TWI408150B - A solder resist composition and a printed circuit board using the same - Google Patents
A solder resist composition and a printed circuit board using the same Download PDFInfo
- Publication number
- TWI408150B TWI408150B TW098120452A TW98120452A TWI408150B TW I408150 B TWI408150 B TW I408150B TW 098120452 A TW098120452 A TW 098120452A TW 98120452 A TW98120452 A TW 98120452A TW I408150 B TWI408150 B TW I408150B
- Authority
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- Taiwan
- Prior art keywords
- mass
- parts
- solder resist
- molecule
- oxide
- Prior art date
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- 150000001875 compounds Chemical class 0.000 claims abstract description 35
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Classifications
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- G—PHYSICS
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- 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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
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- 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
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- 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
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Abstract
Description
本發明係關於，適合作為印刷電路板之永久性光罩使用，且可形成高反射率之抗焊劑之抗焊劑組成物，及具有使用此抗焊劑組成物所形成之抗焊劑的印刷電路板。The present invention relates to a solder resist composition suitable for use as a permanent mask of a printed circuit board, and which can form a high reflectance solder resist, and a printed circuit board having a solder resist formed using the solder resist composition.
印刷電路板係為使用於電子機器等中者，係由承載有電子零件之板(board)與遍佈在其上之電路所成立。作為此電路之形成方法，有著許多種類，例如有藉由蝕刻除去黏著於層合板上之不必要部份之銅箔而形成電路配線之方法。然後，藉由在印刷電路板焊接上電子零件實裝後，進行電性接續。然而，本說明書中，所謂的印刷電路板係指，既形成有電路者及在形成之電路上實裝有電子零件者之兩方。然後，作為此電子零件之焊接時保護電路之保護膜，則使用抗焊劑。此抗焊劑係塗佈抗焊劑組成物於基材上，使其硬化而形成。The printed circuit board is used in an electronic device or the like, and is formed by a board carrying electronic components and a circuit thereover. As a method of forming the circuit, there are many types, for example, a method of forming a circuit wiring by etching to remove an unnecessary portion of the copper foil adhered to the laminate. Then, electrical mounting is performed by mounting the electronic components on the printed circuit board. However, in the present specification, the term "printed circuit board" means both the circuit breaker and the electronic component mounted on the formed circuit. Then, as a protective film for the protective circuit of the electronic component during soldering, a solder resist is used. This solder resist is formed by applying a solder resist composition to a substrate and hardening it.
又，抗焊劑係為，不僅同時防止電子零件在焊接時除了在必須焊接的場所以外防止焊料的附著，也為了不使印刷電路板上之導體曝露於空氣中，防止氧或水份所造成之導體劣化。更進一步，抗焊劑也可運用作為印刷電路板之永久保護膜。因此，對於抗焊劑則要求有密著性、電絕緣性、焊料耐熱性、耐溶劑性、耐藥品性等之特性。Moreover, the solder resist is not only preventing the adhesion of the solder in addition to the place where soldering is necessary at the time of soldering, but also preventing the conductor on the printed circuit board from being exposed to the air to prevent oxygen or moisture. The conductor is degraded. Furthermore, solder resist can also be used as a permanent protective film for printed circuit boards. Therefore, the solder resist is required to have properties such as adhesion, electrical insulation, solder heat resistance, solvent resistance, and chemical resistance.
又，印刷電路板為了實現配線之高密度化、而進行著微細化(細微化，Fine)、多層化及單板化，其實裝方式也逐漸轉移至表面實裝技術(SMT)。因此，對於抗焊劑的細微化、高解析性、高精度、高信賴性之要求也逐漸提高。In addition, in order to increase the density of the wiring, the printed circuit board is miniaturized (Fine), multi-layered, and singulated, and the mounting method is gradually shifted to the surface mounting technology (SMT). Therefore, the requirements for the fineness, high resolution, high precision, and high reliability of the solder resist are gradually increasing.
又近年來，將攜帶終端器、電腦、及電視等之液晶顯示器之背光、照明器具之光源等，以及低電力發光之發光二極體(LED)直接實裝至被覆有抗焊劑所形成之印刷電路板之用塗逐漸增加。因此，為了有效利用此LED等之光，被期望有具有高反射率之抗焊劑之印刷電路板。In recent years, a backlight of a liquid crystal display such as a terminal, a computer, a television, or the like, a light source of a lighting fixture, and the like, and a low-power light-emitting diode (LED) are directly mounted to a printing layer coated with a solder resist. The application of the board is gradually increased. Therefore, in order to effectively utilize the light of the LED or the like, a printed circuit board having a high reflectance solder resist is desired.
作為此高反射率之抗焊劑，可舉出含有氧化鈦等之白色顔料者。Examples of the high reflectance solder resist include those containing a white pigment such as titanium oxide.
在此，形成抗焊劑之圖型(以下，稱為「圖型」)之方法則有許多種類，其中可正確地形成微細之圖型之光微影法則被經常使用。接著，特別係考慮到對環境面的影響，鹼顯像型之光微影法則逐漸成為主流。Here, there are many types of methods for forming a pattern of a solder resist (hereinafter referred to as "pattern"), and a photolithography method in which a fine pattern can be accurately formed is frequently used. Then, in particular, considering the influence on the environmental surface, the alkali imaging type lithography method has gradually become the mainstream.
專利文獻1及專利文獻2中揭示有使酚醛清漆型環氧樹脂與不飽和單羧酸反應，更添加多元酸酐之反應生成物作為基礎聚合物，在鹼水溶液下可顯像之抗焊劑組成。Patent Document 1 and Patent Document 2 disclose a composition of a solder resist which can be used to react a novolak type epoxy resin with an unsaturated monocarboxylic acid, a reaction product obtained by adding a polybasic acid anhydride as a base polymer, and an alkali aqueous solution.
在此光微影法中，對樹脂組成物照射UV光等進行圖型化。但，形成上述高反射率抗焊劑之場合時，因包含於其形成所用之抗焊劑組成物中之氧化鈦等在曝光時會吸收光或反射光，而有抗焊劑組成物在硬化時無法充分吸收必要之光，其解析性下降之問題。因此，關於此般抗焊劑組成物，藉由光微影法之高精細圖型之形成則為困難。In this photolithography method, the resin composition is irradiated with UV light or the like to pattern. However, when the high reflectance solder resist is formed, the titanium oxide or the like contained in the solder resist composition used for the formation absorbs light or reflects light during exposure, and the solder resist composition is insufficient at the time of hardening. The problem of absorbing the necessary light and reducing its resolution. Therefore, it is difficult to form a high-definition pattern by the photolithography method with respect to such a solder resist composition.
[專利文獻1]特公平1-54390號公報[Patent Document 1] Japanese Patent Publication No. 1-54390
[專利文獻2]特公平7-17737號公報[Patent Document 2] Special Fair 7-17737
本發明之目的為提供一種就算含有大量氧化鈦其解析性優良，更且可形成高反射率之抗焊劑的抗焊劑組成物。An object of the present invention is to provide a solder resist composition which is excellent in resolution and which can form a high reflectance solder resist even if it contains a large amount of titanium oxide.
又，本發明之其他目的為提供一種具有高反射率且高精細之抗焊劑的印刷電路板。Further, another object of the present invention is to provide a printed circuit board having a high reflectance and high-definition solder resist.
本發明中，作為光聚合起始劑，倂用雙醯基膦氧化物系光聚合起始劑與單醯基膦氧化物系光聚合起始劑。藉此，就算係含有大量之氧化鈦的高反射率焊劑組成物，其解析性優良，可形成高精細之圖型。In the present invention, as the photopolymerization initiator, a bis-mercaptophosphine oxide photopolymerization initiator and a monothiophosphine oxide photopolymerization initiator are used. Thereby, even if it is a high reflectance flux composition containing a large amount of titanium oxide, it has excellent resolution and can form a high-definition pattern.
即，本發明之抗焊劑組成物，其特徵為含有(1)於1分子內含有乙烯性不飽和基與羧基之樹脂、雙醯基膦氧化物系光聚合起始劑、單醯基膦氧化物系光聚合起始劑、光聚合性單體、氧化鈦、環氧化合物與有機溶劑。That is, the solder resist composition of the present invention is characterized in that it contains (1) a resin containing an ethylenically unsaturated group and a carboxyl group in one molecule, a bisphosphonylphosphine oxide photopolymerization initiator, and a monophosphonium phosphine oxide. The photopolymerization initiator, photopolymerizable monomer, titanium oxide, epoxy compound and organic solvent.
(2)又，本發明之抗焊劑組成物，其中除了(1)以外更含有噻噸酮系光聚合增感劑。(2) Further, the solder resist composition of the present invention contains, in addition to (1), a thioxanthone-based photopolymerization sensitizer.
(3)更進一步，其中本發明之抗焊劑組成物，其中除了(1)以外更含有抗氧化劑。(3) Further, wherein the solder resist composition of the present invention contains an antioxidant in addition to (1).
(4)具體而言，其中氧化鈦係為金紅石型氧化鈦。(4) Specifically, the titanium oxide is rutile-type titanium oxide.
(5)更具體而言，其特徵為具有藉由於1分子內含有乙烯性不飽和基與羧基之樹脂與含羧基(甲基)丙烯酸系共聚合樹脂與於1分子中具有環氧乙烷環與乙烯性不飽和基之化合物反應所得之具有羧基之共聚合系樹脂，又，於1分子中具有環氧乙烷環與乙烯性不飽和基之化合物係以由脂肪族聚合性單體所生成之化合物為理想。(5) More specifically, it is characterized by having a resin containing an ethylenically unsaturated group and a carboxyl group in one molecule and a carboxyl group-containing (meth)acrylic copolymer resin and having an oxirane ring in one molecule a copolymerized resin having a carboxyl group obtained by reacting a compound having an ethylenically unsaturated group, and a compound having an oxirane ring and an ethylenically unsaturated group in one molecule is produced from an aliphatic polymerizable monomer The compound is ideal.
(6)又，本發明之特徵為具有使用此些抗焊劑組成物所形成之抗焊劑之印刷電路板。(6) Further, the present invention is characterized by a printed circuit board having a solder resist formed using such a solder resist composition.
(7)更進一步，本發明之形成於印刷電路板上之抗焊劑，其特徵為含有，具有乙烯性不飽和基之化合物、雙醯基膦氧化物系光聚合起始劑、單醯基膦氧化物系光聚合起始劑、氧化鈦、環氧化合物與羧基之反應物。(7) Further, the solder resist formed on a printed circuit board of the present invention is characterized by containing a compound having an ethylenically unsaturated group, a bisphosphonylphosphine oxide photopolymerization initiator, and a monodecylphosphine. An oxide photopolymerization initiator, a titanium oxide, a reaction product of an epoxy compound and a carboxyl group.
依據本發明，可提供一種就算大量含有氧化鈦且反射率為高，可形成解析性優良，且高精細圖型之抗焊劑組成物。According to the present invention, it is possible to provide a solder resist composition which is excellent in resolution and high-definition pattern even if it contains a large amount of titanium oxide and has a high reflectance.
又，依據本發明，可提供一種為高精細且具有抑制樹脂之劣化可長時間維持高反射率之抗焊劑的印刷電路板。Further, according to the present invention, it is possible to provide a printed circuit board which is high-definition and has a solder resist which can suppress high-reflectance for a long period of time by suppressing deterioration of the resin.
以下，詳細說明本發明。Hereinafter, the present invention will be described in detail.
本發明之抗焊劑組成物含有，於1分子內含有乙烯性不飽和基與羧基之樹脂、雙醯基膦氧化物系光聚合起始劑、單醯基膦氧化物系光聚合起始劑、光聚合性單體、氧化鈦、環氧化合物與有機溶劑。The solder resist composition of the present invention contains a resin containing an ethylenically unsaturated group and a carboxyl group in one molecule, a bisphosphonylphosphine oxide photopolymerization initiator, a monothiophosphonium oxide photopolymerization initiator, Photopolymerizable monomer, titanium oxide, epoxy compound and organic solvent.
但，以下中所指之本案塗膜係指使用本發明之抗焊劑組成物所形成之塗膜。However, the coating film referred to in the following refers to a coating film formed using the solder resist composition of the present invention.
作為於1分子內含有乙烯性不飽和基與羧基之樹脂(以下，稱為「光硬化性樹脂」)，只要係於1分子內具有光硬化性用之乙烯性不飽和基與藉由弱鹼水溶液使可顯像之羧基之樹脂即可，並不限定於特定者。此般之光硬化性樹脂，可適宜使用以下所列舉之(1)至(3)的樹脂(寡聚物或聚合物之任一亦可)。即，The resin containing an ethylenically unsaturated group and a carboxyl group in one molecule (hereinafter referred to as "photocurable resin") is an ethylenically unsaturated group having photocurability in one molecule and a weak base. The aqueous solution may be a resin which can develop a carboxyl group, and is not limited to a specific one. As the photocurable resin, the resins (either oligo or polymer) of the following (1) to (3) can be suitably used. which is,
(1)藉由含羧基(甲基)丙烯酸系共聚合樹脂與於1分子中具有環氧乙烷環與乙烯性不飽和基之化合物反應所得之感光性之含羧基樹脂。(1) A photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth)acrylic copolymer resin with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule.
(2)對於1分子中具有1個環氧基與1個不飽和雙鍵之化合物與具有不飽和雙鍵之化合物之共聚物使其與不飽和單羧酸反應，對藉此反應所生成之第2級羥基，使其與飽和或不飽和多元酸酐反應所得之感光性的含羧基樹脂。(2) a copolymer of a compound having one epoxy group and one unsaturated double bond in one molecule and a compound having an unsaturated double bond, which is reacted with an unsaturated monocarboxylic acid to form a reaction by this reaction The second-order hydroxyl group is a photosensitive carboxyl group-containing resin obtained by reacting it with a saturated or unsaturated polybasic acid anhydride.
(3)使含羥基聚合物與飽和或不飽和多元酸酐反應後，對藉此反應所生成之羧酸，使其與1分子中具有1個環氧基與1個不飽和雙鍵之化合物反應所得之感光性的羥基及含羧基樹脂。(3) reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, and reacting the carboxylic acid formed by the reaction with a compound having one epoxy group and one unsaturated double bond in one molecule The obtained photosensitive hydroxyl group and carboxyl group-containing resin.
此些之中更以(1)的感光性之含羧基樹脂之中，使含羧基(甲基)丙烯酸系共聚合樹脂與1分子中具有環氧乙烷環與乙烯性不飽和基之化合物反應所得之具有羧基之共聚合系樹脂，可理想作為光硬化性樹脂使用。Among these, among the photosensitive carboxyl group-containing resins of (1), a carboxyl group-containing (meth)acrylic copolymer resin is reacted with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule. The obtained copolymerized resin having a carboxyl group can be preferably used as a photocurable resin.
含羧基(甲基)丙烯酸系共聚合樹脂係以(甲基)丙烯酸酯與1分子中具有1個不飽和基與1個以上之羧基的化合物共聚合而得。作為(甲基)丙烯酸酯可舉出，(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯等之(甲基)丙烯酸烷酯類、2-羥基(甲基)丙烯酸乙酯、羥基(甲基)丙烯酸丙酯、羥基(甲基)丙烯酸丁酯、己內酯變性2-羥基(甲基)丙烯酸乙酯等之含羥基之(甲基)丙烯酸酯類、甲氧基二乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、異辛氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯等之二醇變性(甲基)丙烯酸酯類等。此些可單獨或亦可混合複數使用。猶，本說明書中，(甲基)丙烯酸酯係指，將丙烯酸酯及甲基丙烯酸酯總稱之用語，關於其他之類似的表現也係同様。The carboxyl group-containing (meth)acrylic copolymer resin is obtained by copolymerizing a (meth) acrylate with a compound having one unsaturated group and one or more carboxyl groups in one molecule. Examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and amyl (meth)acrylate. (meth)acrylic acid alkyl esters such as (meth) hexyl acrylate, 2-hydroxy (meth) acrylate, hydroxy (meth) acrylate, butyl (meth) acrylate, etc. The ester-denatured hydroxyl group-containing (meth) acrylate such as ethyl 2-hydroxy (meth) acrylate, methoxy diethylene glycol (meth) acrylate, ethoxy diethylene glycol (methyl) Glycol denaturation of acrylate, isooctyloxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, etc. (Meth) acrylates and the like. These may be used singly or in combination. In the present specification, (meth) acrylate means a term generally called acrylate and methacrylate, and other similar expressions are also the same.
又，作為於1分子中具有1個不飽和基與1個以上的羧基之化合物，可舉出將丙烯酸、甲基丙烯酸、不飽和基與羧酸之間被鏈延伸之變性不飽和單羧酸(β-羧乙基(甲基)丙烯酸酯、2-丙烯醯基氧乙基琥珀酸、2-丙烯醯基氧乙基六氫鄰苯二甲酸、藉有內酯變性等而具有酯鍵之不飽和單羧酸、具有醚鍵之變性不飽和單羧酸)、順丁烯二酸等之羧基複數包含於分子中者等。此些可單獨使用，亦可混合複數使用。In addition, as a compound having one unsaturated group and one or more carboxyl groups in one molecule, a denatured unsaturated monocarboxylic acid having a chain extending between acrylic acid, methacrylic acid, an unsaturated group and a carboxylic acid may be mentioned. (β-carboxyethyl (meth) acrylate, 2-propenyl oxy oxy succinic acid, 2-propenyl methoxy hexahydrophthalic acid, esterified by lactone denaturing, etc. An unsaturated monocarboxylic acid, a denatured unsaturated monocarboxylic acid having an ether bond, a maleic acid or the like, and a carboxyl group are contained in a molecule. These may be used alone or in combination.
作為於1分子中具有環氧乙烷環與乙烯性不飽和基之化合物，使用由脂肪族單體所生成之化合物為佳。特別係，若使用由脂肪族聚合性單體所生成之化合物，以光硬化性樹脂之芳香環作為起因，因為由於光所造成之硬化物的劣化被抑制，故為佳。作為由脂肪族單體所生成之化合物，可舉出環氧丙基(甲基)丙烯酸酯、α-甲基環氧丙基(甲基)丙烯酸酯、3,4-環氧環己基甲基(甲基)丙烯酸酯、3,4-環氧環己基乙基(甲基)丙烯酸酯、3,4-環氧環己基丁基(甲基)丙烯酸酯、3,4-環氧環己基甲基胺丙烯酸酯、3,4-環氧環己基甲基(甲基)丙烯酸酯等。於1分子中具有環氧乙烷環與乙烯性不飽和基之化合物，可單獨使用，亦可混合複數使用。As the compound having an oxirane ring and an ethylenically unsaturated group in one molecule, a compound formed from an aliphatic monomer is preferably used. In particular, when a compound produced from an aliphatic polymerizable monomer is used, the aromatic ring of the photocurable resin is used as a cause, and deterioration of the cured product due to light is suppressed, which is preferable. Examples of the compound produced from the aliphatic monomer include a glycidyl (meth) acrylate, an α-methyl propyl propyl (meth) acrylate, and a 3,4-epoxycyclohexylmethyl group. (Meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexyl butyl (meth) acrylate, 3,4-epoxycyclohexyl Amine acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like. The compound having an oxirane ring and an ethylenically unsaturated group in one molecule may be used singly or in combination.
光硬化性樹脂，其酸價必須在50~200mgKOH/g之範圍內。光硬化性樹脂之酸價不滿50mgKOH/g之場合時，在弱鹼水溶液中之本案塗膜之未曝光部分將難以除去。又，若光硬化性樹脂之酸價超過200mgKOH/g時，會產生抗焊劑之耐水性，電特性低劣等之間題。又，光硬化性樹脂之重量平均分子量以在5,000~100,000之範圍為佳。若光硬化性樹脂之重量平均分子量不滿5,000，本案塗膜之指觸乾燥性有顯著拙劣之傾向。又，若光硬化性樹脂之重量平均分子量超過100,000，因本案塗膜之顯像性及抗焊劑組成物之儲藏安定性顯著惡化故不理想。The photocurable resin must have an acid value in the range of 50 to 200 mgKOH/g. When the acid value of the photocurable resin is less than 50 mgKOH/g, the unexposed portion of the coating film of the present invention in the weak alkali aqueous solution is difficult to remove. Moreover, when the acid value of the photocurable resin exceeds 200 mgKOH/g, the water resistance of the solder resist is deteriorated, and the electrical characteristics are inferior. Further, the photocurable resin preferably has a weight average molecular weight of from 5,000 to 100,000. If the weight average molecular weight of the photocurable resin is less than 5,000, the dryness of the touch coating of the present film tends to be remarkably poor. In addition, when the weight average molecular weight of the photocurable resin exceeds 100,000, the development of the coating film of the present invention and the storage stability of the solder resist composition are remarkably deteriorated, which is not preferable.
作為雙醯基膦氧化物系光聚合起始劑(以下，稱為「BAPO」)可舉出，雙-(2,6-二氯苯甲醯基)苯基膦氧化物、雙-(2,6-二氯苯甲醯基)-2,5-二甲基苯基膦氧化物、雙-(2,6-二氯苯甲醯基)-4-丙基苯基膦氧化物、雙-(2,6-二氯苯甲醯基)-1-萘基膦氧化物、雙-(2,6-二甲氧基苯甲醯基)苯基膦氧化物、雙-(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基膦氧化物、雙-(2,6-二甲氧基苯甲醯基)-2,5-二甲基苯基膦氧化物、雙-(2,4,6-三甲基苯甲醯基)苯基膦氧化物、(2,5,6-三甲基苯甲醯基)-2,4,4-三甲基戊基膦氧化物等。其中以雙-(2,4,6-三甲基苯甲醯基)苯基膦氧化物(Ciba‧Japan(股)製、商品名；IRGACURE 819)為容易取得。The bis(indenylphosphine oxide) photopolymerization initiator (hereinafter referred to as "BAPO") may be bis-(2,6-dichlorobenzhydryl)phenylphosphine oxide or bis-(2). ,6-dichlorobenzhydryl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzylidene)-4-propylphenylphosphine oxide, double -(2,6-dichlorobenzylidene)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzylidene)phenylphosphine oxide, bis-(2,6 -dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,5-dimethyl Phenylphosphine oxide, bis-(2,4,6-trimethylbenzylidene)phenylphosphine oxide, (2,5,6-trimethylbenzylidene)-2,4,4 - Trimethylpentylphosphine oxide or the like. Among them, bis-(2,4,6-trimethylbenzylidene)phenylphosphine oxide (manufactured by Ciba‧Japan Co., Ltd., trade name; IRGACURE 819) is easily obtained.
作為單醯基膦氧化物系光聚合起始劑(以下，稱為「MAPO」)可舉出，2,4,6-三甲基苯甲醯基二苯基膦氧化物、2,6-二甲氧基苯甲醯基二苯基膦氧化物、2,6-二氯苯甲醯基二苯基膦氧化物、2,4,6-三甲基苯甲醯基苯基次磷酸甲酯、2-甲基苯甲醯基二苯基膦氧化物、三甲基乙醯基苯基次磷酸異丙酯等。其中以2,4,6-三甲基苯甲醯基二苯基膦氧化物(Ciba‧Japan(股)製、商品名；Darocure TPO)為容易取得。The monothiophosphine oxide photopolymerization initiator (hereinafter referred to as "MAPO") may, for example, be 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, 2,6- Dimethoxybenzhydryldiphenylphosphine oxide, 2,6-dichlorobenzhydryldiphenylphosphine oxide, 2,4,6-trimethylbenzimidylphosphoric acid Ester, 2-methylbenzhydryldiphenylphosphine oxide, isopropyl trimethylethylphosphonylphosphite, and the like. Among them, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (manufactured by Ciba‧Japan Co., Ltd., trade name; Darocure TPO) is easily obtained.
本發明因藉由倂用BAPO與MAPO，就算係配合氧化鈦之高反射率的抗焊劑組成物之塗膜，也可藉由穿透過該塗膜的少量之光將此硬化，使用該塗膜可形成高反射率且高精細之圖型。又，更進一步，藉由改變BAPO與MAPO之配合比率，可進行本發明之抗焊劑組成物之感光性的細微調整。即，形成於基材上之圖型的剖面形狀中，對於該圖型之基材面側的深部硬化性不足且容易產生過切(undercut)時，將BAPO之配合比率變大。又，因由本案塗膜之表面硬化性不足，顯像後之圖型的表面狀態為差時，將MAPO之配合比率變大。BAPO與MAPO之配合比率為90對10~1對99，理想為80對20~2對98。若在此配合比率之範圍外，藉由倂用BAPO與MAPO之效果變少，因無法得到本案塗膜硬化所必需之光感度，而變得無法形成高精細之圖型。又，BAPO與MAPO之合計配合量，相對於光硬化性樹脂100質量份，以1~30質量份為佳，更佳為2~25質量份。BAPO與MAPO之合計配合量相對於光硬化性樹脂100質量份，不滿1質量份之場合時，本案塗膜之光硬化性則降低，曝光‧顯像後之圖型形成則變得困難，故不理想。又，BAPO與MAPO之合計配合量相對於光硬化性樹脂100質量份，超過30質量份之場合時，源自光聚合起始劑之塗膜著色變大，更成為成本提高之原因，故不理想。In the present invention, by using BAPO and MAPO, even if it is coated with a coating film of a high reflectance solder resist composition of titanium oxide, it can be hardened by a small amount of light penetrating the coating film, and the coating film is used. It can form a high reflectivity and high definition pattern. Further, further, by changing the blending ratio of BAPO and MAPO, fine adjustment of the photosensitivity of the solder resist composition of the present invention can be performed. In other words, in the cross-sectional shape of the pattern formed on the substrate, when the deep hardenability of the substrate surface side of the pattern is insufficient and undercut is likely to occur, the blending ratio of BAPO is increased. Further, since the surface hardenability of the coating film of the present invention is insufficient, and the surface state of the pattern after development is poor, the mixing ratio of MAPO is increased. The ratio of BAPO to MAPO is 90 to 10 to 1 to 99, and ideally 80 to 20 to 2 to 98. In addition to the range of the blending ratio, the effect of using BAPO and MAPO is reduced, and the light sensitivity required for the hardening of the coating film in this case cannot be obtained, and a high-definition pattern cannot be formed. In addition, the total amount of BAPO and MAPO is preferably from 1 to 30 parts by mass, more preferably from 2 to 25 parts by mass, per 100 parts by mass of the photocurable resin. When the total amount of BAPO and MAPO is less than 1 part by mass based on 100 parts by mass of the photocurable resin, the photocurability of the coating film of the present invention is lowered, and the pattern formation after exposure and development is difficult. not ideal. In addition, when the total amount of BAPO and MAPO is more than 30 parts by mass based on 100 parts by mass of the photocurable resin, the coloring of the coating film derived from the photopolymerization initiator becomes large, and the cost is increased. ideal.
作為光聚合性單體，可舉出2-羥基乙基丙烯酸酯、2-羥基丁基丙烯酸酯等之羥基烷基丙烯酸酯類；乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等之二醇之物或二丙烯酸酯類；N,N-二甲基丙烯醯胺、N-羥甲基丙烯醯胺等之丙烯醯胺類；N,N-二甲基胺乙基丙烯酸酯等之胺烷基丙烯酸酯類；已二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、參-羥基乙基異三聚氰酸酯等之多價醇或此些之環氧乙烷或環氧丙烷添加物之多價丙烯酸酯類；苯氧基丙烯酸酯、雙酚A二丙烯酸酯及此些酚類的環氧乙烷或環氧丙烷添加物等之丙烯酸酯類；甘油二環氧丙基醚、三羥甲基丙烷三環氧丙基醚等之環氧丙基醚的丙烯酸酯類；三聚氰胺丙烯酸酯；及/或對應上述丙烯酸酯類之甲基丙烯酸酯類等。Examples of the photopolymerizable monomer include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol. a diol or a diacrylate of propylene glycol or the like; an acrylamide such as N,N-dimethyl decylamine or N-methylol acrylamide; N,N-dimethylaminoethyl Amine alkyl acrylates such as acrylates; polyvalent alcohols such as diol, trimethylolpropane, pentaerythritol, dipentaerythritol, cis-hydroxyethyl isomeric cyanurate or the like Or polyvalent acrylates of propylene oxide additives; phenoxy acrylates, bisphenol A diacrylates, and acrylates of such phenolic oxirane or propylene oxide additives; An acrylate of a epoxidized propyl ether such as oxypropyl ether or trimethylolpropane triepoxypropyl ether; a melamine acrylate; and/or a methacrylate corresponding to the above acrylate.
光聚合性單體之配合量，相對於光硬化性樹脂100質量份，以10~100質量份為佳，更佳為20~80質量份。光聚合性單體之配合量相對於光硬化性樹脂100質量份，若超過100質量份，因形成之抗焊劑的物性降低而不理想。又，光聚合性單體之配合量相對於光硬化性樹脂100質量份，若不滿10質量份，因本案塗膜不具有充分之光硬化性，而無法得到高精細之圖型。The amount of the photopolymerizable monomer is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, per 100 parts by mass of the photocurable resin. When the amount of the photopolymerizable monomer is more than 100 parts by mass based on 100 parts by mass of the photocurable resin, the physical properties of the formed solder resist are not preferable. In addition, when the amount of the photopolymerizable monomer is less than 10 parts by mass based on 100 parts by mass of the photocurable resin, the coating film of the present invention does not have sufficient photocurability, and a high-definition pattern cannot be obtained.
氧化鈦，可使用銳鈦礦型氧化鈦也可使用金紅石型氧化鈦，特別係金紅石型氧化鈦為佳。銳鈦礦型氧化鈦與金紅石型氧化鈦相比較，因紫外線領域與可見光領域之境界附近之反射率為高，由白色度與反射率之觀點可理想作為白色顏料。但，因銳鈦礦型氧化鈦具有光觸媒活性，而有由於此光活性而造成抗焊劑組成物之樹脂的變色。相對與此，金紅石型氧化鈦，雖然白色度與銳鈦礦型氧化鈦相比為若干拙劣，但因單幾乎不具有光活性，可抑制抗焊劑組成物之樹脂的劣化，可得到安定之抗焊劑。As the titanium oxide, anatase type titanium oxide or rutile type titanium oxide can be used, and particularly rutile type titanium oxide is preferable. The anatase type titanium oxide has a high reflectance near the boundary between the ultraviolet field and the visible light region as compared with the rutile type titanium oxide, and is desirable as a white pigment from the viewpoint of whiteness and reflectance. However, since the anatase type titanium oxide has photocatalytic activity, the discoloration of the resin of the solder resist composition due to the photoactivity is caused. In contrast, the rutile-type titanium oxide has a whiteness which is somewhat inferior to that of the anatase-type titanium oxide, but since it has almost no photoactivity, it can suppress the deterioration of the resin of the solder resist composition, and can be stabilized. Solder resist.
作為金紅石型氧化鈦，具體而言，可舉出TIPAQUE R-820、TIPAQUE R-830、TIPAQUE R-930、TIPAQUE R-550、TIPAQUE R-630、TIPAQUE R-680、TIPAQUE R-670、TIPAQUE R-680、TIPAQUE R-670、TIPAQUE R-780、TIPAQUE R-850、TIPAQUE CR-50、TIPAQUE CR-57、TIPAQUE CR-80、TIPAQUE CR-90、TIPAQUE CR-93、TIPAQUE CR-95、TIPAQUE CR-97、TIPAQUE CR-60、TIPAQUE CR-63、TIPAQUE CR-67、TIPAQUE CR-58、TIPAQUE CR-85、TIPAQUE UT771(石原產業(股)製)、Ti-Pure R-100、Ti-Pure R-101、Ti-Pure R-102、Ti-Pure R-103、Ti-Pure R-104、Ti-Pure R-105、Ti-Pure R-108、Ti-Pure R-900、Ti-Pure R-902、Ti-Pure R-960、Ti-Pure R-706、Ti-Pure R-931(DU PONT(股)製)、TITON R-25、TITON R-21、TITON R-32、TITON R-7E、TITON R-5N、TITON R-61N、TITON R-62N、TITON R-42、TITON R-45M、TITON R-44、TITON R-49S、TITON GTR-100、TITON GTR-300、TITON D-918、TITON TCR-29、TITON TCR-52、TITON FTR-700(堺化學工業(股)製)等。Specific examples of the rutile-type titanium oxide include TIPAQUE R-820, TIPAQUE R-830, TIPAQUE R-930, TIPAQUE R-550, TIPAQUE R-630, TIPAQUE R-680, TIPAQUE R-670, and TIPAQUE. R-680, TIPAQUE R-670, TIPAQUE R-780, TIPAQUE R-850, TIPAQUE CR-50, TIPAQUE CR-57, TIPAQUE CR-80, TIPAQUE CR-90, TIPAQUE CR-93, TIPAQUE CR-95, TIPAQUE CR-97, TIPAQUE CR-60, TIPAQUE CR-63, TIPAQUE CR-67, TIPAQUE CR-58, TIPAQUE CR-85, TIPAQUE UT771 (Ishihara Industry Co., Ltd.), Ti-Pure R-100, Ti-Pure R-101, Ti-Pure R-102, Ti-Pure R-103, Ti-Pure R-104, Ti-Pure R-105, Ti-Pure R-108, Ti-Pure R-900, Ti-Pure R -902, Ti-Pure R-960, Ti-Pure R-706, Ti-Pure R-931 (made by DU PONT), TITON R-25, TITON R-21, TITON R-32, TITON R- 7E, TITON R-5N, TITON R-61N, TITON R-62N, TITON R-42, TITON R-45M, TITON R-44, TITON R-49S, TITON GTR-100, TITON GTR-300, TITON D- 918, TITON TCR-29, TITON TCR-52, TITON FTR-700 (堺Chemical Industry Co., Ltd.), etc.
猶，作為銳鈦礦型氧化鈦，可舉出TA-100、TA-200、TA-300、TA-400、TA-500(富士鈦工業(股)製)、TIPAQUE A-100、TIPAQUE A-220、TIPAQUE W-10(石原產業(股)製)、TITANIX JA-1、TITANIX JA-3、TITANIX JA-4、TITANIX JA-5(TAYCA(股)製)、KRONOS KA-10、KRONOS KA-15、KRONOS KA-20、KRONOS KA-30(鈦工業(股)製)、A-100、A-100、A-100、SA-1、SA-1L(堺化學工業(股)製)等。As an anatase type titanium oxide, TA-100, TA-200, TA-300, TA-400, TA-500 (made by Fuji Titanium Industry Co., Ltd.), TIPAQUE A-100, TIPAQUE A- 220, TIPAQUE W-10 (Ishihara Industry Co., Ltd.), TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA-5 (TAYCA), KRONOS KA-10, KRONOS KA- 15. KRONOS KA-20, KRONOS KA-30 (manufactured by Titanium Industry Co., Ltd.), A-100, A-100, A-100, SA-1, SA-1L (manufactured by Seiko Chemical Co., Ltd.).
氧化鈦之配合量，相對於光硬化性樹脂100質量份，以50~450質量份為佳，更佳為60~350質量份。氧化鈦之配合量相對於光硬化性樹脂100質量份，若超過450質量份，則本發明之抗焊劑組成物之光硬化性降低下，因硬化深度變低故不佳。另一方面，氧化鈦之配合量相對於光硬化性樹脂100質量份若不滿50質量份，當該抗焊劑組成物之隱蔽力變小，而無法得到高反射率之抗焊劑。The amount of the titanium oxide is preferably 50 to 450 parts by mass, more preferably 60 to 350 parts by mass, per 100 parts by mass of the photocurable resin. When the amount of the titanium oxide is more than 450 parts by mass based on 100 parts by mass of the photocurable resin, the photocurability of the solder resist composition of the present invention is lowered, and the depth of hardening is lowered, which is not preferable. On the other hand, when the amount of the titanium oxide is less than 50 parts by mass based on 100 parts by mass of the photocurable resin, the hiding power of the solder resist composition becomes small, and a high reflectance solder resist cannot be obtained.
作為環氧化合物，可舉出雙酚S環氧樹脂、二環氧丙基鄰苯二甲酸酯樹脂、三環氧丙基異三聚氰酸酯(日產化學工業(股)製之TEPIC-H(相對於S-三嗪環骨架面，持有3個環氧基在同一方向鍵結之構造的β體)，或TEPIC(β體與持有相對於S-三嗪環骨架面，1個環氧基係與其他2個環氧基不同方向所鍵結之構造的α體之混合物)等)等之複素環式環氧樹脂、聯茬酚型環氧樹脂、聯苯型環氧樹脂、四環氧丙基茬酚乙烷樹脂等之在稀釋劑中為難溶性之環氧樹脂，或雙酚A型環氧樹脂、加氫雙酚A型環氧樹脂、雙酚F型樹脂、溴化雙酚A型環氧樹脂、苯酚酚醛型或甲酚酚醛清漆型環氧樹脂、脂環式環氧樹脂、雙酚A之酚醛清漆型環氧樹脂、螯合型環氧樹脂、乙二醛型環氧樹脂、含胺基環氧樹脂、橡膠變性環氧樹脂、二環戊二烯酚型環氧樹脂、聚矽氧變性環氧樹脂、ε-己內酯變性環氧樹脂等在稀釋劑中為可溶性之環氧樹脂等。此些之環氧樹脂，可單獨或複數組合使用。Examples of the epoxy compound include bisphenol S epoxy resin, diepoxypropyl phthalate resin, and triepoxypropyl isomeric cyanurate (TEPIC- manufactured by Nissan Chemical Industries Co., Ltd.). H (relative to the S-triazine ring skeleton surface, a β-body with three epoxy groups bonded in the same direction), or TEPIC (beta body and holding relative to the S-triazine ring skeleton surface, 1 a complex epoxy ring epoxy resin, a hydrazine phenol epoxy resin, a biphenyl epoxy resin, etc., a mixture of an epoxy group and an α-form of a structure in which two epoxy groups are bonded in different directions) Epoxy resin which is poorly soluble in the diluent, such as tetraepoxypropyl nonylphenol ethane resin, or bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type resin, bromine Bisphenol A type epoxy resin, phenol novolac type or cresol novolac type epoxy resin, alicyclic epoxy resin, bisphenol A novolak type epoxy resin, chelating epoxy resin, glyoxal Epoxy resin, amine-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenol epoxy resin, polyoxyn modified epoxy resin, ε-caprolactone denatured epoxy tree In other soluble diluent of epoxy resin. These epoxy resins may be used singly or in combination.
環氧化合物之配合量，相對於光硬化性樹脂100質量份，以5~70質量份為佳，更佳為5~60質量份。環氧化合物之配合量相對於光硬化性樹脂100質量份，若超過70質量份，有關本案塗膜在顯像液中之未曝光部分之溶解性降低，因變得容易產生顯像殘留，圖型之形成變得困難。另一方面，環氧化合物之配合量相對於光硬化性樹脂100質量份，若不滿5質量份，由於光硬化性樹脂之羧基在未反應之狀態下殘留於抗焊劑，而變得難以得到充份的抗焊劑之電特性、焊料耐熱性及耐藥品性。The amount of the epoxy compound is preferably 5 to 70 parts by mass, more preferably 5 to 60 parts by mass, per 100 parts by mass of the photocurable resin. When the amount of the epoxy compound is more than 70 parts by mass based on 100 parts by mass of the photocurable resin, the solubility of the coating film in the unexposed portion of the developing solution is lowered, and the image residue is likely to occur. The formation of the type becomes difficult. On the other hand, when the amount of the epoxy compound is less than 5 parts by mass based on 100 parts by mass of the photocurable resin, the carboxyl group of the photocurable resin remains in the anti-flux in an unreacted state, and it becomes difficult to obtain a charge. The electrical properties of the solder resist, solder heat resistance and chemical resistance.
又，光硬化性樹脂之羧基與環氧化合物之環氧基藉由開環聚合而反應。然後此種場合，若對有機溶劑或抗焊劑組成物之其他的物質，將易溶性之環氧樹脂配合該組成物，而由於形成本案塗膜時的乾燥之熱，上述羧基與環氧基之交聯則變得容易進行。因此，若希望抑制當該交聯反應延長乾燥之時間的場合，對有機溶劑或上述組成物之其他的物質，將難溶性之環氧樹脂或與易溶性之環氧樹脂一起配合為佳。Further, the carboxyl group of the photocurable resin and the epoxy group of the epoxy compound are reacted by ring-opening polymerization. Then, in this case, if the organic solvent or other components of the solder resist composition are mixed with the easily soluble epoxy resin, the carboxyl group and the epoxy group are formed by the heat of drying when the coating film of the present invention is formed. Crosslinking is easy to carry out. Therefore, when it is desired to suppress the time during which the crosslinking reaction is extended and dried, it is preferred to mix the poorly soluble epoxy resin or the easily soluble epoxy resin with the organic solvent or other substances of the above composition.
有機溶劑係為了使本發明之抗焊劑組成物變得容易塗佈於基材等之狀態，及將含有有機溶劑之當該組成物在基材上等塗佈、乾燥而形成塗膜所使用。作為有機溶劑，可舉出甲基乙基酮、環己酮等之酮類；甲苯、茬、四甲基苯等之芳香族烴類；甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、甲基卡必醇、丁基卡必醇、丙二醇單甲基醚、二乙二醇單乙基醚、二丙二醇單乙基醚、三乙二醇單乙基醚等之二醇醚類；醋酸乙酯、醋酸丁酯、溶纖劑醋酸酯、二乙二醇單乙基醚醋酸酯及上述二醇醚類之酯化物等之酯類；乙醇、丙醇、乙二醇、丙二醇等之醇類；辛烷、癸烷等之脂肪族烴類；石油醚、石油腦、氫化石油腦、溶劑油等之石油系溶劑等。The organic solvent is used to form a coating film in a state in which the solder resist composition of the present invention is easily applied to a substrate or the like, and an organic solvent is used, and the composition is applied onto a substrate or the like to form a coating film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, hydrazine, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, and butyl cellosolve; Glycol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether Ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esters of the above glycol ethers; ethanol, propanol, ethylene glycol, propylene glycol, etc. Alcohols; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent oil.
有機溶劑可作為單獨或複數之混合物所使用。有機溶劑之配合量相對於光硬化性樹脂100質量份，以20~300質量份為佳。The organic solvent can be used as a single or plural mixture. The amount of the organic solvent to be added is preferably 20 to 300 parts by mass based on 100 parts by mass of the photocurable resin.
對於本發明之抗焊劑組成物，以提高對於曝光時之光的感度為目的，可配合噻噸酮系光聚合增感劑。For the purpose of improving the sensitivity to light during exposure, the thioxanthone-based photopolymerization sensitizer can be blended with the solder resist composition of the present invention.
若對倂用BAPO與MAPO之組成物配合噻噸酮系光聚合增感劑，可更加提高該組成物之光感度的提升效果。作為噻噸酮系光聚合增感劑，可舉出噻噸酮、2-乙基噻噸酮、2-異丙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等。When a thioxanthone-based photopolymerization sensitizer is blended with a composition of BAPO and MAPO, the effect of improving the light sensitivity of the composition can be further enhanced. Examples of the thioxanthone-based photopolymerization sensitizer include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and 2,4-dimethylthiophene. Tons of ketone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.
噻噸酮系光聚合增感劑之配合量，相對於光硬化性樹脂100質量份，以0.05~2質量份為佳，更佳為0.1~1質量份。噻噸酮系光聚合增感劑之配合量相對於光硬化性樹脂100質量份，若為不滿0.05質量份，本發明之抗焊劑組成物之感度提升的效果為少。又，噻噸酮系光聚合增感劑之配合量相對於光硬化性樹脂100質量份，若超過2質量份，源自噻噸酮之塗膜著色則變大。The amount of the thioxanthone-based photopolymerization sensitizer is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the photocurable resin. When the amount of the thioxanthone-based photopolymerization sensitizer is less than 0.05 parts by mass based on 100 parts by mass of the photocurable resin, the effect of improving the sensitivity of the solder resist composition of the present invention is small. In addition, when the amount of the thioxanthone-based photopolymerization sensitizer is more than 2 parts by mass based on 100 parts by mass of the photocurable resin, the coloration of the coating film derived from the thioxanthone becomes large.
對於本發明之抗焊劑組成物，以減少抗焊劑之因熱劣化所造成之變色作為目的，可配合抗氧化劑。作為抗氧化劑，理想者雖使用受阻酚系化合物，但不限定於此。作為受阻酚系化合物，可舉出NOCRAC 200、NOCRA CM-17、NOCRAC SP、NOCRAC SP-N、NOCRAC NS-5、NOCRAC NS-6、NOCRAC NS-30、NOCRAC 300、NOCRAC NS-7、NOCRAC DAH(以上任一皆為大內新興化學工業(股)製)；MARK AO-30、MARK AO-40、MARK AO-50、MARK AO-60、MARK AO-616、MARK AO-635、MARK AO-658、MARK AO-15、MARK AO-18、MARK 328、MARK AO-37(以上任一皆為ADEKA化學(股)製)；IRGANOX 245、IRGANOX 259、IRGANOX 565、IRGANOX 1010、IRGANOX 1035、IRGANOX 1076、IRGANOX 1081、IRGANOX 1098、IRGANOX 1222、IRGANOX 1330、IRGANOX 1425WL(以上任一皆為Ciba‧Japan(股)製)等。The anti-flux composition of the present invention can be blended with an antioxidant for the purpose of reducing discoloration caused by thermal deterioration of the solder resist. As the antioxidant, a hindered phenol compound is preferably used, but it is not limited thereto. Examples of the hindered phenol-based compound include NOCRAC 200, NOCRA CM-17, NOCRAC SP, NOCRAC SP-N, NOCRAC NS-5, NOCRAC NS-6, NOCRAC NS-30, NOCRAC 300, NOCRAC NS-7, and NOCRAC DAH. (All of the above are the Daein Xinxing Chemical Industry Co., Ltd.); MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO- 658, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all of which are ADEKA Chemicals); IRGANOX 245, IRGANOX 259, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076 IRGANOX 1081, IRGANOX 1098, IRGANOX 1222, IRGANOX 1330, IRGANOX 1425WL (all of which are manufactured by Ciba‧Japan).
抗氧化劑之配合量，相對於光硬化性樹脂100質量份，以0.4~25質量份為佳，更佳為0.8~15質量份。抗氧化劑之配合量相對於光硬化性樹脂100質量份，若為不滿0.4質量份之場合，由於抗焊劑之熱劣化所成之防變色效果為少。又，抗氧化劑之配合量相對於光硬化性樹脂100質量份，若超過25質量份之場合，本案塗膜之顯像性降低，圖型化之不良情況產生。The amount of the antioxidant is preferably 0.4 to 25 parts by mass, more preferably 0.8 to 15 parts by mass, per 100 parts by mass of the photocurable resin. When the amount of the antioxidant is less than 0.4 parts by mass based on 100 parts by mass of the photocurable resin, the anti-tarnishing effect by the thermal deterioration of the solder resist is small. In addition, when the amount of the antioxidant is more than 25 parts by mass based on 100 parts by mass of the photocurable resin, the developability of the coating film in the present invention is lowered, and the problem of patterning occurs.
更進一步，本發明之抗焊劑組成物，以減少光劣化作為目的，可配合受阻胺系光安定劑。Further, the solder resist composition of the present invention can be blended with a hindered amine light stabilizer for the purpose of reducing photodegradation.
作為受阻胺系光安定劑，可舉出TINUVIN 622LD、TINUVIN 144；CHIMASSORB 944LD、CHIMASSORB 119FL(以上任一皆為Ciba Japan(股)製)；MARK LA-57、LA-62、LA-67、LA-63、LA-68(以上任一皆為ADEKA化學(股)製)；Sanol LS-770、LS-765、LS-292、LS-2626、LS-1114、LS-744(以上任一皆為三共LifeTech(股)製)等。Examples of the hindered amine light stabilizers include TINUVIN 622LD and TINUVIN 144; CHIMASSORB 944LD and CHIMASSORB 119FL (all of which are manufactured by Ciba Japan); MARK LA-57, LA-62, LA-67, LA -63, LA-68 (all of which are made by ADEKA Chemical Co., Ltd.); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of the above are Sangong LifeTech (share) system, etc.
受阻胺系光安定劑之配合量，相對於光硬化性樹脂100質量份以0.1~10質量份為佳。The compounding amount of the hindered amine light stabilizer is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the photocurable resin.
又，本發明之抗焊劑組成物，以改善氧化鈦之分散性、沈降性為目的，可配合分散劑。作為分散劑，可舉出ANTI-TERRA-U、ANTI-TERRA-U100、ANTI-TERRA-204、ANTI-TERRA-205、DISPERBYK-101、DISPERBYK-102、DISPERBYK-103、DISPERBYK-106、DISPERBYK-108、DISPERBYK-109、DISPERBYK-110、DISPERBYK-111、DISPERBYK-112、DISPERBYK-116、DISPERBYK-130、DISPERBYK-140、DISPERBYK-142、DISPERBYK-145、DISPERBYK-161、DISPERBYK-162、DISPERBYK-163、DISPERBYK-164、DISPERBYK-166、DISPERBYK-167、DISPERBYK-168、DISPERBYK-170、DISPERBYK-171、DISPERBYK-174、DISPERBYK-180、DISPERBYK-182、DISPERBYK-183、DISPERBYK-185、DISPERBYK-184、DISPERBYK-2000、DISPERBYK-2001、DISPERBYK-2009、DISPERBYK-2020、DISPERBYK-2025、DISPERBYK-2050、DISPERBYK-2070、DISPERBYK-2096、DISPERBYK-2150、BYK-P104、BYK-P104S、BYK-P105、BYK-9076、BYK-9077、BYK-220S(BYK-Chemie‧Japan(股)製)、DISPALON 2150、DISPALON 1210、DISPALONKS-860、DISPALONKS-873N、DISPALON 7004、DISPALON 1830、DISPALON 1860、DISPALON 1850、DISPALON DA-400N、DISPALON PW-36、DISPALON DA-703-50(楠本化成(股)製)、FLORENE G-450、FLORENE G-600、FLORENE G-820、FLORENE G-700、FLORENE DOPA-44、FLORENE DOPA-17(共榮社化學(股)製)。Moreover, the solder resist composition of the present invention can be blended with a dispersing agent for the purpose of improving the dispersibility and sedimentation property of titanium oxide. As the dispersing agent, ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108 are exemplified. DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK -164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK-2000 DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK -9077, BYK-220S (BYK-Chemie‧ Japan), DISPALON 2150, DISALON 1210, DISPALONKS-860, DISPALONKS-873N, DISALON 7004, DISALON 1830, DISPALON 1860, DISALON 1850, DISPALON DA-400N, DISALON PW-36, DISALON DA-703-50 (Nanben Into (shares) Ltd.), FLORENE G-450, FLORENE G-600, FLORENE G-820, FLORENE G-700, FLORENE DOPA-44, FLORENE DOPA-17 (Kyoeisha Chemical (shares) Ltd.).
為了有效達成上述目的，分散劑之配合量，相對於氧化鈦100質量份以0.1~10質量份為佳，更佳為0.5~5質量份。In order to achieve the above object, the amount of the dispersant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the titanium oxide.
更進一步，本發明之抗焊劑組成物，可配合硬化促進劑、熱聚合禁止劑、增黏劑、消泡劑、均平劑、偶合劑、難燃助劑等。Furthermore, the solder resist composition of the present invention may be combined with a hardening accelerator, a thermal polymerization inhibiting agent, a tackifier, an antifoaming agent, a leveling agent, a coupling agent, a flame retardant aid, and the like.
以下，作為本發明之抗焊劑組成物的使用例，說明關於使用該組成物所製造之印刷電路板。Hereinafter, as a use example of the solder resist composition of the present invention, a printed circuit board manufactured using the composition will be described.
首先，調整本發明之抗焊劑組成物成為適合塗佈方法之黏度。First, the solder resist composition of the present invention is adjusted to have a viscosity suitable for the coating method.
其次，將調整黏度後之組成物，在形成有電路之印刷電路板上，藉由網板印刷法、簾塗佈法、噴塗法、或輥塗佈法等之方法進行塗佈。其後，將包含於塗佈在印刷電路板上之組成物中之有機溶劑在70~90℃之溫度下使其揮發乾燥，形成塗膜。Next, the composition after adjusting the viscosity is applied on a printed circuit board on which a circuit is formed by a screen printing method, a curtain coating method, a spray coating method, or a roll coating method. Thereafter, the organic solvent contained in the composition coated on the printed circuit board is volatilized and dried at a temperature of 70 to 90 ° C to form a coating film.
其後，對此塗膜，透過光罩，選擇性地藉由活性能量線進行曝光。接著，將曝光後之該塗膜之未曝光部份使用鹼水溶液顯像，形成圖型。更在其後，藉由將該圖型在100℃~200℃之熱中熱硬化，可製造具有使用本發明之抗焊劑組成物所形成之圖型的印刷電路板，即，本發明之印刷電路板。Thereafter, the coating film is selectively exposed to the active energy ray through the reticle. Next, the unexposed portion of the coated film after exposure is developed using an aqueous alkali solution to form a pattern. Further, after the pattern is thermally hardened in the heat of 100 ° C to 200 ° C, a printed circuit board having a pattern formed using the solder resist composition of the present invention, that is, the printed circuit of the present invention can be manufactured. board.
又，作為用以曝光上述塗膜之照射光源，可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙燈或金屬鹵素燈等。其他，也可利用雷射光線等作為活性光線。Further, as the irradiation light source for exposing the coating film, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halide lamp can be used. Others, it is also possible to use laser light or the like as the active light.
又，作為使用上述塗膜顯像的顯像液的鹼水溶液，一般為0.5~5質量%之碳酸鈉水溶液，也可使用其他之鹼水溶液。作為其他之鹼水溶液，可舉出羥化鉀、羥化鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等之鹼水溶液。Further, as the aqueous alkali solution using the developing solution for coating film development, a sodium carbonate aqueous solution of 0.5 to 5% by mass is generally used, and another aqueous alkali solution may be used. Examples of the other aqueous alkali solution include aqueous alkali solutions such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium phosphate, sodium citrate, ammonia, and amines.
以下，展示實施例及比較例，來具體說明本發明，但本發明並不係受限於此者。Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited thereto.
對具備有攪拌機、溫度計、還流冷卻器、滴下漏斗及氮導入管之2公升可拆式燒瓶，加入溶劑(二乙二醇二甲基醚)900g、及聚合起始劑(t-丁基過氧2-乙基己酸酯、日本油脂(股)製、商品名；PERBUTYL O)21.4g在90℃中加熱。加熱後，於上述燒瓶中，將甲基丙烯酸309.9g、甲基丙烯酸甲酯116.4g、內酯變性2-羥基乙基甲基丙烯酸酯(Daicel化學工業(股)製、商品名；PLACCEL FM1)109.8g、及聚合起始劑(雙(4-t-丁基環己基)過氧二碳酸酯、日本油脂(股)製、商品名；PEROYL TCP)21.4g以3小時滴下加入。更進一步，藉由將該混合物進行6小時熟化，得到含羧基共聚合樹脂。但，此些之反應係在氮雰圍下進行。For a 2 liter separable flask equipped with a stirrer, a thermometer, a reflow cooler, a dropping funnel and a nitrogen introduction tube, 900 g of a solvent (diethylene glycol dimethyl ether) and a polymerization initiator (t-butyl group) were added. Oxygen 2-ethylhexanoate, manufactured by Nippon Oil & Fats Co., Ltd., trade name; PERBUTYL O) 21.4 g was heated at 90 °C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and lactone-denatured 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical Industry Co., Ltd., trade name; PLACCEL FM1) were added to the flask. 109.8 g and a polymerization initiator (bis(4-t-butylcyclohexyl)peroxydicarbonate, manufactured by Nippon Oil & Fats Co., Ltd., trade name; PEROYL TCP) 21.4 g were added dropwise over 3 hours. Further, the mixture was aged for 6 hours to obtain a carboxyl group-containing copolymerized resin. However, such reactions are carried out under a nitrogen atmosphere.
然後，對此含羧基共聚合樹脂，加入3,4-環氧環己基甲基丙烯酸酯(Daicel化學(股)製、商品名；CYCLOMER A200)363.9g、開環觸媒(二甲基芐基胺)3.6g、聚合抑制劑(氫醌單甲基醚)1.80g，將此些在100℃中加熱，藉由攪拌進行環氧基之開環附加反應。從攪拌結束後16小時後，從當該攪拌物，得到含有固形分之酸價為108.9mgKOH/g，重量平均分子量為25,000之不具有芳香環之含羧基樹脂53.8質量%(不揮發分)之溶液。以下，將此反應溶液稱為樹脂溶液1。Then, 3,4-epoxycyclohexyl methacrylate (manufactured by Daicel Chemical Co., Ltd., trade name; CYCLOMER A200) 363.9 g, a ring-opening catalyst (dimethyl benzyl group) was added to the carboxyl group-containing copolymer resin. Amine (3.6 g) and a polymerization inhibitor (hydroquinone monomethyl ether) of 1.80 g were heated at 100 ° C to carry out an open-loop addition reaction of an epoxy group by stirring. 16 hours after the completion of the stirring, from the stirring product, 53.8 mass% (nonvolatile matter) of the carboxyl group-containing resin having a solid content of 108.9 mgKOH/g and a weight average molecular weight of 25,000 and having no aromatic ring was obtained. Solution. Hereinafter, this reaction solution is referred to as a resin solution 1.
依循表1之記載將配合各成分者予以攪拌，更將此於以3支輥使其分散製成抗焊劑組成物(實施例1~5、比較例1~3)。猶，表1中之數字係表示質量份。According to the description of Table 1, the components were stirred, and the mixture was dispersed in three rolls to form a solder resist composition (Examples 1 to 5 and Comparative Examples 1 to 3). In still, the numbers in Table 1 indicate the parts by mass.
光聚合起始劑1：雙-(2,4,6-三甲基苯甲醯基)苯基膦氧化物IRGACURE 819(Ciba‧Japan(股)製)Photopolymerization initiator 1: bis-(2,4,6-trimethylbenzylidene)phenylphosphine oxide IRGACURE 819 (manufactured by Ciba‧Japan)
光聚合起始劑2：2,4,6-三甲基苯甲醯基二苯基膦氧化物Photopolymerization initiator 2: 2,4,6-trimethylbenzimidyldiphenylphosphine oxide
DAROCURE TPO(Ciba‧Japan(股)製)DAROCURE TPO (Ciba‧Japan)
光聚合起始劑3：IRGACURE 907(Ciba‧Japan(股)製)Photopolymerization initiator 3: IRGACURE 907 (manufactured by Ciba‧Japan)
光聚合性單體：二季戊四醇六丙烯酸酯Photopolymerizable monomer: dipentaerythritol hexaacrylate
氧化鈦(金紅石型)：CR-Super70(石原產業(股)製)Titanium oxide (rutile type): CR-Super70 (made by Ishihara Sangyo Co., Ltd.)
環氧化合物(聯苯型)：YX-4000(Japan Epoxy Resin(股)製)Epoxy compound (biphenyl type): YX-4000 (made by Japan Epoxy Resin Co., Ltd.)
增感劑：2,4-二乙基噻噸酮KAYACURE DETX-S(日本化藥(股)製)Sensitizer: 2,4-diethylthioxanthone KAYACURE DETX-S (Nippon Chemical Co., Ltd.)
抗氧化劑：IRGANOX 1010(Ciba‧Japan(股)製)Antioxidant: IRGANOX 1010 (manufactured by Ciba‧Japan)
有機溶劑：卡必醇醋酸酯Organic solvent: carbitol acetate
消泡劑：聚矽氧油KS-66(信越化學工業(股)製)Defoamer: Polyoxygenated oil KS-66 (Shin-Etsu Chemical Industry Co., Ltd.)
為了調查使用各抗焊劑組成物所形成之抗焊劑的諸多性質，用以下的條件進行試驗，且進行評價。In order to investigate the properties of the solder resist formed by using each solder resist composition, the test was carried out under the following conditions and evaluated.
將各抗焊劑組成物，使其塗膜之膜厚成為40μm，使用100篩目聚酯(BIAS製)之版，藉由網板印刷法在FR-4貼銅層合板(大小：100mm×150mm、厚：1.6mm)上全面(基板全面)進行印刷。接著，將該FR-4貼銅層合板以熱風循環式乾燥爐乾燥(溫度：80℃、時間：10分)，形成上述各抗焊劑組成物之塗膜。更進一步，對該各塗膜以與上述同様之方法將各抗焊劑組成物重疊印刷，在熱風循環式乾燥爐中使其乾燥(溫度：80℃、時間：20分)，形成試驗用塗膜。其後，使用印刷電路板用曝光機HMW-680GW((股)ORC製作所製)，使用描繪有80μm及100μm之線路的光罩圖型，以500mJ/cm2 與700mJ/cm2 之2條件的累積光量將上述試驗用塗膜進行紫外線曝光。更於其後，對此曝光之試驗用塗膜，將1質量%之碳酸鈉水溶液(溫度：30℃)作為顯像液，使用印刷電路板用顯像機顯像60秒間。接著，對顯像後之各試驗用塗膜在熱風循環式乾燥爐中進行熱硬化(溫度：150℃、時間：60分)，製成各試驗片。確認於此些之試驗片中殘留之線路幅度，使用以下之評價方法對解析性進行評價。其結果如表2所示。Each of the solder resist compositions was formed to have a film thickness of 40 μm, and a 100 mesh mesh polyester (manufactured by BIAS) was used, and a FR-4 copper-clad laminate was used by screen printing (size: 100 mm × 150 mm). , thickness: 1.6mm) Full-scale (substrate full) printing. Next, the FR-4 copper-clad laminate was dried in a hot air circulating drying oven (temperature: 80 ° C, time: 10 minutes) to form a coating film of each of the above-described solder resist compositions. Furthermore, each of the coating films was superimposed and printed with the same method as described above, and dried in a hot air circulation type drying furnace (temperature: 80 ° C, time: 20 minutes) to form a test coating film. . Then, using a exposure machine HMW-680GW (manufactured by ORC) manufactured by a printed circuit board, a mask pattern of lines of 80 μm and 100 μm was used, and a condition of 500 mJ/cm 2 and 700 mJ/cm 2 was used. The amount of accumulated light was subjected to ultraviolet exposure of the above-mentioned test coating film. Further, the coating film for the test for the exposure was used, and a 1% by mass aqueous sodium carbonate solution (temperature: 30 ° C) was used as a developing solution, and developed by a developing machine using a printed circuit board for 60 seconds. Next, each of the test coating films after the development was thermally cured in a hot air circulation type drying furnace (temperature: 150 ° C, time: 60 minutes) to prepare test pieces. The line width remaining in the test pieces of these samples was confirmed, and the analytical property was evaluated using the following evaluation method. The results are shown in Table 2.
◎ 500mJ/cm2 之曝光條件下有80μm之線路殘留者◎ 80μm line residual under exposure conditions of 500mJ/cm 2
○ 700mJ/cm2 之曝光條件下有80μm之線路殘留者○ 80μm line residual under exposure conditions of 700mJ/cm 2
△ 700mJ/cm2 之曝光條件下有100μm之線路殘留，於顯像時發現膜減少者△ 700mJ/cm 2 under the exposure conditions, there is 100μm line residue, and the film is found in the film reduction
× 於上述之條件中無100μm之線路殘留者× No line residual of 100μm in the above conditions
如表2記載般，由於實施例1~5中全部之線路皆有殘留，得知其解析性良好。比較例1中，使用雙醯基膦氧化物系光聚合起始劑，比較例2中使用單醯基膦氧化物系光聚合起始劑，比較例3中使用胺基甲酸乙酯系之光聚合起始劑，其結果並無殘留充份之線路。As shown in Table 2, all of the lines in Examples 1 to 5 remained, and it was found that the resolution was good. In Comparative Example 1, a bis-decylphosphine oxide photopolymerization initiator was used, a monothiophosphine oxide photopolymerization initiator was used in Comparative Example 2, and an urethane light was used in Comparative Example 3. The polymerization initiator did not leave a sufficient line.
將實施例1~5之抗焊劑組成物，使其塗膜之膜厚成為40μm，使用100篩目聚酯(BIAS製)之版，用網板印刷法對FR-4貼銅層合板(尺寸：100mm×150mm、厚度：1.6mm)以(基板全面)進行印刷圖型。然後，將該FR-4貼銅層合板在熱風循環式乾燥爐中使其乾燥(溫度：80℃、時間：30分)，形成上述各抗焊劑組成物之塗膜。更且，使用印刷電路板用曝光機HMW-680GW((股)ORC製作所製)，使30mm角之負圖型殘留，以700mJ/cm2 之累積光量將上述各塗膜進行紫外線曝光。其後，對曝光後之各塗膜，以1質量%之碳酸鈉水溶液(溫度：30℃)作為顯像液，使用印刷電路板用顯像機進行顯像60秒。接著，對顯像後之各塗膜在熱風循環式乾燥爐中進行熱硬化(溫度：150℃、時間：60分)，製成特性試驗用之各試驗片。The solder resist compositions of Examples 1 to 5 were applied to a film thickness of 40 μm, and a FR-4 copper-clad laminate (size) was screen-printed using a 100 mesh polyester (BIAS) plate. : 100 mm × 150 mm, thickness: 1.6 mm) The printing pattern was performed in (full substrate). Then, the FR-4 copper-clad laminate was dried in a hot air circulating drying oven (temperature: 80 ° C, time: 30 minutes) to form a coating film of each of the above-described solder resist compositions. Further, a negative pattern of a 30 mm angle was left using an exposure machine HMW-680GW (manufactured by ORC Co., Ltd.) for a printed circuit board, and each of the above coating films was subjected to ultraviolet exposure at a cumulative amount of light of 700 mJ/cm 2 . Then, each of the coating films after the exposure was developed with a 1% by mass aqueous sodium carbonate solution (temperature: 30 ° C) as a developing liquid, and developed by a developing machine using a printed circuit board for 60 seconds. Next, each of the coating films after the development was thermally cured in a hot air circulating drying oven (temperature: 150 ° C, time: 60 minutes) to prepare test pieces for the characteristic test.
對上述各試驗片，使用色彩色差計CR-400(Konica Minolta Sensing(股)製)，將XYZ表色系之Y值及L*a*b*表色系之各值作為初始值進行測定。其後，使用輸送型UV照射機QRM-2082-E-01((股)ORC製作所製)，以金屬鹵素燈、冷光鏡、80W/cm×3燈、輸送速度6.5m/分(積算光量1000mJ/cm2 )之條件下，對上述各試驗片以UV重複照射20次。更於其後，使用實裝零件用之輸送式加熱爐，將該各試驗片重複進行加熱2次。對於加熱後之各試驗片與初始值相同之條件測定色差，對各試驗片之劣化狀態進行評價。又，也以目視對該各試驗片進行評價。其結果如表3所示。尚，上述加熱爐之溫度表示於圖1。Each of the above test pieces was measured using a color difference meter CR-400 (manufactured by Konica Minolta Sensing Co., Ltd.), and each value of the Y value of the XYZ color system and the L*a*b* color system was used as an initial value. Thereafter, a transport type UV irradiator QRM-2082-E-01 (manufactured by ORC Manufacturing Co., Ltd.) was used, and a metal halide lamp, a cold mirror, an 80 W/cm×3 lamp, and a conveying speed of 6.5 m/min (integrated light amount of 1000 mJ) was used. Under the conditions of /cm 2 ), each of the above test pieces was repeatedly irradiated with UV for 20 times. Further, each test piece was repeatedly heated twice using a transfer type heating furnace for mounting parts. The color difference was measured for each test piece after heating under the same conditions as the initial value, and the deterioration state of each test piece was evaluated. Moreover, each test piece was also evaluated visually. The results are shown in Table 3. Further, the temperature of the above heating furnace is shown in Fig. 1.
表3中，Y表示XYZ表色系之反射率，L*表示L*a*b*表色系之亮度。ΔE*ab係為，對於L*a*b*之各值，取劣化試驗後之值與初始值之差之平方，取其總和之平方根者。a*表示紅方向、-a*表示綠方向、b*表示黃方向、-b*表示藍方向，越接近零表示無彩度。ΔE*ab表示顏色之變化，此值越小表示顏色之變化也為小。In Table 3, Y represents the reflectance of the XYZ color system, and L* represents the brightness of the L*a*b* color system. ΔE*ab is the square of the difference between the value after the deterioration test and the initial value for each value of L*a*b*, and the square root of the sum is taken. a* indicates the red direction, -a* indicates the green direction, b* indicates the yellow direction, and -b* indicates the blue direction, and the closer to zero indicates no chroma. ΔE*ab indicates a change in color, and a smaller value indicates that the change in color is also small.
又，加熱後之目視評價如以下。Further, the visual evaluation after heating was as follows.
◎ 無變色◎ no discoloration
○ 幾乎無變色○ almost no discoloration
△ 些許有變色△ Some discoloration
× 明顯有變色× obviously discolored
如表3所記載般，實施例1~5，對於加熱後之ΔE*ab值及目視評價其變色為少。As shown in Table 3, in Examples 1 to 5, the ΔE*ab value after heating and the visual evaluation of the discoloration were small.
對於有關實施例1~5，以與(2)同様之方法所製成各試驗片，塗佈松香系焊劑，在260℃之焊劑槽中使其流動10秒。其後，將該各試驗片以丙二醇單甲基醚醋酸酯洗浄，使其乾燥。其後，對乾燥後之各試驗片以玻璃黏著膠帶進行剝離試驗，對硬化塗膜(以下，於本實施例中稱為「塗膜」)之剝離使用以下之評價方法進行評價。其結果顯示於表4。With respect to Examples 1 to 5, each of the test pieces prepared by the method of (2) was coated with a rosin-based flux and allowed to flow in a flux bath at 260 ° C for 10 seconds. Thereafter, each test piece was washed with propylene glycol monomethyl ether acetate and dried. Then, each of the dried test pieces was subjected to a peeling test using a glass adhesive tape, and the peeling of the cured coating film (hereinafter referred to as "coating film" in the present example) was evaluated by the following evaluation method. The results are shown in Table 4.
○ 無塗膜之剝離或變色○ No peeling or discoloration of the film
× 有塗膜之剝離或變色× There is peeling or discoloration of the coating film
對於有關實施例1~5，以與(2)同様之方法所製成之各試驗片浸漬於丙二醇單甲基醚醋酸酯30分鐘，使其乾燥。其後，對乾燥後之各試驗片以玻璃黏著膠帶進行剝離試驗，對塗膜之剝離與變色使用以下之評價方法進行評價。其結果顯示於表4。For each of Examples 1 to 5, each test piece prepared by the method of (2) was immersed in propylene glycol monomethyl ether acetate for 30 minutes, and dried. Thereafter, each of the dried test pieces was subjected to a peeling test using a glass adhesive tape, and the peeling and discoloration of the coating film were evaluated by the following evaluation methods. The results are shown in Table 4.
○ 無塗膜之剝離或變色○ No peeling or discoloration of the film
× 有塗膜之剝離或變色× There is peeling or discoloration of the coating film
對於關於實施例1~5，以與(2)相同様之方法所製成之各試驗片，將筆芯之尖端削磨成平面且由B至9H之鉛筆以約45°之角度押靠進，記錄無產生塗膜之剝離的鉛筆硬度，使用以下之評價方法進行評價。其結果顯示於表4。For each of the test pieces prepared in the same manner as in (2), the tip of the refill was ground to a flat surface and the pencil of B to 9H was placed at an angle of about 45° with respect to Examples 1 to 5. The pencil hardness without peeling of the coating film was recorded and evaluated using the following evaluation method. The results are shown in Table 4.
○‧‧‧無塗膜之剝離或變色○‧‧‧No film peeling or discoloration
×‧‧‧有塗膜之剝離或變色×‧‧‧The peeling or discoloration of the film
對於關於實施例1~5，使用IPC B-25測試圖型之梳型電極B試樣胚替代FR-4貼銅層合板，其他與(2)同様之條件及方法製成試驗片。對此各試驗片，施加DC500V之偏壓，測定絕緣電阻值。其結果顯示於表4。For the examples 1 to 5, the comb-type electrode B sample embryo of the IPC B-25 test pattern was used instead of the FR-4 copper-clad laminate, and the test pieces were prepared by the other conditions and methods of (2). For each of the test pieces, a bias voltage of DC 500 V was applied, and the insulation resistance value was measured. The results are shown in Table 4.
由表4之記載可明顯得知，使用本發明之抗焊劑組成物之實施例1~5，其具有抗焊劑所要求之良好的耐熱性、耐溶劑性、密著性及電絕緣性。As is apparent from the description of Table 4, Examples 1 to 5 using the solder resist composition of the present invention have excellent heat resistance, solvent resistance, adhesion, and electrical insulating properties required for the solder resist.
由以上，依據本實施例，可得到可形成高反射率之抗焊劑的抗焊劑組成物。又，可得知該組成物，就算大量配合氧化鈦，可藉由曝光形成高精細之圖型，且具有良好之解析性。更進一步，使用上述組成物所形成之抗焊劑，其由於光或熱所造成之變色為少，也為具有焊料耐熱性者。From the above, according to the present embodiment, a solder resist composition capable of forming a high reflectance solder resist can be obtained. Further, it was found that the composition can form a high-definition pattern by exposure even if a large amount of titanium oxide is blended, and has good resolution. Further, the solder resist formed by using the above composition has little discoloration due to light or heat, and also has solder heat resistance.
[圖1]表示實施例之耐光耐熱變色性之評價中所使用之加熱爐之溫度的時間性變化之圖。Fig. 1 is a graph showing temporal changes in temperature of a heating furnace used in the evaluation of light resistance and heat discoloration resistance of Examples.
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| JP5117416B2 (en) * | 2009-01-21 | 2013-01-16 | 株式会社タムラ製作所 | Photosensitive resin composition, solder resist composition for printed wiring board, and printed wiring board |
| JP2011170050A (en) * | 2010-02-17 | 2011-09-01 | Taiyo Holdings Co Ltd | Solder resist composition and printed circuit board |
| JP4975834B2 (en) * | 2010-02-17 | 2012-07-11 | 太陽ホールディングス株式会社 | Solder resist composition and printed wiring board |
| CN102844711A (en) * | 2010-03-31 | 2012-12-26 | 太阳控股株式会社 | Solder resist composition and printed-circuit board |
| JP2011227308A (en) * | 2010-04-20 | 2011-11-10 | Taiyo Holdings Co Ltd | Solder resist composition and print circuit board |
| JP2011215384A (en) * | 2010-03-31 | 2011-10-27 | Taiyo Holdings Co Ltd | Solder resist composition and printed-circuit board |
| JP5666868B2 (en) * | 2010-09-30 | 2015-02-12 | 互応化学工業株式会社 | Resin composition for solder resist and printed wiring board |
| TWI519581B (en) * | 2010-12-28 | 2016-02-01 | Tamura Seisakusho Kk | White hardening resin composition |
| CN102762627B (en) * | 2011-02-14 | 2014-03-26 | 积水化学工业株式会社 | Two-liquid mixing first and second liquids and method for producing printed circuit board |
| JP5875821B2 (en) * | 2011-09-30 | 2016-03-02 | 太陽インキ製造株式会社 | Photosensitive resin composition, cured film thereof and printed wiring board |
| JP6095310B2 (en) * | 2012-09-27 | 2017-03-15 | 株式会社タムラ製作所 | Curable white resin composition |
| JP6412585B2 (en) * | 2014-12-10 | 2018-10-24 | 互応化学工業株式会社 | Liquid solder resist composition and coated printed wiring board |
| ES2673878T3 (en) * | 2014-12-10 | 2018-06-26 | Goo Chemical Co., Ltd. | Solder-resistant liquid composition and coated printed circuit board |
| TWI740154B (en) * | 2019-06-05 | 2021-09-21 | 鷹克國際股份有限公司 | Method for forming a solder mask layer on a circuit board using liquid type solder mask materials |
| CN114206018B (en) * | 2021-12-27 | 2022-08-02 | 百强电子（深圳）有限公司 | Efficient thick copper plate solder resist printing method |
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| CN101699351A (en) | 2010-04-28 |
| KR101040781B1 (en) | 2011-06-13 |
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| JP2010117702A (en) | 2010-05-27 |
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