Mitsubishi Chemical Company "YX4000H", "YX4000", "YL6121" (biphenyl-type epoxy resin); "YX4000HK" (bixylenol-type epoxy resin) made by Mitsubishi Chemical Co., Ltd.; "YX8800" (anthracene) made by Mitsubishi Chemical Co., Ltd. Type epoxy resin); "PG-100" and "CG-500" made by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) made by Mitsubishi Chemical Co., Ltd.; "YL7800" made by Mitsubishi Chemical Co., Ltd. (Fluid type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) made by Mitsubishi Chemical Co., Ltd.; "jER1031S" (tetraphenyl ethane type epoxy resin) made by Mitsubishi Chemical Co., Ltd., etc. These systems may be used individually or in combination of two or more types.
(c)環氧樹脂的環氧當量係較佳為50~5000,又較佳為50~3000,更佳為80~2000,更又較佳為110~1000。因為在該範圍內,故感光性樹脂組成物的硬化物的交聯密度將變得充分,從而可得到表面粗糙度為小的絕緣層。尚,可根據JIS K7236來進行測定,環氧當量係包含1當量的環氧基的樹脂質量。(c) The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, more preferably 80 to 2000, and even more preferably 110 to 1000. Since it is within this range, the crosslinking density of the cured product of the photosensitive resin composition becomes sufficient, and an insulating layer with a small surface roughness can be obtained. However, it can be measured according to JIS K7236, and the epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups.
(c)環氧樹脂的重量平均分子量係較佳為100~5000,又較佳為250~3000,更佳為400~1500。於此,環氧樹脂的重量平均分子量係藉由凝膠滲透層析法(GPC)所測定的聚苯乙烯換算的重量平均分子量。(c) The weight average molecular weight of the epoxy resin is preferably 100~5000, more preferably 250~3000, and more preferably 400~1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
就可得到良好的拉伸破壞強度、展現出絕緣可靠性的絕緣層之觀點而言,若將感光性樹脂組成物的固形分整體設為100質量%時,(c)成分的含有量係較佳為1質量%以上,又較佳為5質量%以上,更佳為10質量%以上。環氧樹脂的含有量的上限,只要是可發揮本發明之效果即可並無特別限定,較佳為25質量%以下,又較佳為20質量%以下,更佳為15質量%以下。From the viewpoint of obtaining an insulating layer that has good tensile strength at break strength and exhibits insulation reliability, when the total solid content of the photosensitive resin composition is 100% by mass, the content of component (c) is relatively small. Preferably, it is 1 mass % or more, More preferably, it is 5 mass % or more, More preferably, it is 10 mass % or more. The upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention can be exerted, but it is preferably 25 mass% or less, more preferably 20 mass% or less, and more preferably 15 mass% or less.
((d)光聚合起始劑) 滿足條件(II)的感光性樹脂組成物含有(d)光聚合起始劑。藉由含有(d)光聚合起始劑,從而可有效的使感光性樹脂組成物光硬化。((d) Photopolymerization initiator) The photosensitive resin composition satisfying condition (II) contains (d) photopolymerization initiator. By containing (d) the photopolymerization initiator, the photosensitive resin composition can be effectively photocured.
(d)光聚合起始劑係可使用任意的化合物,可舉例如雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦)、2,4,6-三甲基苯甲醯基-二苯基-氧化膦等的醯基氧化膦系光聚合起始劑;1,2-辛二酮、1-[4-(苯硫基)-2-(O-苯甲醯肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟)等的肟酯系光聚合起始劑;2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-[4-(4-嗎咻基)苯基]-1-丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮等的α-胺基苯烷基酮系光聚合起始劑;二苯甲酮、甲基二苯甲酮、o-苯甲醯苯甲酸、苯甲醯乙基醚、2,2-二乙氧基苯乙酮、2,4-二乙基噻吨酮、二苯基-(2,4,6-三甲基苯甲醯基)氧化膦、乙基-(2,4,6-三甲基苯甲醯基)苯基亞膦酸酯、4,4’-雙(二乙基胺基)二苯甲酮、1-羥基-環己基-苯基酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦;銳鹽系光聚合起始劑等。該等係可使用單獨1種、亦可併用2種以上。該等之中,就更有效率的使感光性樹脂組成物光硬化之觀點而言,以醯基氧化膦系光聚合起始劑、肟酯系光聚合起始劑為較佳,以肟酯系光聚合起始劑為又較佳。 (d) Any compound can be used as the photopolymerization initiator, and examples thereof include bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide), 2,4,6-trimethyl Benzyl phosphine oxide photopolymerization initiators such as benzyl-diphenyl-phosphine oxide; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzyl Acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), etc. Oxime ester photopolymerization initiator; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-(dimethylamino)-2 -[(4-methylphenyl)methyl]-[4-(4-morpholyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl ]-2-morpholinopropan-1-one and other α-aminophenylalkyl ketone photopolymerization initiators; benzophenone, methylbenzophenone, o-benzoyl benzoic acid, benzene Formyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide , Ethyl-(2,4,6-trimethylbenzoyl)phenylphosphonite, 4,4'-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl -Phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2 -Methyl-1-propan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; sharp salt photopolymerization initiator, etc. These systems may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoint of photohardening the photosensitive resin composition more efficiently, phosphine oxide-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferred, and oxime ester-based photopolymerization initiators are preferred. It is also preferred to use a photopolymerization initiator.
作為(d)光聚合起始劑的具體例,可舉出IGM公司製的「Omnirad907」、「Omnirad369」、「Omnirad379」、「Omnirad819」、「OmniradTPO」、BASF公司製的「IrgacureOXE-01」、「IrgacureOXE-02」、「IrgacureTPO」、「Irgacure819」、ADEKA公司製的「N-1919」等。 Specific examples of the (d) photopolymerization initiator include "Omnirad907", "Omnirad369", "Omnirad379", "Omnirad819", "OmniradTPO" manufactured by IGM, "IrgacureOXE-01" manufactured by BASF, "IrgacureOXE-02", "IrgacureTPO", "Irgacure819", "N-1919" manufactured by ADEKA, etc.
進而,感光性樹脂組成物亦可包含作為光聚合起始輔助劑的N,N-二甲基胺基苯甲酸乙酯、N,N-二甲基胺基苯甲酸異戊酯、戊基-4-二甲基胺基苯甲酸酯、三乙基胺、三乙醇胺等的三級胺類來作為光聚合起始輔助劑,或亦可包含吡唑啉類、蒽類、香豆素類、呫噸酮類、噻吨酮類等之類的光增感劑,來與(d)光聚合起始劑組合。該等係可使用任何1種亦可併用2種以上。 Furthermore, the photosensitive resin composition may also contain N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, and amyl- Tertiary amines such as 4-dimethylaminobenzoate, triethylamine, and triethanolamine are used as photopolymerization starting auxiliaries, or may also include pyrazolines, anthracenes, and coumarins. , xanthone, thioxanthone, etc., to be combined with (d) photopolymerization initiator. Any one of these systems may be used, or two or more types may be used in combination.
就使感光性樹脂組成物充分地光硬化、並使絕緣可靠性提升之觀點而言,若將感光性樹脂組成物的不揮發成分設為100質量%時,作為(d)光聚合起始劑的含有量係較佳為0.01質量%以上,又較佳為0.1質量%以上,更佳為0.3質量%以上。另一方面,就抑制因過高感度所導致的解析性降低之觀點而言,上限係較佳為5質量%以下,又較佳為3質量%以下,更較佳為1.5質量%以下。尚,感光性樹脂組成物若包含光聚合起始輔助劑時,(d)光聚合起始劑與光聚合起始輔助劑的合計含有量較佳為上述範圍內。 From the viewpoint of fully photocuring the photosensitive resin composition and improving insulation reliability, when the non-volatile content of the photosensitive resin composition is 100% by mass, as (d) photopolymerization initiator The content of is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and more preferably 0.3 mass% or more. On the other hand, from the viewpoint of suppressing a decrease in resolution due to excessive sensitivity, the upper limit is preferably 5 mass% or less, more preferably 3 mass% or less, and more preferably 1.5 mass% or less. Furthermore, when the photosensitive resin composition contains a photopolymerization initiating auxiliary agent, the total content of (d) the photopolymerization initiator and the photopolymerization initiating auxiliary agent is preferably within the above range.
滿足條件(II)的感光性樹脂組成物係進而能夠含有(e)反應性稀釋劑。藉由含有(e)成分,從而可提升光反應性。作為(e)成分,可使用例如在1分子中具有1個以上的(甲基)丙烯醯基的在室溫下呈液體、固體或半固形的感光性(甲基)丙烯酸酯化合物。所謂的室溫係表示25℃左右。 The photosensitive resin composition satisfying condition (II) can further contain (e) a reactive diluent. By containing component (e), photoreactivity can be improved. As the component (e), for example, a photosensitive (meth)acrylate compound that is liquid, solid or semi-solid at room temperature and has one or more (meth)acrylyl groups per molecule can be used. The so-called room temperature refers to about 25°C.
作為代表性的感光性(甲基)丙烯酸酯化合物,可舉例如三環癸烷二甲醇二丙烯酸酯、丙烯酸2-羥基乙酯、丙烯酸2-羥基丁酯等的丙烯酸羥烷基酯類;乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等的二醇的單或二丙烯酸酯類;N,N-二甲基丙烯醯胺、N-羥甲基丙烯醯胺等的丙烯醯胺類;N,N-二甲基胺基乙基丙烯酸酯等的胺基烷基丙烯酸酯類;三羥甲基丙烷、季戊四醇、二季戊四醇、二季戊四醇六(甲基)丙烯酸酯等的多元醇或該等的環氧乙烷、環氧丙烷或者ε-己內酯加成物的多元丙烯酸酯類;苯氧基丙烯酸酯、苯氧基乙基丙烯酸酯等苯酚類、或其環氧乙烷或者環氧丙烷加成物等的丙烯酸酯類;三羥甲基丙烷三縮水甘油醚等的由縮水甘油醚所衍生的環氧丙烯酸酯類、三聚氰胺丙烯酸酯類、及/或與上述之丙烯酸酯對應的甲基丙烯酸酯類等。該等之中,以多元丙烯酸酯類或多元甲基丙烯酸酯類為較佳,例如作為3價的丙烯酸酯類或甲基丙烯酸酯類,可舉出三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷EO加成三(甲基)丙烯酸酯、甘油PO加成三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、四糠醇寡(甲基)丙烯酸酯、乙基卡必醇寡(甲基)丙烯酸酯、1,4-丁二醇寡(甲基)丙烯酸酯、1,6-己二醇寡(甲基)丙烯酸酯、三羥甲基丙烷寡(甲基)丙烯酸酯、季戊四醇寡(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、N,N,N’,N’-肆(β-羥基乙基)乙基二胺的(甲基)丙烯酸酯等,作為3價以上的丙烯酸酯類或甲基丙烯酸酯類,可舉出三(2-(甲基)丙烯醯基氧基乙基)磷酸酯、三(2-(甲基)丙烯醯基氧基丙基)磷酸酯、三(3-(甲基)丙烯醯基氧基丙基)磷酸酯、三(3-(甲基)丙烯醯基-2-羥基氧基丙基)磷酸酯、二(3-(甲基)丙烯醯基-2-羥基氧基丙基)(2-(甲基)丙烯醯基氧基乙基)磷酸酯、(3-(甲基)丙烯醯基-2-羥基氧基丙基)二(2-(甲基)丙烯醯基氧基乙基)磷酸酯等的磷酸三酯(甲基)丙烯酸酯。該等感光性(甲基)丙烯酸酯化合物係可使用任何1種亦可併用2種以上。Representative photosensitive (meth)acrylate compounds include hydroxyalkyl acrylates such as tricyclodecane dimethanol diacrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate; ethanol; Mono- or diacrylate esters of glycols such as glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N,N-dimethylacrylamide, N-hydroxymethylacrylamide, etc. Acrylamides; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate; trimethylolpropane, pentaerythritol, dipentaerythritol, dipentaerythritol hexa(meth)acrylate, etc. Polyacrylates of polyols or polyethylene oxide, propylene oxide or ε-caprolactone adducts; phenols such as phenoxy acrylate, phenoxyethyl acrylate, or their epoxy Acrylates such as ethane or propylene oxide adducts; epoxy acrylates derived from glycidyl ether such as trimethylolpropane triglycidyl ether, melamine acrylates, and/or combinations with the above Methacrylates corresponding to acrylates, etc. Among these, polyacrylates or polymethacrylates are preferred. Examples of trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylic acid. Ester, pentaerythritol tri(meth)acrylate, trimethylolpropane EO addition to tri(meth)acrylate, glycerol PO addition to tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol Oligo(meth)acrylate, ethylcarbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate , trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, N,N, Examples of trivalent or higher acrylic acid esters or methacrylic acid esters such as (meth)acrylic acid esters of N',N'-4(β-hydroxyethyl)ethyldiamine include tri(2-( Meth)acryloxyethyl)phosphate, tris(2-(meth)acryloxypropyl)phosphate, tris(3-(meth)acryloxypropyl)phosphate Ester, tris(3-(meth)acrylyl-2-hydroxyoxypropyl)phosphate, bis(3-(meth)acrylyl-2-hydroxyoxypropyl)(2-(methyl) (3-(meth)acryloxyethyl)phosphate, (3-(meth)acryloxyethyl)bis(2-(meth)acryloxyethyl)phosphate Phosphate triester (meth)acrylate. These photosensitive (meth)acrylate compounds may be used alone or in combination of two or more types.
(e)反應性稀釋劑係可使用市售品,作為具體例可舉出「DPHA」(二季戊四醇六丙烯酸酯、日本化藥公司製)、「DCA-P」(三環癸烷二甲醇二丙烯酸酯、共榮社化學公司製)等,(e) The reactive diluent system can use commercially available products. Specific examples include "DPHA" (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.), "DCA-P" (tricyclodecane dimethanol dimethacrylate). Acrylate, Kyeisha Chemical Co., Ltd.), etc.
感光性樹脂組成物若含有(e)反應性稀釋劑時,就促進光硬化、且抑制將感光性樹脂組成物作為硬化物時的黏附之觀點而言,若將感光性樹脂組成物的固形分整體設為100質量%時,(e)反應性稀釋劑的含有量係較佳為0.5質量%以上,又較佳為3質量%以上,更佳為5質量%以上,較佳為25質量%以下,又較佳為20質量%以下,更佳為15質量%以下。When the photosensitive resin composition contains (e) a reactive diluent, from the viewpoint of promoting photocuring and suppressing adhesion when the photosensitive resin composition is used as a cured product, if the solid content of the photosensitive resin composition is When the total is 100% by mass, the content of (e) the reactive diluent is preferably 0.5% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, and more preferably 25% by mass. or less, preferably 20% by mass or less, more preferably 15% by mass or less.
((f)有機溶劑) 滿足條件(II)的感光性樹脂組成物係進而能夠含有(f)有機溶劑。藉由含有(f)有機溶劑,從而可調整清漆黏度。作為(f)有機溶劑,可舉例如乙基甲基酮、環己酮等的酮類;甲苯、二甲苯、四甲基苯等的芳香族烴類;甲基溶纖劑、丁基溶纖劑、甲基卡必醇、丁基卡必醇、丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二乙基醚、三乙二醇單乙基醚等的乙二醇醚類;乙酸乙酯、乙酸丁酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、二乙二醇乙醚乙酸酯等的酯類;辛烷、癸烷等的脂肪族烴類;石油醚、石油腦、氫化石油腦、溶劑油等的石油系溶劑等。該等係可單獨1種或組合2種以上來使用。就樹脂組成物的塗佈性之觀點而言,使用有機溶劑時的含有量係可適當地調整。((f) organic solvent) The photosensitive resin composition satisfying condition (II) can further contain (f) organic solvent. By containing (f) organic solvent, the viscosity of the varnish can be adjusted. Examples of the (f) organic solvent include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, butyl cellosolve, Glycol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate Esters such as esters, butyl acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol ether acetate, etc.; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha , hydrogenated naphtha, solvent oil and other petroleum-based solvents. These systems can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of the coating properties of the resin composition, the content when using an organic solvent can be appropriately adjusted.
((g)其他的添加劑) 滿足條件(II)的感光性樹脂組成物,在不妨礙本發明之目的之程度下,進而能夠含有(g)其他的添加劑。作為(g)其他的添加劑,可舉例如離子捕捉劑、熱可塑性樹脂、有機填充材、三聚氰胺、有機膨潤土等的微粒子、酞青藍、酞青綠、碘綠、重氮黃、結晶紫、氧化鈦、NV-7-201(日本Pigment公司製)等的碳黑、萘黑等的著色劑或顏料、氫醌、吩噻嗪、甲基氫醌、氫醌單甲基醚、兒茶酚、鄰苯三酚等的阻聚劑、皂土、微晶高嶺石等的增稠劑、聚矽氧系、氟系、乙烯基樹脂系的消泡劑、溴化環氧化合物、酸改性溴化環氧化合物、銻化合物、芳香族縮合磷酸酯、含鹵素縮合磷酸酯等的阻燃劑、苯酚系硬化劑、氰酸酯系硬化劑等的熱硬化樹脂等的各種添加劑。((g)Other additives) The photosensitive resin composition satisfying condition (II) can further contain (g) other additives to the extent that the object of the present invention is not hindered. Examples of (g) other additives include ion trapping agents, thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, and titanium oxide. , NV-7-201 (manufactured by Japan Pigment Co., Ltd.) and other carbon blacks, naphthalene black and other colorants or pigments, hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, ortho Polymerization inhibitors such as phloroglucinol, thickeners such as bentonite, microcrystalline kaolinite, etc., defoaming agents for polysiloxane, fluorine, and vinyl resins, brominated epoxy compounds, acid-modified brominated Various additives such as flame retardants such as epoxy compounds, antimony compounds, aromatic condensed phosphates, and halogen-containing condensed phosphates, and thermosetting resins such as phenol-based hardeners and cyanate ester-based hardeners.
感光性樹脂組成物係可以是負型感光性樹脂組成物、及正型感光性樹脂組成物中任一者,但就感光性樹脂組成物層的物性提升之觀點而言,以曝光時的照射部成為圖型感光性樹脂組成物層的負型感光性樹脂組成物為較佳。The photosensitive resin composition may be either a negative photosensitive resin composition or a positive photosensitive resin composition. However, from the viewpoint of improving the physical properties of the photosensitive resin composition layer, in terms of the irradiation during exposure A negative photosensitive resin composition in which a portion becomes a patterned photosensitive resin composition layer is preferred.
就提升操作性、且抑制感光性樹脂組成物層內部的感度及解析度的降低之觀點而言,感光性樹脂組成物層的厚度係以設為5μm~500μm的範圍為較佳,以設為10μm~200μm的範圍為又較佳,以設為15μm~150μm的範圍為更佳,以設為20μm~100μm的範圍為進一步較佳,以設為20μm~60μm的範圍為特別更佳。From the viewpoint of improving operability and suppressing decreases in sensitivity and resolution inside the photosensitive resin composition layer, the thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, and is preferably in the range of 5 μm to 500 μm. A range of 10 μm to 200 μm is further preferred, a range of 15 μm to 150 μm is more preferred, a range of 20 μm to 100 μm is further preferred, and a range of 20 μm to 60 μm is particularly preferred.
[樹脂薄片] 本發明之樹脂薄片,其具有支撐體與設置在該支撐體上的包含感光性樹脂組成物的感光性樹脂組成物層,支撐體的霧度為20%以下,於顯影後的感光性樹脂組成物層的支撐體側之面的最大凹谷深度的絕對值(|Rv|)為500nm以上,感光性樹脂組成物滿足以下之條件(I)或(II)。 (I)感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材,若將感光性樹脂組成物的不揮發成分設為100質量%時,(a)成分的含有量為60質量%以上。 (II)感光性樹脂組成物含有(a)平均粒徑0.5μm以上的無機填充材、(b)包含乙烯性不飽和基及羧基的樹脂、(c)環氧樹脂及(d)光聚合起始劑。[Resin sheet] The resin sheet of the present invention has a support body and a photosensitive resin composition layer including a photosensitive resin composition provided on the support body. The haze of the support body is 20% or less. The photosensitive resin composition after development The absolute value of the maximum valley depth (|Rv|) of the support-side surface of the object layer is 500 nm or more, and the photosensitive resin composition satisfies the following conditions (I) or (II). (I) The photosensitive resin composition contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more. When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of component (a) is 60 Quality% or more. (II) The photosensitive resin composition contains (a) an inorganic filler with an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) a photopolymerizable resin. starter.
關於支撐體、支撐體的霧度、感光性樹脂組成物層的最大凹谷深度的絕對值、以及滿足感光性樹脂組成物的條件(I)及條件(II)係如前述般。The support, the haze of the support, the absolute value of the maximum valley depth of the photosensitive resin composition layer, and the conditions (I) and (II) satisfying the photosensitive resin composition are as described above.
條件(I)之情形時,感光性樹脂組成物係可藉由混合作為必須成分的上述(a)成分,並適當混合作為任意成分的上述(b)~(g)成分,又,因應所需藉由利用三輥機、球磨機、珠磨機、混砂機等的混練手段、或者高速旋轉攪拌機、超强攪拌機、行星式混合機等的攪拌手段來進行混練或攪拌,從而製造作為樹脂清漆。In the case of condition (I), the photosensitive resin composition can be obtained by mixing the above-mentioned (a) component as an essential component, and appropriately mixing the above-mentioned (b) to (g) components as optional components, and according to the needs The resin varnish is produced by kneading or stirring using a kneading means such as a three-roller machine, a ball mill, a bead mill, a sand mixer, or the like, or a stirring means such as a high-speed rotating mixer, a super mixer, or a planetary mixer.
又,條件(II)之情形時,感光性樹脂組成物係可藉由混合(a)~(d)成分,並適當混合作為任意成分的上述(e)~(g)成分,又,因應所需藉由利用三輥機、球磨機、珠磨機、混砂機等的混練手段、或者高速旋轉攪拌機、超强攪拌機、行星式混合機等的攪拌手段來進行混練或攪拌,從而製造作為樹脂清漆。In addition, in the case of condition (II), the photosensitive resin composition can be obtained by mixing the components (a) to (d) and appropriately mixing the above-mentioned (e) to (g) components as optional components. Resin varnish needs to be produced by kneading or stirring using a three-roller machine, ball mill, bead mill, sand mixer, etc., or a high-speed rotating mixer, super mixer, planetary mixer, etc. .
可利用保護薄膜來保護感光性樹脂組成物層。藉由利用保護薄膜來保護樹脂薄片的感光性樹脂組成物層側,從而可防止對感光性樹脂組成物層表面的灰塵等的附著或刮傷。作為保護薄膜係可使用藉由與上述之支撐體為相同的材料所構成的薄膜。保護薄膜的厚度並無特別限定,以1μm~40μm的範圍為較佳,以5μm~30μm的範圍為又較佳,以10μm~30μm的範圍為更佳。尚,保護薄膜較佳為:「相對於感光性樹脂組成物層與支撐體的接著力,以感光性樹脂組成物層與保護薄膜的接著力為較小者」。A protective film can be used to protect the photosensitive resin composition layer. By protecting the photosensitive resin composition layer side of the resin sheet with a protective film, it is possible to prevent dust or the like from adhering to or scratching the surface of the photosensitive resin composition layer. As the protective film, a film made of the same material as the above-mentioned support body can be used. The thickness of the protective film is not particularly limited, but it is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and more preferably in the range of 10 μm to 30 μm. Furthermore, the protective film is preferably: "The one in which the adhesive force between the photosensitive resin composition layer and the protective film is smaller than the adhesive force between the photosensitive resin composition layer and the support".
本發明之樹脂薄片係可藉由例如調製溶解感光性樹脂組成物在有機溶劑中的樹脂清漆,在支撐體上塗佈該樹脂清漆,並藉由加熱或吹熱風等使有機溶劑乾燥形成感光性樹脂組成物層,從而來進行製造。具體而言係可藉由首先依真空脫泡法等完全地去除樹脂組成物中之泡後,將感光性樹脂組成物塗佈在支撐體上,並藉由熱風爐或者遠紅外線爐去除溶劑並進行乾燥,接下來因應所需在所得到的感光性樹脂組成物層上層合保護薄膜,從而來製造樹脂薄片。具體的乾燥條件係依感光性樹脂組成物的硬化性或樹脂清漆中之有機溶劑量而有所不同,但對於包含30質量%~60質量%的有機溶劑的樹脂清漆,可以80℃~120℃用3分鐘~13分鐘來使其乾燥。感光性樹脂組成物層中之殘留有機溶劑量,相對於感光性樹脂組成物層的總量,以設為5質量%以下為較佳,以設為2質量%以下為又較佳。該所屬技術領域中具有通常知識者可藉由簡單的實驗來設定成為適當且適合的乾燥條件。The resin sheet of the present invention can be made photosensitive by, for example, preparing a resin varnish that dissolves a photosensitive resin composition in an organic solvent, coating the resin varnish on a support, and drying the organic solvent by heating or blowing hot air. Resin composition layer to produce. Specifically, the bubbles in the resin composition can be completely removed by vacuum degassing, etc., and then the photosensitive resin composition can be coated on the support, and the solvent can be removed using a hot air furnace or a far-infrared furnace. After drying, a protective film is laminated on the obtained photosensitive resin composition layer as necessary to produce a resin sheet. Specific drying conditions vary depending on the hardening properties of the photosensitive resin composition or the amount of organic solvent in the resin varnish. However, for resin varnishes containing 30% to 60% by mass of organic solvents, 80°C to 120°C can be used. Allow 3 to 13 minutes to dry. The amount of residual organic solvent in the photosensitive resin composition layer is preferably 5 mass% or less, and more preferably 2 mass% or less relative to the total amount of the photosensitive resin composition layer. Those with ordinary knowledge in the art can set appropriate and suitable drying conditions through simple experiments.
作為感光性樹脂組成物的塗佈方式,可舉例如凹版塗佈方式、微凹版塗佈方式、逆塗佈方式、逆向吻塗佈法(kiss reverse )方式、模頭塗佈方式、狹縫式塗佈方式、唇式塗佈方式、柯馬(comma)塗佈方式、刮刀塗佈方式、輥塗佈方式、刀片塗佈方式、簾幕塗佈方式、腔室凹版塗佈(chamber gravure)塗佈方式、縫孔塗佈方式、噴霧塗佈方式、浸漬塗佈方式等。Examples of coating methods for the photosensitive resin composition include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, and slit coating. Coating method, lip coating method, comma coating method, blade coating method, roller coating method, blade coating method, curtain coating method, chamber gravure coating cloth method, slot coating method, spray coating method, dip coating method, etc.
感光性樹脂組成物係可分數次來進行塗佈,亦可進行1次塗佈,又亦可組合多種來進行塗佈。其中,以均勻塗佈性為優異的模頭塗佈方式為較佳。又,為避免異物混入等,以在無塵室等的異物產生少的環境下來實施塗佈步驟為較佳。The photosensitive resin composition can be applied in divided portions, can be applied once, or can be applied in combination of multiple types. Among them, a die coating method with excellent uniform coating properties is preferred. In addition, in order to avoid contamination of foreign matter, etc., it is preferable to perform the coating step in an environment such as a clean room where foreign matter is rarely generated.
樹脂薄片的感光性樹脂組成物層之用途並無特別限定,可使用於電路基板(層合板用途、多層印刷配線板用途等)、阻焊劑、底部填充材材、晶粒結著材、半導體密封材、填孔樹脂、零件嵌入樹脂等廣泛範圍。其中,可適合作為阻焊劑形成用的感光性樹脂組成物層(將感光性樹脂組成物層的硬化物作為阻焊劑的印刷配線板)、印刷配線板的絕緣層用感光性樹脂組成物(將感光性樹脂組成物層的硬化物作為絕緣層的印刷配線板)、層間絕緣層用感光性樹脂組成物(將感光性樹脂組成物層的硬化物作為層間絕緣層的印刷配線板)、及鍍敷形成用感光性樹脂組成物(在感光性樹脂組成物層的硬化物上形成鍍敷的印刷配線板)。The use of the photosensitive resin composition layer of the resin sheet is not particularly limited. It can be used in circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, and semiconductor sealing. A wide range of materials, hole-filling resins, and part-embedding resins. Among them, it is suitable as a photosensitive resin composition layer for solder resist formation (a printed wiring board using a cured product of the photosensitive resin composition layer as a solder resist) and a photosensitive resin composition for an insulating layer of a printed wiring board (using a cured product of the photosensitive resin composition layer as a solder resist). A printed wiring board in which a cured product of a photosensitive resin composition layer serves as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a printed wiring board in which a cured product of a photosensitive resin composition layer serves as an interlayer insulating layer), and plating Photosensitive resin composition for coating formation (printed wiring board in which plating is formed on the cured product of the photosensitive resin composition layer).
形成感光性樹脂組成物層的感光性樹脂組成物係顯影性為優異。因此,藉由使用該樹脂組成物,從而可得到顯影性為優異的絕緣層及阻焊劑層。例如依據實施例所記載之方法來製作評估用層合體。此情形時,利用目視來觀察評估用層合體的曝光部1cm×2cm的四角形部分,上述曝光部的樹脂為未剝離或一部分未溶解。The photosensitive resin composition forming the photosensitive resin composition layer has excellent developability. Therefore, by using this resin composition, an insulating layer and a solder resist layer having excellent developability can be obtained. For example, a laminate for evaluation is produced according to the method described in the Examples. In this case, a 1 cm×2 cm quadrangular portion of the exposed portion of the evaluation laminate was visually observed, and it was found that the resin in the exposed portion was not peeled off or partially dissolved.
例如依據實施例所記載之方法來製作評估用層合體。此情形時,評估用層合體的無殘渣的最小開口徑(最小孔徑)係較佳為200μm以下,又較佳為150μm以下,更佳為130μm以下、100μm以下。下限並無特別限定,但能夠設為50μm以上等。For example, a laminate for evaluation is produced according to the method described in the Examples. In this case, the residue-free minimum opening diameter (minimum pore diameter) of the laminate for evaluation is preferably 200 μm or less, more preferably 150 μm or less, more preferably 130 μm or less, and 100 μm or less. The lower limit is not particularly limited, but it can be set to 50 μm or more.
又,將評估用層合體依實施例所記載之方法來評估外觀時,一般而言,不論是任何的未曝光部皆無樹脂成分的殘留,又,即使是觀察任意三點的孔洞(開口部)的圓孔圖型,一般而言亦未發現外伸(overhang)或下切(undercut)。In addition, when the appearance of the laminate for evaluation was evaluated according to the method described in the examples, generally speaking, no resin component remained in any unexposed portion, and even if holes (openings) were observed at any three points Generally speaking, no overhang or undercut is found in the round hole pattern.
感光性樹脂組成物層係可於顯影後形成具有高的最大凹谷深度的絕對值之面,因此可得到配線的遮蔽性為優異的硬化物。因此,可得到遮蔽性為優異的絕緣層及阻焊劑層。例如依據實施例所記載之方法來製作評估用層合體。此情形時,一般而言利用目視在評估用層合體中為看不到圖型。The photosensitive resin composition layer can form a surface with a high absolute value of the maximum valley depth after development, so a cured product with excellent wiring shielding properties can be obtained. Therefore, an insulating layer and a solder resist layer having excellent shielding properties can be obtained. For example, a laminate for evaluation is produced according to the method described in the Examples. In this case, generally speaking, the pattern cannot be seen visually in the laminate for evaluation.
感光性樹脂組成物層係可於顯影後形成具有高的最大凹谷深度的絕對值之面,因此可得到密著性為優異的硬化物。因此,可得到密著性為優異的絕緣層及阻焊劑層。例如依據實施例所記載之方法,在評估用層合體上層合薄片,並依實施例所記載之方法來評估密著性時,一般而言在全部的方格中並未發現剝落。The photosensitive resin composition layer can form a surface with a high absolute value of the maximum valley depth after development, so a cured product with excellent adhesion can be obtained. Therefore, an insulating layer and a solder resist layer having excellent adhesion can be obtained. For example, when a sheet is laminated on a laminate for evaluation according to the method described in the Examples and the adhesion is evaluated according to the method described in the Examples, peeling is generally not found in all squares.
[印刷配線板之製造方法] 本發明之印刷配線板之製造方法包含下述步驟: (1)準備具有支撐體與設置在該支撐體上的包含感光性樹脂組成物的感光性樹脂組成物層的樹脂薄片之步驟、 (2)在基板上層合樹脂薄片之步驟、 (3)將感光性樹脂組成物層進行曝光之步驟及 (4)藉由顯影來形成圖型感光性樹脂組成物層之步驟。[Manufacturing method of printed wiring board] The manufacturing method of the printed wiring board of the present invention includes the following steps: (1) The step of preparing a resin sheet having a support and a photosensitive resin composition layer including a photosensitive resin composition provided on the support, (2) Steps of laminating resin sheets on the substrate, (3) The steps of exposing the photosensitive resin composition layer and (4) A step of forming a patterned photosensitive resin composition layer by development.
本發明之印刷配線板係可使用前述之樹脂薄片來製造。關於支撐體、支撐體的霧度、於(4)步驟後的圖型感光性樹脂組成物層的最大凹谷深度的絕對值、以及感光性樹脂組成物所滿足的條件(I)及條件(II)係如前述般。以下,對於感光性樹脂組成物層的硬化物若為阻焊劑之情形時來進行說明。The printed wiring board of the present invention can be manufactured using the aforementioned resin sheet. Regarding the support, the haze of the support, the absolute value of the maximum valley depth of the patterned photosensitive resin composition layer after step (4), and the conditions (I) and conditions (I) satisfied by the photosensitive resin composition II) is as mentioned above. Hereinafter, a case where the cured product of the photosensitive resin composition layer is a solder resist will be described.
<(1)步驟> (1)步驟係準備具有支撐體與設置在該支撐體上的包含感光性樹脂組成物的感光性樹脂組成物層的樹脂薄片之步驟。支撐體係霧度為20%以下,且感光性樹脂組成物滿足上述之條件(I)或(II)。又,感光性樹脂組成物係滿足條件(I)或(II),因此,於(4)步驟後的與圖型感光性樹脂組成物層的基板側為相反側之面的最大凹谷深度的絕對值(|Rv|)將為500nm以上。(1)步驟中使用的樹脂薄片係如前述般。<(1) Step> The step (1) is a step of preparing a resin sheet having a support and a photosensitive resin composition layer including a photosensitive resin composition provided on the support. The haze of the support system is less than 20%, and the photosensitive resin composition meets the above conditions (I) or (II). Furthermore, the photosensitive resin composition satisfies condition (I) or (II). Therefore, the maximum valley depth of the surface opposite to the substrate side of the patterned photosensitive resin composition layer after step (4) is The absolute value (|Rv|) will be above 500nm. The resin sheet used in the step (1) is as described above.
<(2)步驟> (2)步驟係在基板上層合樹脂薄片之步驟。於(2)步驟中樹脂薄片若具有保護薄膜時,去除該保護薄膜後並因應所需將樹脂薄片及基板進行預熱,將感光性樹脂組成物層進行加壓及加熱之同時壓著在基板上。對於樹脂薄片係可適合使用藉由真空層合法在減壓下層合在基板上之方法。<(2) Step> (2) The step is to laminate the resin sheet on the substrate. If the resin sheet has a protective film in step (2), remove the protective film and preheat the resin sheet and the substrate as needed, and press the photosensitive resin composition layer on the substrate while pressing and heating it. superior. The resin sheet can be suitably laminated on a substrate under reduced pressure by a vacuum lamination method.
作為基板係以在一面或雙面形成經圖型加工的導體層(電路)的電路基板為較佳。作為電路基板,可舉出玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等。對於交互地層合導體層與絕緣層而構成的多層印刷配線板,即使是該多層印刷配線板的最外層之一面或雙面為經圖型加工的導體層(電路)的基板,亦包含在於此所謂的的電路基板中。尚,亦可藉由黑化處理、銅蝕刻等,來對導體層表面事先施予粗化處理。As the substrate, a circuit substrate in which a patterned conductor layer (circuit) is formed on one or both sides is preferred. Examples of the circuit board include a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, a thermosetting polyphenylene ether board, and the like. A multilayer printed wiring board composed of alternately laminated conductor layers and insulating layers is included here even if one or both sides of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit). In the so-called circuit substrate. Alternatively, the surface of the conductor layer can also be roughened in advance through blackening treatment, copper etching, etc.
(2)步驟之條件雖並無特別限定,但以例如將壓著溫度(層合溫度)較佳設為70℃~140℃,壓著壓力較佳設為1kgf/cm2 ~11kgf/cm2 (9.8×104 N/m2 ~107.9×104 N/m2 ),壓著時間較佳設為5秒鐘~300秒鐘,並將空氣壓設為20mmHg(26.7hPa)以下的減壓下來進行層合者為較佳。又,層合步驟可為分批式,亦可為使用輥的連續式。真空層合法可使用市售的真空層合機來進行。作為市售的真空層合機,可舉例如Nikko・Materials公司製真空貼合機、名機製作所公司製真空加壓式層合機、Hitachi Industries公司製輥式乾式塗佈機、Hitachi AIC公司製真空層合機等。以如此之方式在基板上來層合樹脂薄片。(2) The conditions of the step are not particularly limited, but for example, the pressing temperature (laminating temperature) is preferably 70°C to 140°C, and the pressing pressure is preferably 1kgf/cm 2 to 11kgf/cm 2 (9.8×10 4 N/m 2 ~107.9×10 4 N/m 2 ), the pressing time is preferably set to 5 seconds to 300 seconds, and the air pressure is set to a reduced pressure below 20mmHg (26.7hPa) It is better to lay it down. Moreover, the lamination step may be a batch type or a continuous type using a roller. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum laminator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. Vacuum laminator, etc. In this way, the resin sheet is laminated on the substrate.
<(3)步驟> (3)步驟係於(2)步驟後的將感光性樹脂組成物層進行曝光之步驟。詳細而言,若感光性樹脂組成物為負型感光性樹脂組成物之情形時,藉由(2)步驟而於基板上設置樹脂薄片後,通過遮罩圖型並對感光性樹脂組成物層的指定部分照射活性光線,從而使照射部的感光性樹脂組成物層光硬化。<(3) Step> The step (3) is a step of exposing the photosensitive resin composition layer after the step (2). Specifically, when the photosensitive resin composition is a negative photosensitive resin composition, after the resin sheet is placed on the substrate in step (2), the photosensitive resin composition layer is masked with a mask pattern. A designated portion is irradiated with active light, thereby photo-hardening the photosensitive resin composition layer in the irradiated portion.
作為活性光線,可舉例如紫外線、可見光線、電子線、X線等,特別以紫外線為較佳。紫外線的照射量係大致為10mJ/cm2 ~1000mJ/cm2 。曝光方法係有將遮罩圖型與印刷配線板密著來進行的接觸曝光法,與非密著而是使用平行光線來進行曝光的非接觸曝光法,可以採用任一者。Examples of active rays include ultraviolet rays, visible rays, electron rays, X-rays, etc., and ultraviolet rays are particularly preferred. The amount of ultraviolet irradiation is approximately 10mJ/cm 2 ~1000mJ/cm 2 . The exposure method can be either a contact exposure method in which the mask pattern and the printed wiring board are closely adhered to each other, or a non-contact exposure method in which parallel light is used for exposure without close adhesion.
阻焊劑係因為使用前述之感光性樹脂組成物,故顯影性為優異。因此,作為遮罩圖型中之曝光圖型,能夠使用例如電路寬(線;L)與電路間的寬(間隙;S)的比(L/S)為100μm/100μm以下(即,配線間距200μm以下)、L/S=90μm/90μm以下(配線間距180μm以下)、L/S= 80μm/80μm以下(配線間距160μm以下)、L/S=70μm/70μm以下(配線間距140μm以下)、L/S=60μm/60μm以下(配線間距120μm以下)、L/S=50μm/50μm以下(配線間距100μm以下)的圖型。又,作為曝光圖型,能夠使用例如開口為100μm以下的圓孔、90μm以下的圓孔、80μm以下的圓孔、70μm以下的圓孔、60μm以下的圓孔、50μm以下的圓孔的圖型。尚,間距在電路基板的整體中不需要是相同的。Since the solder resist uses the aforementioned photosensitive resin composition, it has excellent developability. Therefore, as the exposure pattern in the mask pattern, for example, the ratio (L/S) of the circuit width (line; L) to the width between circuits (space; S) can be 100 μm/100 μm or less (that is, the wiring pitch L /S=60μm/60μm or less (wiring pitch 120μm or less), L/S=50μm/50μm or less (wiring pitch 100μm or less) patterns. In addition, as the exposure pattern, for example, a pattern having openings of circular holes of 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, or 50 μm or less can be used. . However, the pitch does not need to be the same throughout the circuit substrate.
<(4)步驟> (4)步驟係藉由顯影來形成圖型感光性樹脂組成物層之步驟。詳細而言,若感光性樹脂組成物為負型感光性樹脂組成物之情形時,於(3)步驟後藉由將感光性樹脂組成物層的表面上進行顯影,以濕式顯影來去除未光硬化的部分(未曝光部),從而可形成圖型感光性樹脂組成物層。又,圖型感光性樹脂組成物層係滿足前述之要件,因此藉由濕式顯影中所使用的顯影液,於(4)步驟後的與圖型感光性樹脂組成物層的基板側為相反側之面的最大凹谷深度的絕對值(|Rv|)將為500nm以上。<(4) Step> (4) The step is a step of forming a patterned photosensitive resin composition layer through development. Specifically, when the photosensitive resin composition is a negative photosensitive resin composition, after the step (3), the surface of the photosensitive resin composition layer is developed to remove unidentified layers by wet development. The photohardened portion (unexposed portion) can form a patterned photosensitive resin composition layer. In addition, the patterned photosensitive resin composition layer satisfies the aforementioned requirements. Therefore, by using the developer used in wet development, the substrate side of the patterned photosensitive resin composition layer after step (4) is opposite to that of the patterned photosensitive resin composition layer. The absolute value (|Rv|) of the maximum valley depth on the side surface will be 500 nm or more.
於(4)步驟後的與圖型感光性樹脂組成物層的基板側為相反側之面的最大凹谷深度的絕對值、及算術平均粗糙度Ra係如前先般,較佳的範圍亦為相同。The absolute value of the maximum valley depth and the arithmetic mean roughness Ra of the surface opposite to the substrate side of the patterned photosensitive resin composition layer after step (4) are the same as before, and the preferable ranges are also same.
作為顯影液,可使用鹼性水溶液、水系顯影液、有機溶劑等的安全且穩定、操作性為良好的顯影液,其中以藉由鹼水溶液之顯影步驟為較佳。又,作為顯影方法,可適當地採用噴霧、搖動浸漬、刷塗、刮塗等的周知方法。As the developer, a safe, stable and operable developer such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc. can be used. Among them, the development step using an alkali aqueous solution is preferred. In addition, as the development method, well-known methods such as spraying, shaking dipping, brushing, and blade coating can be appropriately adopted.
被使用作為顯影液的鹼性水溶液,可舉例如氫氧化鋰、氫氧化鈉、氫氧化鉀等的鹼金屬氫氧化物、碳酸鈉、重碳酸鈉等的碳酸鹽或重碳酸鹽、磷酸鈉、磷酸鉀等的鹼金屬磷酸鹽、焦磷酸鈉、焦磷酸鉀等的鹼金屬焦磷酸鹽的水溶液、或四烷基氫氧化銨等的不含有金屬離子的有機鹼的水溶液,就不含有金屬離子而且不會影響半導體晶片之方面而言,以四甲基氫氧化銨(TMAH)的水溶液為較佳。Alkaline aqueous solutions used as the developer include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; sodium phosphate; Aqueous solutions of alkali metal phosphates such as potassium phosphate, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, or aqueous solutions of organic bases such as tetraalkyl ammonium hydroxide that do not contain metal ions do not contain metal ions. In terms of not affecting the semiconductor wafer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.
該等的鹼性水溶液,為了提升顯影效果,可添加界面活性劑、消泡劑等至顯影液中。上述鹼性水溶液的pH係以例如8~12的範圍為較佳,以9~11的範圍為又較佳。 In order to improve the development effect of these alkaline aqueous solutions, surfactants, defoaming agents, etc. can be added to the developer. The pH of the above-mentioned alkaline aqueous solution is, for example, preferably in the range of 8 to 12, and further preferably in the range of 9 to 11.
又,上述鹼性水溶液的鹼濃度係較佳為0.1質量%以上,又較佳為1質量%以上,更佳為5質量%以上,較佳為50質量%以下,又較佳為40質量%以下,更佳為35質量%以下。 Moreover, the alkali concentration of the above-mentioned alkaline aqueous solution is preferably 0.1 mass% or more, more preferably 1 mass% or more, more preferably 5 mass% or more, preferably 50 mass% or less, and more preferably 40 mass%. or less, more preferably 35% by mass or less.
上述鹼性水溶液的溫度係配合樹脂組成物層的顯影性來進行適當選擇,較佳為10℃以上,又較佳為15℃以上,更佳為20℃以上,較佳為50℃以下,又較佳為45℃以下,更佳為40℃以下。 The temperature of the above-mentioned alkaline aqueous solution is appropriately selected according to the developability of the resin composition layer. It is preferably 10°C or higher, more preferably 15°C or higher, more preferably 20°C or higher, and preferably 50°C or lower. The temperature is preferably 45°C or lower, and more preferably 40°C or lower.
被使用作為顯影液的有機溶劑係例如丙酮、乙酸乙酯、具有碳原子數1~4的烷氧基的烷氧基乙醇、乙醇、異丙醇、丁醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚。 Organic solvents used as developers include acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethanol, isopropyl alcohol, butanol, and diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, diethylene glycol monobutyl ether.
如此般的有機溶劑的濃度,相對於顯影液全部量,以2質量%~90質量%為較佳。又,如此般的有機溶劑的溫度,可配合顯影性來進行調節。進而,如此般的有機溶劑係可單獨或組合2種類以上來使用。作為單獨來使用的有機溶劑系顯影液,可舉例如1,1,1-三氯乙烷、N-甲基吡咯啶酮、N,N-二甲基甲醯胺、環己酮、甲基異丁基酮、γ-丁內酯。 The concentration of such an organic solvent is preferably 2 mass % to 90 mass % relative to the total amount of the developer. In addition, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such an organic solvent system can be used individually or in combination of 2 or more types. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl Isobutyl ketone, γ-butyrolactone.
於圖型形成中,因應所需亦可併用上述之2種類以上的顯影方法來使用。顯影之方式係有浸漬方式、攪拌方式、噴霧方式、高壓噴霧方式、刷塗、拍擊等,為 了提升解析度,以高壓噴霧方式為適合。作為採用噴霧方式時的噴霧壓,較佳為0.05MPa以上,又較佳為0.1MPa以上,更佳為0.15MPa以上,較佳為0.5MPa以下,又較佳為0.4MPa以下,更佳為0.3MPa以下。 In pattern formation, two or more of the above-mentioned developing methods may be used in combination as needed. The methods of development include dipping, stirring, spraying, high-pressure spraying, brushing, tapping, etc. In order to improve the resolution, high-pressure spray method is suitable. The spray pressure when using the spray method is preferably 0.05MPa or more, more preferably 0.1MPa or more, more preferably 0.15MPa or more, preferably 0.5MPa or less, further preferably 0.4MPa or less, and more preferably 0.3 Below MPa.
本發明之印刷配線板之製造方法,除了(1)步驟至(4)步驟,另外進而能夠包含(5)將圖型感光性樹脂組成物層進行硬化之步驟。藉由進行(5)步驟,能夠使圖型感光性樹脂組成物層熱硬化,從而形成阻焊劑。(5)步驟係以於(4)步驟結束後來進行為較佳。 The manufacturing method of the printed wiring board of the present invention can further include (5) the step of hardening the patterned photosensitive resin composition layer in addition to the steps (1) to (4). By performing step (5), the patterned photosensitive resin composition layer can be thermally cured to form a solder resist. The step (5) is preferably performed after the step (4) is completed.
加熱之條件係可因應樹脂組成物中之樹脂成分的種類、含有量等來進行適當選擇,較佳為150℃~220℃下20分鐘~180分鐘的範圍,又較佳為160℃~200℃下30分鐘~120分鐘的範圍來做選擇。尚,於加熱前亦可進行藉由高壓水銀燈之紫外線照射或使用潔淨烘箱之加熱步驟等。照射紫外線時係因應所需可調整該照射量,例如可以0.05J/cm2~10J/cm2左右的照射量來進行照射。 The heating conditions can be appropriately selected according to the type and content of the resin component in the resin composition. The preferred range is 150°C to 220°C for 20 minutes to 180 minutes, and the preferred range is 160°C to 200°C. Choose from the range of 30 minutes to 120 minutes. However, before heating, ultraviolet irradiation by a high-pressure mercury lamp or heating steps using a clean oven can also be performed. When irradiating ultraviolet rays, the irradiation dose can be adjusted according to needs. For example, the irradiation dose can be about 0.05J/cm 2 ~10J/cm 2 .
本發明之印刷配線板之製造方法,除了(1)步驟至(4)步驟,另外進而能夠包含(6)剝離支撐體之步驟。剝離支撐體之方法係可藉由周知的方法來實施。 The manufacturing method of the printed wiring board of the present invention can further include (6) the step of peeling off the support in addition to the steps (1) to (4). The method of peeling off the support can be implemented by a well-known method.
進行(6)步驟的時機並無特別限制,例如可於(3)步驟後(4)步驟前來進行。就與圖型感光性樹脂組成物層的基板為相反側之面的最大凹谷深度的絕對值(|Rv|)成為500nm以上,並提升密著性之觀點而言,(6)步驟係以於(2)步驟後(3)步驟前來進行為較佳。即,以於進行曝光前來剝離支撐體為較佳。藉由於(2)步驟後(3)步驟前來進行(6)步驟,(3)步驟將會在與感光性樹脂組成物層的基板為相反側之面上存在氧之狀況下來進行。特別是使用負型的光聚合起始劑的反應系時,藉由空氣中的氧並經光照射而會產生的具有雙自由基構造的光聚合起始劑的自由基,將會鈍化。特別是在最表層上該現象為顯著、且感光性樹脂組成物的最表層會呈現未光硬化的狀態,故藉由顯影液將可容易去除表面附近的一部分。其結果,認為能夠在圖型感光性樹脂組成物層之表面形成指定的最大凹谷深度,且使密著性及遮蔽性提升。The timing of performing step (6) is not particularly limited. For example, it can be performed after step (3) and step (4). From the viewpoint of making the absolute value of the maximum valley depth (|Rv|) on the surface opposite to the substrate of the patterned photosensitive resin composition layer 500 nm or more and improving the adhesion, step (6) is based on It is better to perform step (3) after step (2). That is, it is preferable to peel off the support before exposure. By performing step (6) after step (2) and before step (3), step (3) will be performed under the condition that oxygen exists on the surface opposite to the substrate of the photosensitive resin composition layer. Especially when a reaction system using a negative photopolymerization initiator is used, the free radicals of the photopolymerization initiator with a diradical structure generated by oxygen in the air and irradiation with light will be passivated. This phenomenon is particularly noticeable on the outermost layer, and since the outermost layer of the photosensitive resin composition is in an unphotocured state, a portion near the surface can be easily removed with a developer. As a result, it is considered that a specified maximum valley depth can be formed on the surface of the patterned photosensitive resin composition layer, and the adhesion and shielding properties can be improved.
<其他的步驟> 印刷配線板係於形成阻焊劑後,進而亦可包含開孔步驟、除膠渣步驟。該等的步驟,可根據印刷配線板的製造中所使用的對該所屬技術領域中具有通常知識者而言為周知的各種方法來予以實施。<Other steps> After the solder resist is formed, the printed wiring board may further include a hole opening step and a desmear removal step. These steps can be carried out according to various methods that are well known to those skilled in the art and are used in the manufacture of printed wiring boards.
於形成阻焊劑後,依據所期望對形成在基板上的阻焊劑來進行開孔步驟,從而形成通孔洞、穿通孔。開孔步驟係藉由例如鑽孔、雷射、等離子等的周知方法,又因應所需可組合該等的方法來進行,但以藉由碳酸氣體雷射、YAG雷射等的雷射之開孔步驟為較佳。After the solder resist is formed, a hole opening step is performed on the solder resist formed on the substrate as desired, thereby forming through-holes and through-holes. The hole opening step is performed by well-known methods such as drilling, laser, plasma, etc., and these methods can be combined according to the needs. The hole step is better.
除膠渣步驟係進行除膠渣(desmear)處理之步驟。於開孔步驟中所形成的開口部內部中,通常會附著樹脂殘渣(膠渣)。由於上述膠渣是電連接不良的原因,故於該步驟中來實施去除膠渣的處理(除膠渣處理)。The desmearing step is a step of desmearing. Resin residue (smear) usually adheres to the inside of the opening formed in the hole drilling step. Since the above-mentioned smear is the cause of poor electrical connection, a process of removing smear (smear removal process) is performed in this step.
除膠渣處理係可藉由乾式除膠渣處理、濕式除膠渣處理或該等的組合來實施。The desmearing treatment can be implemented by dry desmearing treatment, wet desmearing treatment or a combination thereof.
作為乾式除膠渣處理,可舉例如使用等離子的除膠渣處理等。使用等離子的除膠渣處理係可使用市售的等離子除膠渣處理裝置來實施。市售的等離子除膠渣處理裝置之中,作為適合於印刷配線板的製造用途的例子,可舉出Nissin公司製的微波等離子裝置、積水化學工業公司製的常壓等離子蝕刻裝置等。Examples of the dry desmearing process include desmearing using plasma. The desmearing treatment using plasma can be carried out using a commercially available plasma desmearing treatment device. Among commercially available plasma desmear treatment devices, examples suitable for use in manufacturing printed wiring boards include a microwave plasma device manufactured by Nissin Co., Ltd. and an atmospheric pressure plasma etching device manufactured by Sekisui Chemical Industry Co., Ltd.
作為濕式除膠渣處理,可舉例如使用氧化劑溶液的除膠渣處理等。使用氧化劑溶液來進行除膠渣處理時,以依序進行藉由膨潤液之膨潤處理、藉由氧化劑溶液之氧化處理、藉由中和液之中和處理為較佳。作為膨潤液,可舉例如Atotech Japan公司製的「Swelling Dip Securiganth P」、「Swelling Dip Securiganth SBU」等。膨潤處理,係以藉由使形成通孔洞等的基板浸漬在加熱至60℃~80℃的膨潤液中5分鐘~10分鐘從而來進行為較佳。作為氧化劑溶液係以鹼性過錳酸水溶液為較佳,可舉例如在氫氧化鈉的水溶液中溶解過錳酸鉀或過錳酸鈉而製成的溶液。藉由氧化劑溶液之氧化處理,係以藉由使膨潤處理後的基板浸漬在加熱至60℃~80℃的氧化劑溶液中10分鐘~30分鐘從而來進行為較佳。作為鹼性過錳酸水溶液的市售品,可舉例如Atotech Japan公司製的「Concentrate Compact CP」、「Dosing solution Securiganth P」等。藉由中和液之中和處理,係以藉由使氧化處理後的基板浸漬在30℃~50℃的中和液中3分鐘~10分鐘從而來進行為較佳。作為中和液係以酸性的水溶液為較佳,作為市售品可舉例如Atotech Japan公司製的「Reduction solution Securiganth P」。Examples of the wet desmearing treatment include desmearing treatment using an oxidizing agent solution. When using an oxidant solution for desmearing, it is preferable to perform swelling treatment with a swelling solution, oxidation treatment with an oxidant solution, and neutralization treatment with a neutralizing solution in this order. Examples of the swelling liquid include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing the substrate on which via holes or the like is formed in a swelling liquid heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganic acid aqueous solution, and an example thereof is a solution prepared by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution. The oxidation treatment by the oxidizing agent solution is preferably performed by immersing the swelling-treated substrate in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Examples of commercially available alkaline permanganic acid aqueous solutions include "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan. The neutralization treatment by the neutralization liquid is preferably performed by immersing the oxidized substrate in a neutralization liquid at 30°C to 50°C for 3 minutes to 10 minutes. An acidic aqueous solution is preferred as the neutralizing liquid, and an example of a commercially available product is "Reduction solution Securiganth P" manufactured by Atotech Japan.
若組合乾式除膠渣處理與濕式除膠渣處理來實施時,可先實施乾式除膠渣處理、亦可先實施濕式除膠渣處理。If a combination of dry desmearing and wet desmearing is performed, the dry desmearing may be performed first or the wet desmearing may be performed first.
將絕緣層使用作為層間絕緣層時,可和阻焊劑之情形時為相同地來進行,亦可因應所需來進行鍍敷步驟。When the insulating layer is used as an interlayer insulating layer, it can be performed in the same manner as in the case of solder resist, and the plating step can also be performed as needed.
鍍敷步驟係在絕緣層上形成導體層之步驟。導體層係可組合無電解鍍敷與電解鍍敷來形成,又,亦可形成與導體層為相反圖型的鍍敷阻劑,並僅只利用無電解鍍敷來形成導體層。作為之後的圖型形成的方法,可使用例如該所屬技術領域中具有通常知識者所周知的消去處理法(subtractive process)、半加成法(semiadditive process)等。The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer can be formed by combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed by electroless plating alone. As a subsequent pattern forming method, for example, a subtractive process, a semiadditive process, etc., which are well known to those skilled in the art, can be used.
[硬化物] 本發明之硬化物係使本發明之樹脂組成物薄片的感光性樹脂組成物層硬化而得到。如同在「[樹脂薄片]」之項目中所說明般,該硬化物係使滿足條件(I)或(II)的感光性樹脂組成物硬化而成者,故於顯影後該表面具有特定的最大凹谷深度。[hardened material] The cured product of the present invention is obtained by curing the photosensitive resin composition layer of the resin composition sheet of the present invention. As explained in the item "[resin sheet]", the hardened material is obtained by hardening the photosensitive resin composition that satisfies the condition (I) or (II). Therefore, the surface has a specific maximum density after development. Valley depth.
感光性樹脂組成物層之硬化條件,只要是使用形成印刷配線板的絕緣層時一般所採用的條件即可,可使用例如前述之(5)步驟的條件。又,在使樹脂組成物熱硬化前,亦可進行預加熱,包含預加熱的加熱係可進行多次。 [實施例]The curing conditions of the photosensitive resin composition layer may be those generally used when forming an insulating layer of a printed wiring board. For example, the conditions of the above-mentioned step (5) may be used. In addition, before thermally curing the resin composition, preheating may be performed, and the heating system including preheating may be performed multiple times. [Example]
以下,藉由實施例來更具體地說明本發明,但本發明並非被限定於該等的實施例中。尚,以下之記載中,表示量的「份」及「%」, 若無特別說明時,分別為「質量份」及「質量%」之涵義。Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. However, in the following description, "parts" and "%" of the amount are expressed. Unless otherwise specified, the meanings are "mass parts" and "mass %" respectively.
((b)成分的主鏈的玻璃轉移溫度之測定) (b)成分的主鏈的玻璃轉移溫度係依據下述所示之FOX公式來算出。 1/Tg=(W1/Tg1)+(W2/Tg2)+・・・+(Wm/Tgm) W1+W2+・・・+Wm=1 Wm係表示構成(b)成分的各單體的含有量(質量%),Tgm係表示構成(b)成分的各單體的玻璃轉移溫度(K)。 ((b) Measurement of the glass transition temperature of the main chain of the component) (b) The glass transition temperature of the main chain of the component is calculated based on the FOX formula shown below. 1/Tg=(W1/Tg1)+(W2/Tg2)+・・・+(Wm/Tgm) W1+W2+・・・+Wm=1 Wm represents the content (mass %) of each monomer constituting the component (b), and Tgm represents the glass transition temperature (K) of each monomer constituting the component (b).
將藉由凝膠滲透層析法(GPC)所測定的聚苯乙烯換算的重量平均分子量作為(b)成分的重量平均分子量。 The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) was defined as the weight average molecular weight of the component (b).
在內容量為2公升的5頸反應容器內,加入甲基異丁基酮350g、甲基丙烯酸縮水甘油酯71g、丙烯酸丁酯136g及偶氮二異丁腈16g,一邊吹入氮氣,一邊以80℃加熱6小時。接下來,在所得到的反應溶液中,加入丙烯酸36g、對羥基苯甲醚(methoquinone)4mg及三苯基膦4mg,並一邊吹入空氣,一邊以100℃加熱24小時。在所得到的反應混合物中,加入四氫鄰苯二甲酸酐48g,以70℃加熱10小時並加入溶劑後從而得到聚合物溶液(聚合物的理論Tg值為-28℃,固形分含量:50質量%,Mw:18000,酸價:52mgKOH/g)。 In a 5-neck reaction vessel with an internal capacity of 2 liters, add 350g of methyl isobutyl ketone, 71g of glycidyl methacrylate, 136g of butyl acrylate, and 16g of azobisisobutyronitrile, while blowing in nitrogen. Heating at 80°C for 6 hours. Next, 36 g of acrylic acid, 4 mg of methoquinone, and 4 mg of triphenylphosphine were added to the obtained reaction solution, and the mixture was heated at 100° C. for 24 hours while blowing air. To the obtained reaction mixture, 48 g of tetrahydrophthalic anhydride was added, heated at 70°C for 10 hours, and a solvent was added to obtain a polymer solution (theoretical Tg value of the polymer is -28°C, solid content: 50 Mass %, Mw: 18000, acid value: 52mgKOH/g).
依下述表所示之調配比例來調配各成分,並使用高速旋轉攪拌機來調整樹脂清漆。 Prepare each component according to the proportion shown in the table below, and use a high-speed rotating mixer to adjust the resin varnish.
表中的簡稱等係如同下述。 The abbreviations in the table are as follows.
‧SC2050:相對於熔融矽石漿料(Admatechs公司製、平均粒徑0.5μm、比表面積5.9m2/g)100質量份,以胺基矽烷(信越化學公司製、「KBM573」)0.5質量份來進行表面處理並加入MEK而成的漿料。固形分濃度70%。 ‧SC2050: 0.5 part by mass of aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") based on 100 parts by mass of molten silica slurry (manufactured by Admatechs, average particle diameter 0.5 μm, specific surface area 5.9 m 2 /g) To carry out surface treatment and add MEK slurry. The solid content concentration is 70%.
‧ZAR-2000:雙酚A型環氧丙烯酸酯(日本化藥公司製、酸價99mgKOH/g、固形分濃度約70%) ‧ZAR-2000: Bisphenol A type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, solid content concentration approximately 70%)
‧NC3000H:聯苯型環氧樹脂(日本化藥公司製、環氧當量約272) ‧NC3000H: biphenyl-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is about 272)
‧IrgacureOXE-02:乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟)(BASF製) ‧IrgacureOXE-02: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime)( BASF system)
‧合成例1:合成例1所合成的(b)成分 ‧Synthesis Example 1: Component (b) synthesized in Synthesis Example 1
・DPHA:二季戊四醇六丙烯酸酯(日本化藥公司製、丙烯酸當量約96) ・NV-7-201:顏料(碳黑、日本Pigment公司製、固形分濃度20%)・DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., acrylic acid equivalent: approximately 96) ・NV-7-201: Pigment (carbon black, manufactured by Japan Pigment Co., Ltd., solid content concentration 20%)
(支撐體的最大凹谷深度的絕對值之測定) 支撐體的最大凹谷深度(Rv)之測定係使用白色光干擾型顯微鏡(Contoure GT-X series Bruker AXS公司製)。將物鏡設定為50倍,並選擇綠色光,將表面形狀的測定範圍設為125μm×100μm。之後,藉由經『Terms Removal(F-Operation)』來進行一次傾斜角校正,從而求得支撐體的表面的最大凹谷深度的絕對值(|Rv|)。(Measurement of the absolute value of the maximum valley depth of the support) The maximum valley depth (Rv) of the support was measured using a white light interference type microscope (Contoure GT-X series Bruker AXS). The objective lens was set to 50x, green light was selected, and the surface shape measurement range was set to 125 μm × 100 μm. After that, by performing a tilt angle correction through "Terms Removal (F-Operation)", the absolute value of the maximum valley depth (|Rv|) of the surface of the support body is obtained.
(支撐體的算術平均粗糙度(Ra)之測定) 支撐體的算術平均粗糙度係使用非接觸型干擾顯微鏡(WYKO Bruker AXS公司製)來進行測定。(Measurement of arithmetic mean roughness (Ra) of the support) The arithmetic mean roughness of the support was measured using a non-contact interference microscope (manufactured by WYKO Bruker AXS).
(支撐體的霧度肢測定) 支撐體的霧度係使用霧度計HZ-V3(Suga試驗機公司製)來進行測量。(Measurement of haze limb of support) The haze of the support was measured using a haze meter HZ-V3 (manufactured by Suga Testing Machine Co., Ltd.).
<實施例1> (支撐體1之製作) 利用模塗佈機,將脫模劑(Lintec公司製、「AL-5」)以脫模劑的厚度成為1μm之方式,均勻地塗佈在PET薄膜(Unitika公司製、「S-25」)上,從而來製作支撐體1。測定支撐體1的霧度時為6%。<Example 1> (Preparation of support body 1) Using a die coater, apply the release agent (manufactured by Lintec Corporation, "AL-5") evenly on the PET film (manufactured by Unitika Corporation, "S-25") so that the thickness of the release agent becomes 1 μm. to produce the support body 1. When the haze of the support 1 was measured, it was 6%.
((1)步驟:準備樹脂薄片之步驟) 藉由利用模塗佈機,將先前製造例1的樹脂清漆以乾燥後的感光性樹脂組成物層的厚度成為20μm之方式,均勻地塗佈在上述支撐體1的脫模劑上,並以80℃至110℃進行乾燥5分鐘,從而得到在平滑PET薄膜上具有感光性樹脂組成物層的樹脂薄片。((1) Step: Preparing the resin sheet) By using a die coater, the resin varnish of the previous production example 1 was evenly coated on the release agent of the support 1 so that the thickness of the dried photosensitive resin composition layer became 20 μm, and then Drying was performed at 80° C. to 110° C. for 5 minutes to obtain a resin sheet having a photosensitive resin composition layer on a smooth PET film.
((2)步驟:在基板上層合樹脂薄片之步驟) 接下來,對於形成有將厚度18μm的銅層(經藉由MEC公司製CZ8100之處理來進行粗化)圖型化的電路的玻璃環氧基板(覆銅層合板),以先前的樹脂薄片的感光性樹脂組成物層與銅電路表面相接之方式來進行配置,並使用真空層合機(Nichigo Materials公司製、VP160)來進行層合,從而形成依序層合前述覆銅層合板、前述感光性樹脂組成物層、與前述支撐體而成的層合體。壓著條件係可設為抽真空的時間30秒鐘、壓著溫度80℃、壓著壓力0.7MPa、加壓時間30秒鐘。((2) Step: Step of laminating resin sheets on the substrate) Next, a glass epoxy substrate (copper-clad laminate) on which a circuit was formed by patterning a copper layer with a thickness of 18 μm (roughened by treatment with CZ8100 manufactured by MEC Corporation) was used. The photosensitive resin composition layer is arranged so as to be in contact with the surface of the copper circuit, and is laminated using a vacuum laminator (VP160 manufactured by Nichigo Materials Co., Ltd.) to form the aforementioned copper-clad laminate, the aforementioned A laminate composed of a photosensitive resin composition layer and the aforementioned support. The pressing conditions can be set as vacuuming time of 30 seconds, pressing temperature of 80°C, pressing pressure of 0.7MPa, and pressurizing time of 30 seconds.
((3)步驟:將感光性樹脂組成物層進行曝光之步驟) 將該層合體靜置在室溫30分以上,並使用採取圓孔圖型的圖型形成裝置,從該層合體的支撐體上方來進行250mJ/cm2 的紫外線曝光。(3)步驟係以不剝離支撐體之狀態下來進行。曝光圖型為開口:50μm、60μm、70μm、80μm、90μm、100μm的圓孔、120μm的圓孔、200μm的圓孔、250μm的圓孔、500μm的圓孔、L/S(線/間隙):50μm/50μm、60μm/60μm、70μm/70μm、80μm/80μm、90μm/90μm、100μm/100μm的線和間隙、並使用描繪具有1cm×2cm四角形的形狀的曝光部與未曝光部的石英玻璃遮罩。以室溫下靜置10分鐘後,自前述層合體上剝去支撐體。((3) Step: Exposing the photosensitive resin composition layer) The laminate is left to stand at room temperature for more than 30 minutes, and a pattern forming device that adopts a circular hole pattern is used to remove the laminate from the support of the laminate. UV exposure of 250mJ/ cm2 was performed above the body. (3) The step is performed without peeling off the support. The exposure pattern is opening: 50μm, 60μm, 70μm, 80μm, 90μm, 100μm round hole, 120μm round hole, 200μm round hole, 250μm round hole, 500μm round hole, L/S (line/space): Lines and gaps of 50μm/50μm, 60μm/60μm, 70μm/70μm, 80μm/80μm, 90μm/90μm, 100μm/100μm, and a quartz glass mask depicting exposed and unexposed parts having a 1cm×2cm square shape . After leaving it to stand at room temperature for 10 minutes, the support was peeled off from the laminate.
((6)步驟:剝離支撐體之步驟) 於(3)步驟後,以手動來剝離支撐體。((6) Step: Step of peeling off the support) After step (3), peel off the support manually.
((顯影前的Rv及顯影前的Ra之測定)) 對於(3)步驟後(4)步驟前的感光性樹脂組成物層的曝光部的表面狀態,使用白色光干擾型顯微鏡(Contoure GT-X series Bruker AXS公司製),將物鏡設定為50倍,選擇綠色光並將表面形狀的測定範圍設為125μm×100μm。之後,藉由經『Terms Removal(F-Operation)』來進行一次傾斜角校正,從而測定感光性樹脂組成物層表面於顯影前的Rv的絕對值(A1)的值。又,顯影前的算術平均粗糙度(Ra)係使用非接觸型干擾顯微鏡(WYKO Bruker AXS公司製)來進行測定。((Measurement of Rv before development and Ra before development)) Regarding the surface state of the exposed portion of the photosensitive resin composition layer after (3) step (4) and before step (4), a white light interference type microscope (Contoure GT-X series manufactured by Bruker AXS Co., Ltd.) was used, and the objective lens was set to 50 times. Select green light and set the surface shape measurement range to 125 μm × 100 μm. Thereafter, a tilt angle correction is performed through "Terms Removal (F-Operation)" to measure the absolute value (A1) of Rv on the surface of the photosensitive resin composition layer before development. In addition, the arithmetic mean roughness (Ra) before development was measured using a non-contact interference microscope (manufactured by WYKO Bruker AXS).
((4)步驟:藉由顯影來形成圖型感光性樹脂組成物層之步驟) 於(6)步驟後,將作為顯影液的30℃的1質量%碳酸鈉水溶液,以噴霧壓0.2MPa,對層合板上的感光性樹脂組成物層的全面進行2分鐘的噴霧顯影,從而形成圖型感光性樹脂組成物層。((4) Step: Step of forming a patterned photosensitive resin composition layer by development) After step (6), the entire photosensitive resin composition layer on the laminate is spray developed for 2 minutes using a 1 mass % sodium carbonate aqueous solution at 30° C. as a developer at a spray pressure of 0.2 MPa to form Graphical photosensitive resin composition layer.
((顯影後的Rv及顯影後的Ra之測定)) 於(4)步驟後,採用與((顯影前的Rv及顯影前的Ra之測定))為相同的方法,測定於顯影後的圖型感光性樹脂組成物層表面的Rv的絕對值(A2)及於顯影後的算術平均粗糙度(Ra)。又,亦算出已事先測定的於顯影前的Rv的絕對值(A1)與前述的A2之比(A2/A1)。((Measurement of Rv after development and Ra after development)) After the step (4), use the same method as ((Measurement of Rv before development and Ra before development)) to measure the absolute value of Rv (A2) on the surface of the patterned photosensitive resin composition layer after development ) and the arithmetic mean roughness (Ra) after development. Furthermore, the ratio of the absolute value of Rv before development (A1) measured in advance to the aforementioned A2 (A2/A1) was also calculated.
((5)步驟:將圖型感光性樹脂組成物層進行硬化之步驟) 於(4)步驟後,對感光性樹脂組成物層表面進行1J/cm2 的紫外線照射,進而以180℃、進行30分鐘的加熱處理,從而形成具有開口部的絕緣層。將此者作為評估用層合體。((5) Step: Step of hardening the patterned photosensitive resin composition layer) After step (4), the surface of the photosensitive resin composition layer is irradiated with ultraviolet rays of 1 J/cm 2 and then heated at 180°C. Heat treatment for 30 minutes to form an insulating layer having an opening. This was used as a laminate for evaluation.
<實施例2> 實施例1中,將於(3)步驟後(4)步驟前所進行的(6)步驟,於(2)步驟後(3)步驟前來進行。即,於剝離支撐體後來進行(3)步驟。除以上之事項以外係採用與實施例1相同之方式樣,測定顯影前的Rv、顯影前的Ra、顯影後的Rv及顯影後的Ra,亦同時製作評估用層合體。<Example 2> In Example 1, step (6), which is performed after step (3) and before step (4), is performed after step (2) and before step (3). That is, step (3) is performed after peeling off the support. Except for the above matters, in the same manner as in Example 1, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced at the same time.
<實施例3> 實施例2中,將製造例1的樹脂清漆變更成製造例2的樹脂清漆。除以上之事項以外係採用與實施例2相同之方式,測定顯影前的Rv、顯影前的Ra、顯影後的Rv及顯影後的Ra,同時亦製作評估用層合體。<Example 3> In Example 2, the resin varnish of Production Example 1 was changed to the resin varnish of Production Example 2. Except for the above matters, in the same manner as in Example 2, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced.
<實施例4> 實施例1中,將製造例1的樹脂清漆變更成製造例3的樹脂清漆。除以上之事項以外係採用與實施例1相同之方式,測定顯影前的Rv、顯影前的Ra、顯影後的Rv及顯影後的Ra,同時亦製作評估用層合體。<Example 4> In Example 1, the resin varnish of Production Example 1 was changed into the resin varnish of Production Example 3. Except for the above matters, in the same manner as in Example 1, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced.
<比較例1> 實施例1中,將製造例1的樹脂清漆變更成製造例2的樹脂清漆。除以上之事項以外係採用與實施例1相同之方式,測定顯影前的Rv、顯影前的Ra、顯影後的Rv及顯影後的Ra,同時亦製作評估用層合體。<Comparative example 1> In Example 1, the resin varnish of Production Example 1 was changed into the resin varnish of Production Example 2. Except for the above matters, in the same manner as in Example 1, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced.
<比較例2> 將實施例1變更如下: 1)將製造例1的樹脂清漆變更成製造例2的樹脂清漆,及 2)將支撐體1變更成支撐體2(混入填充材的PET薄膜、「PTH-25」、Unitika公司製、霧度值25%)。除以上之事項以外係採用與實施例1相同之方式,測定顯影前的Rv、顯影前的Ra、顯影後的Rv及顯影後的Ra,同時亦製作評估用層合體。<Comparative example 2> Modify Example 1 as follows: 1) Change the resin varnish of Production Example 1 to the resin varnish of Production Example 2, and 2) Change the support body 1 to the support body 2 (PET film mixed with filler, "PTH-25", manufactured by Unitika Co., Ltd., haze value 25%). Except for the above matters, in the same manner as in Example 1, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced.
<比較例3> 將實施例1變更如下: 1)將製造例1的樹脂清漆變更成製造例2的樹脂清漆,及 2)將支撐體1變更成支撐體3(經噴砂處理的PET薄膜、「T60」、Toray公司製、霧度值70%)。除以上之事項以外係採用與實施例1相同之方式,測定顯影前的Rv、顯影前的Ra、顯影後的Rv及顯影後的Ra,同時亦製作評估用層合體。<Comparative Example 3> Modify Example 1 as follows: 1) Change the resin varnish of Production Example 1 to the resin varnish of Production Example 2, and 2) Change the support body 1 to the support body 3 (sandblasted PET film, "T60", manufactured by Toray Co., Ltd., haze value 70%). Except for the above matters, in the same manner as in Example 1, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced.
<比較例4> 將實施例1變更如下: 1)將製造例1的樹脂清漆變更成製造例2的樹脂清漆,及 2)將支撐體1變更成支撐體4(塗佈粗化劑的PET薄膜、霧度值60%)。除以上之事項以外係採用與實施例1相同之方式,測定顯影前的Rv、顯影前的Ra、顯影後的Rv及顯影後的Ra,同時亦製作評估用層合體。<Comparative Example 4> Modify Example 1 as follows: 1) Change the resin varnish of Production Example 1 to the resin varnish of Production Example 2, and 2) Change the support body 1 to the support body 4 (PET film coated with roughening agent, haze value 60%). Except for the above matters, in the same manner as in Example 1, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced.
<顯影性之評估> 利用目視來觀察評估用層合體的曝光部的1cm×2cm的四角形部分。將上述曝光部的樹脂為未剝離或一部分未溶解之情形時設為「〇」;將曝光部的樹脂若開始剝離或一部分為溶解之情形,或者在未曝光部存在樹脂殘渣之情形時設為「△」;將曝光部與未曝光部無法對比之情形時設為「×」。<Evaluation of developability> A 1 cm×2 cm square portion of the exposed portion of the evaluation laminate was visually observed. When the resin in the exposed part is not peeled off or partially dissolved, it is set as "0"; when the resin in the exposed part starts to peel off or is partially dissolved, or when there is resin residue in the unexposed part, it is set as "0". "△"; when the exposed part and the unexposed part cannot be compared, it is set as "×".
<孔洞形狀之評估及最小開口徑之測定> 利用SEM(Hitachi High-Technology公司製、S-4800)來觀察(倍率1000倍)形成在評估用層合體的各圓孔圖型,並測定無殘渣的圓孔圖型的最小開口徑(孔洞最小徑)。又,對於圓孔圖型的孔洞形狀(開口形狀)係依下述之基準來進行評估。 ○:觀察任意三點的圓孔圖型,未發現有外伸或下切。 × :觀察任意三點的圓孔圖型,發現有外伸或下切。<Evaluation of hole shape and determination of minimum opening diameter> Each circular hole pattern formed on the evaluation laminate was observed using SEM (S-4800, manufactured by Hitachi High-Technology Co., Ltd.) (magnification: 1000 times), and the minimum opening diameter of the circular hole pattern without residue (the smallest hole) was measured. diameter). In addition, the hole shape (opening shape) of the circular hole pattern is evaluated based on the following criteria. ○: Observe the round hole pattern at any three points, and no overhang or undercut is found. ×: Observe the circular hole pattern at any three points and find that there are overhangs or undercuts.
<配線的遮蔽性(視認性)之評估> 對於評估用層合體,將利用目視而無法看見圖型者設為「〇」,將可看見基底的圖型者設為「×」。<Evaluation of shielding (visibility) of wiring> Regarding the laminate for evaluation, those in which the pattern could not be seen visually were marked as "O", and those in which the pattern of the base was visible were marked as "×".
<密著性之評估> (密封用薄片之製作) 將雙酚型液狀環氧樹脂(新日鐵住金化學公司製「ZX1059」、環氧當量約169、雙酚A型與雙酚F型的1:1混合品)4份、伸萘基醚型環氧樹脂(DIC公司製「EXA-7311-G4」、環氧當量約213)10份、聯二甲酚型環氧樹脂(Mitsubishi Chemical公司製「YX4000HK」、環氧當量約185)6份、聯苯型環氧樹脂(日本化藥公司製「NC3000L」、環氧當量約272)10份、及阻燃劑(大八化學工業公司製「PX-200」)4份,在溶劑油20份及環己酮10份的混合溶媒中一邊攪拌,一邊使其加熱溶解。冷卻至室溫後,於此中混合含有三嗪骨架的甲酚酚醛清漆系硬化劑(DIC公司製「LA3018-50P」、羥基當量約151、固形分50%的2-甲氧基丙醇溶液)10份、含有三嗪骨架的苯酚酚醛清漆系硬化劑(DIC公司製「LA-7054」、羥基當量約125、固形分60%的MEK溶液)4份、萘酚系硬化劑(新日鐵住金化學公司製「SN-495V」、羥基當量約231、固形分60%的MEK溶液)10份、胺系硬化促進劑(4-二甲基胺基吡啶(DMAP)、固形分5質量%的MEK溶液)1份、經胺基矽烷系偶合劑(信越化學工業公司製「KBM573」)進行表面處理的SC4500(Admatechs公司製)220份,利用高速旋轉攪拌機均勻地分散後,藉由利用模塗佈機,以乾燥後的硬化性樹脂組成物層的厚度成為25μm之方式,將樹脂清漆均勻地塗佈在利用醇酸樹脂系脫模劑(Lintec公司製「AL-5」)經脫模處理的PET薄膜(Toray公司製「Lumirror T6AM」、厚度38μm、軟化點130℃、「脫模PET」)上,並以80℃至110℃來進行乾燥4分鐘,從而得到在脫模PET上具有硬化性樹脂組成物層的密封用薄片。<Evaluation of Adhesion> (Preparation of sealing sheets) Mix 4 parts of bisphenol type liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent approximately 169, 1:1 mixture of bisphenol A type and bisphenol F type), alkylene ether 10 parts of type epoxy resin ("EXA-7311-G4" made by DIC Corporation, epoxy equivalent of about 213), 6 parts of dixylenol type epoxy resin ("YX4000HK" made by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185) , 10 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Chemical Industry Co., Ltd., epoxy equivalent approximately 272), and 4 parts of flame retardant ("PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.), in 20 parts of solvent oil part and 10 parts of cyclohexanone in a mixed solvent while stirring and heating to dissolve. After cooling to room temperature, a 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50% was mixed with a cresol novolak-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation). ) 10 parts of a phenol novolak-based hardener containing a triazine skeleton ("LA-7054" manufactured by DIC Corporation, a MEK solution with a hydroxyl equivalent of about 125 and a solid content of 60%), 4 parts of a naphthol-based hardener (Nippon Steel "SN-495V" manufactured by Sumitomo Chemical Co., Ltd., MEK solution with a hydroxyl equivalent of about 231 and a solid content of 60%) 10 parts, an amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), a solid content of 5 mass%) 1 part of MEK solution) and 220 parts of SC4500 (manufactured by Admatechs) that has been surface-treated with an aminosilane coupling agent ("KBM573" produced by Shin-Etsu Chemical Industry Co., Ltd.), dispersed uniformly using a high-speed rotating mixer, and then used die coating Using a cloth machine, the resin varnish is evenly applied to the mold-released surface using an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation) so that the thickness of the curable resin composition layer after drying becomes 25 μm. on a PET film ("Lumirror T6AM" manufactured by Toray Corporation, thickness 38 μm, softening point 130°C, "release PET") and dried at 80°C to 110°C for 4 minutes to obtain hardened release PET Sheet for sealing the flexible resin composition layer.
將所得到的密封用薄片層合在各評估用層合體之上。之後,以180℃的烘箱來進行90分鐘加熱。對於所得到的硬化性樹脂組成物層之面,以1mm間隔來切開10方格×10方格的共計100方格的切口,在其上方貼附賽珞凡膠帶後,急速地朝180°的方向來進行剝離。評估係根據下述之判斷。 ○:全部的方格中未出現剝落。 × :可觀察到至少有一個樹脂的剝落。The obtained sealing sheet was laminated on each evaluation laminate. Thereafter, heating was performed in an oven at 180° C. for 90 minutes. On the surface of the obtained curable resin composition layer, a total of 100 squares of 10 squares × 10 squares were cut at intervals of 1 mm, and after affixing cellulose tape on top, the incisions were quickly made toward the 180° direction for peeling. The evaluation is based on the following judgments. ○: No peeling occurs in all squares. ×: At least one peeling of the resin is observed.
由上述表可得知,實施例1~4中,可不損及開口部的開口形狀來將表面進行粗化,並可提升圖型的遮蔽性或提升圖型感光性樹脂組成物層表面的密著性。It can be seen from the above table that in Examples 1 to 4, the surface can be roughened without damaging the opening shape of the opening, and the shielding property of the pattern can be improved or the density of the surface of the photosensitive resin composition layer of the pattern can be improved. Attachment.
實施例1~3中,即便是未含有(e)~(g)成分等之情形,雖然程度上會有差別,但確認會總結與上述實施例為相同的結果。又,實施例4中,即便是未含有(b)~(g)成分等之情形,雖然程度上會有差別,但確認會總結與上述實施例為相同的結果。In Examples 1 to 3, even when components (e) to (g), etc. are not contained, although there are differences in degree, it is confirmed that the results are the same as those in the above-mentioned Examples. In addition, in Example 4, even when components (b) to (g), etc. are not contained, although there is a difference in degree, it was confirmed that the same result as that of the above-mentioned Example can be summarized.
10‧‧‧樹脂薄片 101‧‧‧支撐體 101a‧‧‧感光性樹脂組成物層側之面 102‧‧‧感光性樹脂組成物層 102a‧‧‧與支撐體相接之面 102b‧‧‧顯影後的圖型感光性樹脂組成物層 102c‧‧‧與基板側為相反側之面 103‧‧‧基板 11‧‧‧以往的樹脂薄片 111‧‧‧支撐體 111a‧‧‧感光性樹脂組成物層側之面 112‧‧‧感光性樹脂組成物層 112a‧‧‧與支撐體相接之面 112b‧‧‧顯影後的圖型感光性樹脂組成物層 112c‧‧‧與基板側為相反側之面 113‧‧‧基板10‧‧‧Resin sheet 101‧‧‧Support 101a‧‧‧Photosensitive resin composition layer side 102‧‧‧Photosensitive resin composition layer 102a‧‧‧The surface connecting with the support body 102b‧‧‧Patterned photosensitive resin composition layer after development 102c‧‧‧The side opposite to the substrate side 103‧‧‧Substrate 11‧‧‧Conventional resin sheets 111‧‧‧Support 111a‧‧‧Photosensitive resin composition layer side 112‧‧‧Photosensitive resin composition layer 112a‧‧‧The surface connecting with the support body 112b‧‧‧Patterned photosensitive resin composition layer after development 112c‧‧‧The side opposite to the substrate side 113‧‧‧Substrate
[圖1]圖1係用來說明本發明之樹脂薄片之一例的概略截面圖。 [圖2]圖2係表示將本發明之樹脂薄片層合在基板上並進行曝光時之模樣之一例的概略截面圖。 [圖3]圖3係表示使用本發明之樹脂薄片並進行顯影時之模樣之一例的概略截面圖。 [圖4]圖4係用來說明以往的樹脂薄片的概略截面圖。 [圖5]圖5係表示將以往的樹脂薄片層合在基板上並進行曝光時之模樣的概略截面圖。 [圖6]圖6係表示使用以往的樹脂薄片並進行顯影時之模樣的概略截面圖。[Fig. 1] Fig. 1 is a schematic cross-sectional view for explaining an example of the resin sheet of the present invention. [Fig. 2] Fig. 2 is a schematic cross-sectional view showing an example of a state in which the resin sheet of the present invention is laminated on a substrate and exposed. [Fig. 3] Fig. 3 is a schematic cross-sectional view showing an example of a development using the resin sheet of the present invention. [Fig. 4] Fig. 4 is a schematic cross-sectional view for explaining a conventional resin sheet. [Fig. 5] Fig. 5 is a schematic cross-sectional view showing a state in which a conventional resin sheet is laminated on a substrate and exposed. [Fig. 6] Fig. 6 is a schematic cross-sectional view showing how a conventional resin sheet is used and developed.
10:樹脂薄片 10:Resin sheet
101:支撐體 101:Support
101a:感光性樹脂組成物層側之面 101a: Photosensitive resin composition layer side
102:感光性樹脂組成物層 102: Photosensitive resin composition layer
102a:與支撐體相接之面 102a: Surface connecting with the support body
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