JP2012184389A - Photosensitive composition, and printed wiring board - Google Patents
Photosensitive composition, and printed wiring board Download PDFInfo
- Publication number
- JP2012184389A JP2012184389A JP2011074888A JP2011074888A JP2012184389A JP 2012184389 A JP2012184389 A JP 2012184389A JP 2011074888 A JP2011074888 A JP 2011074888A JP 2011074888 A JP2011074888 A JP 2011074888A JP 2012184389 A JP2012184389 A JP 2012184389A
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- Prior art keywords
- photosensitive composition
- weight
- silica
- less
- resist film
- Prior art date
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- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- 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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0263—Details about a collection of particles
- H05K2201/0266—Size distribution
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、基板上に形成させるソルダーレジスト膜や、発光ダイオードチップが搭載される基板上に形成される光を反射させるレジスト膜などのレジスト膜を形成するために好適に用いられる感光性組成物、並びに該感光性組成物を用いたプリント配線板に関する。 The present invention relates to a photosensitive composition suitably used for forming a resist film such as a solder resist film formed on a substrate or a resist film reflecting light formed on a substrate on which a light emitting diode chip is mounted. And a printed wiring board using the photosensitive composition.
プリント配線板を高温のはんだから保護するための保護膜として、ソルダーレジスト膜が広く用いられている。 A solder resist film is widely used as a protective film for protecting a printed wiring board from high-temperature solder.
また、様々な電子機器用途において、プリント配線板の上面に発光ダイオード(以下、LEDと略す)チップが搭載されている。LEDから発せられた光の内、上記プリント配線板の上面側に到達した光も利用するために、プリント配線板の上面に白色ソルダーレジスト膜が形成されていることがある。この場合には、LEDチップの表面からプリント配線板とは反対側に直接照射される光だけでなく、プリント配線板の上面側に到達し、白色ソルダーレジスト膜により反射された反射光も利用できる。従って、LEDから生じた光の利用効率を高めることができる。 In various electronic device applications, a light emitting diode (hereinafter abbreviated as LED) chip is mounted on the upper surface of a printed wiring board. A white solder resist film may be formed on the upper surface of the printed wiring board in order to use light that has reached the upper surface side of the printed wiring board among the light emitted from the LEDs. In this case, not only light directly irradiated from the surface of the LED chip to the opposite side of the printed wiring board but also reflected light that reaches the upper surface side of the printed wiring board and is reflected by the white solder resist film can be used. . Therefore, the utilization efficiency of the light generated from the LED can be increased.
上記白色ソルダーレジスト膜を形成するための材料の一例として、下記の特許文献1には、エポキシ樹脂と加水分解性アルコキシシランとの脱アルコール反応により得られたアルコキシ基含有シラン変性エポキシ樹脂を含有し、かつ不飽和基含有ポリカルボン酸樹脂と、希釈剤と、光重合開始剤と、硬化密着性付与剤とをさらに含有するレジスト材料が開示されている。
As an example of a material for forming the white solder resist film, the following
下記の特許文献2には、芳香環を有さないカルボキシル基含有樹脂と、光重合開始剤と、エポキシ化合物と、ルチル型酸化チタンと、希釈剤とを含有する白色ソルダーレジスト材料が開示されている。
基板上にレジスト膜を形成するために、特許文献1〜2に記載のような従来のレジスト材料を基板上や基板上のPETフィルム上に塗工した場合には、レジスト材料中に泡が含有され、該泡が消えずに硬化したレジスト膜中に残存することがある。すなわち、従来のレジスト材料では、消泡性が低いことがある。
In order to form a resist film on a substrate, when a conventional resist material as described in
さらに、従来のレジスト材料を基板上に塗工した場合には、レジスト材料のハジキ特性が低く、レジスト材料が意図しない領域に配置されることがある。 Furthermore, when a conventional resist material is coated on a substrate, the resist material has low repellency characteristics, and the resist material may be disposed in an unintended region.
本発明の目的は、塗工対象部材上に塗工されたときに、消泡性及びハジキ特性に優れている感光性組成物、並びに該感光性組成物を用いたプリント配線板を提供することである。 An object of the present invention is to provide a photosensitive composition excellent in defoaming properties and repelling properties when coated on a coating target member, and a printed wiring board using the photosensitive composition. It is.
本発明によれば、カルボキシル基を有する重合性重合体と、光重合開始剤と、酸化チタンと、第1のシリカと、第2のシリカと、ポリジメチルシロキサンとを含み、上記第1のシリカの一次粒径が5nm以上、100nm以下であり、上記第2のシリカの一次粒径が0.5μm以上、10μm以下であり、せん断速度1rpmにおける25℃での粘度(mPa・s)をη1とし、せん断速度10rpmにおける25℃での粘度(mPa・s)をη10としたときに、粘度比(η1/η10)が1.1以上である、感光性組成物が提供される。 According to the present invention, the first silica includes a polymerizable polymer having a carboxyl group, a photopolymerization initiator, titanium oxide, a first silica, a second silica, and polydimethylsiloxane. The primary particle size of the second silica is 0.5 μm or more and 10 μm or less, and the viscosity (mPa · s) at 25 ° C. at a shear rate of 1 rpm is η1. A photosensitive composition having a viscosity ratio (η1 / η10) of 1.1 or more when the viscosity at 25 ° C. at a shear rate of 10 rpm (mPa · s) is η10 is provided.
本発明に係る感光性組成物のある特定の局面では、フェノール系酸化防止剤がさらに含まれている。 In a specific aspect of the photosensitive composition according to the present invention, a phenol-based antioxidant is further included.
本発明に係る感光性組成物の他の特定の局面では、感光性組成物100重量%中の上記第1のシリカの含有量(重量%)をC1とし、感光性組成物100重量%中の上記第2のシリカの含有量(重量%)をC2としたときに、含有量比(C1/C2)が0.1以上、1以下である。 In another specific aspect of the photosensitive composition according to the present invention, the content (% by weight) of the first silica in 100% by weight of the photosensitive composition is C1, and the amount of the photosensitive composition in 100% by weight of the photosensitive composition is When the content (% by weight) of the second silica is C2, the content ratio (C1 / C2) is 0.1 or more and 1 or less.
本発明に係る感光性組成物は、ソルダーレジスト組成物として好適に用いられる。本発明に係る感光性組成物は、ソルダーレジスト組成物であることが好ましい。 The photosensitive composition according to the present invention is suitably used as a solder resist composition. The photosensitive composition according to the present invention is preferably a solder resist composition.
本発明に係るプリント配線板は、回路を表面に有するプリント配線板本体と、該プリント配線板本体の回路が設けられた表面に積層されたソルダーレジスト膜とを備えており、該ソルダーレジスト膜が本発明に従って構成された感光性組成物を用いて形成されている。 The printed wiring board according to the present invention includes a printed wiring board main body having a circuit on the surface, and a solder resist film laminated on the surface of the printed wiring board main body on which the circuit is provided. It is formed using a photosensitive composition constructed according to the present invention.
本発明に係る感光性組成物は、カルボキシル基を有する重合性重合体と、光重合開始剤と、酸化チタンと、一次粒径が5nm以上、100nm以下である第1のシリカと、一次粒径が0.5μm以上、10μm以下である第2のシリカと、ポリジメチルシロキサンとを含み、更に感光性組成物における上記粘度比(η1/η10)が1.1以上であるので、本発明に係る感光性組成物が塗工対象部材上に塗工されたときに、消泡性を高めることができ、かつハジキ特性を良好にすることができる。 The photosensitive composition according to the present invention includes a polymerizable polymer having a carboxyl group, a photopolymerization initiator, titanium oxide, a first silica having a primary particle size of 5 nm to 100 nm, and a primary particle size. The second silica having a viscosity of 0.5 μm or more and 10 μm or less and polydimethylsiloxane, and the viscosity ratio (η1 / η10) in the photosensitive composition is 1.1 or more, When the photosensitive composition is coated on the coating target member, the defoaming property can be improved and the repelling property can be improved.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明に係る感光性組成物は、カルボキシル基を有する重合性重合体(A)と、光重合開始剤(B)と、酸化チタン(C)と、第1のシリカ(D1)と、第2のシリカ(D2)と、ポリジメチルシロキサン(E)とを含む。上記第1のシリカ(D1)の一次粒径は5nm以上、100nm以下である。上記第2のシリカ(D2)の一次粒径は0.5μm以上、10μm以下である。本発明に係る感光性組成物のせん断速度1rpmにおける25℃での粘度(mPa・s)をη1とし、せん断速度10rpmにおける25℃での粘度(mPa・s)をη10としたときに、本発明に係る感光性組成物における粘度比(η1/η10)は1.1以上である。 The photosensitive composition according to the present invention includes a polymerizable polymer (A) having a carboxyl group, a photopolymerization initiator (B), titanium oxide (C), first silica (D1), and second. Silica (D2) and polydimethylsiloxane (E). The primary particle diameter of the first silica (D1) is 5 nm or more and 100 nm or less. The primary particle diameter of the second silica (D2) is 0.5 μm or more and 10 μm or less. When the viscosity (mPa · s) at 25 ° C. at a shear rate of 1 rpm of the photosensitive composition according to the present invention is η1, and the viscosity (mPa · s) at 25 ° C. at a shear rate of 10 rpm is η10, In the photosensitive composition according to the present invention, the viscosity ratio (η1 / η10) is 1.1 or more.
本発明に係る感光性組成物における上記構成の採用により、基板などの塗工対象部材上に感光性組成物を塗工したときに、感光性組成物の消泡性が良好になる。この結果、本発明に係る感光性組成物により形成されたレジスト膜などの硬化物膜中に、泡が含まれ難くなり、かつボイドが生じ難くなる。この結果、本発明に係る感光性組成物を用いたプリント配線板などの各種の電子部品の信頼性を高めることができる。 By adopting the above-described configuration in the photosensitive composition according to the present invention, the defoaming property of the photosensitive composition is improved when the photosensitive composition is applied onto a coating target member such as a substrate. As a result, the hardened film such as a resist film formed by the photosensitive composition according to the present invention is less likely to contain bubbles and less likely to generate voids. As a result, the reliability of various electronic components such as a printed wiring board using the photosensitive composition according to the present invention can be enhanced.
さらに、本発明に係る感光性組成物における上記構成の採用により、基板などの塗工対象部材上に感光性組成物を塗工したときに、感光性組成物のハジキが生じ難くなる。この結果、本発明に係る感光性組成物により形成されたレジスト膜などの硬化物膜が、意図しない領域に配置され難くなる。このため、本発明に係る感光性組成物を用いたプリント配線板等の電子部品の信頼性を高めることができる。 Furthermore, the adoption of the above-described configuration in the photosensitive composition according to the present invention makes it difficult for the photosensitive composition to be repelled when the photosensitive composition is applied onto a coating target member such as a substrate. As a result, a cured film such as a resist film formed from the photosensitive composition according to the present invention is difficult to be disposed in an unintended region. For this reason, the reliability of electronic components, such as a printed wiring board using the photosensitive composition concerning this invention, can be improved.
上記粘度比(η1/η10)の上限は特に限定されないが、上記粘度比(η1/η10)は好ましくは5以下である。 The upper limit of the viscosity ratio (η1 / η10) is not particularly limited, but the viscosity ratio (η1 / η10) is preferably 5 or less.
以下、本発明に係る感光性組成物に含まれている各成分の詳細を説明する。 Hereinafter, the detail of each component contained in the photosensitive composition concerning this invention is demonstrated.
(重合性重合体(A))
上記重合性重合体(A)はカルボキシル基を有する。カルボキシル基を有する重合性重合体(A)は重合性を有し、重合可能である。上記重合性重合体(A)がカルボキシル基を有することで、感光性組成物の現像性が良好になる。上記重合性重合体(A)としては、例えば、カルボキシル基を有するアクリル樹脂、カルボキシル基を有するエポキシ樹脂及びカルボキシル基を有するオレフィン樹脂が挙げられる。なお、「樹脂」は、固形樹脂に限定されず、液状樹脂及びオリゴマーも含む。
(Polymerizable polymer (A))
The polymerizable polymer (A) has a carboxyl group. The polymerizable polymer (A) having a carboxyl group has polymerizability and can be polymerized. When the polymerizable polymer (A) has a carboxyl group, the developability of the photosensitive composition is improved. Examples of the polymerizable polymer (A) include an acrylic resin having a carboxyl group, an epoxy resin having a carboxyl group, and an olefin resin having a carboxyl group. The “resin” is not limited to a solid resin, and includes a liquid resin and an oligomer.
上記重合性重合体(A)は、下記のカルボキシル基含有樹脂(a)〜(e)であることが好ましい。 The polymerizable polymer (A) is preferably the following carboxyl group-containing resins (a) to (e).
(a)不飽和カルボン酸と重合性不飽和二重結合を有する化合物との共重合によって得られるカルボキシル基含有樹脂 (A) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having a polymerizable unsaturated double bond
(b)カルボキシル基含有(メタ)アクリル共重合樹脂(b1)と、1分子中にオキシラン環及びエチレン性重合性不飽和二重結合を有する化合物(b2)との反応により得られるカルボキシル基含有樹脂 (B) A carboxyl group-containing resin obtained by a reaction between a carboxyl group-containing (meth) acrylic copolymer resin (b1) and a compound (b2) having an oxirane ring and an ethylenically polymerizable unsaturated double bond in one molecule.
(c)1分子中にそれぞれ1個のエポキシ基及び重合性不飽和二重結合を有する化合物と、重合性不飽和二重結合を有する化合物との共重合体に、不飽和モノカルボン酸を反応させた後、生成した反応物の第2級の水酸基に飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂 (C) Reaction of an unsaturated monocarboxylic acid with a copolymer of a compound having one epoxy group and a polymerizable unsaturated double bond in each molecule and a compound having a polymerizable unsaturated double bond A carboxyl group-containing resin obtained by reacting the secondary hydroxyl group of the resulting reaction product with a saturated or unsaturated polybasic acid anhydride
(d)水酸基含有ポリマーに、飽和又は不飽和多塩基酸無水物を反応させた後、生成したカルボキシル基を有するポリマーに、1分子中にそれぞれ1個のエポキシ基及び重合性不飽和二重結合を有する化合物を反応させて得られる水酸基及びカルボキシル基含有樹脂 (D) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, the resulting polymer having a carboxyl group has one epoxy group and one polymerizable unsaturated double bond in each molecule. Hydroxyl and carboxyl group-containing resin obtained by reacting a compound having
(e)芳香環を有するエポキシ化合物と飽和多塩基酸無水物又は不飽和多塩基酸無水物を反応させて得られる樹脂、又は芳香環を有するエポキシ化合物と不飽和二重結合を少なくとも1つ有するカルボキシル基含有化合物とを反応させた後、飽和多塩基酸無水物又は不飽和多塩基酸無水物をさらに反応させて得られる樹脂 (E) A resin obtained by reacting an epoxy compound having an aromatic ring with a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride, or an epoxy compound having an aromatic ring and at least one unsaturated double bond Resin obtained by further reacting with saturated polybasic acid anhydride or unsaturated polybasic acid anhydride after reacting with carboxyl group-containing compound
感光性組成物100重量%中、上記カルボキシル基を有する重合性重合体(A)の含有量は、好ましくは5重量%以上、より好ましくは10重量%以上、好ましくは50重量%以下、より好ましくは40重量%以下である。上記重合性重合体(A)の含有量が上記下限以上及び上記上限以下であると、感光性組成物の硬化性が良好になる。 In 100% by weight of the photosensitive composition, the content of the polymerizable polymer (A) having a carboxyl group is preferably 5% by weight or more, more preferably 10% by weight or more, and preferably 50% by weight or less. Is 40% by weight or less. When the content of the polymerizable polymer (A) is not less than the above lower limit and not more than the above upper limit, the curability of the photosensitive composition is improved.
(光重合開始剤(B))
本発明に係る感光性組成物は、光重合開始剤(B)を含むので、光の照射により感光性組成物を硬化させることができる。光重合開始剤(B)は特に限定されない。光重合開始剤(B)は、1種のみが用いられてもよく、2種以上が併用されてもよい。
(Photopolymerization initiator (B))
Since the photosensitive composition concerning this invention contains a photoinitiator (B), it can harden a photosensitive composition by irradiation of light. The photopolymerization initiator (B) is not particularly limited. As for a photoinitiator (B), only 1 type may be used and 2 or more types may be used together.
上記光重合開始剤(B)としては、例えば、アシルフォスフィンオキサイド、ハロメチル化トリアジン、ハロメチル化オキサジアゾール、イミダゾール、ベンゾイン、ベンゾインアルキルエーテル、アントラキノン、ベンズアンスロン、ベンゾフェノン、アセトフェノン、チオキサントン、安息香酸エステル、アクリジン、フェナジン、チタノセン、α−アミノアルキルフェノン、オキシム、及びこれらの誘導体が挙げられる。上記光重合開始剤(B)は、1種のみが用いられてもよく、2種以上が併用されてもよい。 Examples of the photopolymerization initiator (B) include acylphosphine oxide, halomethylated triazine, halomethylated oxadiazole, imidazole, benzoin, benzoin alkyl ether, anthraquinone, benzanthrone, benzophenone, acetophenone, thioxanthone, and benzoic acid ester. , Acridine, phenazine, titanocene, α-aminoalkylphenone, oxime, and derivatives thereof. As for the said photoinitiator (B), only 1 type may be used and 2 or more types may be used together.
上記カルボキシル基を有する重合性重合体(A)100重量部に対して、上記光重合開始剤(B)の含有量は好ましくは0.1重量部以上、より好ましくは1重量部以上、好ましくは30重量部以下、より好ましくは15重量部以下である。上記光重合開始剤(B)の含有量が上記下限以上及び上記上限以下であると、感光性組成物の感光性をより一層高めることができる。 The content of the photopolymerization initiator (B) is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. 30 parts by weight or less, more preferably 15 parts by weight or less. When the content of the photopolymerization initiator (B) is not less than the above lower limit and not more than the above upper limit, the photosensitivity of the photosensitive composition can be further enhanced.
(酸化チタン(C))
本発明に係る感光性組成物は、酸化チタンを含むので、反射率が高いレジスト膜などの硬化物膜を形成できる。本発明に係る感光性組成物に含まれている酸化チタン(C)は特に限定されない。酸化チタン(C)は、1種のみが用いられてもよく、2種以上が併用されてもよい。
(Titanium oxide (C))
Since the photosensitive composition according to the present invention contains titanium oxide, a cured product film such as a resist film having a high reflectance can be formed. The titanium oxide (C) contained in the photosensitive composition according to the present invention is not particularly limited. As for titanium oxide (C), only 1 type may be used and 2 or more types may be used together.
酸化チタン(C)を用いることによって、酸化チタン(C)以外の他の無機フィラーを用いた場合と比較して、反射率が高いレジスト膜を形成できる。 By using titanium oxide (C), it is possible to form a resist film having a high reflectance as compared with the case of using an inorganic filler other than titanium oxide (C).
上記酸化チタン(C)は、ルチル型酸化チタン又はアナターゼ型酸化チタンであることが好ましい。ルチル型酸化チタンの使用により、耐熱黄変性により一層優れたレジスト膜を形成できる。上記アナターゼ型酸化チタンは、ルチル型酸化チタンよりも、硬度が低い。このため、アナターゼ型酸化チタンの使用により、レジスト膜の加工性を高めることができる。 The titanium oxide (C) is preferably rutile titanium oxide or anatase titanium oxide. By using rutile type titanium oxide, a more excellent resist film can be formed by heat-resistant yellowing. The anatase type titanium oxide has a lower hardness than the rutile type titanium oxide. For this reason, the use of anatase-type titanium oxide can improve the processability of the resist film.
上記酸化チタン(C)は、ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンを含むことが好ましい。上記酸化チタン(C)100重量%中、上記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンの含有量は好ましくは10重量%以上、より好ましくは30重量%以上、好ましくは100重量%以下である。上記酸化チタン(C)の全量が、上記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンであってもよい。上記ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンの使用により、レジスト膜の耐熱黄変性をより一層高めることができる。 It is preferable that the said titanium oxide (C) contains the rutile type titanium oxide surface-treated with the silicon oxide or the silicone compound. In 100% by weight of the titanium oxide (C), the content of the rutile titanium oxide surface-treated with the silicon oxide or the silicone compound is preferably 10% by weight or more, more preferably 30% by weight or more, preferably 100% by weight. % Or less. The total amount of the titanium oxide (C) may be rutile titanium oxide surface-treated with the silicon oxide or the silicone compound. By using rutile type titanium oxide surface-treated with the silicon oxide or silicone compound, the heat-resistant yellowing of the resist film can be further enhanced.
ケイ素酸化物又はシリコーン化合物により表面処理されたルチル型酸化チタンとしては、例えば、ルチル塩素法酸化チタンである石原産業社製の品番:CR−90や、ルチル硫酸法酸化チタンである石原産業社製の品番:R−550等が挙げられる。 Examples of the rutile-type titanium oxide surface-treated with a silicon oxide or a silicone compound include, for example, a product number: CR-90 manufactured by Ishihara Sangyo Co., Ltd., which is a rutile chlorine-based titanium oxide, and a product manufactured by Ishihara Sangyo Co., Ltd., which is a rutile sulfate titanium oxide Product number: R-550 etc. are mentioned.
本発明に係る感光性組成物100重量%中、酸化チタン(C)の含有量は、好ましくは3重量%以上、より好ましくは10重量%以上、更に好ましくは15重量%以上、好ましくは80重量%以下、より好ましくは75重量%以下、更に好ましくは70重量%以下である。酸化チタン(C)の含有量が上記下限以上及び上記上限以下であると、レジスト膜が高温に晒されたときに、黄変し難くなる。さらに、塗工に適した粘度を有する感光性組成物を容易に調製できる。 In 100% by weight of the photosensitive composition according to the present invention, the content of titanium oxide (C) is preferably 3% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, preferably 80% by weight. % Or less, more preferably 75% by weight or less, and still more preferably 70% by weight or less. When the content of titanium oxide (C) is not less than the above lower limit and not more than the above upper limit, it is difficult to yellow when the resist film is exposed to a high temperature. Furthermore, a photosensitive composition having a viscosity suitable for coating can be easily prepared.
(シリカ(D))
本発明に係る感光性組成物は、シリカ(D)として、第1のシリカ(D1)と、第2のシリカ(D2)とを含む。上記第1のシリカ(D1)の一次粒径は5nm以上、100nm以下である。上記第2のシリカ(D2)の一次粒径は0.5μm以上、10μm以下である。上記第1,第2のシリカ(D1),(D2)はいずれも、シリカ粒子である。上記第1,第2のシリカ(D1),(D2)は、後述するポリジメチルシロキサン(E)とは異なる。本発明に係る感光性組成物では、上記第1,第2のシリカ(D1),(D2)は、上記ポリジメチルシロキサン(E)とは別に配合されている。
(Silica (D))
The photosensitive composition concerning this invention contains the 1st silica (D1) and the 2nd silica (D2) as a silica (D). The primary particle diameter of the first silica (D1) is 5 nm or more and 100 nm or less. The primary particle diameter of the second silica (D2) is 0.5 μm or more and 10 μm or less. The first and second silicas (D1) and (D2) are both silica particles. The first and second silicas (D1) and (D2) are different from polydimethylsiloxane (E) described later. In the photosensitive composition according to the present invention, the first and second silicas (D1) and (D2) are blended separately from the polydimethylsiloxane (E).
上記第1,第2のシリカ(D1),(D2)の一次粒径は、レーザー回折法を用いて、粉体粒度を測定することにより測定された値である。 The primary particle diameters of the first and second silicas (D1) and (D2) are values measured by measuring the powder particle size using a laser diffraction method.
特定の一次粒径を有する上記第1,第2のシリカ(D1),(D2)の双方を用いることは、感光性組成物の消泡性及びハジキ特性の向上に大きく寄与する。また、粒子径が比較的小さい上記第1のシリカ(D1)を用いることで、上記粘度比(η1/η10)を1.1以上にすることが容易になる。 The use of both the first and second silicas (D1) and (D2) having a specific primary particle size greatly contributes to the improvement of defoaming properties and repelling properties of the photosensitive composition. Moreover, it becomes easy to make the said viscosity ratio ((eta) 1 / (eta) 10) 1.1 or more by using the said 1st silica (D1) with a comparatively small particle diameter.
本発明に係る感光性組成物100重量%中、上記第1,第2のシリカ(D1),(D2)の合計の含有量は、好ましくは3重量%以上、より好ましくは5重量%以上、好ましくは50重量%以下、より好ましくは40重量%以下である。上記第1,第2のシリカ(D1),(D2)の合計の含有量が上記下限以上及び上記上限以下であると、感光性組成物の消泡性及びハジキ特性がより一層良好になる。 In 100% by weight of the photosensitive composition according to the present invention, the total content of the first and second silicas (D1) and (D2) is preferably 3% by weight or more, more preferably 5% by weight or more, Preferably it is 50 weight% or less, More preferably, it is 40 weight% or less. When the total content of the first and second silicas (D1) and (D2) is not less than the above lower limit and not more than the above upper limit, the defoaming property and repelling properties of the photosensitive composition are further improved.
上記感光性組成物100重量%中の上記第1のシリカ(D1)の含有量(重量%)をC1とし、上記感光性組成物100重量%中の上記第2のシリカ(D2)の含有量(重量%)をC2としたときに、含有量比(C1/C2)は好ましくは0.1以上、好ましくは1以下である。上記含有量比(C1/C2)が上記下限以上及び上記上限以下であると、感光性組成物の消泡性及びハジキ特性がより一層良好になる。 The content (% by weight) of the first silica (D1) in 100% by weight of the photosensitive composition is C1, and the content of the second silica (D2) in 100% by weight of the photosensitive composition. When (wt%) is C2, the content ratio (C1 / C2) is preferably 0.1 or more, and preferably 1 or less. When the content ratio (C1 / C2) is not less than the above lower limit and not more than the above upper limit, the defoaming property and repelling properties of the photosensitive composition are further improved.
(ポリジメチルシロキサン(E))
本発明に係る感光性組成物が、ポリジメチルシロキサン(E)を含むことにより、感光性組成物の消泡性及びハジキ特性が良好になる。上記ポリジメチルシロキサン(E)は特に限定されない。上記ポリジメチルシロキサン(E)は、上記第1,第2のシリカ(D1),(D2)とは異なる。本発明に係る感光性組成物では、上記ポリジメチルシロキサン(E)は、上記第1,第2のシリカ(D1),(D2)とは別に配合されている。上記ポリジメチルシロキサン(E)は、1種のみが用いられてもよく、2種以上が併用されてもよい。
(Polydimethylsiloxane (E))
When the photosensitive composition which concerns on this invention contains polydimethylsiloxane (E), the defoaming property and repelling property of a photosensitive composition become favorable. The polydimethylsiloxane (E) is not particularly limited. The polydimethylsiloxane (E) is different from the first and second silicas (D1) and (D2). In the photosensitive composition according to the present invention, the polydimethylsiloxane (E) is blended separately from the first and second silicas (D1) and (D2). As for the said polydimethylsiloxane (E), only 1 type may be used and 2 or more types may be used together.
本発明に係る感光性組成物100重量%中、上記ポリジメチルシロキサン(E)の含有量は、好ましくは0.1重量%以上、より好ましくは0.3重量%以上、好ましくは5重量%以下、より好ましくは3重量%以下である。上記ポリジメチルシロキサン(E)の含有量が上記下限以上及び上記上限以下であると、感光性組成物の消泡性及びハジキ特性がより一層良好になる。 In 100% by weight of the photosensitive composition according to the present invention, the content of the polydimethylsiloxane (E) is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, preferably 5% by weight or less. More preferably, it is 3% by weight or less. When the content of the polydimethylsiloxane (E) is not less than the above lower limit and not more than the above upper limit, the defoaming property and repelling properties of the photosensitive composition are further improved.
(他の成分)
硬化性をより一層高めるために、本発明に係る感光性組成物は、カルボキシル基を有する重合性重合体(A)とは異なる成分として、重合性単量体を含むことが好ましい。本発明に係る感光性組成物は、カルボキシル基を有する重合性重合体(A)と重合性単量体との双方を含むことが好ましい。上記重合性単量体は重合性を有し、重合可能である。上記重合性単量体は特に限定されない。上記重合性単量体は、1種のみが用いられてもよく、2種以上が併用されてもよい。
(Other ingredients)
In order to further improve the curability, the photosensitive composition according to the present invention preferably contains a polymerizable monomer as a component different from the polymerizable polymer (A) having a carboxyl group. The photosensitive composition according to the present invention preferably contains both a polymerizable polymer (A) having a carboxyl group and a polymerizable monomer. The polymerizable monomer is polymerizable and can be polymerized. The polymerizable monomer is not particularly limited. As for the said polymerizable monomer, only 1 type may be used and 2 or more types may be used together.
上記重合性単量体における重合性不飽和基としては、例えば、(メタ)アクリロイル基及びビニルエーテル基などの重合性不飽和二重結合を有する官能基が挙げられる。中でも、レジスト膜の架橋密度を高めることができるため、(メタ)アクリロイル基が好ましい。 Examples of the polymerizable unsaturated group in the polymerizable monomer include functional groups having a polymerizable unsaturated double bond such as a (meth) acryloyl group and a vinyl ether group. Among these, a (meth) acryloyl group is preferable because the crosslinking density of the resist film can be increased.
上記重合性不飽和基含有単量体は、(メタ)アクリロイル基を有する化合物であることが好ましい。上記(メタ)アクリロイル基を有する化合物としては、エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコールもしくはプロピレングリコールなどのグリコールのジ(メタ)アクリレート変性物や、多価アルコール、多価アルコールのエチレンオキサイド付加物もしくは多価アルコールのプロピレンオキサイド付加物の多価(メタ)アクリレート変性物や、フェノール、フェノールのエチレンオキサイド付加物もしくはフェノールのプロピレンオキサイド付加物の(メタ)アクリレート変性物や、グルセリンジグリシジルエーテルもしくはトリメチロールプロパントリグリシジルエーテルなどのグリシジルエーテルの(メタ)アクリレート変性物や、メラミン(メタ)アクリレートが挙げられる。 The polymerizable unsaturated group-containing monomer is preferably a compound having a (meth) acryloyl group. Examples of the compound having the (meth) acryloyl group include a di (meth) acrylate modified product of glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol or propylene glycol, polyhydric alcohol, and ethylene oxide adduct of polyhydric alcohol. Or a polyhydric (meth) acrylate modified product of a propylene oxide adduct of a polyhydric alcohol, a (meth) acrylate modified product of phenol, an ethylene oxide adduct of phenol or a propylene oxide adduct of phenol, glycerin diglycidyl ether or (Meth) acrylate modified products of glycidyl ether such as trimethylolpropane triglycidyl ether and melamine (meth) acrylate are exemplified.
上記多価アルコールとしては、例えば、ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール及びトリス−ヒドロキシエチルイソシアヌレートが挙げられる。上記フェノールの(メタ)アクリレートとしては、例えば、フェノキシ(メタ)アクリレート及びビスフェノールAのジ(メタ)アクリレート変性物が挙げられる。 Examples of the polyhydric alcohol include hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate. Examples of the (meth) acrylate of phenol include phenoxy (meth) acrylate and di (meth) acrylate modified products of bisphenol A.
「(メタ)アクリロイル」は、アクリロイルとメタクリロイルとを意味する。「(メタ)アクリル」は、アクリルとメタクリルとを意味する。「(メタ)アクリレート」は、アクリレートとメタクリレートとを意味する。 “(Meth) acryloyl” means acryloyl and methacryloyl. “(Meth) acryl” means acrylic and methacrylic. “(Meth) acrylate” means acrylate and methacrylate.
上記重合性単量体が含まれる場合には、該重合性単量体と上記カルボキシル基を有する重合性重合体(A)との合計100重量%中、上記重合性単量体の含有量は好ましくは5重量%以上、好ましくは50重量%以下である。上記重合性単量体の含有量が上記下限以上及び上記上限以下であると、感光性組成物を十分に硬化させることができる。さらに、レジスト膜の架橋密度が適度になり、十分な解像度を得ることができ、かつレジスト膜が黄変しにくくなる。 When the polymerizable monomer is contained, the content of the polymerizable monomer is 100% by weight in total of the polymerizable monomer and the polymerizable polymer (A) having a carboxyl group. Preferably it is 5 weight% or more, Preferably it is 50 weight% or less. A photosensitive composition can fully be hardened as content of the said polymerizable monomer is more than the said minimum and below the said upper limit. Furthermore, the crosslink density of the resist film becomes appropriate, sufficient resolution can be obtained, and the resist film is hardly yellowed.
レジスト膜の切り出し加工性を高めるために、感光性組成物は、環状エーテル骨格を有する化合物を含むことが好ましい。また、上記環状エーテル骨格を有する化合物の使用により、感光性組成物の硬化性も良好になる。 In order to improve the cutting processability of the resist film, the photosensitive composition preferably contains a compound having a cyclic ether skeleton. Further, the use of the compound having the cyclic ether skeleton also improves the curability of the photosensitive composition.
上記環状エーテル骨格を有する化合物としては、例えば、ビスフェノールS型エポキシ樹脂、ジグリシジルフタレート樹脂、トリグリシジルイソシアヌレートなどの複素環式エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂、テトラグリシジルキシレノイルエタン樹脂、ビスフェノールA型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールF型樹脂、臭素化ビスフェノールA型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ビスフェノールAのノボラック型エポキシ樹脂、キレート型エポキシ樹脂、グリオキザール型エポキシ樹脂、アミノ基含有エポキシ樹脂、ゴム変性エポキシ樹脂、ジシクロペンタジエンフェノリック型エポキシ樹脂、シリコーン変性エポキシ樹脂及びε−カプロラクトン変性エポキシ樹脂が挙げられる。上記環状エーテル骨格を有する化合物は、1種のみが用いられてもよく、2種以上が併用されてもよい。 Examples of the compound having a cyclic ether skeleton include heterocyclic epoxy resins such as bisphenol S type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate, bixylenol type epoxy resin, biphenol type epoxy resin, and tetraglycidyl xyleno. Irethane resin, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type resin, brominated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic Type epoxy resins, silicone-modified epoxy resin and ε- caprolactone-modified epoxy resin. As for the compound which has the said cyclic ether frame | skeleton, only 1 type may be used and 2 or more types may be used together.
環状エーテル骨格を有する化合物は、重合性重合体(A)が有するカルボキシル基と反応して、感光性組成物を硬化させるように作用する。 The compound having a cyclic ether skeleton reacts with the carboxyl group of the polymerizable polymer (A) to act to cure the photosensitive composition.
重合性重合体(A)100重量部に対して、上記環状エーテル骨格を有する化合物の含有量は好ましくは0.1重量部以上、より好ましくは1重量部以上、好ましくは50重量部以下、より好ましくは30重量部以下である。上記環状エーテル骨格を有する化合物の含有量が上記下限以上及び上記上限以下であると、レジスト膜の電気絶縁性をより一層高めることができる。 The content of the compound having a cyclic ether skeleton is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 50 parts by weight or less, based on 100 parts by weight of the polymerizable polymer (A). The amount is preferably 30 parts by weight or less. When the content of the compound having a cyclic ether skeleton is not less than the above lower limit and not more than the above upper limit, the electrical insulation of the resist film can be further enhanced.
高温に晒されたときにソルダーレジスト膜が黄変するおそれを小さくするために、本発明に係る感光性組成物は、酸化防止剤を含有することが好ましい。上記酸化防止剤は、ルイス塩基性部位を有することが好ましい。レジスト膜の黄変をより一層抑制する観点からは、上記酸化防止剤は、フェノール系酸化防止剤、リン系酸化防止剤及びアミン系酸化防止剤からなる群から選択された少なくとも1種であることが好ましい。レジスト膜の黄変をさらに一層抑制する観点からは、上記酸化防止剤は、フェノール系酸化防止剤であることが好ましい。すなわち、本発明に係る感光性組成物は、フェノール系酸化防止剤を含むことが好ましい。また、上記酸化防止剤として、フェノール系酸化防止剤を用いた場合には、フェノール系酸化防止剤以外の酸化防止剤を用いた場合と比較して、感光性組成物の消泡性及びハジキ特性の双方がより一層良好になる。 In order to reduce the risk of yellowing of the solder resist film when exposed to high temperatures, the photosensitive composition according to the present invention preferably contains an antioxidant. The antioxidant preferably has a Lewis basic site. From the viewpoint of further suppressing yellowing of the resist film, the antioxidant is at least one selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. Is preferred. From the viewpoint of further suppressing the yellowing of the resist film, the antioxidant is preferably a phenolic antioxidant. That is, the photosensitive composition according to the present invention preferably contains a phenolic antioxidant. In addition, when a phenolic antioxidant is used as the antioxidant, the antifoaming property and repellency characteristics of the photosensitive composition are compared with the case of using an antioxidant other than the phenolic antioxidant. Both are even better.
上記フェノール系酸化防止剤の市販品としては、IRGANOX 1010、IRGANOX 1035、IRGANOX 1076、IRGANOX 1135、IRGANOX 245、IRGANOX 259、及びIRGANOX 295(以上、いずれもチバジャパン社製)、アデカスタブ AO−30、アデカスタブ AO−40、アデカスタブ AO−50、アデカスタブ AO−60、アデカスタブ AO−70、アデカスタブ AO−80、アデカスタブ AO−90、及びアデカスタブ AO−330(以上、いずれもADEKA社製)、Sumilizer GA−80、Sumilizer MDP−S、Sumilizer BBM−S、Sumilizer GM、Sumilizer GS(F)、及びSumilizer GP(以上、いずれも住友化学工業社製)、HOSTANOX O10、HOSTANOX O16、HOSTANOX O14、及びHOSTANOX O3(以上、いずれもクラリアント社製)、アンテージ BHT、アンテージ W−300、アンテージ W−400、及びアンテージ W500(以上、いずれも川口化学工業社製)、並びにSEENOX 224M、及びSEENOX 326M(以上、いずれもシプロ化成社製)等が挙げられる。 Examples of commercially available phenolic antioxidants include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, and IRGANOX 295 (all of which are manufactured by Ciba Japan), ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, and ADK STAB AO-330 (all of which are manufactured by ADEKA), Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and Sumilizer GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, and HOSTANOX O3 (all of which are manufactured by Clariant), Antage BHT, Antage W-300, Antage W-400, and Antage W500 (all are manufactured by Kawaguchi Chemical Industry Co., Ltd.), SEENOX 224M, and SENOX 326M (all are manufactured by Sipro Kasei Co., Ltd.).
上記リン系酸化防止剤としては、シクロヘキシルフォスフィン及びトリフェニルフォスフィン等が挙げられる。上記リン系酸化防止剤の市販品としては、アデアスタブ PEP−4C、アデアスタブ PEP−8、アデアスタブ PEP−24G、アデアスタブ PEP−36、アデアスタブ HP−10、アデアスタブ 2112、アデアスタブ 260、アデアスタブ 522A、アデアスタブ 1178、アデアスタブ 1500、アデアスタブ C、アデアスタブ 135A、アデアスタブ 3010、及びアデアスタブ TPP(以上、いずれもADEKA社製)、サンドスタブ P−EPQ、及びホスタノックス PAR24(以上、いずれもクラリアント社製)、並びにJP−312L、JP−318−0、JPM−308、JPM−313、JPP−613M、JPP−31、JPP−2000PT、及びJPH−3800(以上、いずれも城北化学工業社製)等が挙げられる。 Examples of the phosphorus antioxidant include cyclohexylphosphine and triphenylphosphine. Commercially available products of the above phosphorus antioxidants include Adeastab PEP-4C, Adeastab PEP-8, Adeastab PEP-24G, Adeastab PEP-36, Adeastab HP-10, Adeastab 2112, Adeastab 260, Adeastab 522A, Adeastab 1178, Adeastab 1500, Adeastab C, Adeastab 135A, Adeastab 3010, and Adeastab TPP (all of which are manufactured by ADEKA), Sandstub P-EPQ, and Hostanox PAR24 (all of which are manufactured by Clariant), and JP-312L, JP -318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT, and JPH-3800 (all of which are Johoku Manabu Kogyo Co., Ltd.), and the like.
上記アミン系酸化防止剤としては、トリエチルアミン、ジシアンジアミド、メラミン、エチルジアミノ−S−トリアジン、2,4−ジアミノ−S−トリアジン、2,4−ジアミノ−6−トリル−S−トリアジン、2,4−ジアミノ−6−キシリル−S−トリアジン及び第四級アンモニウム塩誘導体等が挙げられる。 Examples of the amine antioxidant include triethylamine, dicyandiamide, melamine, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-tolyl-S-triazine, 2,4- And diamino-6-xylyl-S-triazine and quaternary ammonium salt derivatives.
上記カルボキシル基を有する重合性重合体(A)100重量部に対して、上記酸化防止剤の含有量は好ましくは0.1重量部以上、より好ましくは5重量部以上、好ましくは30重量部以下、より好ましくは15重量部以下である。上記酸化防止剤の含有量が上記下限以上及び上限以下であると、耐熱黄変性により一層優れたレジスト膜を形成できる。 The content of the antioxidant is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more, and preferably 30 parts by weight or less with respect to 100 parts by weight of the polymerizable polymer (A) having a carboxyl group. More preferably, it is 15 parts by weight or less. When the content of the antioxidant is not less than the above lower limit and not more than the upper limit, a more excellent resist film can be formed by heat yellowing.
本発明に係る感光性組成物は、溶剤を含有してもよい。溶剤の双極子モーメントは1Debye以上であることが好ましい。双極子モーメントが1Debye以上である溶剤の使用により、ポットライフに優れた感光組成物を提供できる。 The photosensitive composition according to the present invention may contain a solvent. The dipole moment of the solvent is preferably 1 Debye or more. By using a solvent having a dipole moment of 1 Debye or more, a photosensitive composition excellent in pot life can be provided.
また、本発明に係る感光性組成物は、着色剤、充填剤、硬化剤、硬化促進剤、離型剤、表面処理剤、難燃剤、粘度調節剤、分散剤、分散助剤、表面改質剤、可塑剤、抗菌剤、防黴剤、レベリング剤、安定剤、カップリング剤、タレ防止剤又は蛍光体等を含んでいてもよい。 The photosensitive composition according to the present invention includes a colorant, a filler, a curing agent, a curing accelerator, a release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a dispersant, a dispersion aid, and a surface modification. An agent, a plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent, or a phosphor may be included.
さらに、本発明に係る感光性組成物は、第1の液と、第2の液とを有し、該第1,第2の液が混合されて用いられる2液混合型の感光性組成物であってもよい。2液混合型の感光性組成物の場合には、使用前に重合又は硬化反応が進行するのを抑制できる。このため、2液それぞれのポットライフを向上できる。また、本発明に係る感光性組成物は、第1の液のみを有する1液型の感光性組成物であってもよい。本発明に係る感光性組成物には、1液型の感光性組成物と2液混合型などの多液混合型の感光性組成物とが含まれる。 Furthermore, the photosensitive composition according to the present invention has a first liquid and a second liquid, and the two-liquid mixed photosensitive composition used by mixing the first and second liquids. It may be. In the case of a two-component mixed photosensitive composition, the progress of polymerization or curing reaction before use can be suppressed. For this reason, the pot life of each of the two liquids can be improved. Further, the photosensitive composition according to the present invention may be a one-component type photosensitive composition having only the first liquid. The photosensitive composition according to the present invention includes a one-component type photosensitive composition and a two-component mixed type photosensitive composition such as a two-component mixed type.
2液混合型の感光性組成物の場合には、重合性重合体(A)と光重合開始剤(B)と酸化チタン(C)と第1のシリカ(D1)と第2のシリカ(D2)とポリジメチルシロキサン(E)とはそれぞれ、上記第1の液及び上記第2の液の内の少なくとも一方に含まれる。また、上記重合性単量体、上記環状エーテル骨格を有する化合物及び上記酸化防止剤が含まれる場合には、上記重合性単量体、上記環状エーテル骨格を有する化合物及び上記酸化防止剤はそれぞれ、上記第1の液及び上記第2の液の内の少なくとも一方に含まれる。 In the case of a two-component mixed photosensitive composition, a polymerizable polymer (A), a photopolymerization initiator (B), titanium oxide (C), first silica (D1), and second silica (D2). ) And polydimethylsiloxane (E) are contained in at least one of the first liquid and the second liquid, respectively. When the polymerizable monomer, the compound having the cyclic ether skeleton, and the antioxidant are included, the polymerizable monomer, the compound having the cyclic ether skeleton, and the antioxidant are respectively It is contained in at least one of the first liquid and the second liquid.
上記第1,第2の液が混合された混合物は、感光性組成物であり、重合性重合体(A)と光重合開始剤(B)と酸化チタン(C)と第1のシリカ(D1)と第2のシリカ(D2)とポリジメチルシロキサン(E)とを含む。 The mixture in which the first and second liquids are mixed is a photosensitive composition, which is a polymerizable polymer (A), a photopolymerization initiator (B), titanium oxide (C), and first silica (D1). ), Second silica (D2), and polydimethylsiloxane (E).
本発明に係る感光性組成物は、例えば、各配合成分を撹拌混合した後、3本ロールにて均一に混合することにより調製できる。 The photosensitive composition according to the present invention can be prepared by, for example, stirring and mixing each compounding component and then uniformly mixing with three rolls.
感光性組成物を硬化させるために用いられる光源としては、紫外線又は可視光線等の活性エネルギー線を発光する照射装置が挙げられる。上記光源としては、例えば、超高圧水銀灯、Deep UV ランプ、高圧水銀灯、低圧水銀灯、メタルハライドランプ及びエキシマレーザーが挙げられる。これらの光源は、感光性組成物の構成成分の感光波長に応じて適宜選択される。光の照射エネルギーは、所望とする膜厚又は感光性組成物の構成成分により適宜選択される。光の照射エネルギーは、一般に、10〜3000mJ/cm2の範囲内である。 Examples of the light source used for curing the photosensitive composition include an irradiation device that emits active energy rays such as ultraviolet rays or visible rays. Examples of the light source include an ultrahigh pressure mercury lamp, a deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and an excimer laser. These light sources are appropriately selected according to the photosensitive wavelength of the constituent components of the photosensitive composition. The irradiation energy of light is appropriately selected depending on the desired film thickness or the constituent components of the photosensitive composition. The irradiation energy of light is generally in the range of 10 to 3000 mJ / cm 2 .
(LEDデバイス)
本発明に係る感光性組成物は、LEDデバイスのレジスト膜を形成するために好適に用いられ、ソルダーレジスト膜を形成するためにより好適に用いられる。本発明に係る感光性組成物は、レジスト組成物であることが好ましく、ソルダーレジスト組成物であることが好ましい。
(LED device)
The photosensitive composition concerning this invention is used suitably in order to form the resist film of an LED device, and is used more suitably in order to form a soldering resist film. The photosensitive composition according to the present invention is preferably a resist composition, and is preferably a solder resist composition.
本発明に係るプリント配線板は、回路を表面に有するプリント配線板本体と、該プリント配線板本体の上記回路が設けられた表面に積層されたソルダーレジスト膜とを備える。該ソルダーレジスト膜が、本発明に係る感光性組成物により形成されている。 The printed wiring board according to the present invention includes a printed wiring board body having a circuit on the surface, and a solder resist film laminated on the surface of the printed wiring board body on which the circuit is provided. The solder resist film is formed of the photosensitive composition according to the present invention.
図1に、本発明の一実施形態に係る感光性組成物を用いて形成されたソルダーレジスト膜を有するLEDデバイスの一例を模式的に部分切欠正面断面図で示す。 In FIG. 1, an example of the LED device which has a soldering resist film formed using the photosensitive composition which concerns on one Embodiment of this invention is typically shown with a partial notch front sectional drawing.
図1に示すLEDデバイス1では、基板2の上面2aに、感光性組成物により形成されたレジスト膜3が積層されている。レジスト膜3は、パターン膜である。よって、基板2の上面2aの一部の領域では、レジスト膜3は形成されていない。レジスト膜3が形成されていない部分の基板2の上面2aには、電極4a,4bが設けられている。基板2は、プリント配線板本体であることが好ましい。
In the
レジスト膜3の上面3aに、LEDチップ7が積層されている。レジスト膜3を介して、基板2上にLEDチップ7が積層されている。LEDチップ7の下面7aの外周縁には、端子8a,8bが設けられている。はんだ9a,9bにより、端子8a,8bが電極4a,4bと電気的に接続されている。この電気的な接続により、LEDチップ7に電力を供給できる。
The LED chip 7 is laminated on the
以下、本発明の具体的な実施例及び比較例を挙げることにより、本発明を明らかにする。本発明は以下の実施例に限定されない。 Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.
実施例及び比較例では、以下の材料1)〜15)を用いた。 In the examples and comparative examples, the following materials 1) to 15) were used.
1)アクリルポリマー1(カルボキシル基を有する重合性重合体、下記合成例1で得られたアクリルポリマー1)
1) Acrylic polymer 1 (polymerizable polymer having a carboxyl group,
(合成例1)
温度計、攪拌機、滴下ロート及び還流冷却器を備えたフラスコに、溶剤であるエチルカルビトールアセテートと、触媒であるアゾビスイソブチロニトリルとを入れ、窒素雰囲気下で80℃に加熱し、メタクリル酸とメチルメタクリレートとを30:70のモル比で混合したモノマーを2時間かけて滴下した。滴下後、1時間攪拌し、温度を120℃に上げた。その後、冷却した。得られた樹脂の全てのモノマー単位の総量のモル量に対するモル比が10となる量のグリシジルアクリレートを加え、触媒として臭化テトラブチルアンモニウムを用い100℃で30時間加熱して、グリシジルアクリレートとカルボキシル基とを付加反応させた。冷却後、フラスコから取り出して、固形分酸価60mgKOH/g、重量平均分子量15000、二重結合当量1000のカルボキシル基含有樹脂を50重量%(不揮発分)含む溶液を得た。以下、この溶液をアクリルポリマー1と呼ぶ。
(Synthesis Example 1)
A flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser is charged with ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst, heated to 80 ° C. in a nitrogen atmosphere, and methacrylic. A monomer in which acid and methyl methacrylate were mixed at a molar ratio of 30:70 was added dropwise over 2 hours. After dropping, the mixture was stirred for 1 hour, and the temperature was raised to 120 ° C. Then it was cooled. Glycidyl acrylate was added in such an amount that the molar ratio of the total amount of all the monomer units of the obtained resin was 10 and then heated at 100 ° C. for 30 hours using tetrabutylammonium bromide as a catalyst. The group was subjected to an addition reaction. After cooling, it was taken out from the flask to obtain a solution containing 50 wt% (nonvolatile content) of a carboxyl group-containing resin having a solid content acid value of 60 mg KOH / g, a weight average molecular weight of 15000, and a double bond equivalent of 1000. Hereinafter, this solution is referred to as
2)DPHA(アクリルモノマー、ジペンタエリスリトールヘキサアクリレート、比重1.1)
3)TPO(光ラジカル発生剤である光重合開始剤、BASFジャパン社製)
4)828(ビスフェノールA型エポキシ樹脂、三菱化学社製、比重1.2)
5)CR−50(酸化チタン、石原産業社製、塩素法により製造されたルチル型酸化チタン)
6)R202(シリカ、日本アエロジル社製、一次粒径14nm)
7)RX50(シリカ、日本アエロジル社製、一次粒径40nm)
8)5X(シリカ、龍森社製、一次粒径1.5μm)
9)VX−S(シリカ、龍森社製、一次粒径4μm)
10)AA(シリカ、龍森社製、一次粒径6μm)
11)KF−96(ポリジメチルシロキサン、信越化学工業社製)
12)KS−7710(コンパウンド型シリコーンオイル、ポリジメチルシロキサン、信越化学工業社製)
13)IRGANOX1010(フェノール系酸化防止剤、チバジャパン社製)
14)IRGAFOS168(リン系酸化防止剤、チバジャパン社製)
15)エチルカルビトールアセテート(溶剤、双極子モーメント1Debye以上、比重1.0)
2) DPHA (acrylic monomer, dipentaerythritol hexaacrylate, specific gravity 1.1)
3) TPO (photopolymerization initiator which is a photo radical generator, manufactured by BASF Japan)
4) 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, specific gravity 1.2)
5) CR-50 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd., rutile titanium oxide manufactured by the chlorine method)
6) R202 (silica, manufactured by Nippon Aerosil Co., Ltd., primary particle size: 14 nm)
7) RX50 (silica, manufactured by Nippon Aerosil Co., Ltd., primary particle size 40 nm)
8) 5X (silica, manufactured by Tatsumori, primary particle size 1.5 μm)
9) VX-S (Silica, manufactured by Tatsumori, primary particle size 4 μm)
10) AA (silica, manufactured by Tatsumori, primary particle size 6 μm)
11) KF-96 (polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.)
12) KS-7710 (compound type silicone oil, polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.)
13) IRGANOX 1010 (phenolic antioxidant, manufactured by Ciba Japan)
14) IRGAFOS168 (phosphorus antioxidant, manufactured by Ciba Japan)
15) Ethyl carbitol acetate (solvent,
(実施例1)
合成例1で得られたアクリルポリマー1を15重量部と、DPHA(ジペンタエリスリトールヘキサアクリレート)5重量部と、TPO(光ラジカル発生剤である光重合開始剤、BASFジャパン社製)2重量部と、828(ビスフェノールA型エポキシ樹脂、三菱化学社製)8重量部と、CR−50(酸化チタン、石原産業社製)40重量部と、R202(シリカ、日本アエロジル社製、一次粒径14nm)3重量部と、VX−S(シリカ、龍森社製、一次粒径4μm)15重量部と、KS−7710(コンパウンド型シリコーンオイル、ポリジメチルシロキサン、信越化学工業社製)1重量部と、エチルカルビトールアセテート30重量部とを配合し、混合機(練太郎SP−500、シンキー社製)にて3分間混合した後、3本ロールにて混合し、混合物を得た。その後、SP−500を用いて、得られた混合物を3分間脱泡することにより、感光性組成物であるレジスト材料を得た。
Example 1
15 parts by weight of the
(実施例2〜10及び比較例1〜3)
使用した材料の種類及び配合量を下記の表1に示すように変更したこと以外は、実施例1と同様にして、レジスト材料を得た。
(Examples 2 to 10 and Comparative Examples 1 to 3)
A resist material was obtained in the same manner as in Example 1 except that the type and blending amount of the material used were changed as shown in Table 1 below.
(評価)
(1)粘度
粘度計(東機産業社製「TVE22L」)を用いて、得られたレジスト材料のせん断速度1rpmにおける25℃での粘度η1(mPa・s)と、せん断速度10rpmにおける25℃での粘度をη10(mPa・s)とを測定した。
(Evaluation)
(1) Viscosity Using a viscometer (“TVE22L” manufactured by Toki Sangyo Co., Ltd.), the obtained resist material has a viscosity η1 (mPa · s) at 25 ° C. at a shear rate of 1 rpm and 25 ° C. at a shear rate of 10 rpm. The viscosity of η10 (mPa · s) was measured.
(2)消泡性
表面に銅箔が貼り付けられている100mm×100mmのFR−4基板を用意した。また、得られたレジスト材料を50回手動で攪拌した。撹拌直後のレジスト材料を、上記FR−4基板の銅箔が貼り付けられている面に、スクリーン印刷により塗布して、レジスト材料層を形成した。その後、室温(25℃)で1分間放置した後、印刷された100mm×100mmの領域のレジスト材料層中において、直径0.5mm以上の泡が存在するか否かを目視により観察した。泡の個数に応じて、レジスト材料(感光性組成物)の消泡性を下記の基準で判定した。
(2) Antifoaming property A FR-4 substrate of 100 mm × 100 mm having a copper foil attached to the surface was prepared. The obtained resist material was manually stirred 50 times. The resist material immediately after stirring was applied to the surface of the FR-4 substrate on which the copper foil was attached by screen printing to form a resist material layer. Then, after leaving it to stand at room temperature (25 ° C.) for 1 minute, whether or not bubbles having a diameter of 0.5 mm or more exist in the printed resist material layer in a 100 mm × 100 mm region was visually observed. Depending on the number of bubbles, the defoaming property of the resist material (photosensitive composition) was determined according to the following criteria.
[消泡性の判定基準]
○○:泡が確認されない
○:泡が1〜20個確認された
×:泡が21個以上確認された
[Decision criteria for defoaming]
○○: No bubbles were confirmed ○: 1-20 bubbles were confirmed ×: 21 or more bubbles were confirmed
(3)ハジキ特性
上記(2)消泡性の評価に用いたFR−4基板の銅箔が貼り付けられている面に、離型フィルムであるPETフィルムを貼り付けた。また、得られたレジスト材料を50回手動で攪拌した。撹拌直後のレジスト材料を、上記FR−4基板上のPETフィルム上に、スクリーン印刷により印刷して、レジスト材料層を形成した。印刷後、室温(25℃)で1時間放置し、レジスト材料層のPETフィルムの表面に対するハジキの状態を目視により確認した。すなわち、印刷領域の端縁から、外側に拡がっている場合、又は端縁から外側にレジスト材料の液滴が分離している場合、ハジキが生じているとみなした。このハジキの状態について、上記印刷領域の端縁から外側に拡がっているレジスト材料層の最外側端縁までの距離、又は上記印刷領域の端縁から外側に位置しているレジスト材料液滴までの距離をハジキ距離とした。ハジキ特性を、以下の3段階の基準で判定した。
(3) Repelling property A PET film as a release film was attached to the surface of the FR-4 substrate used for the evaluation of (2) defoaming properties. The obtained resist material was manually stirred 50 times. The resist material immediately after stirring was printed on the PET film on the FR-4 substrate by screen printing to form a resist material layer. After printing, it was allowed to stand at room temperature (25 ° C.) for 1 hour, and the repelling state of the resist material layer on the surface of the PET film was visually confirmed. That is, when the printing area spreads outward from the edge, or when the resist material droplets are separated outward from the edge, it was considered that repelling occurred. For this repellency, the distance from the edge of the printed area to the outermost edge of the resist material layer extending outward, or from the edge of the printed area to the resist material droplet located outside. The distance was defined as a repel distance. The repellency characteristics were determined based on the following three criteria.
[ハジキ特性の判定基準]
○○:ハジキ距離が10mm未満
○:ハジキ距離が10mm以上、20mm未満
×:ハジキ距離が20mm以上
[Criteria for repelling properties]
○○: Repel distance is less than 10 mm ○: Repel distance is 10 mm or more and less than 20 mm ×: Repel distance is 20 mm or more
結果を下記の表1に示す。なお、下記の表1において、粘度比(η1/η10)は、せん断速度1rpmにおける25℃での粘度η1(mPa・s)の、せん断速度10rpmにおける25℃での粘度η10(mPa・s)に対する比を示す。また、下記の表1において、含有量比(C1/C2)は、感光性組成物100重量%中の第1のシリカの含有量(重量%)C1の、感光性組成物100重量%中の第2のシリカの含有量(重量%)C2に対する比を示す。 The results are shown in Table 1 below. In Table 1 below, the viscosity ratio (η1 / η10) is based on the viscosity η1 (mPa · s) at 25 ° C. at a shear rate of 1 rpm and the viscosity η10 (mPa · s) at 25 ° C. at a shear rate of 10 rpm. Indicates the ratio. In Table 1 below, the content ratio (C1 / C2) is the content (% by weight) of the first silica in 100% by weight of the photosensitive composition C1 in 100% by weight of the photosensitive composition. The ratio with respect to content (weight%) C2 of 2nd silica is shown.
1…LEDデバイス
2…基板
2a…上面
3…レジスト膜
3a…上面
4a,4b…電極
7…LEDチップ
7a…下面
8a,8b…端子
9a,9b…はんだ
DESCRIPTION OF
Claims (5)
前記第1のシリカの一次粒径が5nm以上、100nm以下であり、
前記第2のシリカの一次粒径が0.5μm以上、10μm以下であり、
せん断速度1rpmにおける25℃での粘度(mPa・s)をη1とし、せん断速度10rpmにおける25℃での粘度(mPa・s)をη10としたときに、粘度比(η1/η10)が1.1以上である、感光性組成物。 A polymerizable polymer having a carboxyl group, a photopolymerization initiator, titanium oxide, a first silica, a second silica, and polydimethylsiloxane;
The primary particle size of the first silica is 5 nm or more and 100 nm or less,
A primary particle size of the second silica is 0.5 μm or more and 10 μm or less;
When the viscosity (mPa · s) at 25 ° C. at a shear rate of 1 rpm is η1, and the viscosity (mPa · s) at 25 ° C. at a shear rate of 10 rpm is η10, the viscosity ratio (η1 / η10) is 1.1. The photosensitive composition which is above.
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PCT/JP2011/064778 WO2012111183A1 (en) | 2011-02-14 | 2011-06-28 | Photosensitive composition and printed circuit board |
CN201180000962.1A CN102754027B (en) | 2011-02-14 | 2011-06-28 | Photosensitive composition and printed circuit board |
TW100123688A TWI418936B (en) | 2011-02-14 | 2011-07-05 | Photosensitive compositions and printed circuit boards |
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JP6947492B2 (en) * | 2015-03-25 | 2021-10-13 | 積水化学工業株式会社 | Method for manufacturing two-component mixed type first and second liquids and printed wiring board |
KR20160115718A (en) * | 2015-03-25 | 2016-10-06 | 세키스이가가쿠 고교가부시키가이샤 | First liquid and second liquid of two-liquid mixing type, and method for manufacturing printed wiring board |
JP6618829B2 (en) * | 2015-03-25 | 2019-12-11 | 積水化学工業株式会社 | Two-liquid mixed type first and second liquid and method for producing printed wiring board |
KR102625987B1 (en) * | 2015-03-25 | 2024-01-18 | 다이요 홀딩스 가부시키가이샤 | First liquid and second liquid of two-liquid mixing type, and method for manufacturing printed wiring board |
JP6688875B2 (en) * | 2016-03-14 | 2020-04-28 | 富士フイルム株式会社 | Composition, film, cured film, optical sensor and method for manufacturing film |
JP6815507B2 (en) * | 2017-06-29 | 2021-01-20 | 京セラ株式会社 | Circuit board and light emitting device equipped with this |
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US5288589A (en) * | 1992-12-03 | 1994-02-22 | Mckeever Mark R | Aqueous processable, multilayer, photoimageable permanent coatings for printed circuits |
JP2746031B2 (en) * | 1992-12-14 | 1998-04-28 | 松下電工株式会社 | Liquid resist composition |
CN101016402A (en) * | 2003-01-07 | 2007-08-15 | 积水化学工业株式会社 | Curing resin composition, adhesive epoxy resin paste, adhesive epoxy resin sheet, conductive connection paste, conductive connection sheet, and electronic component joined body |
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JP2007310201A (en) * | 2006-05-19 | 2007-11-29 | Kaneka Corp | Photosensitive dry film resist and printed wiring board using the same |
JP4340272B2 (en) * | 2006-05-30 | 2009-10-07 | 太陽インキ製造株式会社 | Photocurable / thermosetting solder resist composition and printed wiring board using the same |
JP2008015285A (en) * | 2006-07-06 | 2008-01-24 | Toyo Ink Mfg Co Ltd | Photosensitive thermosetting resin composition |
CN101679613A (en) * | 2007-06-15 | 2010-03-24 | 积水化学工业株式会社 | Sealing agent for optical semiconductor element, and optical semiconductor element |
JP5104101B2 (en) * | 2007-07-30 | 2012-12-19 | Jsr株式会社 | INORGANIC POWDER-CONTAINING RESIN COMPOSITION, PATTERN FORMING METHOD, AND METHOD FOR PRODUCING ELECTRODE FOR FLAT PANEL DISPLAY |
JP5352340B2 (en) * | 2009-05-13 | 2013-11-27 | 株式会社タムラ製作所 | Photosensitive resin composition, solder resist composition for printed wiring board, and printed wiring board |
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JP7405803B2 (en) | 2021-08-27 | 2023-12-26 | 株式会社タムラ製作所 | Photosensitive resin composition, photocured product of the photosensitive resin composition, and printed wiring board coated with the photosensitive resin composition |
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