WO2011001485A1 - Photocurable heat-curable resin composition - Google Patents
Photocurable heat-curable resin composition Download PDFInfo
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- WO2011001485A1 WO2011001485A1 PCT/JP2009/006737 JP2009006737W WO2011001485A1 WO 2011001485 A1 WO2011001485 A1 WO 2011001485A1 JP 2009006737 W JP2009006737 W JP 2009006737W WO 2011001485 A1 WO2011001485 A1 WO 2011001485A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/038—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
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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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
Abstract
Description
さらに本発明の目的は、このような光硬化性熱硬化性樹脂組成物を用いることによって得られる上記のような諸特性に優れたドライフィルム及び硬化物、並びに該ドライフィルムや硬化物によりソルダーレジスト等の硬化皮膜が形成されてなるプリント配線板を提供することにある。 The present invention has been made in view of the problems of the prior art as described above, and its main purpose is to have PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance, which are important as solder resists for semiconductor packages. It is providing the photocurable thermosetting resin composition which can form a cured film.
Furthermore, the object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable thermosetting resin composition, and a solder resist using the dry film and the cured product. An object of the present invention is to provide a printed wiring board on which a cured film such as the above is formed.
このカルボキシル基含有樹脂は、エポキシ樹脂から誘導されたものでないことが好ましい。好適な態様においては、本発明の光硬化性熱硬化性樹脂組成物は、さらに熱硬化性成分を含有し、好ましくはさらに着色剤を含有するソルダーレジスト用である。 In order to achieve the above object, according to the present invention, a photocurable heat developable with an aqueous alkaline solution comprising a carboxyl group-containing resin, a photopolymerization initiator, a vinyl group-containing elastomer, and a mercapto compound. A curable resin composition is provided.
This carboxyl group-containing resin is preferably not derived from an epoxy resin. In a preferred embodiment, the photocurable thermosetting resin composition of the present invention further contains a thermosetting component, and preferably for a solder resist containing a colorant.
さらにまた、本発明によれば、前記光硬化性熱硬化性樹脂組成物又はドライフィルムを、活性エネルギー線の照射、好ましくは紫外線の直接描画によりパターン状に光硬化させた後、熱硬化して得られる硬化皮膜を有するプリント配線板も提供される。 Furthermore, according to the present invention, a photocurable thermosetting dry film obtained by applying and drying the photocurable thermosetting resin composition on a carrier film, and the photocurable thermosetting resin composition There is provided a cured product obtained by photocuring a product or a dry film, preferably by photocuring in a pattern with a light source having a wavelength of 350 nm to 410 nm.
Furthermore, according to the present invention, the photocurable thermosetting resin composition or the dry film is photocured in a pattern by irradiation with active energy rays, preferably by direct drawing of ultraviolet rays, and then thermally cured. A printed wiring board having the resulting cured film is also provided.
なお、本明細書において、(メタ)アクリレートとは、アクリレート、メタクリレートおよびそれらの混合物を総称する用語であり、他の類似の表現についても同様である。 The photocurable thermosetting resin composition of the present invention contains a vinyl group-containing elastomer and a mercapto compound in combination with a carboxyl group-containing resin as a component that can be developed with an alkaline aqueous solution. The vinyl group-containing elastomer is effective not only in improving the crack resistance of the resulting cured coating film to the thermal cycle, but also in improving the adhesion of the solder resist, particularly the PCT resistance. On the other hand, the mercapto compound is added for the purpose of addition reaction and crosslinking of the photosensitive component to the vinyl group-containing elastomer, and can prevent deterioration of the coating film properties due to oxidation of the vinyl group. Therefore, it contributes to improving characteristics such as PCT resistance and HAST resistance. In addition, since the mercapto compound also functions as a chain transfer agent and / or an adhesion imparting agent, it is possible to simultaneously improve the sensitivity of the composition and the adhesion. As a result, not only the flexibility of the obtained cured coating film is improved and the crack resistance against the cooling and heating cycle is improved, but also the adhesion of the solder resist, particularly the PCT resistance can be improved. Therefore, by using the photocurable thermosetting resin composition of the present invention, it is possible to form a cured film having PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance important as a solder resist for semiconductor packages.
In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
上記カルボキシル基含有樹脂としては、公知慣用のカルボキシル基を用いることができる。好ましくは、絶縁信頼性を悪くしない(ハロゲン化物イオン含有量が非常に少ない)と考えられるカルボキシル基含有樹脂として、エポキシ樹脂を出発原料として使用していないカルボキシル基含有樹脂を用いることが望ましい。それらの中でも、分子中にエチレン性不飽和二重結合を有するカルボキシル基含有感光性樹脂が、光硬化性や耐現像性の面から好ましい。そして、その不飽和二重結合は、アクリル酸もしくはメタアクリル酸又はそれらの誘導体由来のものが好ましい。尚、エチレン性不飽和二重結合を有さないカルボキシル基含有樹脂のみを用いる場合、組成物を光硬化性とするためには、後述するような分子中に1個以上のエチレン性不飽和基を有する化合物(感光性モノマー)を併用する必要がある。 As described above, the photocurable thermosetting resin composition of the present invention is characterized by containing a carboxyl group-containing resin, a photopolymerization initiator, a vinyl group-containing elastomer, and a mercapto compound.
As the carboxyl group-containing resin, known and commonly used carboxyl groups can be used. Preferably, it is desirable to use a carboxyl group-containing resin that does not use an epoxy resin as a starting material, as the carboxyl group-containing resin that is considered not to deteriorate the insulation reliability (has a very low halide ion content). Among them, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. In the case where only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, one or more ethylenically unsaturated groups are contained in the molecule as described later. It is necessary to use a compound having a photosensitivity (photosensitive monomer) in combination.
(1)後述するような2官能又はそれ以上の多官能(固形)エポキシ樹脂に(メタ)アクリル酸を反応させ、側鎖に存在する水酸基に無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸等の2塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。 Specific examples of the carboxyl group-containing resin that can be used in the present invention include the compounds listed below (any of oligomers and polymers).
(1) (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride are added to the hydroxyl group present in the side chain. A carboxyl group-containing photosensitive resin to which a dibasic acid anhydride such as
一方、類似のフェノールノボラック樹脂より合成されたエポキシ樹脂のエポキシ基を全てアクリル化し、全ての水酸基に酸無水物を導入すると、二重結合等量400~500で酸価が非常に大きくなってしまい、露光後でも耐現像性を有する塗膜が得られなくなる。さらには、酸価が高いことから、耐水性に劣り、絶縁信頼性、PCT耐性を著しく低下させる。即ち、類似のフェノールノボラック型エポキシ樹脂より誘導されたエポキシアクリレート系樹脂から完全に水酸基を無くすことは非常に困難である。 A phenol novolak resin free from chlorine can be easily obtained. Resin that has no hydroxyl group in the range of double bond equivalent 300-550, acid value 40-120 mgKOH / g by partial acrylation of phenol resin modified with alkyl oxide and introduction of acid anhydride It is possible to obtain
On the other hand, if all the epoxy groups of an epoxy resin synthesized from a similar phenol novolac resin are acrylated and acid anhydrides are introduced into all the hydroxyl groups, the acid value becomes very large with a double bond equivalent of 400 to 500. Even after exposure, a coating film having development resistance cannot be obtained. Furthermore, since the acid value is high, the water resistance is inferior, and the insulation reliability and PCT resistance are significantly reduced. That is, it is very difficult to completely eliminate the hydroxyl group from an epoxy acrylate resin derived from a similar phenol novolac type epoxy resin.
このような観点から、先に具体例として示したカルボキシル基含有樹脂(1)~(3)も用いることができるが、半導体パッケージ用ソルダーレジストとしてより優れたPCT耐性、HAST耐性、冷熱衝撃耐性を有するソルダーレジスト組成物を得るためには、前記カルボキシル基含有樹脂(4)~(8)がより好適に用いることができる。 Moreover, urethane resin can also synthesize | combine easily the resin which does not contain a hydroxyl group by match | combining the equivalent of a hydroxyl group and an isocyanate group. A preferred resin is an isocyanate compound not using phosgene as a starting material and a carboxyl group-containing resin having a chlorine ion impurity amount of 0 to 30 ppm synthesized from a raw material not using epihalohydrin, and more preferably so as not to theoretically contain a hydroxyl group. It is a synthesized resin.
From this point of view, the carboxyl group-containing resins (1) to (3) described above as specific examples can also be used. However, they have better PCT resistance, HAST resistance, and thermal shock resistance as a solder resist for semiconductor packages. In order to obtain a solder resist composition having the above, the carboxyl group-containing resins (4) to (8) can be more preferably used.
また、上記カルボキシル基含有樹脂の酸価は、40~150mgKOH/gの範囲が望ましく、より好ましくは40~130mgKOH/gの範囲である。カルボキシル基含有樹脂の酸価が40mgKOH/g未満であるとアルカリ現像が困難となり、一方、150mgKOH/gを超えると現像液による露光部の溶解が進むために、必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となるので好ましくない。 Since the carboxyl group-containing resin as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with an alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin is desirably in the range of 40 to 150 mgKOH / g, more preferably in the range of 40 to 130 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when it exceeds 150 mgKOH / g, dissolution of the exposed area by the developing solution proceeds, so that the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.
オキシムエステル系光重合開始剤としては、市販品として、チバ・スペシャルティ・ケミカルズ社製のCGI-325、イルガキュアー OXE01、イルガキュアー OXE02、アデカ社製N-1919、アデカアークルズ NCI-831などが挙げられる。また、分子内に2個のオキシムエステル基を有する光重合開始剤も好適に用いることができ、具体的には、下記一般式で表されるカルバゾール構造を有するオキシムエステル化合物が挙げられる。 As the photopolymerization initiator, one or more light selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. A polymerization initiator can be used.
Examples of the oxime ester-based photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, N-1919 manufactured by Adeka, Adeka Arcles NCI-831, and the like as commercially available products. It is done. In addition, a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used. Specific examples include oxime ester compounds having a carbazole structure represented by the following general formula.
(式中、Xは、水素原子、炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、フェニル基、フェニル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)、ナフチル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)を表し、Y、Zはそれぞれ、水素原子、炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、ハロゲン基、フェニル基、フェニル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)、ナフチル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Arは、炭素数1~10のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、2,5-ピロール-ジイル、4,4'-スチルベン-ジイル、4,2'-スチレン-ジイルで表される)。nは0か1の整数であらわされる。特に化式中、X、Yが、それぞれ、メチル基またはエチル基であり、Zはメチルまたはフェニルであり、nは0であり、Arは、フェニレン、ナフチレン、チオフェンまたはチエニレンであることが好ましい。)
(Wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), And Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number 1), and substituted with an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group. Alkyl group having 8 to 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkyl group having 1 to 8 carbon atoms, or a dialkyl group) Anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar represents alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene , Furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl). n is represented by an integer of 0 or 1. In particular, in the chemical formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is preferably phenylene, naphthylene, thiophene or thienylene. )
また、好適に用いることができるブタジエン誘導体にエポキシ基や水酸基、アクリル基等の官能基を有するものは、他の材料との相溶性が向上し、保存安定性に優れるといった特徴を有する。 The vinyl group-containing elastomer used in the photocurable thermosetting resin composition of the present invention not only improves the crack resistance to the cooling cycle of the cured film obtained, but also the adhesion of the solder resist, especially the PCT resistance. It is effective in improving. Such a compound can be used without particular limitation as long as it is an elastomer having a vinyl group in the skeleton, and among them, a butadiene derivative can be suitably used for imparting the above properties.
Moreover, what has functional groups, such as an epoxy group, a hydroxyl group, an acryl group, in the butadiene derivative which can be used suitably has the characteristics that compatibility with other materials improves and it is excellent in storage stability.
このような1分子中に複数のイソシアネート基又はブロック化イソシアネート基を有する化合物の配合量は、前記カルボキシル基含有樹脂100質量部に対して、1~100質量部、より好ましくは、2~70質量部の割合が適当である。前記配合量が、1質量部未満の場合、十分な塗膜の強靭性が得られず、好ましくない。一方、100質量部を超えた場合、保存安定性が低下するので好ましくない。 The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass, more preferably 2 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. The proportion of parts is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable.
赤色着色剤としてはモノアゾ系、ジズアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系などがあり、具体的には以下のようなカラ-インデックス(C.I.;ザ ソサイエティ オブ ダイヤーズ アンド カラリスツ(The Society of Dyers and Colourists)発行)番号が付されているものが挙げられる。
モノアゾ系:Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269。
ジスアゾ系:Pigment Red 37, 38, 41。
モノアゾレーキ系:Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1,68。
ベンズイミダゾロン系:Pigment Red 171、Pigment Red 175、Pigment Red 176、Pigment Red 185、Pigment Red 208。
ぺリレン系:Solvent Red 135、Solvent Red 179、Pigment Red 123、Pigment Red 149、Pigment Red 166、Pigment Red 178、Pigment Red 179、Pigment Red 190、Pigment Red 194、Pigment Red 224。
ジケトピロロピロール系:Pigment Red 254、Pigment Red 255、Pigment Red 264、Pigment Red 270、Pigment Red 272。
縮合アゾ系:Pigment Red 220、Pigment Red 144、Pigment Red 166、Pigment Red 214、Pigment Red 220、Pigment Red 221、Pigment Red 242。
アンスラキノン系:Pigment Red 168、Pigment Red 177、Pigment Red 216、Solvent Red 149、Solvent Red 150、Solvent Red 52、Solvent Red 207。
キナクリドン系:Pigment Red 122、Pigment Red 202、Pigment Red 206、Pigment Red 207、Pigment Red 209。 Red colorant:
Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. -Indexes (CI; issued by The Society of Dyers and Colorists) are listed.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.
青色着色剤としてはフタロシアニン系、アントラキノン系があり、顔料系はピグメント(Pigment)に分類されている化合物、具体的には、下記のようなものを挙げることができる:Pigment Blue 15、Pigment Blue 15:1、Pigment Blue 15:2、Pigment Blue 15:3、Pigment Blue 15:4、Pigment Blue 15:6、Pigment Blue 16、Pigment Blue 60。
染料系としては、Solvent Blue 35、Solvent Blue 63、Solvent Blue 68、Solvent Blue 70、Solvent Blue 83、Solvent Blue 87、Solvent Blue 94、Solvent Blue 97、Solvent Blue 122、Solvent Blue 136、Solvent Blue 67、Solvent Blue 70等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Blue colorant:
Examples of blue colorants include phthalocyanine and anthraquinone, and pigments include compounds classified as Pigment, specifically, Pigment Blue 15 and Pigment Blue 15 : 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, and Pigment Blue 60.
The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
緑色着色剤としては、同様にフタロシアニン系、アントラキノン系、ペリレン系があり、具体的にはPigment Green 7、Pigment Green 36、Solvent Green 3、Solvent Green 5、Solvent Green 20、Solvent Green 28等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Green colorant:
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
黄色着色剤としてはモノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等があり、具体的には以下のものが挙げられる。
アントラキノン系:Solvent Yellow 163、Pigment Yellow 24、Pigment Yellow 108、Pigment Yellow 193、Pigment Yellow 147、Pigment Yellow 199、Pigment Yellow 202。
イソインドリノン系:Pigment Yellow 110、Pigment Yellow 109、Pigment Yellow 139、Pigment Yellow 179、Pigment Yellow 185。
縮合アゾ系:Pigment Yellow 93、Pigment Yellow 94、Pigment Yellow 95、Pigment Yellow 128、Pigment Yellow 155、Pigment Yellow 166、Pigment Yellow 180。
ベンズイミダゾロン系:Pigment Yellow 120、Pigment Yellow 151、Pigment Yellow 154、Pigment Yellow 156、Pigment Yellow 175、Pigment Yellow 181。
モノアゾ系:Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183。
ジスアゾ系:Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198。 Yellow colorant:
Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.
具体的に例示すれば、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet 13、36、C.I.ピグメントオレンジ1、C.I.ピグメントオレンジ5、C.I.ピグメントオレンジ13、C.I.ピグメントオレンジ14、C.I.ピグメントオレンジ16、C.I.ピグメントオレンジ17、C.I.ピグメントオレンジ24、C.I.ピグメントオレンジ34、C.I.ピグメントオレンジ36、C.I.ピグメントオレンジ38、C.I.ピグメントオレンジ40、C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ46、C.I.ピグメントオレンジ49、C.I.ピグメントオレンジ51、C.I.ピグメントオレンジ61、C.I.ピグメントオレンジ63、C.I.ピグメントオレンジ64、C.I.ピグメントオレンジ71、C.I.ピグメントオレンジ73、C.I.ピグメントブラウン23、C.I.ピグメントブラウン25、C.I.ピグメントブラック1、C.I.ピグメントブラック7等がある。 In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.
上記の酸化防止剤は、1種を単独で又は2種以上を組み合わせて用いることができる。 The peroxide decomposing agent may be a commercially available one, for example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Sumilyzer TPS (Sumitomo Chemical). Company name, product name).
Said antioxidant can be used individually by 1 type or in combination of 2 or more types.
上記の紫外線吸収剤は、1種を単独で又は2種以上を組み合わせて用いることができ、前記酸化防止剤と併用することで本発明の光硬化性熱硬化性樹脂組成物より得られる成形物の安定化が図れる。 Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Specialty Chemicals, Inc., trade name).
Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, The molded product obtained from the photocurable thermosetting resin composition of this invention by using together with the said antioxidant. Can be stabilized.
ソルダーレジスト層は、アルカリ現像性光硬化性熱硬化性樹脂組成物をブレードコーター、リップコーター、コンマコーター、フィルムコーター等でキャリアフィルム又はカバーフィルムに10~150μmの厚さで均一に塗布し乾燥して形成される。
カバーフィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム等を使用することができるが、ソルダーレジスト層との接着力が、キャリアフィルムよりも小さいものが良い。 As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
For the solder resist layer, the alkali-developable photo-curable thermosetting resin composition is uniformly applied to a carrier film or cover film with a thickness of 10 to 150 μm using a blade coater, lip coater, comma coater, film coater, etc., and dried. Formed.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.
ジエチレングリコールモノエチルエーテルアセテート600gにオルソクレゾールノボラック型エポキシ樹脂(大日本インキ化学工業(株)製、EPICLON N-695、軟化点95℃、エポキシ当量214、平均官能基数7.6)1070g(グリシジル基数(芳香環総数):5.0モル)、アクリル酸360g(5.0モル)、及びハイドロキノン1.5gを仕込み、100℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン4.3gを仕込み、110℃に加熱して2時間反応後、120℃に昇温してさらに12時間反応を行った。得られた反応液に芳香族系炭化水素(ソルベッソ150)415g、テトラヒドロ無水フタル酸456.0g(3.0モル)を仕込み、110℃で4時間反応を行い、冷却後、固形分酸価89mgKOH/g、固形分65%の樹脂溶液を得た。以下、これをワニスA-1と称す。 Synthesis example 1:
Orthocresol novolac type epoxy resin (manufactured by Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups) (diethylene glycol monoethyl ether acetate 600 g) Total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. Hereinafter, this is referred to as varnish A-1.
クレゾールノボラック型エポキシ樹脂(日本化薬(株)製、EOCN-104S、軟化点92℃、エポキシ当量220)2200部、ジメチロールプロピオン酸134部、アクリル酸648.5部、メチルハイドロキノン4.6部、カルビトールアセテート1131部及びソルベントナフサ484.9部を仕込み、9 0℃に加熱し撹拌し、反応混合物を溶解した。次いで、反応液を60℃まで冷却し、トリフェニルフォスフィン13.8部を仕込み、100℃に加熱し、約32時間反応させ、酸価が0.5mgKOH/gの反応物を得た。次に、これにテトラヒドロ無水フタル酸364.7部、カルビトールアセテート137.5部及びソルベントナフサ58.8部を仕込み、95℃に加熱し、約6時間反応させ、冷却し、固形分酸価40mgKOH/g、不揮発分65%のカルボキシル基含有感光性樹脂の樹脂溶液を得た。以下、これをワニスA-2と称す。 Synthesis example 2:
Cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220) 2200 parts, dimethylolpropionic acid 134 parts, acrylic acid 648.5 parts, methylhydroquinone 4.6 parts Then, 1131 parts of carbitol acetate and 484.9 parts of solvent naphtha were charged, heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 13.8 parts of triphenylphosphine, heated to 100 ° C., and allowed to react for about 32 hours to obtain a reaction product having an acid value of 0.5 mg KOH / g. Next, 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of solvent naphtha were added to this, heated to 95 ° C., reacted for about 6 hours, cooled, and solid acid value A resin solution of a carboxyl group-containing photosensitive resin having 40 mg KOH / g and a nonvolatile content of 65% was obtained. Hereinafter, this is referred to as varnish A-2.
エポキシ当量800、軟化点79℃のビスフェノールF型固型エポキシ樹脂400部をエピクロルヒドリン925部とジメチルスルホキシド462.5部を溶解させた後、攪拌下70℃で98.5%NaOH 81.2部を100分かけて添加した。添加後さらに70℃で3時間反応を行なった。次いで、過剰の未反応エピクロルヒドリン及びジメチルスルホキシドの大半を減圧下に留去し、副生塩とジメチルスルホキシドを含む反応生成物をメチルイソブチルケトン750部に溶解させ、さらに30%NaOH 10部を加え、70℃で1時間反応させた。反応終了後、水200部で2回水洗を行った。油水分離後、油層よりメチルイソブチルケトンを蒸留回収して、エポキシ当量290、軟化点62℃のエポキシ樹脂(a-1)370部を得た。得られたエポキシ樹脂(a-1)2900部(10当量)、アクリル酸720部(10当量)、メチルハイドロキノン2.8部、カルビトールアセテート1950部を仕込み、90℃に加熱、攪拌し、反応混合物を溶解した。次いで、反応液を60℃に冷却し、トリフェニルフォスフィン16.7部を仕込み、100℃に加熱し、約32時間反応し、酸価が1.0mgKOH/gの反応物を得た。次に、これに無水コハク酸786部(7.86モル)、カルビトールアセテート423部を仕込み、95℃に加熱し、約6時間反応を行い、固形分酸価100mgKOH/g、固形分65%の樹脂溶液を得た。以下、これをワニスA-3と称す。 Synthesis Example 3:
After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide in 400 parts of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C., 81.2 parts of 98.5% NaOH at 70 ° C. with stirring. Added over 100 minutes. After the addition, the reaction was further performed at 70 ° C. for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, the reaction product containing the by-product salt and dimethyl sulfoxide is dissolved in 750 parts of methyl isobutyl ketone, and 10 parts of 30% NaOH is further added. The reaction was carried out at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After the oil / water separation, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ° C. 2900 parts (10 equivalents) of the obtained epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone and 1950 parts of carbitol acetate were charged, heated to 90 ° C., stirred and reacted. The mixture was dissolved. Next, the reaction solution was cooled to 60 ° C., charged with 16.7 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, solid content acid value 100 mg KOH / g, solid content 65% A resin solution was obtained. Hereinafter, this is referred to as varnish A-3.
温度計、窒素導入装置兼アルキレンオキシド導入装置及び撹拌装置を備えたオートクレーブに、ノボラック型クレゾール樹脂(昭和高分子(株)製、商品名「ショーノールCRG951」、OH当量:119.4)119.4g、水酸化カリウム1.19g及びトルエン119.4gを仕込み、撹拌しつつ系内を窒素置換し、加熱昇温した。次に、プロピレンオキシド63.8gを徐々に滴下し、125~132℃、0~4.8kg/cm2で16時間反応させた。その後、室温まで冷却し、この反応溶液に89%リン酸1.56gを添加混合して水酸化カリウムを中和し、不揮発分62.1%、水酸基価が182.2g/eq.であるノボラック型クレゾール樹脂のプロピレンオキシド反応溶液を得た。これは、フェノール性水酸基1当量当りアルキレンオキシドが平均1.08モル付加しているものであった。
次いで、得られたノボラック型クレゾール樹脂のアルキレンオキシド反応溶液293.0g、アクリル酸43.2g、メタンスルホン酸11.53g、メチルハイドロキノン0.18g及びトルエン252.9gを、撹拌機、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を10ml/分の速度で吹き込み、撹拌しながら、110℃で12時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、12.6gの水が留出した。その後、室温まで冷却し、得られた反応溶液を15%水酸化ナトリウム水溶液35.35gで中和し、次いで水洗した。その後、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート118.1gで置換しつつ留去し、ノボラック型アクリレート樹脂溶液を得た。次に、得られたノボラック型アクリレート樹脂溶液332.5g及びトリフェニルホスフィン1.22gを、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を10ml/分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物60.8gを徐々に加え、95~101℃で6時間反応させた。固形物の酸価88mgKOH/g、不揮発分71%のカルボキシル基含有感光性樹脂の樹脂溶液を得た。以下、これをワニスA-4と称す。 Synthesis Example 4:
A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
Next, 293.0 g of the resulting novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, thermometer and air. A reactor equipped with a blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as varnish A-4.
温度計、撹拌機及び環流冷却器を備えた5リットルのセパラブルフラスコに、ポリマーポリオールとしてポリカプロラクトンジオール(ダイセル化学工業(株)製PLACCEL208、分子量830)1,245g、カルボキシル基を有するジヒドロキシル化合物としてジメチロールプロピオン酸201g、ポリイソシアナートとしてイソホロンジイソシアナート777g及びヒドロキシル基を有する(メタ)アクリレートとして2-ヒドロキシエチルアクリレート119g、さらにp-メトキシフェノール及びジ-t-ブチル-ヒドロキシトルエンを各々0.5gずつ投入した。攪拌しながら60℃まで加熱して停止し、ジブチル錫ジラウレート0.8gを添加した。反応容器内の温度が低下し始めたら再度加熱して、80℃で攪拌を続け、赤外線吸収スペクトルでイソシアナート基の吸収スペクトル(2280cm-1)が消失したことを確認して反応を終了し、粘稠液体のウレタンアクリレート化合物を得た。カルビトールアセテートを用いて不揮発分=50質量%に調整した。固形物の酸価47mgKOH/g、不揮発分50%のカルボキシル基を有するウレタン(メタ)アクリレート化合物の樹脂溶液を得た。以下、これをワニスA-5と称す。 Synthesis Example 5:
In a 5 liter separable flask equipped with a thermometer, a stirrer and a reflux condenser, 1,245 g of polycaprolactone diol (PLACCEL 208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.) as a polymer polyol, a dihydroxyl compound having a carboxyl group Dimethylolpropionic acid 201 g as polyisocyanate, 777 g of isophorone diisocyanate as polyisocyanate, 119 g of 2-hydroxyethyl acrylate as hydroxyl group-containing (meth) acrylate, p-methoxyphenol and di-t-butyl-hydroxytoluene each of 0 .5 g was added. The mixture was stopped by heating to 60 ° C. while stirring, and 0.8 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again and stirred at 80 ° C., and the reaction is completed after confirming that the absorption spectrum of the isocyanate group (2280 cm−1) has disappeared in the infrared absorption spectrum. A viscous liquid urethane acrylate compound was obtained. The volatile content was adjusted to 50% by mass using carbitol acetate. A resin solution of a urethane (meth) acrylate compound having a carboxyl group having a solid acid value of 47 mgKOH / g and a nonvolatile content of 50% was obtained. Hereinafter, this is referred to as varnish A-5.
攪拌機、温度計、還流冷却器、滴下ロート及び窒素導入管を備えた2リットルのセパラブルフラスコに、溶媒としてジエチレングリコールジメチルエーテル900g、及び重合開始剤としてt-ブチルパーオキシ2-エチルヘキサノエート(日本油脂(株)製、商品名;パーブチルO)21.4gを加えて90℃に加熱した。加熱後、ここに、メタクリル酸309.9g、メタクリル酸メチル116.4g、及びラクトン変性2-ヒドロキシエチルメタクリレート(プラクセルFM1:ダイセル化学工業(株)製)109.8gを、重合開始剤であるビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート(日本油脂(株)製、商品名;パーロイルTCP)21.4gと共に3時間かけて滴下して加え、さらに6時間熟成することにより、カルボキシル基含有共重合樹脂を得た。なお、反応は、窒素雰囲気下で行った。
次に、得られたカルボキシル基含有共重合樹脂に、3,4-エポキシシクロヘキシルメチルアクリレート(ダイセル化学工業(株)製、商品名;サイクロマーA200)363.9g、開環触媒としてジメチルベンジルアミン3.6g、重合抑制剤としてハイドロキノンモノメチルエーテル1.80gを加え、100℃に加熱し、攪拌することによりエポキシの開環付加反応を行った。16時間後、固形分酸価が108.9mgKOH/g、重量平均分子量が25,000、固形分54%の樹脂溶液を得た。以下、これをワニスA-6と称す。 Synthesis Example 6:
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate as a polymerization initiator (Japan) 21.4 g of oil and fat Co., Ltd., trade name: Perbutyl O) was added and heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Placcel FM1: manufactured by Daicel Chemical Industries, Ltd.) were added as a polymerization initiator. (4-t-butylcyclohexyl) peroxydicarbonate (trade name: Parroyl TCP, manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise with 31.4 hours over 3 hours, and further aged for 6 hours to contain a carboxyl group. A copolymer resin was obtained. The reaction was performed under a nitrogen atmosphere.
Next, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name: Cyclomer A200) and dimethylbenzylamine 3 as a ring-opening catalyst were added to the obtained carboxyl group-containing copolymer resin. .6 g, 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor was added, and the mixture was heated to 100 ° C. and stirred to carry out an epoxy ring-opening addition reaction. After 16 hours, a resin solution having a solid content acid value of 108.9 mgKOH / g, a weight average molecular weight of 25,000, and a solid content of 54% was obtained. Hereinafter, this is referred to as varnish A-6.
上記各合成例で得られた樹脂溶液を用い、下記表1に示す種々の成分と共に表1に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、3本ロールミルで混練し、光硬化性熱硬化性樹脂組成物を調製した。得られた光硬化性熱硬化性樹脂組成物をJPCA規格に基づくフラスコ燃焼処理イオンクロマトグラフ法を用いることにより、ハロゲン化物含有量(塩素物と臭素物の合計)を定量した。その結果を表1に併せて示す。 Reference example:
Using the resin solutions obtained in each of the above synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1 below, premixed with a stirrer, and then kneaded with a three-roll mill. A photocurable thermosetting resin composition was prepared. The obtained photocurable thermosetting resin composition was quantified in halide content (total of chloride and bromide) by using a flask combustion treatment ion chromatography method based on the JPCA standard. The results are also shown in Table 1.
上記合成例の樹脂溶液を用い、下記表2に示す種々の成分と共に表2に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、3本ロールミルで混練し、ソルダーレジスト用感光性樹脂組成物を調製した。ここで、得られた感光性樹脂組成物の分散度をエリクセン社製グラインドメータによる粒度測定にて評価したところ、15μm以下であった。 Examples 1 to 14 and Comparative Examples 1 to 3
Using the resin solution of the above synthesis example, blended in the proportions (parts by mass) shown in Table 2 together with various components shown in Table 2 below, premixed with a stirrer, kneaded with a three-roll mill, and used for solder resist A photosensitive resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.
*1 : 2-メチル-1-(4-メチルチオフェニル)-2-モルフォリオノフ゜ロハ゜ン-1-オン (イルカ゛キュア907:チハ゛・スヘ゜シャルティ・ケミカルス゛社製)
*2 : 2,4-シ゛エチルチオキサントン(KAYACURE DETX-S:日本化薬社製)
*3 : エタノン,1-[9-エチル-6-(2-メチルヘ゛ンソ゛イル)-9H-カルハ゛ソ゛ール-3-イル]-1,1-(O-アセチルオキシム) (イルカ゛キュア OXE 02:チハ゛・スヘ゜シャルティ・ケミカルス゛社製)
*4 : アテ゛カアークルス゛ NCI-831(ADEKA社製)
*5 : フェノールノホ゛ラック型エホ゜キシ樹脂(RE306CA90:日本化薬社製)
*6 : ヒ゛キシレノール型エホ゜キシ樹脂(YX-4000:シ゛ャハ゜ンエホ゜キシレシ゛ン社製)
*7 : 水酸基末端液状ホ゜リフ゛タシ゛エン(出光興産社製)
*8 : エホ゜キシ化ホ゜リフ゛タシ゛エン(タ゛イセル化学工業社製)
*9 : 2-メルカフ゜トヘ゛ンソ゛チアソ゛ール(川口化学工業社製)
*10: 1,4-ヒ゛ス(3-メルカフ゜トフ゛チリルオキシ)フ゛タン(昭和電工社製)
*11: 2-シ゛フ゛チルアミノ-4.6-シ゛メルカフ゜ト-s-トリアシ゛ン(三協化成社製)
*12: 1,3,5-トリス(3-メルカフ゜トフ゛チルオキシエチル)-1,3,5-トリアシ゛ン-2,4,6(1H,3H,5H)-トリオン(昭和電工社製)
*13: 2,4,6-トリメルカフ゜ト-s-トリアシ゛ン(三協化成社製)
*14: ヘ゜ンタエリスリトール テトラキス(3-メルカフ゜トフ゛チレート)(昭和電工社製)
*15: C.I.Pigment Blue 15:3
*16: C.I.Pigment Yellow 147
*17: 酸化防止剤(チハ゛・スヘ゜シャルティ・ケミカルス゛社製)
*18: B-30(堺化学社製)
*19: ハイト゛ロタルサイト(協和化学工業社製)
*20: シ゛エチレンク゛リコールモノエチルエーテルアセテート
*21: シ゛ヘ゜ンタエリスリトールヘ゜ンタアクリレート
*22: フ゛ロックイソシアネート(旭化成ケミカルス゛社製)
*23: メチル化メラミン樹脂(三和ケミカル社製) [Supplement under rule 26 17.02.2010]
* 1: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinofluoro-1-one (Irgacure 907: Ciba Specialty Chemicals)
* 2: 2,4-diethylthioxanthone (KAYACURE DETX-S: Nippon Kayaku Co., Ltd.)
* 3: Ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1,1- (O-acetyloxime) (Irgacure OXE 02: Chiva Specialty Chemicals (Made by company)
* 4: Adeka Arc NCI-831 (made by ADEKA)
* 5: Phenol novolac type epoxy resin (RE306CA90: manufactured by Nippon Kayaku Co., Ltd.)
* 6: Hexylenol type epoxy resin (YX-4000: manufactured by JAPHENE epoxy resin)
* 7: Hydroxyl-terminated liquid polybutadiene (made by Idemitsu Kosan)
* 8: Epoxylated polybutadiene (manufactured by Daicel Chemical Industries)
* 9: 2-Mercapto Benzo thiazol (manufactured by Kawaguchi Chemical Industry Co., Ltd.)
* 10: 1,4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko)
* 11: 2-Dibutylamino-4.6-Dimercapto-s-Triazine (manufactured by Sankyo Kasei)
* 12: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (made by Showa Denko)
* 13: 2,4,6-trimercaps-s-triazine (manufactured by Sankyo Kasei)
* 14: Hentaerythritol tetrakis (3-mercaptobutyrate) (Showa Denko)
* 15: CIPigment Blue 15: 3
* 16: CIPigment Yellow 147
* 17: Antioxidant (manufactured by Chiba Specialty Chemicals)
* 18: B-30 (manufactured by Sakai Chemical)
* 19: Hydratal site (manufactured by Kyowa Chemical Industry Co., Ltd.)
* 20: Diethylene glycol monoethyl ether acetate * 21: Diethyl erythritol hexane acrylate * 22: Block isocyanate (manufactured by Asahi Kasei Chemicals)
* 23: Methylated melamine resin (Sanwa Chemical Co., Ltd.)
<最適露光量>
銅厚18μmの回路パターン基板を銅表面粗化処理(メック(株)製メックエッチボンドCZ-8100)後、水洗し、乾燥した後、前記実施例及び比較例の光硬化性熱硬化性樹脂組成物をスクリーン印刷法により全面に塗布し、80℃の熱風循環式乾燥炉で60分間乾燥させた。乾燥後、高圧水銀灯搭載の露光装置を用いてステップタブレット(Kodak No.2)を介して露光し、現像(30℃、0.2MPa、1wt%炭酸ナトリウム水溶液)を90秒で行った際残存するステップタブレットのパターンが7段の時を最適露光量とした。 Performance evaluation:
<Optimum exposure amount>
A circuit pattern substrate having a copper thickness of 18 μm was subjected to a copper surface roughening treatment (MEC etch bond CZ-8100 manufactured by MEC Co., Ltd.), washed with water, dried, and then subjected to photocurable thermosetting resin compositions of the above examples and comparative examples. The product was applied to the entire surface by a screen printing method, and dried for 60 minutes in an 80 ° C. hot air circulation drying oven. After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and remains when development (30 ° C., 0.2 MPa, 1 wt% sodium carbonate aqueous solution) is performed in 90 seconds. When the step tablet pattern is 7 steps, the optimum exposure was set.
前記実施例及び比較例の光硬化性熱硬化性樹脂組成物を、銅ベタ基板上にスクリーン印刷法により乾燥後の膜厚が約25μmになるように塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させた。乾燥後、1wt%炭酸ナトリウム水溶液によって現像を行い、乾燥塗膜が除去されるまでの時間をストップウォッチにより計測した。 <Developability>
The photocurable thermosetting resin compositions of the examples and comparative examples were applied to a solid copper substrate by a screen printing method so that the film thickness after drying was about 25 μm, and a hot air circulation drying oven at 80 ° C. For 30 minutes. After drying, development was performed with a 1 wt% sodium carbonate aqueous solution, and the time until the dried coating film was removed was measured with a stopwatch.
前記実施例及び比較例の組成物を、パターン形成された銅箔基板上にスクリーン印刷で全面塗布し、80℃で乾燥し20分から80分まで10分おきに基板を取り出し、室温まで放冷した。この基板に30℃の1wt%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で90秒間現像を行い、残渣が残らない最大許容乾燥時間を最大現像ライフとした。 <Maximum development life>
The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C., taken out every 20 minutes from 20 to 80 minutes, and allowed to cool to room temperature. . This substrate was developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 90 seconds, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.
前記実施例及び比較例の組成物を、パターン形成された銅箔基板上にスクリーン印刷で全面塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させ、室温まで放冷した。この基板にPET製ネガフィルムを当て、ORC社製HMW-GW20で1分間減圧条件下で圧着させ、その後、ネガフィルムを剥がしたときのフィルムの張り付き状態を、以下の基準で評価した。
○:フィルムを剥がすときに、全く抵抗が無く、塗膜に跡が残らない。
△:フィルムを剥がす時に、僅かに抵抗があり、塗膜に跡が少しついている。
×:フィルムを剥がす時に、抵抗があり、塗膜にはっきり跡がついている。 <Tackiness>
The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. A negative film made of PET was applied to this substrate, pressure-bonded under a reduced pressure condition with HMW-GW20 manufactured by ORC for 1 minute, and then the sticking state of the film when the negative film was peeled was evaluated according to the following criteria.
○: When peeling off the film, there is no resistance at all and no mark is left on the coating film.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.
前記実施例及び比較例の組成物を、パターン形成された銅箔基板上にスクリーン印刷で全面塗布し、80℃で30分乾燥し、室温まで放冷した。この基板に高圧水銀灯を搭載した露光装置を用いて最適露光量でソルダーレジストパターンを露光し、30℃の1wt%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で90秒間現像を行い、レジストパターンを得た。この基板を、UVコンベア炉にて積算露光量1000mJ/cm2の条件で紫外線照射した後、160℃で60分加熱して硬化した。得られたプリント基板(評価基板)に対して以下のように特性を評価した。 Characteristic test:
The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Using an exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the solder resist pattern is exposed at an optimum exposure amount, and developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 90 seconds. Obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 160 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
評価基板を10vol%H2SO4水溶液に室温で30分間浸漬し、染み込みや塗膜の溶け出しを目視にて確認し、さらにテープビールによる剥がれを確認した。
○:変化が認められないもの
△:ほんの僅か変化しているもの
×:塗膜に膨れあるいは膨潤脱落があるもの <Acid resistance>
The evaluation substrate was immersed in a 10 vol% H 2 SO 4 aqueous solution at room temperature for 30 minutes, and the penetration and dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed.
○: No change is observed Δ: Only a slight change ×: The coating film swells or swells and falls off
評価基板を10vol%NaOH水溶液に室温で30分間浸漬し、染み込みや塗膜の溶け出しを目視にて確認し、さらにテープビールによる剥がれを確認した。
○:変化が認められないもの
△:ほんの僅か変化しているもの
×:塗膜に膨れあるいは膨潤脱落があるもの <Alkali resistance>
The evaluation substrate was immersed in a 10 vol% NaOH aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed, and further, peeling by tape beer was confirmed.
○: No change is observed Δ: Only a slight change ×: The coating film swells or swells and falls off
ロジン系フラックスを塗布した評価基板を、予め260℃に設定したはんだ槽に浸漬し、変性アルコールでフラックスを洗浄した後、目視によるレジスト層の膨れ・剥がれについて評価した。判定基準は以下のとおりである。
○:10秒間浸漬を3回以上繰り返しても剥がれが認められない。
△:10秒間浸漬を3回以上繰り返すと少し剥がれる。
×:10秒間浸漬を3回以内にレジスト層に膨れ、剥がれがある。 <Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.
市販品の無電解ニッケルめっき浴及び無電解金めっき浴を用いて、ニッケル5μm、金0.05μmの条件でめっきを行い、テープピーリングにより、レジスト層の剥がれの有無やめっきの染み込みの有無を評価した後、テープピーリングによりレジスト層の剥がれの有無を評価した。判定基準は以下のとおりである。
◎:染み込み、剥がれが見られない。
○:めっき後に少し染み込みが確認されるが、テープピール後に剥がれはない。
△:めっき後に僅かな染み込みが見られ、テープピール後に剥がれも見られる。
×:めっき後に剥がれがある。 <Electroless gold plating resistance>
Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 5 μm and gold 0.05 μm, and the presence or absence of peeling of the resist layer or plating penetration is evaluated by tape peeling. Then, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
A: No soaking or peeling is observed.
○: Slight penetration was confirmed after plating, but there was no peeling after tape peeling.
Δ: Slight penetration was observed after plating, and peeling was also observed after tape peeling.
X: There is peeling after plating.
ソルダーレジスト硬化塗膜を形成した評価基板を、PCT装置(エスペック(株)製HAST SYSTEM TPC-412MD)を用いて、121℃、飽和、0.2MPaの条件で240時間処理し、塗膜の状態を評価した後、テープピールにより剥がれの評価を行った。判定基準は以下の通りである。
◎:膨れ、剥がれ、変色、溶出が見られず、テープピールでも剥がれが全く確認されない。
○:膨れ、剥がれ、変色、溶出は無いが、テープピールで僅かに剥がれが確認される。
△:若干の膨れ、剥がれ、変色、溶出があり、テープピールにより剥がれが確認される。
×:膨れ、剥がれ、変色、溶出が多く見られ、テープピールでも多くの剥がれが確認される。 <PCT resistance>
The evaluation substrate on which the solder resist cured coating film was formed was treated for 240 hours under the conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Corporation), and the state of the coating film After the evaluation, peeling was evaluated with a tape peel. Judgment criteria are as follows.
A: No swelling, peeling, discoloration or elution is observed, and no peeling is confirmed even with a tape peel.
○: No swelling, peeling, discoloration, or elution, but slight peeling is confirmed with a tape peel.
Δ: Slight swelling, peeling, discoloration and elution, and peeling is confirmed by tape peel.
X: Swelling, peeling, discoloration, and elution are often observed, and a lot of peeling is confirmed even with a tape peel.
□抜き、○抜きパターンを形成したソルダーレジスト硬化塗膜を有する評価基板を作製した。得られた評価基板を冷熱衝撃試験器(エタック(株)製)で-55℃/30分~150℃/30分を1サイクルとして1000サイクルの耐性試験を行った。試験後、処理後の硬化膜を目視により観察し、クラックの発生状況を下記の基準にて判断した。
○:クラック発生率30%未満
△:クラック発生率30~50%
×:クラック発生率50%以上 <Cold shock resistance>
The evaluation board | substrate which has a soldering resist cured coating film in which (square) extraction and (circle) extraction pattern were formed was produced. The obtained evaluation substrate was subjected to 1000 cycles of resistance test using a thermal shock tester (manufactured by ETAC Co., Ltd.) with one cycle of −55 ° C./30 minutes to 150 ° C./30 minutes. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged according to the following criteria.
○: Crack generation rate of less than 30% △: Crack generation rate of 30-50%
×: Crack occurrence rate of 50% or more
クシ型電極(ライン/スペース=30ミクロン/30ミクロン)が形成されたBT基板に、ソルダーレジスト硬化塗膜を形成し、評価基板を作製した。この評価基板を、130℃、湿度85%の雰囲気下の高温高湿槽に入れ、電圧5Vを荷電し、168時間、槽内HAST試験を行った。168時間経過時の槽内絶縁抵抗値を下記の判断基準に従い評価した。
◎:108Ω以上
○:107~108Ω
△:106~107Ω
×:106Ω以下 <HAST characteristics>
A solder resist cured coating film was formed on a BT substrate on which comb-type electrodes (line / space = 30 microns / 30 microns) were formed, and an evaluation substrate was prepared. This evaluation board | substrate was put into the high-temperature, high-humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 5V was charged, and the in-chamber HAST test was done for 168 hours. The insulation resistance value in the tank when 168 hours passed was evaluated according to the following criteria.
◎: 108Ω or more ○: 107-108Ω
Δ: 106-107Ω
×: 106Ω or less
表2に示す配合割合で調製した実施例2~13及び比較例1、2、3の各組成物をメチルエチルケトンにて希釈し、PETフィルム上に塗布して80℃で30分乾燥し、厚さ20μmの感光性樹脂組成物層を形成した。さらにその上にカバーフィルムを貼り合わせてドライフィルムを作製し、それぞれを実施例15~27及び比較例4~6とした。 Examples 15 to 27 and Comparative Examples 4 to 6
The compositions of Examples 2 to 13 and Comparative Examples 1, 2, and 3 prepared at the blending ratios shown in Table 2 were diluted with methyl ethyl ketone, applied onto a PET film, dried at 80 ° C. for 30 minutes, A 20 μm photosensitive resin composition layer was formed. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 15 to 27 and Comparative Examples 4 to 6, respectively.
上記のようにして得られたドライフィルムからカバーフィルムを剥がし、パターン形成された銅箔基板に、フィルムを熱ラミネートし、次いで、前記実施例の塗膜特性評価に用いた基板と同様の条件で露光した。露光後、キャリアフィルムを剥がし、30℃の1wt%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で90秒間現像を行い、レジストパターンを得た。この基板を、UVコンベア炉にて積算露光量1000mJ/cm2の条件で紫外線照射した後、160℃で60分加熱して硬化した。得られた硬化皮膜を有する試験基板について、前述した試験方法及び評価方法にて、各特性の評価試験を行った。結果を表4に示す。 <Dry film evaluation>
The cover film is peeled off from the dry film obtained as described above, the film is thermally laminated on the patterned copper foil substrate, and then, under the same conditions as the substrate used for the coating film property evaluation of the above example. Exposed. After the exposure, the carrier film was peeled off, and a 1 wt% sodium carbonate aqueous solution at 30 ° C. was developed for 90 seconds under a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 160 ° C. for 60 minutes. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 4.
Claims (5)
- カルボキシル基含有樹脂、光重合開始剤、ビニル基含有エラストマー、及びメルカプト化合物を含有することを特徴とするアルカリ水溶液により現像可能な光硬化性熱硬化性樹脂組成物。 A photocurable thermosetting resin composition developable with an alkaline aqueous solution, comprising a carboxyl group-containing resin, a photopolymerization initiator, a vinyl group-containing elastomer, and a mercapto compound.
- 前記カルボキシル基含有樹脂がエポキシ樹脂から誘導されたものでないことを特徴とする請求項1に記載の光硬化性熱硬化性樹脂組成物。 The photocurable thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin is not derived from an epoxy resin.
- 前記請求項1又は2に記載の光硬化性熱硬化性樹脂組成物を、フィルム上に塗布乾燥して得られる光硬化性熱硬化性のドライフィルム。 A photocurable thermosetting dry film obtained by applying and drying the photocurable thermosetting resin composition according to claim 1 or 2 on a film.
- 前記請求項1又は2に記載の光硬化性熱硬化性樹脂組成物を基材上に塗布乾燥して得られる塗膜、又は前記光硬化性熱硬化性樹脂組成物をフィルム上に塗布乾燥して得られるドライフィルムを基材上にラミネートして得られた乾燥塗膜を、光硬化して得られる硬化物。 A coating obtained by applying and drying the photocurable thermosetting resin composition according to claim 1 or 2 on a substrate, or applying and drying the photocurable thermosetting resin composition on a film. A cured product obtained by photocuring a dried coating film obtained by laminating a dry film obtained on the substrate.
- 前記請求項1又は2に記載の光硬化性熱硬化性樹脂組成物を基材上に塗布乾燥して得られる塗膜、又は前記光硬化性熱硬化性樹脂組成物をフィルム上に塗布乾燥させて得られるドライフィルムを基材上にラミネートして得られた乾燥塗膜を、活性エネルギー線の照射によりパターン状に光硬化させた後、熱硬化して得られる硬化皮膜を有するプリント配線板。 A coating film obtained by applying and drying the photocurable thermosetting resin composition according to claim 1 or 2 on a substrate, or applying and drying the photocurable thermosetting resin composition on a film. A printed wiring board having a cured film obtained by photocuring a dry coating film obtained by laminating a dry film obtained on the substrate on a base material in a pattern by irradiation with active energy rays.
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2012159657A (en) * | 2011-01-31 | 2012-08-23 | Asahi Kasei E-Materials Corp | Photocurable resin composition and method for manufacturing patterned base material using the same, and electronic component having the base material |
WO2013164409A1 (en) | 2012-05-04 | 2013-11-07 | Kendlbacher Andreas | Device for the jet cutting of bones |
Also Published As
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JP5475350B2 (en) | 2014-04-16 |
TW201102405A (en) | 2011-01-16 |
KR20120031023A (en) | 2012-03-29 |
JP2011013487A (en) | 2011-01-20 |
CN102472970A (en) | 2012-05-23 |
TWI438236B (en) | 2014-05-21 |
KR101382071B1 (en) | 2014-04-04 |
CN102472970B (en) | 2016-10-19 |
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