JP2006190848A - Photosetting/thermosetting one-liquid type solder resist composite and printed wiring board using the same - Google Patents
Photosetting/thermosetting one-liquid type solder resist composite and printed wiring board using the same Download PDFInfo
- Publication number
- JP2006190848A JP2006190848A JP2005001970A JP2005001970A JP2006190848A JP 2006190848 A JP2006190848 A JP 2006190848A JP 2005001970 A JP2005001970 A JP 2005001970A JP 2005001970 A JP2005001970 A JP 2005001970A JP 2006190848 A JP2006190848 A JP 2006190848A
- Authority
- JP
- Japan
- Prior art keywords
- solder resist
- acid
- printed wiring
- wiring board
- thermosetting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 55
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 16
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- 239000002131 composite material Substances 0.000 title abstract 3
- -1 organic acid salt Chemical class 0.000 claims abstract description 34
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 235000019260 propionic acid Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J13/00—Details of machines for forging, pressing, or hammering
- B21J13/02—Dies or mountings therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J13/00—Details of machines for forging, pressing, or hammering
- B21J13/08—Accessories for handling work or tools
- B21J13/14—Ejecting devices
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Materials For Photolithography (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、プリント配線板の永久マスクとしての使用に適し、露光後、アルカリ水溶液で現像することによって画像形成し、加熱硬化することにより、耐熱性、密着性、無電解金めっき耐性、無電解すずめっき耐性並びに電気特性に優れたソルダーレジスト膜を形成できるアルカリ現像可能な光硬化性・熱硬化性の一液型ソルダーレジスト組成物に関する。本発明はまた、ソルダーレジストパターンの形成に上記組成物を用いたプリント配線板に関するものである。 The present invention is suitable for use as a permanent mask of a printed wiring board. After exposure, an image is formed by developing with an alkaline aqueous solution, and heat-cured to provide heat resistance, adhesion, electroless gold plating resistance, electroless The present invention relates to a photocurable / thermosetting one-component solder resist composition capable of forming an alkali developable solder resist film having excellent tin plating resistance and electrical characteristics. The present invention also relates to a printed wiring board using the above composition for forming a solder resist pattern.
現在、ほとんどのプリント配線板のソルダーレジストには、高精度、高密度化の観点から、露光後、現像することにより画像形成し、加熱硬化して塗膜を形成する液状アルカリ現像型ソルダーレジストが使用されている。このような希アルカリ水溶液を用いるアルカリ現像タイプのソルダーレジストとしては、例えば、ノボラック型エポキシ化合物と不飽和一塩基酸の反応生成物に酸無水物を付加した感光性樹脂、光重合開始剤、希釈剤、及びエポキシ化合物からなる二液型の液状ソルダーレジスト組成物が、提案されている（例えば特許文献１参照）。 Currently, from the viewpoint of high accuracy and high density, most of the printed wiring board solder resists are liquid alkaline development type solder resists that form an image by developing after exposure and heat cure to form a coating film. in use. As an alkali development type solder resist using such a dilute alkaline aqueous solution, for example, a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a dilution A two-component liquid solder resist composition composed of an agent and an epoxy compound has been proposed (see, for example, Patent Document 1).
しかしながら、このような液状のアルカリ現像型ソルダーレジストのほとんどが、ノボラック型エポキシ化合物と不飽和一塩基酸の反応生成物に酸無水物を付加した感光性樹脂、光重合開始剤などを主成分とする主剤と、希釈剤やエポキシ化合物を主成分とする硬化剤とからなる二液型のソルダーレジストであり、主剤と硬化剤をよく混合してから使用しなければならない。また、混合後のポットライフは２４時間以内と短く、さらに、乾燥工程と現像工程の間にも主剤の感光性樹脂に含まれるカルボキシル基と硬化剤中のエポキシ化合物のエポキシ基が徐々に反応するため現像不良（熱かぶり）を起こすなど、作業上の問題点がある。更に特性面では、鉛フリー化への対応の為に要求が増えつつある無電解すずめっき耐性が十分で無いという問題がある。 However, most of such liquid alkali development type solder resists are mainly composed of a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, and the like. It is a two-component solder resist composed of a main agent to be cured and a curing agent mainly composed of a diluent or an epoxy compound, and must be used after the main agent and the curing agent are mixed well. Moreover, the pot life after mixing is as short as 24 hours or less, and further, the carboxyl group contained in the main photosensitive resin and the epoxy group of the epoxy compound in the curing agent gradually react between the drying step and the developing step. Therefore, there are operational problems such as development failure (hot fogging). Furthermore, in terms of characteristics, there is a problem that the electroless tin plating resistance, which is increasing in demand for dealing with lead-free, is not sufficient.
また上記作業性、保存安定性の問題を解決する為に、例えば、分子内にカルボキシル基と光反応性を有する高分子化合物、希釈剤、光重合開始剤、メラミン又はその誘導体、あるいは更に２，４，６−トリスメルカプト−Ｓ−トリアジンを含む一液型のソルダーレジストが提案されている（例えば特許文献２参照）。しかしながらこの一液型ソルダーレジストは，作業性は優れるものの、耐熱性、無電解金めっき耐性が二液型の液状ソルダーレジストに比べ不安定であり、実用化されるに至っていない。また当然、無電解すずめっき耐性は有していない
従って、本発明は、上記従来技術が抱える問題を解決する為になされたものであり、その主な目的は、一液型としての特徴である保存安定性や作業性を有するとともにソルダーレジストとして十分満足できる耐熱性、密着性、無電解金めっき耐性、電気特性等の塗膜特性を有し、且つ従来二液型ソルダーレジストでも十分ではない無電解すずめっき耐性を有する、アルカリ現像可能な光硬化・熱硬化性の一液型のソルダーレジスト組成物とそれを用いたドライフィルム及びプリント配線板を提供することにある。 Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art, and its main purpose is storage stability and workability, which are features of a one-pack type, and is sufficient as a solder resist. Photo-curing capable of alkali development with satisfactory heat resistance, adhesion, electroless gold plating resistance, coating characteristics such as electrical properties, and electroless tin plating resistance that is not sufficient even with conventional two-component solder resists The object is to provide a thermosetting one-component solder resist composition, a dry film using the same, and a printed wiring board.
前記目的を達成するべく鋭意研究を重ねた結果、本発明の第一の態様は、（Ａ）不飽和一塩基酸(a)と１種類以上の１分子内に１つの不飽和基を有する化合物(b)とからなる共重合物に、１分子内に脂環式エポキシ基と不飽和基を併せ持つ化合物(c)を付加してなるカルボキシル基を有する共重合系樹脂、（Ｂ）希釈剤、（Ｃ）光重合開始剤、（Ｄ）メラミン又はその有機酸塩、及び（Ｅ）無機フィラーを含むことを特徴としたアルカリ現像可能な光硬化・熱硬化性の一液型のソルダーレジスト組成物が提供される。また別の提供形態として、上記ソルダーレジスト組成物をキャリアフィルムに塗布乾燥して得られる光硬化性・熱硬化性のドライフィルムがある。第二の態様は、回路形成されたプリント配線板表面に前記一液型ソルダーレジスト組成物を塗布し乾燥後、又は前記ドライフィルムをラミネート後、活性エネルギー線によりパターン露光し、未露光部をアルカリ水溶液により現像し、加熱硬化してソルダーレジスト膜を形成してなるプリント配線板が提供される。 As a result of extensive research to achieve the above object, the first aspect of the present invention is (A) an unsaturated monobasic acid (a) and one or more compounds having one unsaturated group in one molecule. (b) a copolymer resin having a carboxyl group formed by adding a compound (c) having both an alicyclic epoxy group and an unsaturated group in one molecule to the copolymer comprising (b), (B) a diluent, (C) a photopolymerization initiator, (D) a melamine or an organic acid salt thereof, and (E) an alkali-developable photocurable / thermosetting one-component solder resist composition characterized by comprising an inorganic filler Is provided. As another providing form, there is a photocurable / thermosetting dry film obtained by applying and drying the above solder resist composition on a carrier film. In the second aspect, the one-component solder resist composition is applied to the surface of a printed wiring board on which a circuit has been formed and dried, or after laminating the dry film, pattern exposure is performed with active energy rays, and the unexposed portion is alkalinized. A printed wiring board is provided that is developed with an aqueous solution, heat-cured, and forms a solder resist film.
本発明のアルカリ現像可能な光硬化・熱硬化性の一液型のソルダーレジスト組成物は、一液としての特徴である保存安定性や乾燥管理幅の長い現像性を有し、且つ、ソルダーレジストとして十分満足できる耐熱性、密着性、無電解金めっき耐性、電気特性等の塗膜特性を有する事から、生産性に優れ、信頼性の高いプリント配線板を低価格で提供することも可能となる。更に無電解すずめっき耐性を有することから、鉛フリー化への対応の要求にも応えることができる。また本発明に用いる共重合樹脂（Ａ）はハロゲンを完全になくすことができる為、ハロゲンフリー化の要求にも応えることができる。 The alkali-developable photocurable / thermosetting one-pack type solder resist composition of the present invention has a storage stability and developability with a long drying control width, which are characteristics as a single solution, and is a solder resist. As it has coating properties such as heat resistance, adhesion, electroless gold plating resistance, and electrical properties that can be fully satisfied, it is possible to provide highly reliable printed wiring boards with excellent productivity and low price. Become. Furthermore, since it has electroless tin-plating resistance, it can respond to the request | requirement of corresponding to lead-free. Further, since the copolymer resin (A) used in the present invention can completely eliminate halogen, it can meet the demand for halogen-free.
本発明のアルカリ現像可能な光硬化・熱硬化性の一液型ソルダーレジスト組成物の基本的態様は、（Ａ）不飽和一塩基酸(a)と１種類以上の１分子内に１つの不飽和基を有する化合物(b)とからなる共重合物に、１分子内に脂環式エポキシ基と不飽和基を併せ持つ化合物(c)を付加してなるカルボキシル基を有する共重合系樹脂、（Ｂ）希釈剤、（Ｃ）光重合開始剤、（Ｄ）メラミン又はその有機酸塩、及び（Ｅ）無機フィラーを含むソルダーレジスト組成物が、保存安定性や作業性を有し、且つソルダーレジストとして満足できる耐熱性、密着性、無電解金めっき耐性、無電解すずめっき耐性、電気特性等の諸特性を有する事を見出し本発明を完成するに至ったものである。 The basic aspect of the alkali-developable photocurable / thermosetting one-component solder resist composition of the present invention is as follows. (A) Unsaturated monobasic acid (a) A copolymer resin having a carboxyl group formed by adding a compound (c) having both an alicyclic epoxy group and an unsaturated group in one molecule to a copolymer comprising a compound (b) having a saturated group; A solder resist composition containing B) a diluent, (C) a photopolymerization initiator, (D) melamine or an organic acid salt thereof, and (E) an inorganic filler has storage stability and workability, and is a solder resist. As a result, the inventors have found that the present invention has various characteristics such as heat resistance, adhesion, electroless gold plating resistance, electroless tin plating resistance, and electrical characteristics, and the present invention has been completed.
すなわち、本発明のアルカリ現像可能な光硬化・熱硬化性の一液型ソルダーレジスト組成物は、第一の特徴は、熱硬化性組成物を用いずともソルダーレジストとしての特性を発現する為に、造膜性に優れた、不飽和一塩基酸と１種類以上の１分子内に１つの不飽和基を有する化合物とからなる共重合物に、１分子内に脂環式エポキシ基と不飽和基を併せ持つ化合物を付加してなるカルボキシル基を有する共重合系樹脂とメラミン又はその有機酸塩を併用したことにある。メラミン又はその有機酸塩は、エポキシ樹脂等の熱硬化成分を配合した二液型のソルダーレジスト組成物では、その硬化促進触媒として使用されているが、エポキシ樹脂等の熱硬化成分を使用しない組成物では、効果がみられないと考えられていた。
本発明では、この特定の共重合系樹脂（Ａ）とメラミン又はその有機酸塩を併用した時に限って耐熱性、無電解金めっき耐性、無電解すずめっき耐性が、著しく向上することを見出した。これは、先に述べた引用例に記載されているような、別の分子骨格で構成された共重合系樹脂との併用ではこれらの特性を得ることはできない。これは、この特定の共重合系樹脂（Ａ）の不飽和二重結合と、メラミン又はその有機酸塩の活性水素が、加熱硬化中に一部付加反応し分子鎖に取り込まれ、銅箔へのキレート効果と防錆効果により、塗膜と銅箔の密着性を向上させるものと考えられる。
また無電解すずめっき液は、強酸性液であり、これに耐性を得る為にはレジストと銅箔の界面の優れた密着性に加え、優れた表面硬化性が必要であるが、この共重合系高分子化合物は、クレゾールもしくはフェノールノボラック型エポキシ樹脂のアクリレート化物に二塩基酸無水物を付加した不飽和基とカルボキシル基を併せ持つ感光性樹脂と違い、主鎖に共役の二重結合を有しないため、優れた光硬化性を有することができる。
また第二の特徴は、一液化を達成するために、熱反応性のエポキシ樹脂やメラミン樹脂を用いず、塗膜形成成分の反応性基としては不飽和基を主体としたことにある。この不飽和基は、光重合開始剤の存在下、光照射による反応は容易に進行するが、熱による反応は起きにくい為、このような組成物は優れた保存安定性を示し、本発明の目的の一つである一液化は達成される。
第三の特徴は、無機フィラーを必須成分とし、しかも比較的多量に使用することにより硬化収縮を少なくした点にある。
That is, the alkali-developable photocurable / thermosetting one-component solder resist composition of the present invention is characterized in that the first feature is to exhibit characteristics as a solder resist without using a thermosetting composition. , A copolymer comprising an unsaturated monobasic acid and one or more types of compounds having one unsaturated group in one molecule, excellent in film-forming properties, and an alicyclic epoxy group and unsaturated in one molecule That is, a copolymer resin having a carboxyl group formed by adding a compound having a group together with melamine or an organic acid salt thereof. Melamine or its organic acid salt is a composition that does not use a thermosetting component such as an epoxy resin, although it is used as a curing acceleration catalyst in a two-part solder resist composition containing a thermosetting component such as an epoxy resin. Things were thought to have no effect.
In the present invention, it has been found that heat resistance, electroless gold plating resistance, and electroless tin plating resistance are remarkably improved only when this specific copolymer resin (A) and melamine or an organic acid salt thereof are used in combination. . This is because these properties cannot be obtained in combination with a copolymer resin composed of another molecular skeleton as described in the above-mentioned cited example. This is because the unsaturated double bond of this specific copolymer resin (A) and the active hydrogen of melamine or its organic acid salt are partially added and reacted into the molecular chain during heat-curing, to the copper foil. It is considered that the adhesion between the coating film and the copper foil is improved by the chelating effect and the antirust effect.
In addition, the electroless tin plating solution is a strongly acidic solution. In order to obtain resistance to this, in addition to excellent adhesion at the interface between the resist and the copper foil, excellent surface curability is required. Unlike high-sensitivity resins in which a dibasic acid anhydride is added to an acrylated product of cresol or phenol novolac type epoxy resin, the polymer compound does not have a conjugated double bond in the main chain. Therefore, it can have excellent photocurability.
The second feature is that a thermally reactive epoxy resin or melamine resin is not used in order to achieve a one-component solution, and an unsaturated group is mainly used as a reactive group of the coating film forming component. This unsaturated group easily reacts by light irradiation in the presence of a photopolymerization initiator, but the reaction by heat hardly occurs. Therefore, such a composition exhibits excellent storage stability. One liquefaction, one of the objectives, is achieved.
The third feature is that an inorganic filler is an essential component and the curing shrinkage is reduced by using a relatively large amount.
以下、本発明の一液型ソルダーレジスト組成物の各構成成分について詳しく説明する。
まず、本発明に用いられる（Ａ）不飽和一塩基酸(a)と１種類以上の１分子内に１つの不飽和基を有する化合物(b)とからなる共重合物に、１分子内に脂環式エポキシ基と不飽和基を併せ持つ化合物(c)を付加してなるカルボキシル基を有する共重合系樹脂は、酸価３０〜１５０ｍｇＫＯＨ／ｇ、より好ましくは酸価５０〜１４０ｍｇＫＯＨ／ｇである。酸価が３０ｍｇＫＯＨ／ｇ未満のときは、アルカリ水溶液に対する溶解性が悪くなり、現像が困難になる。一方、酸価が１５０ｍｇＫＯＨ／ｇより超えると、露光の条件によらず露光部の塗膜表面まで現像されてしまうので好ましくない。
また、この共重合系樹脂の重量平均分子量は８，０００〜７０，０００、より好ましくは１０，０００〜５０，０００である。本発明は、樹脂の分子量効果による造膜性が重要であり８，０００未満では十分な造膜性が得られず、一方７０，０００以上では現像性が得られない。
Hereinafter, each component of the one-component solder resist composition of the present invention will be described in detail.
First, (A) an unsaturated monobasic acid (a) used in the present invention and one or more kinds of a copolymer (b) having one unsaturated group in one molecule are converted into one molecule. The copolymer resin having a carboxyl group formed by adding the compound (c) having both an alicyclic epoxy group and an unsaturated group has an acid value of 30 to 150 mgKOH / g, more preferably an acid value of 50 to 140 mgKOH / g. . When the acid value is less than 30 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated and development is difficult. On the other hand, an acid value exceeding 150 mgKOH / g is not preferable because the surface of the coating in the exposed area is developed regardless of the exposure conditions.
Moreover, the weight average molecular weight of this copolymer resin is 8,000-70,000, More preferably, it is 10,000-50,000. In the present invention, the film forming property due to the molecular weight effect of the resin is important, and if it is less than 8,000, sufficient film forming property cannot be obtained, whereas if it is 70,000 or more, developability cannot be obtained.
この共重合系樹脂の調製に用いられる不飽和一塩基酸(a)の代表的なものとしては、アクリル酸、メタクリル酸、イタコン酸、β−カルボキシルエチル（メタ）アクリレートや、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート等のヒドロキシル基含有の（メタ）アクリレートにニ塩基酸無水物を付加した化合物などがあり、二塩基酸無水物としては無水フタル酸、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水コハク酸、無水マレイン酸、無水イタコン酸、無水ナジック酸などが挙げられる。これらの中で、感光性、保存安定性の面から、アクリル酸又はメタクリル酸が特に好ましい。これら不飽和一塩基酸(a)は、単独又は２種類以上を混合して用いてもよい。
なお、本明細書において（メタ)アクリレートとは、アクリレート及びメタクリレートを総称するものであり、他の類似の表現についても同様である。
Typical examples of the unsaturated monobasic acid (a) used for the preparation of the copolymer resin include acrylic acid, methacrylic acid, itaconic acid, β-carboxylethyl (meth) acrylate, 2-hydroxyethyl ( There are compounds that add dibasic acid anhydrides to hydroxyl group-containing (meth) acrylates such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Examples include phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, nadic anhydride, and the like. Among these, acrylic acid or methacrylic acid is particularly preferable from the viewpoint of photosensitivity and storage stability. These unsaturated monobasic acids (a) may be used alone or in admixture of two or more.
In this specification, (meth) acrylate is a general term for acrylate and methacrylate, and the same applies to other similar expressions.
また、１分子内に１つの不飽和基を有する化合物(b)としては、スチレン、酢酸ビニルなどのビニル化合物；メチル（メタ）アクリレート、エチル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレートなどのアルキル（メタ）アクリレート類；２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、フェニルグリシジルエーテル（メタ）アクリレートなどの（メタ）アクリル酸エステル類などが挙げられる。 The compound (b) having one unsaturated group in one molecule includes vinyl compounds such as styrene and vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, lauryl (meth) acrylate, isopropyl (meta ) Acrylate, alkyl (meth) acrylates such as t-butyl (meth) acrylate; 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate , (Meth) acrylic acid esters such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and phenylglycidyl ether (meth) acrylate.
１分子内に１つの脂環式エポキシ基と１つの不飽和基を併せ持つ化合物(c)としては、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、３，４−エポキシシクロヘキシルエチル（メタ）アクリレート、３，４−エポキシシクロヘキシルブチル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチルアミノアクリレートなどが挙げられる。これらの中で特に３，４−エポキシシクロヘキシルメチル（メタ）アクリレートが好ましい。 As the compound (c) having one alicyclic epoxy group and one unsaturated group in one molecule, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, Examples include 3,4-epoxycyclohexylbutyl (meth) acrylate and 3,4-epoxycyclohexylmethylamino acrylate. Among these, 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
本発明に用いられる希釈剤（Ｂ）は、インキ組成物の粘度を調整して作業性を向上させるとともに、架橋密度を上げたり、密着性などを向上するために用いられ、光重合性モノマーなどの反応性希釈剤（Ｂ−１）や公知慣用の有機溶剤（Ｂ−２）が使用できる。
反応性希釈剤（Ｂ−１）としては、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート類；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類；エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等のアルキレンオキシド誘導体のモノ又はジ（メタ）アクリレート類；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、ジトリメチロールプロパン、ジペンタエリスリトール、トリスヒドロキシエチルイソシアヌレート等の多価アルコール又はこれらのエチレンオキシド或いはプロピレンオキシド付加物の多価（メタ）アクリレート類；フェノキシエチル（メタ）アクリレート、ビスフェノールＡのポリエトキシジ（メタ）アクリレート等のフェノール類のエチレンオキシドあるいはプロピレンオキシド付加物の（メタ）アクリレート類；グリセリンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリジジルエーテルの（メタ）アクリレート類；及びメラミン（メタ）アクリレート等を挙げることができる。
これらは、単独または２種以上組み合わせて使用でき、密着性の点で親水性基含有の（メタ）アクリレート類が、また光硬化性の点で多官能性の（メタ）アクリレート類が好ましい。これらの光重合モノマーの配合量は、共重合系樹脂（Ａ）１００質量部に対して２０〜１２０質量部、より好ましく２０〜１００質量部であることが望ましい。２０質量部未満では、光反応性が悪く、１２０質量部より多い場合は、指触乾燥性が悪くなるので好ましくない。
The diluent (B) used in the present invention is used to adjust the viscosity of the ink composition to improve workability, and to increase the crosslink density or improve adhesion, such as a photopolymerizable monomer. The reactive diluent (B-1) or a known and commonly used organic solvent (B-2) can be used.
Examples of the reactive diluent (B-1) include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxyalkyl (meth) acrylates such as acrylates; Mono- or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane Polyhydric alcohols such as dipentaerythritol and trishydroxyethyl isocyanurate, or poly (meth) acrylates of these ethylene oxide or propylene oxide adducts Relates; (Meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl (Meth) acrylates of glycidyl ether such as isocyanurate; and melamine (meth) acrylate.
These can be used alone or in combination of two or more, and (meth) acrylates containing a hydrophilic group are preferable in terms of adhesion, and polyfunctional (meth) acrylates are preferable in terms of photocurability. The blending amount of these photopolymerization monomers is preferably 20 to 120 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the copolymer resin (A). If it is less than 20 parts by mass, the photoreactivity is poor.
前記有機溶剤（Ｂ−２）としては、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、トリプロピレングリコールモノメ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、乳酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエステル類；オクタン、デカン等の脂肪族炭化水素類；石油エーテル、石油ナフサ、ソルベントナフサ等の石油系溶剤など、公知慣用の有機溶剤が使用できる。これらの有機溶剤は、単独で又は二種類以上組み合わせて用いることができる。
このような有機溶剤の配合量は、コーティング方法や使用する有機溶剤の沸点により異なり、特に制限されるものでは無いが、高沸点の有機溶剤が多量に含まれる場合、指触乾燥性が低下したり、コーティング後、仮乾燥するまでに、ダレ等を発生するので好ましくない。
Examples of the organic solvent (B-2) include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbi Toluene, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether and other glycol ethers; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl Carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Seteto, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents can be used alone or in combination of two or more.
The amount of such an organic solvent varies depending on the coating method and the boiling point of the organic solvent to be used, and is not particularly limited. However, when a high-boiling organic solvent is contained in a large amount, the dryness to touch decreases. Or sagging after the coating and before temporary drying.
本発明に用いられる光重合開始剤（Ｃ）としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類；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、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等のアセトフェノン類；２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１等のアミノアセトフェノン類；２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリーブチルアントラキノン、１−クロロアントラキノン等のアントラキノン類；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等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン等のベンゾフェノン類；又はキサントン類；（２，６−ジメトキシベンゾイル）−２，４，４−ペンチルホスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、エチル−２，４，６−トリメチルベンゾイルフェニルフォスフィネイト等のフォスフィンオキサイド類；各種パーオキサイド類、チタノセン系開始剤などが挙げられ、これらは、Ｎ，Ｎ−ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ−ジメチルアミノ安息香酸イソアミルエステル、ペンチル−４−ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類のような光増感剤等と併用しても良い。これらの光重合開始剤は単独で又は２種以上を組み合わせて用いることができる。またこれらの光重合開始剤（Ｃ）の配合量は、共重合系樹脂（Ａ）１００質量部に対して１〜２５質量部、より好ましくは２〜２０質量部である。前記配合量が１質量部未満の場合、光硬化性が低下し、露光・現像後のパターン形成が困難になるので好ましくない。一方、２５質量部を超えた場合、厚膜硬化性が低下し、またコスト高の原因となるので好ましくない。 Examples of the photopolymerization initiator (C) used in the present invention include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl]- Aminoacetophenones such as 2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2-methylanthraquinone, 2-ethylanthraquinone, 2- Tertiary Anthraquinones such as tilanthraquinone and 1-chloroanthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; Acetophenone dimethyl ketal, benzyldimethyl ketal, etc. Benzophenones such as benzophenone; or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and ethyl-2,4,6-trimethylbenzoylphenylphosphinate; And N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, and the like. You may use together with photosensitizers, such as tertiary amines, such as. These photopolymerization initiators can be used alone or in combination of two or more. Moreover, the compounding quantity of these photoinitiators (C) is 1-25 mass parts with respect to 100 mass parts of copolymer resin (A), More preferably, it is 2-20 mass parts. When the amount is less than 1 part by mass, the photocurability is lowered, and pattern formation after exposure / development becomes difficult. On the other hand, when the amount exceeds 25 parts by mass, the thick film curability is lowered and the cost is increased.
メラミン又はその有機酸塩（Ｄ）としては、メラミン又は、メラミンと当モルの有機酸を反応させたものが使用できる。メラミンの有機酸塩はメラミンを沸騰水中に溶解し、水あるいはアルコール等の親水性溶剤に溶解した有機酸を添加し、析出した塩をろ過することで得られる。メラミン分子中の１個のアミノ基は、反応性が速いが他の２個の反応性は低い為、反応は化学量論的に進行し、メラミン分子中の１個のアミノ基に有機酸が１個付加したメラミン塩が生成する。有機酸としては、カルボキシル基含有化合物、酸性リン酸エステル化合物、スルホン酸含有化合物が考えられ、いずれも使用することができるが、カルボキシル基含有化合物がより好ましい。 As melamine or its organic acid salt (D), melamine or a product obtained by reacting melamine with an equimolar amount of organic acid can be used. The organic acid salt of melamine can be obtained by dissolving melamine in boiling water, adding an organic acid dissolved in water or a hydrophilic solvent such as alcohol, and filtering the deposited salt. One amino group in the melamine molecule is fast reactive but the other two are low in reactivity, so the reaction proceeds stoichiometrically, and an organic acid is attached to one amino group in the melamine molecule. One added melamine salt is formed. Examples of the organic acid include a carboxyl group-containing compound, an acidic phosphate ester compound, and a sulfonic acid-containing compound, and any of them can be used, but a carboxyl group-containing compound is more preferable.
前記カルボキシル基含有化合物としては、モノカルボン酸としては、蟻酸、酢酸、プロピオン酸、酪酸、乳酸、グリコール酸、アクリル酸、メタクリル酸などがあり、ジカルボン酸としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸、マレイン酸、イタコン酸、フタル酸、ヘキサヒドロフタル酸、３−メチルヘキサヒドロフタル酸、４−メチルヘキサヒドロフタル酸、３−エチルヘキサヒドロフタル酸、４−エチルヘキサヒドロフタル酸、テトラヒドロフタル酸、３−メチルテトラヒドロフタル酸、４−メチルテトラヒドロフタル酸、３−エチルテトラヒドロフタル酸、４−エチルテトラヒドロフタル酸、クロトン酸があり、またトリカルボン酸としては、トリメリット酸などがある。これらのなかでも、特にジカルボン酸とメラミンの等モル反応により得られる塩が、これを添加するソルダーレジストの特性低下が少なく、好ましい。また、多塩基酸無水物を用いることもできる。一般に多塩基酸無水物は、例えば沸騰水中に溶解することにより容易に開環して対応するポリカルボン酸を生成する。
これらのメラミン又はその有機酸塩（Ｄ）の配合量は、共重合系樹脂（Ａ）１００質量部に対して１〜２５質量部、より好ましくは２〜２０質量部であることが望ましい。前記配合量が１質量部未満である場合、密着性、耐熱性が低下し、２５質量部を越えると光反応性が低下する。なおメラミンの有機酸塩を使用する場合は、通常メラミンを使用する場合の約１．５〜２倍が必要である
Examples of the carboxyl group-containing compound include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, acrylic acid, and methacrylic acid as monocarboxylic acids, and oxalic acid, malonic acid, and succinic acid as dicarboxylic acids. , Glutaric acid, adipic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4- There are ethylhexahydrophthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, and crotonic acid. There are merit acids. Among these, a salt obtained by an equimolar reaction of dicarboxylic acid and melamine is particularly preferable because there is little deterioration in the properties of the solder resist to which it is added. Polybasic acid anhydrides can also be used. In general, polybasic acid anhydrides are easily opened by, for example, dissolving in boiling water to produce the corresponding polycarboxylic acids.
The blending amount of these melamines or organic acid salts (D) thereof is desirably 1 to 25 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the copolymer resin (A). When the blending amount is less than 1 part by mass, the adhesion and heat resistance are lowered, and when it exceeds 25 parts by mass, the photoreactivity is lowered. In addition, when using the organic acid salt of melamine, about 1.5 to 2 times the case of using melamine is necessary.
無機フィラー（Ｅ）としては、硫酸バリウム、チタン酸バリウム、酸化ケイ素紛、微粉状酸化ケイ素、無定形シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、マイカ等の公知慣用の無機フィラーを単独で又は２種以上を組み合わせて用いることができる。これらは塗膜の硬化収縮を抑制し、密着性、硬度などの特性を向上する目的で用いられる。その配合量は、共重合系樹脂（Ａ）１００質量部に対して５０〜２５０質量部であることが望ましい。上記範囲より少ない場合、密着性、耐熱性の低下などを生じ、一方多い場合、塗膜強度の低下や感度低下などを生じ、いずれも好ましくない。 Known inorganic fillers (E) such as barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, etc. These inorganic fillers can be used alone or in combination of two or more. These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion and hardness. As for the compounding quantity, it is desirable that it is 50-250 mass parts with respect to 100 mass parts of copolymer resin (A). When the amount is less than the above range, adhesion and heat resistance are reduced. On the other hand, when the amount is more than the above range, the coating strength is lowered and the sensitivity is lowered.
さらに、必要に応じて、公知慣用の着色顔料、着色染料、熱重合禁止剤、増粘剤、消泡剤、レベリング剤、カップリング剤、難燃助剤等が使用できる。
また、本発明では必要に応じて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、ビスフェノール型エポキシ樹脂、ビフェニール型エポキシ樹脂やトリグリシジルイソシアヌレート等の公知慣用のエポキシ樹脂を使用することができるが、一液性であり、保存安定性が損なわれないよう注意が必要である。
Furthermore, if necessary, known and commonly used color pigments, coloring dyes, thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents, coupling agents, flame retardant aids, and the like can be used.
Further, in the present invention, a known and commonly used epoxy resin such as a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a bisphenol type epoxy resin, a biphenyl type epoxy resin or triglycidyl isocyanurate can be used as necessary. Care must be taken so that the storage stability is not impaired.
なお本発明の一液型ソルダーレジスト組成物は、液状、ペースト状またはドライフィルムの形態で提供することができる。ドライフィルムとして供給する場合は、例えばキャリアフィルム上にロールコーターやドクターバー、ワイヤーバー方式、スピンコート方式、ドクタープレート方式等により本発明のソルダーレジスト組成物を塗布した後、６０〜１００℃に設定した乾燥炉で乾燥し有機溶剤を除去することにより、また必要に応じて離型フィルムを貼りつけることにより得ることができる。この際キャリアフィルム上のレジストの膜厚は、５〜１５０μｍ好ましくは１０〜６０μｍに調整される。上記キャリアフィルムとしては、ポリエチレンテレフタレート、ポリプロピレン等のフィルムが好適に使用される。 The one-component solder resist composition of the present invention can be provided in the form of a liquid, a paste, or a dry film. When supplying as a dry film, for example, after applying the solder resist composition of the present invention on a carrier film by a roll coater, a doctor bar, a wire bar method, a spin coating method, a doctor plate method, etc., the temperature is set to 60 to 100 ° C. It can be obtained by drying in a drying oven to remove the organic solvent and, if necessary, attaching a release film. At this time, the thickness of the resist on the carrier film is adjusted to 5 to 150 μm, preferably 10 to 60 μm. As the carrier film, a film of polyethylene terephthalate, polypropylene or the like is preferably used.
以上のような組成を有する本発明の一液型ソルダーレジスト組成物は、必要に応じて希釈して塗布方法に適した粘度に調整し、これを例えば、回路形成されたプリント配線板にスクリーン印刷法、カーテンコート法、スプレーコート法、ロールコート法等の方法により塗布し、例えば７０〜９０℃の温度で組成物中に含まれる有機溶剤を揮発乾燥させることにより、タックフリーの塗膜を形成できる。その後、フォトマスクを通して選択的に活性エネルギー線により露光し、未露光部を希アルカリ水溶液により現像してレジストパターンを形成でき、さらに、加熱硬化させることにより、耐熱性、密着性、無電解金めっき耐性、無電解すずめっき耐性、電気特性等に優れたソルダーレジスト膜を有するプリント基板が形成される。 The one-component solder resist composition of the present invention having the above composition is diluted as necessary to adjust the viscosity to be suitable for the coating method, and this is screen-printed on a printed wiring board on which a circuit is formed, for example. A tack-free coating film is formed by applying the organic solvent contained in the composition at a temperature of 70 to 90 ° C. by evaporating and drying, for example, by a method such as a coating method, curtain coating method, spray coating method or roll coating method. it can. Then, it can be exposed selectively with active energy rays through a photomask, and the unexposed part can be developed with a dilute alkaline aqueous solution to form a resist pattern. Furthermore, by heat curing, heat resistance, adhesion, electroless gold plating A printed circuit board having a solder resist film excellent in resistance, electroless tin plating resistance, electrical characteristics and the like is formed.
前記希アルカリ水溶液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類などのアルカリ水溶液が使用できる。また、露光するための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ又はメタルハライドランプなどを用いることができる。その他、レーザー光線なども活性光線として利用できる。 As the dilute alkaline aqueous solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used. As an irradiation light source for exposure, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. In addition, a laser beam can also be used as an actinic beam.
以下に実施例及び比較例を示して本発明について具体的に説明するが、本発明が下記実施例に限定されるものでないことはもとよりである。なお、以下において「部」とあるのは、特に断りのない限り全て「質量部」を示す。 EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “part” means “part by mass” unless otherwise specified.
合成例１
温度計、撹拌機、滴下ロート、及び還流冷却器を備えたフラスコに、溶媒としてジプロピレングリコールモノメチルエーテル３００．０ｇを１００℃まで加熱し、メタクリル酸１７２．０ｇ、ε−カプロラクトン変性メタクリル酸（平均分子量３４４）１７２．０ｇ、メタクリル酸メチル１５０．０ｇ、ジプロピレングリコールモノメチルエーテル１４２．０ｇ、及び重合触媒としてアゾビスイソブチロニトリル１０．０ｇの混合物を３時間かけて滴下し、更に１１０℃，３時間攪拌し重合触媒を失活させて共重合樹脂溶液を得た。この樹脂溶液を冷却後、３，４−エポキシシクロヘキシルメチルアクリレート（ダイセル化学工業（株）製サイクロマーＡ４００）１７０．０ｇ、トリフェニルホスフィン３．０ｇ、ハイドロキノンモノメチルエーテル１．３ｇを加え、１００℃に昇温し、攪拌することによってエポキシの開環付加反応を行った。このようにして得られた１分子中に２個以上のアクリロイル基とカルボキシル基を併せ持つ共重合系樹脂は、重量平均分子量が２５，０００でかつ、不揮発分が６０ｗｔ％、固形物の酸価が９０ｍｇＫＯＨ／ｇであった。以下、この反応溶液を ワニスＡ−１と称す。
Synthesis example 1
In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, 300.0 g of dipropylene glycol monomethyl ether as a solvent was heated to 100 ° C., and 172.0 g of methacrylic acid, ε-caprolactone-modified methacrylic acid (average) (Molecular weight 344) 172.0 g, methyl methacrylate 150.0 g, dipropylene glycol monomethyl ether 142.0 g, and a mixture of azobisisobutyronitrile 10.0 g as a polymerization catalyst were added dropwise over 3 hours. The mixture was stirred for 3 hours to deactivate the polymerization catalyst to obtain a copolymer resin solution. After cooling this resin solution, 170.0 g of 3,4-epoxycyclohexylmethyl acrylate (Daicel Chemical Industries, Ltd., Cyclomer A400), 3.0 g of triphenylphosphine, and 1.3 g of hydroquinone monomethyl ether were added, and the mixture was heated to 100 ° C. Epoxy ring-opening addition reaction was carried out by heating and stirring. The copolymer resin having two or more acryloyl groups and carboxyl groups in one molecule thus obtained has a weight average molecular weight of 25,000, a nonvolatile content of 60 wt%, and a solid acid value. It was 90 mgKOH / g. Hereinafter, this reaction solution is referred to as Varnish A-1.
合成例２
温度計、撹拌機、滴下ロート、及び還流冷却器を備えたフラスコに、溶媒としてジプロピレングリコールモノメチルエール２７６．０ｇと重合触媒としてアゾビスイソブチロニトリル８．０ｇを入れた。窒素雰囲気下で、８０℃に加熱し、メタクリル酸１７２．０ｇとメタクリル酸メチル１００．０ｇとメタクリル酸エチル１１４．０ｇを混合したモノマーを約３時間かけて滴下し、さらに１時間撹拌後、温度を１１５℃まで上げ、重合触媒を失活させて共重合樹脂溶液を得た。
この樹脂溶液を、８５〜９５℃まで下げた後、重合禁止剤としてメチルハイドロキノン０．３ｇと触媒としてトリフェニルホスフィン２．０ｇを加え、グリシジルメタクリレート１６０．０ｇを徐々に滴下し、約２４時間反応させた。このようにして得られた１分子中に２個以上の（メタ）アクリロイル基とカルボキシル基を併せ持つ共重合系樹脂は、重量平均分子量が１６，０００で、かつ、不揮発分が６０ｗｔ％、固形物の酸価が９０ｍｇＫＯＨ／ｇであった。以下、この反応溶液を ワニスＡ−２と称す。
Synthesis example 2
A flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser was charged with 276.0 g of dipropylene glycol monomethyl ale as a solvent and 8.0 g of azobisisobutyronitrile as a polymerization catalyst. In a nitrogen atmosphere, the mixture was heated to 80 ° C., and a monomer mixed with 172.0 g of methacrylic acid, 100.0 g of methyl methacrylate and 114.0 g of ethyl methacrylate was added dropwise over about 3 hours, and the mixture was further stirred for 1 hour. Was increased to 115 ° C., and the polymerization catalyst was deactivated to obtain a copolymer resin solution.
After this resin solution was lowered to 85-95 ° C., 0.3 g of methylhydroquinone as a polymerization inhibitor and 2.0 g of triphenylphosphine as a catalyst were added, and 160.0 g of glycidyl methacrylate was gradually added dropwise, followed by reaction for about 24 hours. I let you. The copolymer resin having two or more (meth) acryloyl groups and carboxyl groups in one molecule thus obtained has a weight average molecular weight of 16,000 and a non-volatile content of 60 wt%. The acid value of was 90 mgKOH / g. Hereinafter, this reaction solution is referred to as Varnish A-2.
合成例３
温度計、撹拌機、滴下ロート、及び還流冷却器を備えたフラスコに、溶媒としてジエチレングリコールモノエチルエーテルアセテート２８０．０ｇと重合触媒としてアゾビスイソブチロニトリル２．８ｇを入れた。窒素雰囲気下で、６０℃に加熱し、メタクリル酸メチル１００．０ｇとグリシジルメタアクリレート１４２．０ｇを混合したモノマーを約４時間かけて滴下し、さらに２時間撹拌後、温度を１１５℃まで上げ、重合触媒を失活させて共重合樹脂溶液を得た。
この樹脂溶液を冷却後、重合禁止剤としてメチルハイドロキノン０．２ｇと触媒としてトリフェニルホスフィン２．０ｇを加え、９５〜１０５℃に加熱した。この混合溶液に、アクリル酸７２．０ｇを徐々に滴下し、酸価が４．０ｍｇＫＯＨ／ｇ以下になるまで、２４時間反応させた。更に、テトラヒドロフタル酸無水物１０６．０ｇを加え、赤外吸光分析で酸無水物の吸収が無くなるまで、８時間反応させた。このようにして得られた１分子中に２個以上のアクリロイル基とカルボキシル基を併せ持つ共重合系樹脂は、重量平均分子量が２４，０００でかつ、不揮発分が６０ｗｔ％、固形物の酸価が９２ｍｇＫＯＨ／ｇであった。以下、この反応溶液を ワニスＡ−３と称す。
Synthesis example 3
A flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was charged with 280.0 g of diethylene glycol monoethyl ether acetate as a solvent and 2.8 g of azobisisobutyronitrile as a polymerization catalyst. In a nitrogen atmosphere, the mixture was heated to 60 ° C., and a monomer mixed with 100.0 g of methyl methacrylate and 142.0 g of glycidyl methacrylate was added dropwise over about 4 hours. After further stirring for 2 hours, the temperature was raised to 115 ° C. The polymerization catalyst was deactivated to obtain a copolymer resin solution.
After cooling this resin solution, 0.2 g of methylhydroquinone as a polymerization inhibitor and 2.0 g of triphenylphosphine as a catalyst were added and heated to 95 to 105 ° C. To this mixed solution, 72.0 g of acrylic acid was gradually added dropwise and reacted for 24 hours until the acid value became 4.0 mgKOH / g or less. Furthermore, 106.0 g of tetrahydrophthalic anhydride was added, and the reaction was continued for 8 hours until the absorption of the acid anhydride disappeared by infrared absorption analysis. The copolymer resin having two or more acryloyl groups and carboxyl groups in one molecule thus obtained has a weight average molecular weight of 24,000, a nonvolatile content of 60 wt%, and a solid acid value. It was 92 mgKOH / g. Hereinafter, this reaction solution is called varnish A-3.
実施例１〜７、及び比較例１〜４
合成例１〜３で得られた各ワニスを用い、下記表１に示す配合割合で各成分を配合し、３本ロールミルを用いて混練し、アルカリ現像可能な光硬化性・熱硬化性の一液型ソルダーレジスト組成物を調製した。尚、印刷時、必要に応じて、有機溶剤で希釈した。
Examples 1-7 and Comparative Examples 1-4
Using each of the varnishes obtained in Synthesis Examples 1 to 3, the components are blended in the blending ratios shown in Table 1 below, kneaded using a three-roll mill, and photocurable and thermosetting that can be alkali-developed. A liquid solder resist composition was prepared. In addition, it diluted with the organic solvent as needed at the time of printing.
上記実施例１〜７及び比較例１〜４の一液型ソルダーレジスト組成物について、以下の各項目について試験を行い、評価した。評価の結果を下記表２に示す。尚評価試験の方法は以下に示す。 About the one-pack type solder resist composition of the said Examples 1-7 and Comparative Examples 1-4, it tested about each following item and evaluated. The evaluation results are shown in Table 2 below. The evaluation test method is shown below.
（１）一液粘度安定性：上記各実施例及び比較例の組成物を２０℃の恒温槽に保管し、ＥＨＤ型粘度計の５回転値を６ヶ月後まで測定し、増粘の有無を確認した。判定基準は以下のとおりである。
○：増粘率が１２０％以内。
△：増粘率が１２０〜２００％以内。
×：ゲル化もしくは増粘率が２００％以上。
(1) One-component viscosity stability: The compositions of the above examples and comparative examples are stored in a constant temperature bath at 20 ° C., and the 5-rotation value of the EHD viscometer is measured up to 6 months later. confirmed. The judgment criteria are as follows.
○: Thickening rate is within 120%.
(Triangle | delta): Thickening rate is 120 to 200% or less.
X: Gelation or thickening rate is 200% or more.
（２）現像性
上記実施例１〜７及び比較例１〜４で得られた一液型ソルダーレジスト組成物を、それぞれ銅張り基板上にスクリーン印刷で全面塗布し、熱風循環式乾燥炉で９０℃で６０分乾燥させ、スプレー圧０．２ＭＰaの１ｗｔ％Ｎａ２ＣＯ３水溶液で１分間現像し、その塗膜表面の現像性を以下の基準で評価した。
○：塗膜が完全に除去され、残渣なし。
△：ほんの僅かにフィラー残りあり、
×：塗膜の残渣あり
(2) Developability Each of the one-component solder resist compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 was applied on the entire surface of a copper-clad substrate by screen printing, and then heated in a hot air circulating drying oven. The film was dried at 60 ° C. for 60 minutes, developed with a 1 wt% Na 2 CO 3 aqueous solution having a spray pressure of 0.2 MPa for 1 minute, and the developability of the coating film surface was evaluated according to the following criteria.
○: The coating film is completely removed and there is no residue.
Δ: Slightly filler remaining,
X: Residual film residue
（３）感度
上記実施例１〜７及び比較例１〜４で得られた一液型ソルダーレジスト組成物を、回路形成されたプリント配線板にスクリーン印刷でそれぞれ全面塗布し、熱風循環式乾燥炉で８０℃，３０分乾燥した。これらの基板に、コダックＮｏ．２のステップタブレットを当て、２００ｍＪ／ｃｍ２で露光し、スプレー圧０．２ＭＰaの１ｗｔ％Ｎａ２ＣＯ３水溶液で１分間現像し、塗膜が完全に残っている段数を評価した。
(3) Sensitivity The one-pack type solder resist compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were applied to the entire surface of the printed wiring board on which the circuit was formed by screen printing. And dried at 80 ° C. for 30 minutes. On these substrates, Kodak No. 2 step tablets were applied, exposed at 200 mJ / cm 2 , developed with 1 wt% Na 2 CO 3 aqueous solution with a spray pressure of 0.2 MPa for 1 minute, and the number of steps where the coating film remained completely was evaluated.
（４）はんだ耐熱性
上記実施例１〜７及び比較例１〜４で得られた一液型ソルダーレジスト組成物を、回路形成されたプリント配線板にスクリーン印刷でそれぞれ全面塗布し、熱風循環式乾燥炉で８０℃，３０分乾燥した。これらの基板にソルダーレジストパターンが描かれたネガフィルムを当て、露光量３００ｍＪ／ｃｍ２の露光条件で露光し、スプレー圧２ＭＰaの１ｗｔ％Ｎａ２ＣＯ３水溶液で１分間現像し、ソルダーレジストパターンを形成した。この基板を、１５０℃で６０分熱硬化し、評価基板を作製した。
この評価基板に、ロジン系フラックスを塗布して、予め２６０℃に設定したはんだ槽に３０秒間浸漬し、イソプロピルアルコールでフラックスを洗浄した後、テープピールテストを行い、レジスト層の膨れ・剥がれ・変色について評価した。
○： 全く変化が認められないもの
△： ほんの僅か変色等の変化があるもの
×： レジスト層の膨れ、剥がれがあるもの
(4) Solder heat resistance The one-pack type solder resist compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were respectively applied to the printed circuit board on which the circuit was formed by screen printing. It was dried at 80 ° C. for 30 minutes in a drying furnace. A negative film on which a solder resist pattern is drawn is applied to these substrates, exposed under an exposure condition of an exposure amount of 300 mJ / cm 2 , developed with a 1 wt% Na 2 CO 3 aqueous solution with a spray pressure of 2 MPa, and a solder resist pattern is developed. Formed. This substrate was thermally cured at 150 ° C. for 60 minutes to produce an evaluation substrate.
A rosin-based flux is applied to this evaluation substrate, immersed in a solder bath set at 260 ° C. for 30 seconds in advance, and the flux is washed with isopropyl alcohol, and then a tape peel test is performed, and the resist layer is swollen / peeled / discolored. Was evaluated.
○: No change at all △: Slight change in color, etc. ×: Resist layer swelling or peeling
（５）無電解金めっき耐性
上記（４）と同様にして評価基板を作製した。この評価基板を、市販の無電解ニッケルめっき液と無電解金めっき液を用いて、ニッケル５μｍ、金０．０３μｍとなるような条件で無電解金めっきを行なった。このめっき後の評価基板について、テープピールテストを行ない、レジスト層の剥がれ、めっきのしみ込みについて評価した。
○： 全く変化が認められないもの
△ ： ほんの僅かに剥がれ、しみ込みがあるもの
× ： 塗膜に剥がれがあるもの
(5) Resistance to electroless gold plating An evaluation substrate was produced in the same manner as in (4) above. This evaluation substrate was subjected to electroless gold plating using commercially available electroless nickel plating solution and electroless gold plating solution under the conditions of nickel 5 μm and gold 0.03 μm. The evaluation substrate after plating was subjected to a tape peel test to evaluate the peeling of the resist layer and the penetration of the plating.
○: No change at all △: Slightly peeled off, with smudges ×: Painted film with peeling
（６）無電解すずめっき耐性
上記（４）と同様にして評価基板を作製した。この評価基板を、前処理（酸性脱脂＋ソフトエッチ＋硫酸処理）を行い、市販の無電解すずめっき液を用いて、めっき厚が１μｍとなるような条件（７０℃ １２分）で無電解すずめっきを行なった。このめっき後の評価基板について、セロハン粘着テープによるピールテストを行ない、レジスト層の剥がれについて評価した。
○： 全く変化が認められないもの
△： ほんの僅か剥がれ、しみ込みがあるもの
×： レジスト層全体に剥がれがあるもの
(6) Electroless tin plating resistance An evaluation substrate was produced in the same manner as in (4) above. This evaluation substrate is pretreated (acid degreasing + soft etch + sulfuric acid treatment), and using a commercially available electroless tin plating solution, electroless tin under conditions (70 ° C., 12 minutes) such that the plating thickness is 1 μm. Plating was performed. About the evaluation board | substrate after this plating, the peel test by a cellophane adhesive tape was done, and peeling of the resist layer was evaluated.
◯: No change at all △: Slightly peeled off, with penetration ×: Resisted over the entire resist layer
（７）電気絶縁性
ＩＰＣ Ｂ−２５テストパターンのクシ型電極Ｂクーポンを用い、上記（４）と同様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１０００時間後の絶縁抵抗値を測定した。
(7) Electrical Insulation An evaluation substrate was prepared under the same conditions as in (4) above using the comb-type electrode B coupon of the IPC B-25 test pattern, and a bias voltage of DC 100 V was applied to the comb-type electrode. ° C, 85% R.V. H. The insulation resistance value after 1000 hours was measured in a constant temperature and humidity chamber.
表２に示す結果から明らかなように、本発明にかかる実施例１〜７の一液型ソルダーレジスト組成物は一液安定性に優れ、乾燥管理幅、感度も高く、また得られた硬化塗膜もはんだ耐熱性、無電解金めっき耐性、無電解すずめっき耐性及び電気特性に優れている事がわかる。一方合成例２，３で得られた共重合系樹脂を使用した比較例２〜４の一液型ソルダーレジスト組成物では、はんだ耐熱性、無電解金めっき耐性、無電解すずめっき耐性がいずれも良好ではなかった。また、合成例１で得られた共重合系樹脂を用いてもメラミンまたはメラミンの有機酸塩を添加していない比較例１の一液型ソルダーレジスト組成物は、はんだ耐熱性、無電解金めっき耐性、無電解すずめっき耐性がいずれも良好ではなかった。
As is apparent from the results shown in Table 2, the one-component solder resist compositions of Examples 1 to 7 according to the present invention are excellent in one-component stability, have a high dry management width and high sensitivity, and the obtained cured coating. It can be seen that the film is also excellent in solder heat resistance, electroless gold plating resistance, electroless tin plating resistance and electrical characteristics. On the other hand, in the one-pack type solder resist compositions of Comparative Examples 2 to 4 using the copolymer resins obtained in Synthesis Examples 2 and 3, the solder heat resistance, electroless gold plating resistance, and electroless tin plating resistance are all. It was not good. Further, even if the copolymer resin obtained in Synthesis Example 1 is used, the one-component solder resist composition of Comparative Example 1 in which melamine or an organic acid salt of melamine is not added is solder heat resistant, electroless gold plating Both resistance and electroless tin plating resistance were not good.
Claims (6)
The printed wiring board formed by forming a soldering resist film with the dry film of the said Claim 4 on the printed wiring board surface in which the circuit was formed.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005001970A JP4649212B2 (en) | 2005-01-07 | 2005-01-07 | Photo-curable thermosetting one-component solder resist composition and printed wiring board using the same |
| TW094145125A TWI426346B (en) | 2005-01-07 | 2005-12-19 | A photohardenable thermosetting one of the liquid solder resist compositions and a printed circuit board using the same |
| KR1020060001656A KR20060081361A (en) | 2005-01-07 | 2006-01-06 | Photocuring/thermosetting one-component solder resist composition and print wiring board using same |
| CN200610000185.1A CN1800979B (en) | 2005-01-07 | 2006-01-06 | Solder resist composition of light-curing single liquid style and printing circuit board use same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005001970A JP4649212B2 (en) | 2005-01-07 | 2005-01-07 | Photo-curable thermosetting one-component solder resist composition and printed wiring board using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006190848A true JP2006190848A (en) | 2006-07-20 |
| JP4649212B2 JP4649212B2 (en) | 2011-03-09 |
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| JP2005001970A Active JP4649212B2 (en) | 2005-01-07 | 2005-01-07 | Photo-curable thermosetting one-component solder resist composition and printed wiring board using the same |
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| Country | Link |
|---|---|
| JP (1) | JP4649212B2 (en) |
| KR (1) | KR20060081361A (en) |
| CN (1) | CN1800979B (en) |
| TW (1) | TWI426346B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009272431A (en) * | 2008-05-07 | 2009-11-19 | Taiyo Ink Mfg Ltd | Thermosetting resin composition for padding, combination unit of photo-curing and thermosetting resin composition for forming solder mask and printed wiring board |
| JP2013133459A (en) * | 2011-12-27 | 2013-07-08 | Tamura Seisakusho Co Ltd | Resin and photosensitive composition containing the resin |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI455954B (en) * | 2008-05-07 | 2014-10-11 | Taiyo Holdings Co Ltd | a thermosetting resin composition for hole filling, a combination unit of the composition and a photocurable thermosetting resin composition for forming a solder resist layer, and a printed circuit board |
| KR101197987B1 (en) * | 2010-08-18 | 2012-11-05 | 삼성전기주식회사 | Plating solution for forming tin alloy and method for forming tin alloy film using the same |
| CN102636955A (en) * | 2011-02-10 | 2012-08-15 | 台湾永光化学工业股份有限公司 | Photosensitive resin composition |
| JP5766671B2 (en) * | 2012-09-05 | 2015-08-19 | 株式会社タムラ製作所 | Black curable resin composition and printed wiring board using the same |
| CN110402020B (en) * | 2019-08-22 | 2022-03-18 | 江苏上达电子有限公司 | Flexible printed circuit board and manufacturing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08291214A (en) * | 1995-04-21 | 1996-11-05 | Daicel Chem Ind Ltd | New polyfunctional epoxy resin composition and photo-setting resin composition using the same |
| JPH08335768A (en) * | 1995-06-06 | 1996-12-17 | Taiyo Ink Mfg Ltd | Alkaline developable one liquid photosolder resist composition and solder resist film obtainable from the resist |
| JPH11172176A (en) * | 1997-12-08 | 1999-06-29 | Goo Chem Ind Co Ltd | Photocurable printing ink and ink for producing printed wiring board |
| WO2003059975A1 (en) * | 2001-12-28 | 2003-07-24 | Taiyo Ink Mfg. Co., Ltd. | Photosensitive resin composition and printed wiring boards |
| JP2003277480A (en) * | 2002-03-25 | 2003-10-02 | Taiyo Ink Mfg Ltd | Curable resin composition and printed circuit board using the same |
-
2005
- 2005-01-07 JP JP2005001970A patent/JP4649212B2/en active Active
- 2005-12-19 TW TW094145125A patent/TWI426346B/en active
-
2006
- 2006-01-06 KR KR1020060001656A patent/KR20060081361A/en not_active Application Discontinuation
- 2006-01-06 CN CN200610000185.1A patent/CN1800979B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08291214A (en) * | 1995-04-21 | 1996-11-05 | Daicel Chem Ind Ltd | New polyfunctional epoxy resin composition and photo-setting resin composition using the same |
| JPH08335768A (en) * | 1995-06-06 | 1996-12-17 | Taiyo Ink Mfg Ltd | Alkaline developable one liquid photosolder resist composition and solder resist film obtainable from the resist |
| JPH11172176A (en) * | 1997-12-08 | 1999-06-29 | Goo Chem Ind Co Ltd | Photocurable printing ink and ink for producing printed wiring board |
| WO2003059975A1 (en) * | 2001-12-28 | 2003-07-24 | Taiyo Ink Mfg. Co., Ltd. | Photosensitive resin composition and printed wiring boards |
| JP2003277480A (en) * | 2002-03-25 | 2003-10-02 | Taiyo Ink Mfg Ltd | Curable resin composition and printed circuit board using the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009272431A (en) * | 2008-05-07 | 2009-11-19 | Taiyo Ink Mfg Ltd | Thermosetting resin composition for padding, combination unit of photo-curing and thermosetting resin composition for forming solder mask and printed wiring board |
| JP2013133459A (en) * | 2011-12-27 | 2013-07-08 | Tamura Seisakusho Co Ltd | Resin and photosensitive composition containing the resin |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200641526A (en) | 2006-12-01 |
| CN1800979B (en) | 2014-05-14 |
| CN1800979A (en) | 2006-07-12 |
| KR20060081361A (en) | 2006-07-12 |
| TWI426346B (en) | 2014-02-11 |
| JP4649212B2 (en) | 2011-03-09 |
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