JP2018024791A - Resist composition - Google Patents
Resist composition Download PDFInfo
- Publication number
- JP2018024791A JP2018024791A JP2016158285A JP2016158285A JP2018024791A JP 2018024791 A JP2018024791 A JP 2018024791A JP 2016158285 A JP2016158285 A JP 2016158285A JP 2016158285 A JP2016158285 A JP 2016158285A JP 2018024791 A JP2018024791 A JP 2018024791A
- Authority
- JP
- Japan
- Prior art keywords
- resist composition
- mass
- resist
- acrylic resin
- mgkoh
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
【課題】無電解めっきの際には優れためっき液耐性を有し、剥離の際にはレジスト剥離液に対して優れた剥離性を有するレジスト組成物の提供。【解決手段】アクリル樹脂とクマロン樹脂とを含むレジスト組成物であって、前記アクリル樹脂と前記クマロン樹脂との合計１００質量％中の前記アクリル樹脂の含有率が３０質量％以上９０質量％以下、前記クマロン樹脂の含有率が１０質量％以上７０質量％以下であり、前記アクリル樹脂の酸価が５０ｍｇＫＯＨ／ｇ以上１４０ｍｇＫＯＨ／ｇ以下であり、前記クマロン樹脂の水酸基価が２０ｍｇＫＯＨ／ｇ以下である、レジスト組成物。【選択図】なしKind Code: A1 A resist composition is provided which has excellent resistance to a plating solution during electroless plating and exhibits excellent strippability to a resist stripping solution during stripping. A resist composition containing an acrylic resin and a coumarone resin, wherein the content of the acrylic resin in a total of 100% by mass of the acrylic resin and the coumarone resin is 30% by mass or more and 90% by mass or less, The content of the coumarone resin is 10% by mass or more and 70% by mass or less, the acid value of the acrylic resin is 50 mgKOH/g or more and 140 mgKOH/g or less, and the hydroxyl value of the coumarone resin is 20 mgKOH/g or less. resist composition. [Selection figure] None
Description
本発明は、レジスト組成物に係り、特にプリント配線板に無電解めっきによって金めっき層を形成する際に使用するレジスト組成物に関する。 The present invention relates to a resist composition, and more particularly to a resist composition used when a gold plating layer is formed on a printed wiring board by electroless plating.
プリント配線板は、基材と主に銅などを用いて基材の少なくとも一方の面上に設けられた回路とで構成される。この回路の保護及び接触抵抗の低減等を目的として、回路表面に金めっき層が形成されることがある。金めっき層の形成法としては、電解めっき法又は無電解めっき法が知られているが、プリント配線板の小型化及び高度化に伴い、金めっき層の形成方法は、電解めっき法から無電解めっき法へと急速に移行している。 The printed wiring board includes a base material and a circuit provided on at least one surface of the base material mainly using copper or the like. For the purpose of protecting the circuit and reducing contact resistance, a gold plating layer may be formed on the circuit surface. As a method for forming a gold plating layer, an electrolytic plating method or an electroless plating method is known. However, with the miniaturization and advancement of printed wiring boards, the gold plating layer forming method is changed from an electrolytic plating method to an electroless method. There is a rapid shift to plating.
無電解めっき法においては、プリント配線板の面上において金めっき層の形成を望まない領域についてはレジスト組成物を用いて形成したレジスト膜で被覆する。レジスト組成物には、無電解めっきが行われている間は、金めっき層を形成するためのめっき液がレジスト膜に接触してもプリント配線板から剥離しにくくすること、すなわち、優れためっき液耐性が要求される。一方、無電解めっきによりプリント配線板上に金めっき層が形成された後は、塩基性のレジスト剥離液によってレジスト膜が容易に剥離しやすくすること、すなわち、優れた剥離性が要求される。 In the electroless plating method, a region where it is not desired to form a gold plating layer on the surface of the printed wiring board is covered with a resist film formed using a resist composition. While the electroless plating is being performed on the resist composition, the plating solution for forming the gold plating layer is difficult to peel off from the printed wiring board even if it contacts the resist film, that is, excellent plating. Liquid resistance is required. On the other hand, after a gold plating layer is formed on a printed wiring board by electroless plating, it is required that the resist film be easily peeled off with a basic resist stripping solution, that is, excellent peelability is required.
このようなレジスト組成物として、例えば特許文献１に記載のレジスト組成物が知られている。特許文献１には、（メタ）アクリル酸等の重合体又は（メタ）アクリル酸とスチレンとの共重合体からなるバインダーポリマーを含有するレジスト組成物が開示されている。 As such a resist composition, for example, a resist composition described in Patent Document 1 is known. Patent Document 1 discloses a resist composition containing a binder polymer made of a polymer such as (meth) acrylic acid or a copolymer of (meth) acrylic acid and styrene.
しかし、特許文献１に記載のレジスト組成物は以下に示す課題を有していた。 However, the resist composition described in Patent Document 1 has the following problems.
すなわち、無電解めっきにおいては、無電解めっき液のｐＨの管理範囲は５．８〜６．１とされている。しかし、実際には、無電解めっき液のｐＨは管理範囲から外れて７．０（中性）に近づくこと、具体的には６．５以上となることがある。この場合、特許文献１に記載のレジスト組成物からなるレジスト膜では、プリント配線板の面上に被着した状態で無電解めっき液に接触すると、プリント配線板の面上から剥離しやすくなる場合があった。すなわち、特許文献１に記載のレジスト組成物は、無電解めっきの際のめっき液耐性の点で改善の余地を有していた。ここで、無電解めっき液のｐＨが無電解めっき液の管理範囲を外れて６．５以上になっても特許文献１に記載のレジスト組成物からなるレジスト膜をプリント配線板の面上から剥離しにくくするためには、バインダーポリマーの酸価を低くすることが考えられる。しかし、この場合、塩基性のレジスト剥離液を用いてレジスト組成物を剥離させる際にその剥離が困難になってしまう。 That is, in electroless plating, the pH control range of the electroless plating solution is 5.8 to 6.1. However, in practice, the pH of the electroless plating solution may deviate from the control range and approach 7.0 (neutral), specifically 6.5 or more. In this case, in the resist film made of the resist composition described in Patent Document 1, when it comes into contact with the electroless plating solution in a state of being deposited on the surface of the printed wiring board, it tends to be peeled off from the surface of the printed wiring board. was there. That is, the resist composition described in Patent Document 1 has room for improvement in terms of plating solution resistance during electroless plating. Here, even if the pH of the electroless plating solution deviates from the control range of the electroless plating solution and becomes 6.5 or more, the resist film made of the resist composition described in Patent Document 1 is peeled off from the surface of the printed wiring board. In order to make it difficult to do so, it is conceivable to lower the acid value of the binder polymer. However, in this case, when the resist composition is stripped using a basic resist stripping solution, the stripping becomes difficult.
このため、無電解めっきの際には優れためっき液耐性を有し、剥離の際にはレジスト剥離液に対して優れた剥離性を有するレジスト組成物が求められていた。 For this reason, the resist composition which has the outstanding plating solution tolerance in the case of electroless plating, and has the peelability outstanding with respect to the resist stripping solution in the case of peeling was calculated | required.
本発明は、上記事情に鑑みてなされたものであり、無電解めっきの際には優れためっき液耐性を有し、剥離の際にはレジスト剥離液に対して優れた剥離性を有するレジスト組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and has a resist composition having excellent plating solution resistance in the case of electroless plating and having excellent releasability with respect to the resist stripping solution in the case of peeling. The purpose is to provide goods.
本発明者らは上記課題を解決するため検討を重ねた。その結果、本発明者らは、アクリル樹脂とクマロン樹脂とを特定の割合で配合し、アクリル樹脂の酸価及びクマロン樹脂の水酸基価をそれぞれ特定の範囲とすることで、上記課題を解決し得ることを見出した。 The present inventors have repeatedly studied in order to solve the above problems. As a result, the present inventors can solve the above-mentioned problems by blending acrylic resin and coumarone resin at a specific ratio, and setting the acid value of acrylic resin and the hydroxyl value of coumarone resin to specific ranges, respectively. I found out.
すなわち本発明は、アクリル樹脂とクマロン樹脂とを含むレジスト組成物であって、前記アクリル樹脂と前記クマロン樹脂との合計１００質量％中の前記アクリル樹脂の含有率が３０質量％以上９０質量％以下、前記クマロン樹脂の含有率が１０質量％以上７０質量％以下であり、前記アクリル樹脂の酸価が５０ｍｇＫＯＨ／ｇ以上１４０ｍｇＫＯＨ／ｇ以下であり、前記クマロン樹脂の水酸基価が２０ｍｇＫＯＨ／ｇ以下である、レジスト組成物である。 That is, the present invention is a resist composition containing an acrylic resin and a coumarone resin, and the content of the acrylic resin in a total of 100 mass% of the acrylic resin and the coumarone resin is 30 mass% or more and 90 mass% or less. The content of the coumarone resin is 10% by mass or more and 70% by mass or less, the acid value of the acrylic resin is 50 mgKOH / g or more and 140 mgKOH / g or less, and the hydroxyl value of the coumarone resin is 20 mgKOH / g or less. A resist composition.
本発明のレジスト組成物は、無電解めっきの際には優れためっき液耐性を有し、剥離の際にレジスト剥離液には対して優れた剥離性を有する。 The resist composition of the present invention has excellent plating solution resistance at the time of electroless plating, and has excellent peelability against the resist stripping solution at the time of peeling.
本発明のレジスト組成物は無機フィラーをさらに含むことが好ましい。 The resist composition of the present invention preferably further contains an inorganic filler.
この場合、レジスト組成物が無機フィラーを含まない場合に比べて、レジスト組成物の粘度を、レジスト組成物がプリント配線板に対して塗布しやすく且つ良好な密着性を有する範囲（一般的には１０〜３００ｄＰａ・ｓ、以下、「適正範囲」と呼ぶ）内に調整することが可能となる。 In this case, compared to the case where the resist composition does not contain an inorganic filler, the viscosity of the resist composition is a range in which the resist composition is easy to apply to a printed wiring board and has good adhesion (generally 10 to 300 dPa · s, hereinafter referred to as “appropriate range”).
本発明のレジスト組成物においては、無機フィラーが板状フィラーを含むことが好ましい。 In the resist composition of the present invention, the inorganic filler preferably contains a plate-like filler.
この場合、レジスト組成物をプリント配線板の面上に塗布し乾燥させることによってレジスト膜を形成した後、レジスト膜内において板状フィラーが積み重なった状態となる。このため、無電解めっきの際にめっき液がレジスト膜を通過して、レジスト膜とプリント配線板との界面に溜まることを十分に抑制することができる。このため、レジスト膜をより剥離しにくくすることができる。 In this case, after a resist film is formed by applying the resist composition onto the surface of the printed wiring board and drying it, the plate-like fillers are stacked in the resist film. For this reason, it is possible to sufficiently suppress the plating solution from passing through the resist film and collecting at the interface between the resist film and the printed wiring board during electroless plating. For this reason, it is possible to make the resist film more difficult to peel off.
本発明によれば、無電解めっきの際には優れためっき液耐性を有し、剥離の際にはレジスト剥離液に対して優れた剥離性を有するレジスト組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the resist composition which has the outstanding plating solution tolerance in the case of electroless plating, and has the peelability outstanding with respect to the resist stripping solution in the case of peeling is provided.
以下、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明は、アクリル樹脂とクマロン樹脂とを含むレジスト組成物である。このレジスト組成物においては、アクリル樹脂とクマロン樹脂との合計１００質量％中の前記アクリル樹脂の含有率が３０質量％以上９０質量％以下、前記クマロン樹脂の含有率が１０質量％以上７０質量％以下であり、アクリル樹脂の酸価が５０ｍｇＫＯＨ／ｇ以上１４０ｍｇＫＯＨ／ｇ以下であり、クマロン樹脂の水酸基価が２０ｍｇＫＯＨ／ｇ以下である。 The present invention is a resist composition containing an acrylic resin and a coumarone resin. In this resist composition, the content of the acrylic resin in the total 100% by mass of the acrylic resin and the coumarone resin is 30% by mass to 90% by mass, and the content of the coumarone resin is 10% by mass to 70% by mass. The acid value of the acrylic resin is 50 mgKOH / g or more and 140 mgKOH / g or less, and the hydroxyl value of the coumarone resin is 20 mgKOH / g or less.
本発明のレジスト組成物は、無電解めっきの際には優れためっき液耐性を有し、剥離の際にはレジスト剥離液に対して優れた剥離性を有する。 The resist composition of the present invention has excellent plating solution resistance in the case of electroless plating, and has excellent peelability with respect to the resist stripping solution in the case of peeling.
以下、レジスト組成物について詳細に説明する。 Hereinafter, the resist composition will be described in detail.
＜アクリル樹脂＞
アクリル樹脂は、アクリルモノマーの重合体であり、アクリルモノマーとしては、（メタ）アクリル酸及び（メタ）アクリル酸エステルが挙げられる。これらは単独で又は２種以上を組み合せて用いることができる。
<Acrylic resin>
The acrylic resin is a polymer of acrylic monomers, and examples of the acrylic monomers include (meth) acrylic acid and (meth) acrylic acid esters. These can be used alone or in combination of two or more.
アクリル樹脂の酸価は５０ｍｇＫＯＨ／ｇ以上１４０ｍｇＫＯＨ／ｇ以下である。アクリル樹脂の酸価が５０ｍｇＫＯＨ／ｇ以上である場合、レジスト組成物は、酸価が５０ｍｇＫＯＨ／ｇ未満である場合と比べて、剥離の際にレジスト剥離液に対してより優れた剥離性を有する。一方、アクリル樹脂の酸価が１４０ｍｇＫＯＨ／ｇ以下である場合、レジスト組成物は、アクリル樹脂の酸価が１４０ｍｇＫＯＨ／ｇを超える場合と比べて、無電解めっきの際に優れためっき液耐性を有する。なお、アクリル樹脂の酸価は７０ｍｇＫＯＨ／ｇ以下であることが好ましい。この場合、アクリル樹脂の酸価が７０ｍｇＫＯＨ／ｇより大きい場合と比べて、より優れためっき液耐性が得られる。 The acid value of the acrylic resin is 50 mgKOH / g or more and 140 mgKOH / g or less. When the acid value of the acrylic resin is 50 mgKOH / g or more, the resist composition has more excellent releasability with respect to the resist stripping solution at the time of stripping than when the acid value is less than 50 mgKOH / g. . On the other hand, when the acid value of the acrylic resin is 140 mgKOH / g or less, the resist composition has excellent plating solution resistance during electroless plating as compared with the case where the acid value of the acrylic resin exceeds 140 mgKOH / g. . In addition, it is preferable that the acid value of an acrylic resin is 70 mgKOH / g or less. In this case, more excellent plating solution resistance can be obtained as compared with the case where the acid value of the acrylic resin is larger than 70 mgKOH / g.
＜クマロン樹脂＞
クマロン樹脂は、その骨格構造にクマロン残基を含む平均重合度４〜８の共重合体のことを示し、クマロン残基の他にインデン、スチレン残基を有しているものである。
<Coumarone resin>
The coumarone resin indicates a copolymer having an average polymerization degree of 4 to 8 including a coumarone residue in its skeleton structure, and has an indene and a styrene residue in addition to the coumarone residue.
クマロン樹脂の水酸基価は２０ｍｇＫＯＨ／ｇ以下である。この場合、レジスト組成物は、クマロン樹脂の水酸基価が２０ｍｇＫＯＨ／ｇを超える場合と比べて、剥離の際にレジスト剥離液に対してより優れた剥離性を有する。 The hydroxyl value of the coumarone resin is 20 mgKOH / g or less. In this case, the resist composition has more excellent releasability with respect to the resist stripping solution at the time of stripping compared to the case where the hydroxyl value of the coumarone resin exceeds 20 mgKOH / g.
アクリル樹脂とクマロン樹脂との合計１００質量％中のアクリル樹脂の含有率が３０質量％以上９０質量％以下、クマロン樹脂の含有率が１０質量％以上７０質量％以下である。この場合、レジスト組成物は、アクリル樹脂の含有率が３０質量％未満、すなわちクマロン樹脂の含有率が７０質量％より大きい場合と比べて、剥離の際にレジスト剥離液に対して優れた剥離性を有する。また、アクリル樹脂の含有率が９０質量％より大きい、すなわちクマロン樹脂の含有率が１０質量％未満の場合と比べて、無電解めっきの際により優れためっき液耐性を有する。 The content of acrylic resin in the total 100% by mass of acrylic resin and coumarone resin is 30% by mass to 90% by mass, and the content of coumarone resin is 10% by mass to 70% by mass. In this case, the resist composition has excellent peelability with respect to the resist stripping solution at the time of stripping as compared with the case where the acrylic resin content is less than 30% by mass, that is, the coumarone resin content is greater than 70% by mass. Have Moreover, compared with the case where the content rate of an acrylic resin is larger than 90 mass%, ie, the content rate of a coumarone resin is less than 10 mass%, it has the plating solution resistance outstanding at the time of electroless plating.
なお、アクリル樹脂の含有率が３０質量％以上５０質量％以下、すなわちクマロン樹脂の含有率が５０質量％以上７０質量％以下であることが好ましい。この場合、アクリル樹脂の含有率が５０％より大きい、すなわちクマロン樹脂の含有率が５０質量％未満である場合と比べて、無電解めっきの際により優れためっき液耐性を有する。 In addition, it is preferable that the content rate of an acrylic resin is 30 to 50 mass%, ie, the content rate of a coumarone resin is 50 to 70 mass%. In this case, compared with the case where the acrylic resin content is greater than 50%, that is, the coumarone resin content is less than 50% by mass, the plating solution has better resistance to electroless plating.
＜無機フィラー＞
本発明のレジスト組成物は無機フィラーを含んでいても含んでいなくてもよいが、無機フィラーを含むことが好ましい。この場合、レジスト組成物が無機フィラーを含まない場合と比べて、レジスト組成物の粘度を適正範囲内にすることが可能となる。
<Inorganic filler>
The resist composition of the present invention may or may not contain an inorganic filler, but preferably contains an inorganic filler. In this case, compared with the case where a resist composition does not contain an inorganic filler, it becomes possible to make the viscosity of a resist composition in an appropriate range.
無機フィラーの形状は特に限定されるものではないが、無機フィラーとしては、板状フィラー及び非板状フィラーなどが挙げられる。これらはそれぞれ単独で又は２種以上を組み合せて用いることができる。中でも、無機フィラーは板状フィラーを含むことが好ましい。この場合、レジスト組成物をプリント配線板に塗布し乾燥させることによってレジスト膜を形成した後、レジスト膜内において板状フィラーが積み重なった状態となる。このため、無電解めっきの際にめっき液がレジスト膜を通過して、レジスト膜とプリント配線板上との界面に溜まることを十分に抑制することができる。このため、レジスト膜をより剥離しにくくすることができる。非板状フィラーとしては、例えば球状フィラーが挙げられる。なお、板状とは厚み方向が他の方向よりも薄い形状のものをいう。加えて板状フィラーはアスペクト比が２以上であることが好ましい。 The shape of the inorganic filler is not particularly limited, and examples of the inorganic filler include plate-like fillers and non-plate-like fillers. These can be used alone or in combination of two or more. Especially, it is preferable that an inorganic filler contains a plate-shaped filler. In this case, after forming a resist film by applying the resist composition to a printed wiring board and drying it, the plate-like fillers are stacked in the resist film. For this reason, it is possible to sufficiently suppress the plating solution from passing through the resist film and remaining at the interface between the resist film and the printed wiring board during electroless plating. For this reason, it is possible to make the resist film more difficult to peel off. Examples of the non-plate filler include a spherical filler. In addition, plate shape means the thing whose thickness direction is thinner than another direction. In addition, the plate-like filler preferably has an aspect ratio of 2 or more.
ここで、板状フィラーを構成する材料としては、例えばタルク、シリカ、及びアルミナなどが挙げられ、非板状フィラーとしてはシリカなどが挙げられる。これらはそれぞれ単独で又は２種以上を組み合せて用いることができる。中でも、板状フィラーはタルクであることが好ましい。この場合、板状フィラーがタルクでない場合と比べて、レジスト組成物のプリント配線板への塗布が容易となる。 Here, examples of the material constituting the plate-like filler include talc, silica, and alumina, and examples of the non-plate-like filler include silica. These can be used alone or in combination of two or more. Among these, the plate filler is preferably talc. In this case, compared with the case where a plate-like filler is not talc, application | coating to a printed wiring board of a resist composition becomes easy.
アクリル樹脂とクマロン樹脂との合計１００質量部に対する板状フィラー及び／又は非板状フィラーの配合量は特に制限されるものではないが、１０〜１５０質量部であることが好ましい。この場合、レジスト組成物の粘度を適正範囲内とすることが容易となる。 Although the compounding quantity of the plate-like filler and / or non-plate-like filler with respect to 100 parts by mass in total of the acrylic resin and the coumarone resin is not particularly limited, it is preferably 10 to 150 parts by mass. In this case, it becomes easy to make the viscosity of the resist composition within an appropriate range.
本発明のレジスト組成物は、さらにマグネタイトを配合することが好ましい。マグネタイトを配合することにより、レジスト組成物が着色されるため、レジスト組成物を剥離する際にレジスト組成物が十分に除去されたかどうかを目視にて容易に確認できる。 The resist composition of the present invention preferably further contains magnetite. Since the resist composition is colored by blending magnetite, it can be easily confirmed visually whether or not the resist composition has been sufficiently removed when the resist composition is peeled off.
アクリル樹脂とクマロン樹脂との合計１００質量部に対するマグネタイトの配合量は特に制限されるものではないが、１質量部以上５０質量部以下であることが好ましい。この場合、レジスト組成物の粘度を適正範囲内に調整することが容易となる。特に、アクリル樹脂とクマロン樹脂との合計１００質量部に対するマグネタイトの配合量が１質量部未満である場合と比べて、レジスト剥離液でレジスト組成物の剥離を行った後、プリント配線板からレジスト組成物が十分に除去されたかどうかを目視にてより容易に確認できる。 The blending amount of magnetite with respect to 100 parts by mass in total of acrylic resin and coumarone resin is not particularly limited, but is preferably 1 part by mass or more and 50 parts by mass or less. In this case, it becomes easy to adjust the viscosity of the resist composition within an appropriate range. In particular, compared with the case where the blending amount of magnetite with respect to 100 parts by mass of acrylic resin and coumarone resin is less than 1 part by mass, the resist composition is removed from the printed wiring board after removing the resist composition with a resist remover. It can be more easily confirmed visually whether or not the object has been sufficiently removed.
上記レジスト組成物は、溶剤、分散剤、消泡剤、レベリング剤及び難燃剤等の添加剤を必要に応じてさらに含んでもよい。 The said resist composition may further contain additives, such as a solvent, a dispersing agent, an antifoamer, a leveling agent, and a flame retardant, as needed.
なお、溶剤は、アクリル樹脂及びクマロン樹脂を溶解し得るものであれば特に制限されるものではないが、このような溶剤としては、例えば、石油ナフサ、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルアセテート又は１−(２−メトキシ−２−メチルエトキシ)−２−プロパノールなどの有機溶剤を用いることができる。 The solvent is not particularly limited as long as it can dissolve acrylic resin and coumarone resin. Examples of such a solvent include petroleum naphtha, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate. Alternatively, an organic solvent such as 1- (2-methoxy-2-methylethoxy) -2-propanol can be used.
本発明のレジスト組成物は、無電解めっき液としてＮｉ／Ａｕめっき液が用いられ、レジスト剥離液として、濃度が２．０〜３．０質量％である水酸化ナトリウム水溶液などの強塩基性の液体が用いられる場合に有用である。 The resist composition of the present invention uses a Ni / Au plating solution as an electroless plating solution, and a strong basic solution such as a sodium hydroxide aqueous solution having a concentration of 2.0 to 3.0% by mass as a resist stripping solution. Useful when a liquid is used.
以下、実施例及び比較例を挙げて本発明の内容をより具体的に説明するが、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the content of the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.
（実施例１〜２５及び比較例１〜５）
アクリル樹脂、クマロン樹脂及び無機フィラー（合わせて固形分とする）を、表１〜６に示す配合量でジエチレングリコールモノエチルエーテルアセテートからなる有機溶剤中に溶解又は分散させ、固形分の濃度が５５質量％であるレジスト組成物を得た。
(Examples 1 to 25 and Comparative Examples 1 to 5)
Acrylic resin, coumarone resin and inorganic filler (combined solid content) are dissolved or dispersed in an organic solvent composed of diethylene glycol monoethyl ether acetate in the blending amounts shown in Tables 1 to 6, and the solid content concentration is 55 mass. % Of a resist composition was obtained.
上述のアクリル樹脂、クマロン樹脂及び無機フィラーとしては具体的には以下のものを用いた。
（１）アクリル樹脂
アクリル樹脂Ａ：星光ＰＭＣ株式会社製、酸価＝１０５ｍｇＫＯＨ／ｇ
アクリル樹脂Ｂ：星光ＰＭＣ株式会社製、酸価＝５０ｍｇＫＯＨ／ｇ
アクリル樹脂Ｃ：東亞合成株式会社製、酸価＝７４ｍｇＫＯＨ／ｇ
アクリル樹脂Ｄ：星光ＰＭＣ株式会社製、酸価＝１４０ｍｇＫＯＨ／ｇ
アクリル樹脂Ｅ：星光ＰＭＣ株式会社製、酸価＝４０ｍｇＫＯＨ／ｇ
アクリル樹脂Ｆ：星光ＰＭＣ株式会社製、酸価＝１５０ｍｇＫＯＨ／ｇ
（２）クマロン樹脂
クマロン樹脂Ａ：日塗化学株式会社製、水酸基価＝１０ｍｇＫＯＨ／ｇ
クマロン樹脂Ｂ：日塗化学株式会社製、水酸基価＝２５ｍｇＫＯＨ／ｇ
（３）無機フィラー
板状フィラーＡ：タルク、日本タルク社製
板状フィラーＢ：シリカ、ＡＧＣエスアイテック社製
板状フィラーＣ：アルミナ、キンセイマテック社製
非板状フィラー：シリカ（球状フィラー）、日本アエロジル社製
（４）マグネタイト：戸田工業株式会社製
Specific examples of the acrylic resin, coumarone resin, and inorganic filler described above were as follows.
(1) Acrylic resin Acrylic resin A: manufactured by Seiko PMC Co., Ltd., acid value = 105 mgKOH / g
Acrylic resin B: manufactured by Seiko PMC Co., Ltd., acid value = 50 mgKOH / g
Acrylic resin C: manufactured by Toagosei Co., Ltd., acid value = 74 mgKOH / g
Acrylic resin D: manufactured by Seiko PMC Co., Ltd., acid value = 140 mgKOH / g
Acrylic resin E: manufactured by Seiko PMC Co., Ltd., acid value = 40 mgKOH / g
Acrylic resin F: manufactured by Seiko PMC Co., Ltd., acid value = 150 mgKOH / g
(2) Coumarone resin Coumarone resin A: manufactured by Nikkiso Chemical Co., Ltd., hydroxyl value = 10 mgKOH / g
Coumarone resin B: manufactured by Nikko Chemical Co., Ltd., hydroxyl value = 25 mgKOH / g
(3) Inorganic filler plate filler A: talc, plate filler B manufactured by Nippon Talc Co., silica, plate filler C manufactured by AGC S-Tech Co., Ltd., alumina, non-plate filler manufactured by Kinsei Matech Co., silica (spherical filler), Nippon Aerosil Co., Ltd. (4) Magnetite: Toda Kogyo Co., Ltd.
［特性評価］
上述のようにして得られた実施例１〜２５及び比較例１〜５のレジスト組成物について、以下のようにして、無電解めっきの際に用いられるめっき液によるめっき液耐性、剥離の際のレジスト剥離液に対する剥離性、粘度及び視認性の評価を行った。
[Characteristic evaluation]
About the resist compositions of Examples 1 to 25 and Comparative Examples 1 to 5 obtained as described above, the plating solution resistance by the plating solution used at the time of electroless plating is as follows. The peelability, viscosity, and visibility of the resist stripper were evaluated.
＜めっき液耐性＞
上述のようにして得られたレジスト組成物を、乾燥後の厚さが約１５μｍとなるように厚さ２５μｍのポリイミドフィルム（東レ・デュポン株式会社製）に塗布して乾燥させ、ポリイミドフィルム上にレジスト膜を形成してなる構造体を作製した。そして、この構造体を３ｃｍ角に切断したものを測定サンプルとした。次に、無電解金めっき液（日本高純度化学株式会社製）に伝導塩調整剤（日本高純度化学株式会社製）を添加し、ｐＨの異なる１１種類の無電解金めっき液を用意した。１１種類の無電解めっき液は、ｐＨ６．５から７．５まで０．１ずつ増加するように用意した。その後、ｐＨ調整した１１種類の無電解金めっき液を８０℃に加熱し、これらのめっき液の各々に対して測定サンプルを５分間浸漬させた後、レジスト膜の剥がれの有無を調べた。結果を表１〜６に示す。なお、表１〜６においては、ｐＨ６．５においてレジスト膜の剥離が見られなかった実施例又は比較例については合格であるとして「○」と表示し、ｐＨ６．５においてレジスト膜の剥離が見られた比較例については不合格であるとして「×」と表示した。また表１〜６においては、レジスト膜の剥離が見られたときのｐＨを併記した。
<Plating solution resistance>
The resist composition obtained as described above is applied to a 25 μm-thick polyimide film (manufactured by Toray DuPont Co., Ltd.) so that the thickness after drying is about 15 μm, and is dried. A structure formed by forming a resist film was produced. And what cut | disconnected this structure to a 3 cm square was made into the measurement sample. Next, a conductive salt adjuster (manufactured by Nippon Kojun Chemical Co., Ltd.) was added to the electroless gold plating solution (manufactured by Nippon Kojun Chemical Co., Ltd.) to prepare 11 types of electroless gold plating solutions having different pHs. Eleven kinds of electroless plating solutions were prepared so as to increase by 0.1 from pH 6.5 to 7.5. Thereafter, 11 types of electroless gold plating solutions adjusted in pH were heated to 80 ° C., and the measurement samples were immersed in each of these plating solutions for 5 minutes, and then the presence or absence of peeling of the resist film was examined. The results are shown in Tables 1-6. In Tables 1 to 6, “Example” or “Comparative Example” in which peeling of the resist film was not observed at pH 6.5 was indicated as “O”, and the peeling of the resist film was observed at pH 6.5. About the obtained comparative example, it displayed as "x" noting that it was disqualified. Moreover, in Tables 1-6, pH when peeling of the resist film was seen was written together.
＜レジスト剥離液に対する剥離性＞
上述のようにして得られたレジスト組成物を、ベースフィルムの両面に銅箔が設けられている両面ＣＣＬ（新日鉄住金化学社製）からその両面の銅箔を全面エッチングして得られるベースフィルム上に乾燥後の厚さが約１５μｍとなるように塗布し、乾燥させてベースフィルム上にレジスト膜を形成してなる構造体を作製した。そして、この構造体を３ｃｍ角に切断したものを測定サンプルとし、この測定サンプルについて以下のようにしてレジスト剥離液に対する剥離性の評価を行った。具体的には、レジスト剥離液として、４８℃の２．８質量％ＮａＯＨ水溶液を用意し、このレジスト剥離液中に測定サンプルを１８０秒間浸漬させ、レジスト膜の残留の有無を調べた。結果を表１〜６に示す。なお、表１〜６において、レジスト膜の残留が見られなかった実施例又は比較例については合格として「○」と表記し、レジスト膜の残留が見られた比較例については不合格として「×」と表記した。
<Removability to resist stripper>
On the base film obtained by etching the resist composition obtained as described above from the double-sided CCL (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) where the copper foil is provided on both sides of the base film. The structure was formed by applying a coating film on the base film to a thickness of about 15 μm and drying to form a resist film on the base film. And what cut | disconnected this structure to a 3 cm square was made into the measurement sample, and peelability with respect to resist stripping solution was evaluated about this measurement sample as follows. Specifically, a 2.8 mass% NaOH aqueous solution at 48 ° C. was prepared as a resist stripping solution, and the measurement sample was immersed in this resist stripping solution for 180 seconds to examine whether or not the resist film remained. The results are shown in Tables 1-6. In Tables 1 to 6, Examples or Comparative Examples in which no resist film residue was found were indicated as “O” as a pass, and Comparative Examples in which resist film residue was found were shown as “No”. ".
＜粘度＞
上述のようにして得られたレジスト組成物について、Ｂ型粘度計（ブルックフィールド社製）を用いて粘度を測定した。結果を表１〜６に示す。なお、測定条件は以下の通りとした。
（測定条件）
ロータ ：Ｎｏ．６
回転数 ：６０ｒｐｍ
測定時間：６０秒
測定温度：２５℃
The viscosity of the resist composition obtained as described above was measured using a B-type viscometer (manufactured by Brookfield). The results are shown in Tables 1-6. The measurement conditions were as follows.
(Measurement condition)
Rotor: No. 6
Rotation speed: 60rpm
Measurement time: 60 seconds Measurement temperature: 25 ° C
表１〜６に示す結果より、実施例１〜２５のレジスト組成物は、無電解めっきの際のめっき液耐性、及び、剥離の際のレジスト剥離液に対する剥離性について合格基準に達していた。これに対し、比較例１〜５のレジスト組成物は、無電解めっきの際のめっき液耐性又は剥離の際のレジスト剥離液に対する剥離性のいずれかについて合格基準に達していなかった。 From the results shown in Tables 1 to 6, the resist compositions of Examples 1 to 25 reached the acceptance criteria for the plating solution resistance during electroless plating and the releasability to the resist stripping solution at the time of peeling. On the other hand, the resist compositions of Comparative Examples 1 to 5 did not reach the acceptance criteria for either the plating solution resistance during electroless plating or the releasability to the resist stripping solution during stripping.
このことから、本発明のレジスト組成物が、無電解めっきの際には優れためっき液耐性を有し、剥離の際にはレジスト剥離液に対して優れた剥離性を有することが確認された。 From this, it was confirmed that the resist composition of the present invention has excellent plating solution resistance at the time of electroless plating and has excellent releasability with respect to the resist stripping solution at the time of peeling. .
Claims (3)
前記アクリル樹脂と前記クマロン樹脂との合計１００質量％中の前記アクリル樹脂の含有率が３０質量％以上９０質量％以下、前記クマロン樹脂の含有率が１０質量％以上７０質量％以下であり、
前記アクリル樹脂の酸価が５０ｍｇＫＯＨ／ｇ以上１４０ｍｇＫＯＨ／ｇ以下であり、
前記クマロン樹脂の水酸基価が２０ｍｇＫＯＨ／ｇ以下である、レジスト組成物。 A resist composition comprising an acrylic resin and a coumarone resin,
The content of the acrylic resin in the total 100% by mass of the acrylic resin and the coumarone resin is 30% by mass to 90% by mass, and the content of the coumarone resin is 10% by mass to 70% by mass,
The acid value of the acrylic resin is 50 mgKOH / g or more and 140 mgKOH / g or less,
The resist composition whose hydroxyl value of the said coumarone resin is 20 mgKOH / g or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016158285A JP6165943B1 (en) | 2016-08-11 | 2016-08-11 | Resist composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016158285A JP6165943B1 (en) | 2016-08-11 | 2016-08-11 | Resist composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP6165943B1 JP6165943B1 (en) | 2017-07-19 |
| JP2018024791A true JP2018024791A (en) | 2018-02-15 |
Family
ID=59351440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016158285A Expired - Fee Related JP6165943B1 (en) | 2016-08-11 | 2016-08-11 | Resist composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6165943B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111918914A (en) * | 2018-04-23 | 2020-11-10 | 伍德利有限公司 | Homogeneous polymer mixtures, methods associated therewith and uses thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61292632A (en) * | 1985-06-20 | 1986-12-23 | Japan Synthetic Rubber Co Ltd | Liquid photosensitive resin composition |
| JPH01201355A (en) * | 1988-02-04 | 1989-08-14 | Nippon Steel Chem Co Ltd | Resin emulsion composition and adhesive |
| JPH0286645A (en) * | 1988-09-22 | 1990-03-27 | Nippon Steel Chem Co Ltd | Coumarone indene resin emulsion composition and adhesive |
| JPH0643646A (en) * | 1992-07-24 | 1994-02-18 | Kawasaki Steel Corp | Photoresist composition |
| JPH0675377A (en) * | 1992-08-25 | 1994-03-18 | Toshiba Corp | Photosensitive composition |
| JPH07314603A (en) * | 1993-12-28 | 1995-12-05 | Nippon Denkai Kk | Copper clad laminate, multilayered printed circuit board and treatment of them |
| JP2000204480A (en) * | 1999-01-08 | 2000-07-25 | Origin Electric Co Ltd | Partial plating method and article provided with the method |
| JP2011221084A (en) * | 2010-04-05 | 2011-11-04 | Hitachi Chem Co Ltd | Method for manufacturing photosensitive resin composition, photosensitive element and print circuit board |
| JP2013040285A (en) * | 2011-08-17 | 2013-02-28 | Dai Ichi Kogyo Seiyaku Co Ltd | Acrylic resin pressure-sensitive adhesive |
| WO2014098195A1 (en) * | 2012-12-20 | 2014-06-26 | ソマール株式会社 | Masking film support for plating, and masking film using same |
-
2016
- 2016-08-11 JP JP2016158285A patent/JP6165943B1/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61292632A (en) * | 1985-06-20 | 1986-12-23 | Japan Synthetic Rubber Co Ltd | Liquid photosensitive resin composition |
| JPH01201355A (en) * | 1988-02-04 | 1989-08-14 | Nippon Steel Chem Co Ltd | Resin emulsion composition and adhesive |
| JPH0286645A (en) * | 1988-09-22 | 1990-03-27 | Nippon Steel Chem Co Ltd | Coumarone indene resin emulsion composition and adhesive |
| JPH0643646A (en) * | 1992-07-24 | 1994-02-18 | Kawasaki Steel Corp | Photoresist composition |
| JPH0675377A (en) * | 1992-08-25 | 1994-03-18 | Toshiba Corp | Photosensitive composition |
| JPH07314603A (en) * | 1993-12-28 | 1995-12-05 | Nippon Denkai Kk | Copper clad laminate, multilayered printed circuit board and treatment of them |
| JP2000204480A (en) * | 1999-01-08 | 2000-07-25 | Origin Electric Co Ltd | Partial plating method and article provided with the method |
| JP2011221084A (en) * | 2010-04-05 | 2011-11-04 | Hitachi Chem Co Ltd | Method for manufacturing photosensitive resin composition, photosensitive element and print circuit board |
| JP2013040285A (en) * | 2011-08-17 | 2013-02-28 | Dai Ichi Kogyo Seiyaku Co Ltd | Acrylic resin pressure-sensitive adhesive |
| WO2014098195A1 (en) * | 2012-12-20 | 2014-06-26 | ソマール株式会社 | Masking film support for plating, and masking film using same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111918914A (en) * | 2018-04-23 | 2020-11-10 | 伍德利有限公司 | Homogeneous polymer mixtures, methods associated therewith and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6165943B1 (en) | 2017-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101605449B1 (en) | Copper foil with adhesive layer, copper-clad laminate and printed wiring board | |
| JP5560014B2 (en) | Conductive paste | |
| JP6084716B1 (en) | Resist composition | |
| TW201247803A (en) | Resin composition and method of manufacturing circuit board | |
| JP6136851B2 (en) | Solder flux and solder paste | |
| CN103966606A (en) | Copper reduction etching liquid for printed circuit boards | |
| CN104345555B (en) | Solder bump formation resin combination, solder bump forming method and the component for having solder bump | |
| JP6165943B1 (en) | Resist composition | |
| JP6138312B1 (en) | Resist composition | |
| JP6325723B1 (en) | Resist composition | |
| TWI417357B (en) | Resin composition for adhesive sheet and adhesive sheet for flexible printed circuit board using the same | |
| JP2730826B2 (en) | Alkaline water-soluble adhesive used for plating masking tape in electronic material field and plating masking tape in electronic material field | |
| CN101407706B (en) | Adhesive compositions | |
| JP6462375B2 (en) | Porous metal foil with support and method for producing transparent metal foil | |
| JP2016170929A (en) | Conductive paste composition | |
| JP5437541B1 (en) | Resist stripper | |
| JP5158759B2 (en) | Entry sheet for drilling | |
| JP6737873B2 (en) | Photo-sintering of polymer thick film copper conductor composition | |
| JPS62230869A (en) | Electrically conductive coating compound to be soldered | |
| TW201120162A (en) | Polymer thick film silver electrode composition for use as a plating link | |
| JP6301366B2 (en) | Electronic component adhesive material and electronic component bonding method | |
| CN117230450B (en) | Nickel-chromium alloy etching solution and application thereof in prefabricated circuit board | |
| JP2001350275A (en) | Stripper for resist | |
| CN117467382A (en) | A kind of special hot melt adhesive for circuit board etching protection and its preparation method | |
| KR101804265B1 (en) | Etching paste compositon for screen-printing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20170515 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170523 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170621 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6165943 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |