WO2010016258A1 - Flame-retardant photocurable resin composition, dry film and cured product of the same, and printed wiring board using the composition, dry film or cured product - Google Patents
Flame-retardant photocurable resin composition, dry film and cured product of the same, and printed wiring board using the composition, dry film or cured product Download PDFInfo
- Publication number
- WO2010016258A1 WO2010016258A1 PCT/JP2009/003770 JP2009003770W WO2010016258A1 WO 2010016258 A1 WO2010016258 A1 WO 2010016258A1 JP 2009003770 W JP2009003770 W JP 2009003770W WO 2010016258 A1 WO2010016258 A1 WO 2010016258A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- flame
- resin composition
- composition
- group
- photocurable resin
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/05—Forming flame retardant coatings or fire resistant coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2400/00—Characterised by the use of unspecified polymers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
さらに本発明の目的は、このような光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難燃性の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難燃性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 prior art as described above, has a non-halogen composition, has a low environmental load, is excellent in both flame retardancy and storage stability, is rich in flexibility of a cured film, and is suitable for various substrates. A flame retardant photocurable resin composition that can form a cured film with a fine pattern that is excellent in adhesion, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc., and is particularly suitable for FPC It is intended to provide.
Furthermore, the object of the present invention is to provide a flame retardant dry film and cured product excellent in the above-mentioned various characteristics obtained by using such a photocurable resin composition, and a solder with the dry film or cured product. An object of the present invention is to provide a printed wiring board on which a flame-retardant cured film such as a resist is formed.
好適な態様においては、さらに(D)光重合性モノマーを含有し、あるいはさらに(E)熱硬化性樹脂を含有する。該熱硬化性樹脂(E)は、ビフェニル骨格を有するエポキシ樹脂を含むことが好ましい。このような難燃性光硬化性樹脂組成物、特に熱硬化性樹脂(E)を含有する難燃性の光硬化性・熱硬化性樹脂組成物は、ソルダーレジストとして好適に用いることができる。 In order to achieve the above object, according to the present invention, a flame retardant comprising (A) a phosphazene compound that is liquid at room temperature, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator. A photocurable resin composition is provided. Preferably, the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin. Here, “room temperature” means the working room temperature, generally 20 to 30 ° C., usually 25 ° C.
In a suitable aspect, it further contains (D) a photopolymerizable monomer, or further contains (E) a thermosetting resin. The thermosetting resin (E) preferably contains an epoxy resin having a biphenyl skeleton. Such a flame-retardant photocurable resin composition, particularly a flame-retardant photocurable / thermosetting resin composition containing the thermosetting resin (E), can be suitably used as a solder resist.
さらに本発明によれば、前記難燃性光硬化性樹脂組成物又はドライフィルムを硬化させて得られる難燃性硬化皮膜を有することを特徴とするプリント配線板も提供される。 Further, according to the present invention, a flame retardant photocurable dry film obtained by applying and drying the flame retardant photocurable resin composition on a carrier film, or the flame retardant photocurable resin. A flame retardant cured product obtained by curing the composition or the dry film is also provided.
Furthermore, according to this invention, the printed wiring board characterized by having the flame-retardant cured film obtained by hardening | curing the said flame-retardant photocurable resin composition or a dry film is also provided.
従って、本発明の難燃性光硬化性樹脂組成物は、プリント配線板、特にFPCのソルダーレジスト等の難燃性硬化皮膜の形成に有利に適用できる。 Since the flame-retardant photocurable resin composition of the present invention uses a phosphazene derivative that is liquid at room temperature together with a carboxyl group-containing resin, once dissolved in a photosensitive composition as in the past, it is re-used during storage. There is no phenomenon of crystallization or precipitation of crystals with time after coating and drying, so that a relatively large amount of the phosphazene compound can be added, the flame retardancy effect becomes very large, and the liquid composition And it is excellent in stability as a dry film. Therefore, non-halogen composition with low environmental impact and excellent flame retardancy, rich cured film flexibility, adhesion to various substrates, solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc. Can form a cured film with a fine pattern.
Therefore, the flame-retardant photocurable resin composition of the present invention can be advantageously applied to the formation of a flame-retardant cured film such as a printed wiring board, particularly an FPC solder resist.
-ハロゲンを含まない(イオン不純物以外)。
-5%重量減少が260℃以上であること。
-下記一般式(I)で示される構造を有する化合物であること。
また、一般式(I)で表されるホスファゼン化合物は、線状又は環状であってもよく、複数の混合物で分子量分布を持っていてもよい。 The phosphazene compound (A) that is liquid at room temperature contained in the flame-retardant photocurable resin composition of the present invention is a viscous liquid or liquid at 25 ° C., and is preferably subjected to the following conditions. Those having characteristics are preferred.
-Halogen free (other than ionic impurities).
-5% weight loss is 260 ° C or higher.
-A compound having a structure represented by the following general formula (I).
Further, the phosphazene compound represented by the general formula (I) may be linear or cyclic, and may have a molecular weight distribution in a plurality of mixtures.
上記範囲より少ない場合、得られる硬化皮膜の充分な難燃性が得られず、また可撓性においても良好な結果が得られない。一方、上記範囲より多い場合、塗膜のタックフリー性能が低下したり、組成物の粘性が高くなったりするので好ましくない。 The blending amount of the phosphazene compound (A) which is liquid at room temperature is 0.5 to 30% by mass, preferably 1 to 20% by mass in the total composition.
When less than the said range, sufficient flame retardance of the cured film obtained is not acquired, and a favorable result is not acquired also in flexibility. On the other hand, when the amount is more than the above range, the tack-free performance of the coating film is lowered or the viscosity of the composition is increased, which is not preferable.
カルボキシル基含有樹脂(B)の具体例としては、以下に列挙するような化合物(オリゴマー及びポリマーのいずれでもよい)を好適に使用できる。 As the carboxyl group-containing resin (B) contained in the flame retardant photocurable resin composition of the present invention, a known and commonly used resin compound containing a carboxyl group in the molecule can be used. Furthermore, it is preferable to use a carboxyl group-containing photosensitive resin (B ′) having an ethylenically unsaturated double bond in the molecule because photocurability can be imparted and an alkali developable composition is obtained. The unsaturated double bond is preferably derived from (meth) acrylic acid or a (meth) acrylic acid derivative. In addition, when using only the carboxyl group-containing resin which does not have an ethylenically unsaturated double bond, in order to make a composition photocurable, it has two or more ethylenically unsaturated groups in the molecule | numerator mentioned later. It is necessary to use a photopolymerizable monomer (D) in combination.
As specific examples of the carboxyl group-containing resin (B), compounds listed below (any of oligomers and polymers) can be suitably used.
(2)ジイソシアネートと、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型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、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等の2官能エポキシ樹脂の(メタ)アクリレートもしくはその部分酸無水物変性物、カルボキシル基含有ジアルコール化合物及びジオール化合物の重付加反応による感光性カルボキシル基含有ウレタン樹脂。
(3)上記(1)又は(2)の樹脂の合成中に、ヒドロキシアルキル(メタ)アクリレート等の分子内に1つの水酸基と1つ以上の(メタ)アクリル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有ウレタン樹脂。
(4)上記(1)又は(2)の樹脂の合成中に、イソホロンジイソシアネートとペンタエリスリトールトリアクリレートの等モル反応物など、分子内に1つのイソシアネート基と1つ以上の(メタ)アクリル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有ウレタン樹脂。
(5)(メタ)アクリル酸等の不飽和カルボン酸と、スチレン、α-メチルスチレン、低級アルキル(メタ)アクリレート、イソブチレン等の不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。
(6)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2塩基酸無水物を付加させた感光性カルボキシル基含有樹脂。
(7)2官能(固形)エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に(メタ)アクリル酸を反応させ、生じた水酸基に2塩基酸無水物を付加させた感光性カルボキシル基含有樹脂。
(8)後述するような2官能オキセタン樹脂にジカルボン酸を反応させ、生じた1級の水酸基に2塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂。
(9)上記(1)~(8)の樹脂にさらに1分子内に1つのエポキシ基と1つ以上の(メタ)アクリル基を有する化合物を付加してなる感光性カルボキシル基含有樹脂。 (1) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(2) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.
(3) During the synthesis of the resin of the above (1) or (2), a compound having one hydroxyl group and one or more (meth) acryl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing urethane resin.
(4) During the synthesis of the resin of the above (1) or (2), one isocyanate group and one or more (meth) acryl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.
(5) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(6) A photosensitive carboxyl group obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin as described later with (meth) acrylic acid and adding a dibasic acid anhydride to the hydroxyl group present in the side chain. Containing resin.
(7) Photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Functional carboxyl group-containing resin.
(8) A carboxyl group-containing polyester resin obtained by reacting a difunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
(9) A photosensitive carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resins (1) to (8).
尚、本明細書において、(メタ)アクリレートとは、アクリレート、メタクリレート及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。 Among these carboxyl group-containing resins, preferred are (X) carboxy group-containing polyurethane resins, particularly those in which the isocyanate groups of the urethane resin containing isocyanate groups (including diisocyanates) are not directly bonded to the benzene ring. From the viewpoint of photosensitivity and flexibility, (Y) the polyfunctional epoxy resin used in the synthesis of the resins of (6) and (7) above is bisphenol A structure, bisphenol F structure, biphenol structure, bisxylenol. In the case of a compound having a structure and its hydrogenated compound, it is preferable from the viewpoints of heat resistance and flame retardancy. Further, in another aspect, the carboxylic group-containing polyurethane resins (1), (2), (3) and (4) and the modified products such as (9) have a urethane bond in the main chain. And preferred for warping. Furthermore, in order to achieve both properties such as flexibility and solder heat resistance, the carboxyl group-containing urethane resins (1), (2), (3), (4) and modified products such as those (9) And, it is most preferable to use the carboxyl group-containing resins (5), (6), (7) and (8) and modified products such as (9) in combination.
In the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
また、前記カルボキシル基含有樹脂(B)の酸価は、40~200mgKOH/ggの範囲、より好ましくは45~120mgKOH/gの範囲にあることが望ましい。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、200mgKOH/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 (B) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.
The acid value of the carboxyl group-containing resin (B) is desirably in the range of 40 to 200 mgKOH / gg, more preferably in the range of 45 to 120 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 the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and 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.
特に好ましい光重合開始剤としてはリン元素含有光重合開始剤があり、光重合開始剤でありながら難燃性を向上させる効果も有している。このようなリン元素含有光重合開始剤としては、下記一般式(II-1)で表される基を有するアシルホスフィンオキサイド系光重合開始剤を好適に用いることができる。
As a particularly preferred photopolymerization initiator, there is a phosphorus element-containing photopolymerization initiator, which has an effect of improving flame retardancy while being a photopolymerization initiator. As such a phosphorus element-containing photopolymerization initiator, an acylphosphine oxide photopolymerization initiator having a group represented by the following general formula (II-1) can be preferably used.
R7は、フェニル基(炭素数1~6のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい)、炭素数1~20のアルキル基(1個以上の水酸基で置換されていてもよく、アルキル鎖の中間に1個以上の酸素原子を有していてもよい)、炭素数5~8のシクロアルキル基、炭素数2~20のアルカノイル基又はベンゾイル基(炭素数が1~6のアルキル基もしくはフェニル基で置換されていてもよい)を表し、
R8及びR9は、それぞれ独立に、炭素数1~12のアルキル基又はアリールアルキル基を表し、
R10及びR11は、それぞれ独立に、水素原子、炭素数1~6のアルキル基、又は2つが結合した環状アルキルエーテル基を表す。 The photopolymerization initiator that can be added in addition to the phosphorus element-containing photopolymerization initiator includes an oxime ester photopolymerization initiator having a group represented by the following general formula (III), represented by the following general formula (IV): There are α-aminoacetophenone photopolymerization initiators having the following groups.
R 7 is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). It may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R 8 and R 9 each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R 10 and R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded.
R13、R15は、それぞれ独立に、フェニル基(炭素数1~6のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい)、炭素数1~20のアルキル基(1個以上の水酸基で置換されていてもよく、アルキル鎖の中間に1個以上の酸素原子を有していてもよい)、炭素数5~8のシクロアルキル基、炭素数2~20のアルカノイル基又はベンゾイル基(炭素数が1~6のアルキル基もしくはフェニル基で置換されていてもよい)を表し、
R14は、水素原子、フェニル基(炭素数1~6のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい)、炭素数1~20のアルキル基(1個以上の水酸基で置換されていてもよく、アルキル鎖の中間に1個以上の酸素原子を有していてもよい)、炭素数5~8のシクロアルキル基、炭素数2~20のアルカノイル基又はベンゾイル基(炭素数が1~6のアルキル基もしくはフェニル基で置換されていてもよい)を表す。
R 13 and R 15 are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R 14 is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). Optionally substituted with 1 to 6 alkyl groups or phenyl groups.
R18、R19、R20及びR21は、それぞれ独立に、水素原子又は炭素数1~6のアルキル基を表し、
Mは、O、S又はNHを表し、
n及びpは、それぞれ独立に0~5の整数を表す。
R 18 , R 19 , R 20 and R 21 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
M represents O, S or NH;
n and p each independently represents an integer of 0 to 5.
尚、前記式(III)で表される基を有するオキシムエステル系光重合開始剤の場合、その配合量は、前記カルボキシル基含有樹脂(B)100質量部に対して、好ましくは0.01~20質量部、より好ましくは0.01~5質量部の範囲から選ぶことが望ましい。 The blending amount of the photopolymerization initiator (C) as described above is in the range of 0.01 to 50 parts by mass, preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). You can choose from. If it is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. On the other hand, if it exceeds 50 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (C) becomes violent and the deep curability tends to decrease, which is not preferable.
In the case of the oxime ester-based photopolymerization initiator having a group represented by the formula (III), the blending amount is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). It is desirable to select from the range of 20 parts by mass, more preferably from 0.01 to 5 parts by mass.
アセトフェノン化合物の具体例を挙げると、例えば、アセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、2,2-ジエトキシ-2-フェニルアセトフェノン、1,1-ジクロロアセトフェノンである。 Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.
チオキサントン化合物の具体例を挙げると、例えば、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、2-クロロチオキサントン、2,4-ジイソプロピルチオキサントンである。 Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.
ベンゾフェノン化合物の具体例を挙げると、例えば、ベンゾフェノン、4-ベンゾイルジフェニルスルフィド、4-ベンゾイル-4’-メチルジフェニルスルフィド、4-ベンゾイル-4’-エチルジフェニルスルフィド、4-ベンゾイル-4’-プロピルジフェニルスルフィドである。 Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.
このようなチオキサントン化合物の配合量としては、前記カルボキシル基含有樹脂(B)100質量部に対して、好ましくは20質量部以下、より好ましくは10質量部以下の割合が適当である。チオキサントン化合物の配合量が多すぎると、厚膜硬化性が低下して、製品のコストアップに繋がるので、好ましくない。 Among the above-mentioned compounds, thioxanthone compounds and tertiary amine compounds are preferable. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
The amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxyl group-containing resin (B). If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.
このような光重合開始剤、光開始助剤、及び増感剤の総量は、前記カルボキシル基含有樹脂(B)100質量部に対して35質量部以下となる範囲であることが好ましい。35質量部を超えると、これらの光吸収により深部硬化性が低下する傾向にある。 These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably in the range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin (B). When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
上記一般式(IX)で表される化合物の市販品としてはHCA、SANKO-220、M-ESTER、HCA-HQ等がある。 The photocurable resin composition of the present invention can further contain a phosphorus-containing compound as a flame retardant auxiliary. As the phosphorus-containing compound, those conventionally known as organic phosphorus flame retardants may be used, and examples include phosphoric acid esters and condensed phosphoric acid esters, cyclic phosphazene compounds, phosphazene oligomers, and compounds represented by the following general formula (IX).
Commercially available products of the compound represented by the general formula (IX) include HCA, SANKO-220, M-ESTER, HCA-HQ and the like.
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、下記のようなカラーインデックス(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:
Blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment, specifically, the following color index (CI; The Society of Dyers and Colorists) (Issued by The Society of Dyers and Colorists) can be listed with numbers: 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.
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 yellow colorants 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.
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 red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
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.
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, for the purpose of adjusting the color tone, a colorant such as purple, orange, brown, or black may be added.
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.
このような有機溶剤としては、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤などを挙げることができる。より具体的には、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのエステル類;エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類;オクタン、デカン等の脂肪族炭化水素;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などである。このような有機溶剤は、単独で又は2種以上の混合物として用いられる。 Furthermore, the photocurable resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing resin (B), the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. can do.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.
ドライフィルム化に際しては、本発明の光硬化性樹脂組成物を前記有機溶剤で希釈して適切な粘度に調整し、コンマコーター、ブレードコーター、リップコーター、ロッドコーター、スクイズコーター、リバースコーター、トランスファロールコーター、グラビアコーター、スプレーコーター等でキャリアフィルム上に均一な厚さに塗布し、通常、50~130℃の温度で1~30分間乾燥して膜を得ることができる。塗布膜厚については特に制限はないが、一般に、乾燥後の膜厚で、10~150μm、好ましくは20~60μmの範囲で適宜選択される。 The photocurable resin composition of the present invention can also be in the form of a dry film comprising a carrier film (support) and a layer made of the photocurable resin composition formed on the carrier film. .
When forming a dry film, the photocurable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and is applied to a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll. A film can be obtained by applying a uniform thickness on a carrier film with a coater, gravure coater, spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes. The coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 10 to 150 μm, preferably 20 to 60 μm.
剥離可能なカバーフィルムとしては、例えば、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、表面処理した紙等を用いることができ、カバーフィルムを剥離するときに膜とキャリアフィルムとの接着力よりも膜とカバーフィルムとの接着力がより小さいものであればよい。 After the film is formed on the carrier film, it is desirable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.
As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.
上記活性エネルギー線照射に用いられる露光機としては、レーザー直接描画装置(レーザーダイレクトイメージング装置)、メタルハライドランプを搭載した露光機、(超)高圧水銀ランプを搭載した露光機、水銀ショートアークランプを搭載した露光機、もしくは(超)高圧水銀ランプなどの紫外線ランプを使用した直接描画装置を使用することができる。尚、活性エネルギー線として最大波長が350~410nmの範囲にあるレーザー光を用いていれば、ガスレーザー、固体レーザーどちらでもよい。また、その露光量は膜厚等によって異なるが、一般には5~200mJ/cm2、好ましくは5~100mJ/cm2、さらに好ましくは5~50mJ/cm2の範囲内とすることができる。上記直接描画装置としては、例えば日本オルボテック社製、ペンタックス社製等のものを使用することができ、最大波長が350~410nmのレーザー光を発振する装置であればいずれの装置を用いてもよい。 As mentioned above, after apply | coating the photocurable resin composition of this invention and evaporating and drying, exposure (irradiation of an active energy ray) is performed with respect to the obtained coating film. In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.
The exposure equipment used for the active energy ray irradiation includes a laser direct lithography system (laser direct imaging system), an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, and a mercury short arc lamp. Or a direct drawing apparatus using an ultraviolet lamp such as a (super) high-pressure mercury lamp can be used. As long as a laser beam having a maximum wavelength in the range of 350 to 410 nm is used as the active energy ray, either a gas laser or a solid laser may be used. The exposure amount varies depending on the film thickness and the like, but can be generally in the range of 5 to 200 mJ / cm 2 , preferably 5 to 100 mJ / cm 2 , more preferably 5 to 50 mJ / cm 2 . As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .
配合例1~3、比較配合例1~3
表1に示す各成分を表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、ソルダーレジスト用主剤組成物のワニスを調製した。ここで、得られたワニス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。 <Preparation of base varnish>
Formulation Examples 1 to 3, Comparative Formulation Examples 1 to 3
Each component shown in Table 1 was blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a varnish of a main composition for solder resist. Here, when the dispersion degree of the obtained varnish was evaluated by particle size measurement using a grindometer manufactured by Eriksen, it was 15 μm or less.
硬化剤配合例1、2
表2に示す各成分を表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硬化剤組成物のワニスを調製した。 <Preparation of curing agent varnish>
Curing agent formulation examples 1 and 2
Each component shown in Table 2 was blended in the proportions (parts by mass) shown in Table 2, preliminarily mixed with a stirrer, and then kneaded with a three-roll mill to prepare a varnish of a hardener composition for solder resist.
前記表1に示す主剤組成物のワニスを5℃に設定されている冷蔵庫に1週間静置させた。室温に戻してからワニスをガラス板に塗布し、粒の確認を行った。その結果を表3に示す。 <Grade stability over time>
The base composition varnish shown in Table 1 was allowed to stand in a refrigerator set at 5 ° C. for 1 week. After returning to room temperature, the varnish was applied to a glass plate to confirm the grains. The results are shown in Table 3.
前記表1に示す主剤組成物のワニスと、前記表2に示す硬化剤組成物のワニスを、下記表4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、性能評価用組成物のワニスを調製した。 <Preparation of composition for performance evaluation>
After mixing the varnish of the main agent composition shown in Table 1 and the varnish of the curing agent composition shown in Table 2 in the ratio (parts by mass) shown in Table 4 below, and premixing with a stirrer, three It knead | mixed with the roll mill and prepared the varnish of the composition for performance evaluation.
<最適露光量>
前記実施例1~4及び比較例1~3の難燃性光硬化性樹脂組成物を、銅厚35μmの回路パターン基板をバフロール研磨後、水洗し、乾燥してから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30分間乾燥させる。乾燥後、メタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いてステップタブレット(コダック No.2)を介して露光し、現像(30℃、0.2MPa、1wt%Na2CO3水溶液)を60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6段の時を最適露光量とした。 Performance evaluation:
<Optimum exposure amount>
The flame retardant photocurable resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were coated on the entire surface by screen printing after the circuit pattern substrate having a copper thickness of 35 μm was polished with buffalo, washed with water and dried. And dried for 30 minutes in a hot air circulation drying oven at 80 ° C. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and development (30 ° C., 0.2 MPa, 1 wt% Na 2 CO 3 aqueous solution) When the pattern of the step tablet remaining when performing for 60 seconds was 6 steps, the optimum exposure amount was set.
前記実施例1~4及び比較例1~3の難燃性光硬化性樹脂組成物を、パターン形成されたポリイミドフィルム基板上にスクリーン印刷で全面塗布し、80℃で30分乾燥し、室温まで放冷する。この基板にメタルハライドランプ搭載の露光装置(HMW-680-GW20)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%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒間現像を行い、レジストパターンを得た。この基板を、150℃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 flame-retardant photocurable resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were applied onto the patterned polyimide film substrate by screen printing, dried at 80 ° C. for 30 minutes, and brought to room temperature. Allow to cool. This substrate was exposed to a solder resist pattern at an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. was applied under a spray pressure of 0.2 MPa. Development was performed for 2 seconds to obtain a resist pattern. This substrate was cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
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2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2回以上繰り返すと少し剥がれる。
×:10秒間浸漬を1回でレジスト層に膨れ、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 twice or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated twice or more.
X: The resist layer swells and peels off once in 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3μm、金0.03μm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し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、テープピール後は剥がれない。
×:めっき後にしみ込みが見られ、テープピール後に剥がれも見られる。 <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 3 μm and gold 0.03 μm, and the presence or absence of peeling of the resist layer or plating penetration is confirmed by tape peeling. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
○: Infiltration and peeling are not seen.
Δ: Slight penetration is observed after plating, but does not peel off after tape peeling.
X: Permeation is observed after plating, and peeling is also observed after tape peeling.
銅箔基板に代えてIPC B-25のクシ型電極Bクーポンを用い、上記の条件で評価基板を作製し、このクシ型電極にDC100Vのバイアス電圧を印加し、85℃、85%R.H.の恒温恒湿槽にて1,000時間後の抵抗値及びマイグレーションの有無を確認した。判定基準は以下のとおりである。
◎:加湿後の絶縁抵抗値1012Ω以上、銅のマイグレーションなし
○:加湿後の絶縁抵抗値1012Ω未満、109Ω以上、銅のマイグレーションなし
△:加湿後の絶縁抵抗値109Ω以上、銅のマイグレーションあり
×:加湿後の絶縁抵抗値108Ω以下、銅のマイグレーションあり <Electrical characteristics>
Using an IPC B-25 comb-type electrode B coupon instead of the copper foil substrate, an evaluation board was prepared under the above conditions, and a bias voltage of DC 100 V was applied to the comb-type electrode, and 85 ° C., 85% R.D. H. The resistance value after 1,000 hours and the presence or absence of migration were confirmed in a constant temperature and humidity chamber. The judgment criteria are as follows.
A: Insulation resistance value after humidification of 1012Ω or more, no copper migration ○: Insulation resistance value after humidification of less than 1012Ω, 109Ω or more, no copper migration Δ: Insulation resistance value after humidification of 109Ω or more, copper migration ×: Insulation resistance value after humidification of 108Ω or less, with copper migration
前記実施例1~4及び比較例1~3の組成物を、25um厚のポリイミドフィルム(カプトン100H)又は12.5um厚のポリイミドフィルム(カプトン50H)にスクリーン印刷で全面塗布し、80℃で20分乾燥して室温まで放冷する。さらに裏面を同様にスクリーン印刷で全面塗布し、80℃で20分乾燥して室温まで放冷し両面塗布基板を得た。この基板にメタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いて最適露光量でソルダーレジストを全面露光し、30℃の1wt%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒間現像を行い、150℃で60分間熱硬化を行い評価サンプルとした。この難燃性評価用サンプルついて、UL94規格に準拠した薄材垂直燃焼試験を行った。評価はUL94規格に基づいて、VTM-0又はVTM-1と表した。 <Flame retardance>
The compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were applied to the entire surface by screen printing on a 25 μm-thick polyimide film (Kapton 100H) or 12.5 μm-thick polyimide film (Kapton 50H). Dry in minutes and allow to cool to room temperature. Further, the entire back surface was similarly applied by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature to obtain a double-side coated substrate. The entire surface of the solder resist is exposed to this substrate with an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. Development was performed for 1 second, and thermosetting was performed at 150 ° C. for 60 minutes to obtain an evaluation sample. This flame retardant evaluation sample was subjected to a thin material vertical combustion test based on the UL94 standard. The evaluation was expressed as VTM-0 or VTM-1 based on the UL94 standard.
各実施例及び比較例の組成物を、25μmのポリイミドフィルム(カプトン100H)にスクリーン印刷で全面塗布し、80℃で30分乾燥して室温まで放冷し、片面塗布基板を得た。この基板にメタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いて最適露光量でソルダーレジストを全面露光し、30℃の1wt%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒現像を行い、150℃で60分間熱硬化を行った。得られたサンプルのソルダーレジストを外側にして、ハゼ折による180°折り曲げを数回繰り返して行い、その際の塗膜におけるクラック発生状況を目視及び倍率200の光学顕微鏡で観察し、クラックが発生しない回数を評価した。 <Flexibility>
The compositions of each Example and Comparative Example were applied to a 25 μm polyimide film (Kapton 100H) by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature to obtain a single-side coated substrate. The entire surface of the solder resist is exposed to this substrate with an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. Second development was performed, and thermosetting was performed at 150 ° C. for 60 minutes. The solder resist of the obtained sample is turned outside, and 180 ° bending by goat folding is repeated several times, and the crack occurrence state in the coating film at that time is observed visually and with an optical microscope with a magnification of 200, and no crack is generated. The number of times was evaluated.
表4に示す実施例1~4に従って調製した難燃性光硬化性樹脂組成物をメチルエチルケトンで希釈し、キャリアフィルム上に塗布し、加熱乾燥して、厚さ20μmの感光性樹脂組成物層を形成し、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得た。その後、カバーフィルムを剥がし、パターン形成されたポリイミドフィルム基板に、ラミネーターを用いフィルムを貼り合わせた。この基板にメタルハライドランプ搭載の露光装置(HMW-680-GW20)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、キャリアフィルムを剥がした後、30℃の1wt%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒間現像を行い、レジストパターンを得た。その後、150℃の熱風乾燥器で60分加熱硬化を行ない、試験基板を作製した。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と同様にして、各特性の評価試験を行なった。結果は、実施例1~4と同等であった。
また、ドライフィルム状態での経時粒安定性の評価を以下のとおり実施した。
すなわち、表4に示す実施例1と比較例1に従って調製した難燃性光硬化性樹脂組成物をメチルエチルケトンで希釈し、キャリアフィルム上に塗布し、加熱乾燥して、厚さ20μmの感光性樹脂組成物層を形成し、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成した。作成したドライフィルムについて、前述した<経時粒安定性>評価と同様に5℃で一週間保管したところ、実施例1の組成物から得られたドライフィルムでは粒は確認されなかったが、比較例1の組成物から作成したドライフィルムでは粒が確認された。 Examples 5-8
A flame-retardant photocurable resin composition prepared according to Examples 1 to 4 shown in Table 4 was diluted with methyl ethyl ketone, applied onto a carrier film, and dried by heating to form a photosensitive resin composition layer having a thickness of 20 μm. Then, a cover film was laminated thereon to obtain a dry film. Thereafter, the cover film was peeled off, and the film was bonded to the patterned polyimide film substrate using a laminator. The substrate is exposed to the solder resist pattern at an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, the carrier film is peeled off, and then a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. is sprayed. Development was performed for 60 seconds under the condition of 0.2 MPa to obtain a resist pattern. Thereafter, heat curing was performed for 60 minutes in a hot air dryer at 150 ° C. to prepare a test substrate. About the test board | substrate which has the obtained cured film, the evaluation test of each characteristic was done like the test method and evaluation method which were mentioned above. The results were equivalent to those in Examples 1 to 4.
Moreover, the evaluation of the grain stability over time in the dry film state was performed as follows.
That is, the flame retardant photocurable resin composition prepared according to Example 1 and Comparative Example 1 shown in Table 4 was diluted with methyl ethyl ketone, applied onto a carrier film, dried by heating, and a photosensitive resin having a thickness of 20 μm. A composition layer was formed, and a cover film was laminated thereon to create a dry film. The prepared dry film was stored for one week at 5 ° C. in the same manner as in the above-mentioned <Grade stability over time> evaluation. No grain was confirmed in the dry film obtained from the composition of Example 1, but a comparative example. Grain was confirmed in the dry film prepared from the composition of No. 1.
Claims (9)
- (A)室温で液状のホスファゼン化合物、(B)カルボキシル基含有樹脂、及び(C)光重合開始剤を含有することを特徴とする難燃性光硬化性樹脂組成物。 (A) A flame-retardant photocurable resin composition comprising a phosphazene compound that is liquid at room temperature, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator.
- さらに(D)光重合性モノマーを含有することを特徴とする請求項1に記載の光硬化性難燃性樹脂組成物。 The photocurable flame retardant resin composition according to claim 1, further comprising (D) a photopolymerizable monomer.
- さらに(E)熱硬化性樹脂を含有することを特徴とする請求項1に記載の難燃性光硬化性樹脂組成物。 The flame retardant photocurable resin composition according to claim 1, further comprising (E) a thermosetting resin.
- 前記熱硬化性樹脂(E)が、ビフェニル骨格を有するエポキシ樹脂を含むことを特徴とする請求項3に記載の難燃性光硬化性樹脂組成物。 The flame retardant photocurable resin composition according to claim 3, wherein the thermosetting resin (E) includes an epoxy resin having a biphenyl skeleton.
- 前記カルボキシル基含有樹脂(B)が、カルボキシル基含有ポリウレタン樹脂であることを特徴とする請求項1に記載の難燃性光硬化性樹脂組成物。 The flame retardant photocurable resin composition according to claim 1, wherein the carboxyl group-containing resin (B) is a carboxyl group-containing polyurethane resin.
- ソルダーレジストである請求項1乃至5のいずれか一項に記載の難燃性光硬化性樹脂組成物 It is a solder resist, The flame-retardant photocurable resin composition as described in any one of Claims 1 thru | or 5
- 請求項1乃至5のいずれか一項に記載の難燃性光硬化性樹脂組成物を、キャリアフィルム上に塗布・乾燥させて得られる難燃性光硬化性のドライフィルム。 A flame-retardant photocurable dry film obtained by applying and drying the flame-retardant photocurable resin composition according to any one of claims 1 to 5 on a carrier film.
- 請求項1乃至5のいずれか一項に記載の難燃性光硬化性樹脂組成物又は前記難燃性光硬化性樹脂組成物をキャリアフィルム上に塗布・乾燥させて得られるドライフィルムを硬化させて得られる難燃性硬化物。 A flame retardant photocurable resin composition according to any one of claims 1 to 5 or a dry film obtained by applying and drying the flame retardant photocurable resin composition on a carrier film is cured. Flame-retardant cured product obtained by
- 請求項1乃至5のいずれか一項に記載の難燃性光硬化性樹脂組成物又は前記難燃性光硬化性樹脂組成物をキャリアフィルム上に塗布・乾燥させて得られるドライフィルムを硬化させて得られる難燃性硬化皮膜を有することを特徴とするプリント配線板。 A flame retardant photocurable resin composition according to any one of claims 1 to 5 or a dry film obtained by applying and drying the flame retardant photocurable resin composition on a carrier film is cured. A printed wiring board having a flame-retardant cured film obtained by
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009801305593A CN102112921B (en) | 2008-08-07 | 2009-08-06 | Flame-retardant photocurable resin composition, dry film and cured product of same, and printed circuit board using composition thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008-204731 | 2008-08-07 | ||
JP2008204731A JP5301915B2 (en) | 2008-08-07 | 2008-08-07 | Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010016258A1 true WO2010016258A1 (en) | 2010-02-11 |
Family
ID=41663486
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/003770 WO2010016258A1 (en) | 2008-08-07 | 2009-08-06 | Flame-retardant photocurable resin composition, dry film and cured product of the same, and printed wiring board using the composition, dry film or cured product |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5301915B2 (en) |
KR (1) | KR101613330B1 (en) |
CN (1) | CN102112921B (en) |
TW (1) | TWI394002B (en) |
WO (1) | WO2010016258A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102792226A (en) * | 2010-03-31 | 2012-11-21 | 太阳控股株式会社 | Photosensitive resin composition |
JP2016000782A (en) * | 2014-06-12 | 2016-01-07 | パナソニックIpマネジメント株式会社 | Epoxy resin composition, metal-clad laminate, and substrate material for package |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5563256B2 (en) * | 2009-08-18 | 2014-07-30 | 京セラケミカル株式会社 | Photosensitive resin composition, and photosensitive film and photosensitive resist using the same |
JP5415923B2 (en) * | 2009-12-14 | 2014-02-12 | 太陽ホールディングス株式会社 | Photosensitive resin composition, dry film thereof, and printed wiring board using them |
US20120305295A1 (en) * | 2010-02-03 | 2012-12-06 | Showa Denko K.K. | Thermosetting composition |
US9081276B2 (en) | 2010-09-29 | 2015-07-14 | Kaneka Corporation | Photosensitive resin composition production kit, and use thereof |
JP2012098470A (en) * | 2010-11-01 | 2012-05-24 | Kaneka Corp | Novel photosensitive resin composition and utilization of the same |
JP2012237864A (en) * | 2011-05-11 | 2012-12-06 | Kaneka Corp | Novel black photosensitive resin composition and use of the same |
JP5789454B2 (en) * | 2011-09-05 | 2015-10-07 | 株式会社カネカ | Novel photosensitive resin composition preparation kit and use thereof |
JP5789455B2 (en) * | 2011-09-05 | 2015-10-07 | 株式会社カネカ | Novel photosensitive resin composition preparation kit and use thereof |
JP5858739B2 (en) * | 2011-11-15 | 2016-02-10 | 株式会社カネカ | Novel photosensitive resin composition preparation kit and use thereof |
JP5858740B2 (en) * | 2011-11-15 | 2016-02-10 | 株式会社カネカ | Novel photosensitive resin composition preparation kit and use thereof |
JP5877690B2 (en) * | 2011-11-15 | 2016-03-08 | 株式会社カネカ | Novel photosensitive resin composition preparation kit and use thereof |
JP5887106B2 (en) * | 2011-11-15 | 2016-03-16 | 株式会社カネカ | Novel photosensitive resin composition preparation kit and use thereof |
JP5858747B2 (en) * | 2011-11-21 | 2016-02-10 | 株式会社カネカ | Novel photosensitive resin composition preparation kit and use thereof |
JP5858746B2 (en) * | 2011-11-21 | 2016-02-10 | 株式会社カネカ | Novel photosensitive resin composition preparation kit and use thereof |
JP6211780B2 (en) * | 2012-03-27 | 2017-10-11 | 太陽インキ製造株式会社 | Flame-retardant curable resin composition, dry film, flame-retardant coating and printed wiring board |
JP6211781B2 (en) * | 2012-03-27 | 2017-10-11 | 太陽インキ製造株式会社 | Flame-retardant curable resin composition, dry film, flame-retardant coating and printed wiring board |
KR102050619B1 (en) * | 2012-05-17 | 2019-11-29 | 다이요 잉키 세이조 가부시키가이샤 | Liquid-developable maleimide composition and printed circuit board |
JP5575858B2 (en) * | 2012-10-01 | 2014-08-20 | 太陽ホールディングス株式会社 | Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them |
CN104950574A (en) * | 2014-03-31 | 2015-09-30 | 太阳油墨(苏州)有限公司 | Photocuring and thermosetting resin composition, dry film, cured product and printed circuit board |
JP6573181B2 (en) * | 2018-04-03 | 2019-09-11 | パナソニックIpマネジメント株式会社 | Metal-clad laminate and packaging substrate material |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005019231A1 (en) * | 2003-06-05 | 2005-03-03 | Kaneka Corporation | Phosphazene compound, photosensitive resin composition and use thereof |
JP2007016184A (en) * | 2005-07-11 | 2007-01-25 | Fujifilm Holdings Corp | Elastomer, photosensitive composition, photosensitive film, and method for forming permanent pattern |
JP2008107458A (en) * | 2006-10-24 | 2008-05-08 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element |
JP2008107492A (en) * | 2006-10-24 | 2008-05-08 | Kaneka Corp | Flame-retardant photosensitive resin composition and its use |
WO2008065905A1 (en) * | 2006-11-15 | 2008-06-05 | Asahi Kasei Kabushiki Kaisha | Photosensitive resin composition, and flexible print circuit board using the same |
-
2008
- 2008-08-07 JP JP2008204731A patent/JP5301915B2/en active Active
-
2009
- 2009-08-06 WO PCT/JP2009/003770 patent/WO2010016258A1/en active Application Filing
- 2009-08-06 KR KR1020117002701A patent/KR101613330B1/en active IP Right Grant
- 2009-08-06 CN CN2009801305593A patent/CN102112921B/en active Active
- 2009-08-06 TW TW098126553A patent/TWI394002B/en active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005019231A1 (en) * | 2003-06-05 | 2005-03-03 | Kaneka Corporation | Phosphazene compound, photosensitive resin composition and use thereof |
JP2007016184A (en) * | 2005-07-11 | 2007-01-25 | Fujifilm Holdings Corp | Elastomer, photosensitive composition, photosensitive film, and method for forming permanent pattern |
JP2008107458A (en) * | 2006-10-24 | 2008-05-08 | Hitachi Chem Co Ltd | Photosensitive resin composition and photosensitive element |
JP2008107492A (en) * | 2006-10-24 | 2008-05-08 | Kaneka Corp | Flame-retardant photosensitive resin composition and its use |
WO2008065905A1 (en) * | 2006-11-15 | 2008-06-05 | Asahi Kasei Kabushiki Kaisha | Photosensitive resin composition, and flexible print circuit board using the same |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102792226A (en) * | 2010-03-31 | 2012-11-21 | 太阳控股株式会社 | Photosensitive resin composition |
CN102792226B (en) * | 2010-03-31 | 2014-07-09 | 太阳控股株式会社 | Photosensitive resin composition,dry film and printed circuit board |
JP2016000782A (en) * | 2014-06-12 | 2016-01-07 | パナソニックIpマネジメント株式会社 | Epoxy resin composition, metal-clad laminate, and substrate material for package |
Also Published As
Publication number | Publication date |
---|---|
TWI394002B (en) | 2013-04-21 |
TW201027242A (en) | 2010-07-16 |
CN102112921A (en) | 2011-06-29 |
KR20110039453A (en) | 2011-04-18 |
CN102112921B (en) | 2013-11-20 |
JP5301915B2 (en) | 2013-09-25 |
KR101613330B1 (en) | 2016-04-18 |
JP2010039389A (en) | 2010-02-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5301915B2 (en) | Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them | |
JP5043516B2 (en) | Photocurable / thermosetting resin composition and printed wiring obtained using the same | |
JP4616863B2 (en) | Photosensitive resin composition and flexible wiring board obtained using the same | |
JP5377020B2 (en) | Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them | |
JP5513711B2 (en) | Photosensitive resin composition and cured product thereof | |
JP5449688B2 (en) | Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them | |
JP5183425B2 (en) | Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them | |
JP5688116B2 (en) | Photo-curable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using them | |
JP2010113241A (en) | Photosetting resin composition, dry film and cured product of the same, and printed wiring board using them | |
JP5043775B2 (en) | Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them | |
JP5285648B2 (en) | Photocurable resin composition, dry film and printed wiring board using the same | |
JP5660690B2 (en) | Photosensitive resin composition and cured product thereof | |
JP5113298B2 (en) | Photocurable / thermosetting resin composition and printed wiring board obtained using the same | |
JP5575858B2 (en) | Flame-retardant photocurable resin composition, dry film and cured product thereof, and printed wiring board using them | |
JP5433209B2 (en) | Photocurable resin composition, dry film and cured product thereof, and printed wiring board using them |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980130559.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09804745 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20117002701 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 09804745 Country of ref document: EP Kind code of ref document: A1 |