JP5178308B2 - Thermosetting solder resist composition, solder resist layer comprising the cured product, and printed wiring board - Google Patents
Thermosetting solder resist composition, solder resist layer comprising the cured product, and printed wiring board Download PDFInfo
- Publication number
- JP5178308B2 JP5178308B2 JP2008122305A JP2008122305A JP5178308B2 JP 5178308 B2 JP5178308 B2 JP 5178308B2 JP 2008122305 A JP2008122305 A JP 2008122305A JP 2008122305 A JP2008122305 A JP 2008122305A JP 5178308 B2 JP5178308 B2 JP 5178308B2
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- Prior art keywords
- solder resist
- resist composition
- thermosetting
- printed wiring
- mol
- Prior art date
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Landscapes
- Epoxy Resins (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
本発明は、熱硬化性ソルダーレジスト組成物、その硬化物からなるソルダーレジスト層及びプリント配線板に関し、詳しくは、プリント配線板などのソルダーレジスト層として好適な、耐薬品性、耐熱性、硬度、電気絶縁性、密着性、及び印刷性を有し、更に保色性にも優れた熱硬化性ソルダーレジスト組成物、その硬化物からなるソルダーレジスト層及びプリント配線板に関する。 The present invention relates to a thermosetting solder resist composition, a solder resist layer comprising the cured product, and a printed wiring board, and more specifically, suitable for a solder resist layer such as a printed wiring board, chemical resistance, heat resistance, hardness, The present invention relates to a thermosetting solder resist composition having electrical insulation, adhesion, and printability, and excellent color retention, a solder resist layer made of the cured product, and a printed wiring board.
プリント配線板に保護膜として用いられるソルダーレジスト被膜の形成方法としては、スクリーン印刷が従来から用いられており、熱硬化型ソルダーレジストにおいては、主として印刷性の理由からビスフェノールA型のエポキシ樹脂が用いられている(例えば、特許文献1を参照)。 As a method for forming a solder resist film used as a protective film on a printed wiring board, screen printing has been conventionally used. In thermosetting solder resist, a bisphenol A type epoxy resin is mainly used for printability reasons. (For example, see Patent Document 1).
しかし、かかるビスフェノールA型エポキシ系の熱硬化型ソルダーレジストでは、印刷性は優れるものの、ソルダーレジスト被膜に通常要求される耐薬品性や耐熱性、密着性に問題があった。 However, such a bisphenol A type epoxy-based thermosetting solder resist has excellent printability, but has problems in chemical resistance, heat resistance and adhesion usually required for a solder resist film.
また、近年、プリント配線板においては、携帯端末、パソコン、テレビ等の液晶ディスプレイのバックライト、また照明器具の光源など、低電力で発光する発光ダイオード(LED)に直接実装して用いられる用途が増えてきている(例えば、特許文献2を参照)。 In recent years, printed wiring boards have applications that are directly mounted on light emitting diodes (LEDs) that emit light at low power, such as backlights for liquid crystal displays of portable terminals, personal computers, televisions, etc., and light sources of lighting fixtures. (See, for example, Patent Document 2).
その場合に、プリント配線板に保護膜として被覆形成されるソルダーレジスト被膜には、通常要求される特性に加え、LEDの発光を有効に利用することができるよう、光の反射率に優れることが所望される。 In that case, the solder resist coating formed on the printed wiring board as a protective film has excellent light reflectance so that the light emission of the LED can be used effectively in addition to the characteristics normally required. Desired.
しかしながら、ビスフェノールA型エポキシ系の熱硬化型ソルダーレジストでは、上記問題点に加え保色性が悪いという問題点があり、白色ソルダーレジストにおいてはLEDより照射される光や発熱により樹脂の酸化が進んで黄変してしまい、反射率が経時により低下したり、後工程によるめっき液中の触媒が白色ソルダーレジスト上に吸着し変色するという問題がある。また、回路の外観不良などの隠蔽性の観点から白色以外の色においても優れた着色力を有するソルダーレジスト組成物が求められており、保色性に優れることはソルダーレジスト組成物において重要である。
本発明は、かかる背景技術が抱える問題点に鑑み開発されたものであり、その目的は、プリント配線板用ソルダーレジスト層に要求される耐薬品性、耐熱性、硬度、電気絶縁性、密着性、及び印刷性を満たし、更に保色性にも優れた熱硬化性ソルダーレジスト組成物、その硬化物からなるソルダーレジスト層及びプリント配線板を提供することにある。 The present invention was developed in view of the problems of the background art, and its purpose is to have chemical resistance, heat resistance, hardness, electrical insulation, adhesion required for a solder resist layer for printed wiring boards. Another object of the present invention is to provide a thermosetting solder resist composition that satisfies printability and is excellent in color retention, and a solder resist layer and a printed wiring board comprising the cured product.
本発明者は、上記課題を解決すべく鋭意研究した結果、ソルダーレジスト組成物の硬化物における架橋密度とガラス転移温度が保色性に重要な影響を及ぼすことを見出し、本発明を開発するに至った。
すなわち、本発明の第1の側面によれば、式(1)により算出される硬化後の架橋密度が12000mol/m3超であり、ガラス転移温度が150℃以上である熱硬化性ソルダーレジスト組成物が提供される。
n=E’min/3ΦRT (1)
式中、nは架橋密度、E’minは貯蔵弾性率E’の最小値、Φはフロント係数(Φ≒1)、Rは気体定数8.31451(J/mol・K)、TはE’minの絶対温度を表わす。
As a result of diligent research to solve the above problems, the present inventor has found that the crosslink density and glass transition temperature in the cured product of the solder resist composition have an important influence on the color retention, and develops the present invention. It came.
That is, according to the first aspect of the present invention, the thermosetting solder resist composition having a crosslinked density calculated by the formula (1) of more than 12000 mol / m 3 and a glass transition temperature of 150 ° C. or higher. Things are provided.
n = E'min / 3ΦRT (1)
In the formula, n is the crosslink density, E′min is the minimum value of the storage elastic modulus E ′, Φ is the front coefficient (Φ≈1), R is the gas constant 8.31451 (J / mol · K), and T is E ′. Represents the absolute temperature of min.
本発明の一態様において、上記式(1)により算出される硬化後の架橋密度は30000mol/m3以上である。
また、本発明の他の態様において、上記熱硬化性ソルダーレジスト組成物は、(A)核体数が3以上のエポキシ化合物、及び(B)イミダゾール系化合物を含有する。
また、本発明の他の態様において、上記エポキシ化合物(A)の核体数は4以上であり、更に他の対応において7以上である。
In one embodiment of the present invention, the crosslinking density after curing calculated by the above formula (1) is 30000 mol / m 3 or more.
In another embodiment of the present invention, the thermosetting solder resist composition contains (A) an epoxy compound having 3 or more nuclei and (B) an imidazole compound.
In another embodiment of the present invention, the number of nuclei of the epoxy compound (A) is 4 or more, and 7 or more in other correspondence.
さらに、本発明の第2の側面によれば、式(1)により算出される硬化後の架橋密度が12000mol/m3超であり、ガラス転移温度が150℃以上である硬化物からなるソルダーレジスト層が提供される。
n=E’min/3ΦRT (1)
式中、nは架橋密度、E’minは貯蔵弾性率E’の最小値、Φはフロント係数(Φ≒1)、Rは気体定数8.31451(J/mol・K)、TはE’minの絶対温度を表わす。
Furthermore, according to the second aspect of the present invention, a solder resist comprising a cured product having a crosslink density after curing calculated by the formula (1) of more than 12000 mol / m 3 and a glass transition temperature of 150 ° C. or higher. A layer is provided.
n = E'min / 3ΦRT (1)
In the formula, n is the crosslink density, E′min is the minimum value of the storage elastic modulus E ′, Φ is the front coefficient (Φ≈1), R is the gas constant 8.31451 (J / mol · K), and T is E ′. Represents the absolute temperature of min.
本発明の一態様において、上記式(1)により算出される硬化後の架橋密度は、30000mol/m3以上である。
また、本発明の他の態様において、上記ソルダーレジスト層を構成する硬化物は、(A)核体数が3以上のエポキシ化合物、及び(B)イミダゾール系化合物を含有する熱硬化性ソルダーレジスト組成物を熱硬化してなる。
また、本発明の他の態様において、上記エポキシ化合物(A)の核体数は4以上であり、更に他の対応において7以上である。
さらに、本発明の第3の側面によれば、上記ソルダーレジスト層を有するプリント配線板が提供される。
In one embodiment of the present invention, the crosslinking density after curing calculated by the above formula (1) is 30000 mol / m 3 or more.
In another embodiment of the present invention, the cured product constituting the solder resist layer is a thermosetting solder resist composition containing (A) an epoxy compound having 3 or more nuclei and (B) an imidazole compound. It is made by thermosetting the product.
In another embodiment of the present invention, the number of nuclei of the epoxy compound (A) is 4 or more, and 7 or more in other correspondence.
Furthermore, according to the 3rd side surface of this invention, the printed wiring board which has the said soldering resist layer is provided.
本発明に係るソルダーレジスト組成物は、特にビスフェノールA型エポキシ系の熱硬化型ソルダーレジストにおいて両立が困難であった印刷性と保色性に優れ、更にプリント配線板用ソルダーレジスト層として一般に要求される他の諸特性にも優れるため、特に被膜形成方法として印刷技術が用いられる場合に好適な熱硬化性ソルダーレジスト組成物として用いることができる。 The solder resist composition according to the present invention is particularly required as a solder resist layer for printed wiring boards, particularly excellent in printability and color retention, which has been difficult to achieve in both bisphenol A type epoxy thermosetting solder resists. In addition, since it is excellent in other properties, it can be used as a thermosetting solder resist composition suitable particularly when a printing technique is used as a film forming method.
本発明の熱硬化性ソルダーレジスト組成物は、その硬化後における架橋密度が12000mol/m3超であり、ガラス転移温度(Tg)が150℃以上であることを特徴とする。熱硬化性ソルダーレジスト組成物の硬化物における架橋密度とガラス転移温度は、特に保色性を改善するために技術的に密接な関連性を有する。本発明において硬化後における架橋密度は、好ましくは30000mol/m3以上であり、より好ましくは50000mol/m3以上であり、その上限は好ましくは65000mol/m3である。架橋密度が高いことは、保色性に加え耐吸湿性(電気特性)及び密着性が向上することからも好ましく、一方、耐衝撃性、大きな収縮応力によるワレやはがれを生ずるなどの理由から、65000mol/m3を超えないことが好ましい。また、ガラス転移温度は150℃以上であり、好ましくは160℃以上である。ガラス転移温度を高めることによって寸法安定性や耐熱信頼性を向上させることができる。しかし、ガラス転移温度を高めることによって、内部応力の上昇にともなう密着性や耐クラック性の低下をきたす場合があることから250℃以下であることが好ましい。 The thermosetting solder resist composition of the present invention is characterized in that the crosslinking density after curing is more than 12000 mol / m 3 and the glass transition temperature (Tg) is 150 ° C. or more. The crosslink density and the glass transition temperature in the cured product of the thermosetting solder resist composition have a technically close relationship particularly in order to improve the color retention. In the present invention, the crosslinking density after curing is preferably 30000 mol / m 3 or more, more preferably 50000 mol / m 3 or more, and the upper limit thereof is preferably 65000 mol / m 3 . High crosslink density is preferable because it improves moisture absorption (electrical properties) and adhesion in addition to color retention, while impact resistance, cracking and peeling due to large shrinkage stress, etc. It is preferable not to exceed 65000 mol / m 3 . The glass transition temperature is 150 ° C. or higher, preferably 160 ° C. or higher. By increasing the glass transition temperature, dimensional stability and heat resistance reliability can be improved. However, increasing the glass transition temperature may cause a decrease in adhesion and crack resistance associated with an increase in internal stress.
本発明において架橋密度(n)、及びガラス転移温度(Tg)は、後掲の実施例に記載のJIS K7244−4に記載の熱硬化性塗料の動的粘弾性試験方法及び計算式により求められる。すなわち、ガラス転移温度(Tg)は、JIS K7244−4に記載の試験方法に準拠し得られる動的粘弾性試験結果によるE’(貯蔵弾性率)、E”(損失弾性率)から下式:
Tanδ=E”/E’
に従い求められるTanδ(損失正接)の値が最大値のときの温度がガラス転移温度(Tg)である。
In the present invention, the crosslinking density (n) and the glass transition temperature (Tg) are determined by the dynamic viscoelasticity test method and calculation formula for thermosetting paints described in JIS K7244-4 described in the examples given later. . That is, the glass transition temperature (Tg) is calculated from E ′ (storage elastic modulus) and E ″ (loss elastic modulus) based on the dynamic viscoelasticity test result obtained according to the test method described in JIS K7244-4:
Tanδ = E "/ E '
The glass transition temperature (Tg) is the temperature at which the value of Tan δ (loss tangent) determined in accordance with the above is the maximum value.
また、架橋密度(n)は、E’(貯蔵弾性率)から式(1)に従い求められる。 Further, the crosslinking density (n) is obtained from E ′ (storage elastic modulus) according to the formula (1).
n=ρ/Mc=E’min/3ΦRT (1)
式(1)中、E’minは、貯蔵弾性率E’の最小値を表わし、Φはフロント係数(Φ≒1)を表わし、ρは試料密度を表わし、Rは気体定数8.31451(J/mol・K)を表わし、TはE’minの絶対温度を表わし、Mcは架橋間分子量を表わす。
n = ρ / Mc = E′min / 3ΦRT (1)
In Equation (1), E′min represents the minimum value of the storage elastic modulus E ′, Φ represents the front coefficient (Φ≈1), ρ represents the sample density, and R represents a gas constant of 8.3451 (J / mol · K), T represents the absolute temperature of E′min, and Mc represents the molecular weight between crosslinks.
硬化後の架橋密度が、12000mol/m3超であり、ガラス転移温度(Tg)が150℃以上である熱硬化性ソルダーレジスト組成物の構成成分は、限定されるものではないが、特に、熱硬化性樹脂として(A)核体数が3以上、より好ましくは4以上、特に好ましくは7以上のエポキシ化合物、及び硬化触媒として(B)イミダゾール系化合物を使用することが、上記課題を解決するために特に有効であることが見出された。
以下に本発明のソルダーレジスト組成物を構成する各成分について詳細に説明する。
The components of the thermosetting solder resist composition having a crosslinking density after curing of more than 12000 mol / m 3 and a glass transition temperature (Tg) of 150 ° C. or higher are not particularly limited, Using the epoxy compound (A) having 3 or more, more preferably 4 or more, particularly preferably 7 or more as the curable resin, and (B) an imidazole compound as the curing catalyst solves the above problem. Has been found to be particularly effective.
Below, each component which comprises the soldering resist composition of this invention is demonstrated in detail.
(A)エポキシ化合物
本発明において用いられる熱硬化性樹脂としては、(A)核体数が3以上のエポキシ化合物が好ましく、核体数が4以上のエポキシ化合物がより好ましく、核体数が7以上のエポキシ化合物が特に好ましい(以下において、これらを「エポキシ化合物(A)」と総称する。)。核体数が高くなると架橋密度が高くなり、より優れた保色性が得られるため好ましい。核体数は官能基数と等しく、例えば核体数3以上のエポキシ化合物とは、1分子当たりの平均エポキシ基数が3以上であることを意味し、次式により算出することができる。
核体数(n)=重量平均分子量/エポキシ当量
核体数の要件を満たすものであれば、公知慣用のエポキシ化合物を使用することができ、例えば、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、臭素化フェノールノボラック型エポキシ樹脂、ビスフェノールAのノボラック型エポキシ樹脂などのグリシジルエーテル化合物、テレフタル酸グリシジルエステル化合物、ヘキサヒドロフタル酸グリシジルエステル化合物、ダイマー酸グリシジルエステル化合物、トリグリシジルイソシアヌレート、N,N,N’,N’−テトラグリシジルメタキシレンジアミン、N,N,N’,N’−テトラグリシジルビスアミノメチルシクロヘキサン、N,N−グリシジルアニリンなどのグリシジルアミン化合物などのエポキシ化合物がある。これらは、単独で又は2種類以上を組み合わせて用いることができる。これらの中でも、水酸基を持たない多官能エポキシ樹脂であるフェノールもしくはクレゾールノボラック型エポキシ樹脂が特に好ましい。
(A) Epoxy compound The thermosetting resin used in the present invention is preferably (A) an epoxy compound having 3 or more nuclei, more preferably an epoxy compound having 4 or more nuclei, and 7 nuclei. The above epoxy compounds are particularly preferable (hereinafter, these are collectively referred to as “epoxy compound (A)”). A higher number of nuclei is preferable because the crosslink density is increased and more excellent color retention is obtained. The number of nuclei is equal to the number of functional groups. For example, an epoxy compound having 3 or more nuclei means that the average number of epoxy groups per molecule is 3 or more, and can be calculated by the following formula.
Nucleotide number (n) = weight average molecular weight / epoxy equivalent Any known epoxy compound can be used as long as it satisfies the requirement for the number of nuclei, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin. , Glycidyl ether compounds such as brominated phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl terephthalic acid ester compound, glycidyl hexahydrophthalic acid ester compound, glycidyl dimer acid compound, triglycidyl isocyanurate, N, N Epoxies such as glycidylamine compounds such as N, N ', N'-tetraglycidylmetaxylenediamine, N, N, N', N'-tetraglycidylbisaminomethylcyclohexane, N, N-glycidylaniline A. These can be used alone or in combination of two or more. Among these, a phenol or cresol novolac type epoxy resin which is a polyfunctional epoxy resin having no hydroxyl group is particularly preferable.
また、硬化物の架橋密度及びガラス転移温度が本発明の範囲となる限りにおいて、本発明のエポキシ化合物(A)以外のエポキシ化合物を併用することができる。 Moreover, as long as the crosslinking density and glass transition temperature of hardened | cured material become the range of this invention, epoxy compounds other than the epoxy compound (A) of this invention can be used together.
エポキシ化合物(A)のソルダーレジスト組成物中の含有率は、組成物の全固形分を基準として好ましくは20〜80質量%であり、より好ましくは20〜60質量%である。なお、上記エポキシ化合物(A)の含有率や、後掲の(B)成分〜(E)成分、並びに他の任意成分の含有率は、本明細書に記載の範囲内において、且つ架橋密度及びガラス転移温度が本発明の範囲内となるよう調節することが好ましい。 The content of the epoxy compound (A) in the solder resist composition is preferably 20 to 80% by mass, more preferably 20 to 60% by mass, based on the total solid content of the composition. In addition, the content rate of the said epoxy compound (A), the following (B) component-(E) component, and the content rate of another arbitrary component are within the range as described in this specification, and a crosslinking density and It is preferable to adjust the glass transition temperature to be within the range of the present invention.
(B)イミダゾール系化合物
本発明では、エポキシ硬化触媒としてイミダゾール系化合物(B)を用いることが、特に所望とするガラス転移温度を得る観点から好ましい。
イミダゾール系化合物(B)としては、例えば、2−メチルイミダゾール(2MZ)、2−ウンデシルイミダゾール(C112)、2−ヘプタデシルイミダゾール(C17Z)、1,2ジメチルイミダゾール(1,2DMZ)、2−エチル−4−メチルイミダゾール(2E4MZ)、2−フェニルイミダゾール(2PZ)、2−フェニル−4−メチルイミダゾール(2P4MZ)、1−ベンジル−2−メチルイミダゾール(1B2MZ)、1−シアノエチル−2−メチルイミダゾール(2MZ−CN)、1−シアノエチル−2−エチル−4−メチルイミダゾール(2E4MZ−CN)、1−シアノエチル−2−ウンデシルイミダゾール(C11Z−CN)、1−シアノエチル−2−フェニルイミダゾール(2PZ−CN)、1−シアノエチル−2−エチル−4−メチルイミダゾリウムトリメリテイト(2E4MZ−CNS)、1−シアノエチル−2−ウンデシルイミダゾリウムトリメリテイト(C11Z−CNS)、1−シアノエチル−2−フェニルイミダゾリウムトリメリテイト(2PZ−CNS)、2,4−ジアミノ−6−(2’−メチルイミダゾリル−(1’))−エチル−s−トリアジン(2MZ−A)、2,4−ジアミノ−6−(2’−ウンデシルイミダゾリル)−エチル−s−トリアジン(C11Z−A)、2,4−ジアミノ−6−(2’−エチル−4−メチルイミダゾリル−(1’))−エチル−s−トリアジン(2E4MZ−A)、2,4−ジアミノ−6−(2’メチルイミダゾリル−(1’))−エチル−sトリアジン イソシアヌル酸付加物(2MA−OK)、2−フェニルイミダゾール イソシアヌル酸付加物(2PZ−OK)、2−メチルイミダゾール イソシアヌル酸付加物(2MZ−OK)、2−フェニル−4,5−ジヒドロキシメチルイミダゾール(2PHZ)、2−フェニル−4−メチル−5−ヒドロキシメチルイミダゾール(2P4MHZ)、1−シアノエチル−2−フェニル−4,5−ジ(2−シアノエトキシ)メチルイミダゾール(2PHZ−CN)、2−メチルイミダゾリン(2MZL−F)、2−フェニルイミダゾリン(2PZL)、1−ドデシル−2−メチル−3−ベンジルイミダゾリウムクロライド(SFZ)、1−ベンジル−2−フェニルイミダゾール・塩酸塩(1B2PZ−HCL)、1−ベンジル−2−フェニルイミダゾリウムトリメリテイト(1B2PZ−S)、2,4−ジアミノ−6−ビニル−s−トリアジン(VT)、2,4−ジアミノ−6−メタクリロイルオキシ−s−トリアジン(MAVT)、2,4−ジアミノ−6−ビニル−1,3,5−トリアジン イソシアヌル酸付加物(VT−OK)、2,4−ジアミノ−6−メタクリロイルオキシ−1,3,5−トリアジン イソシアヌル酸付加物又はこれらの有機酸塩類などが挙げられる。カッコ内はいずれも四国化成工業(株)製の商品名である。
(B) Imidazole-based compound In the present invention, it is preferable to use an imidazole-based compound (B) as an epoxy curing catalyst from the viewpoint of obtaining a desired glass transition temperature.
Examples of the imidazole compound (B) include 2-methylimidazole (2MZ), 2-undecylimidazole (C112), 2-heptadecylimidazole (C17Z), 1,2 dimethylimidazole (1,2DMZ), 2- Ethyl-4-methylimidazole (2E4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methylimidazole (2P4MZ), 1-benzyl-2-methylimidazole (1B2MZ), 1-cyanoethyl-2-methylimidazole (2MZ-CN), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), 1-cyanoethyl-2-undecylimidazole (C11Z-CN), 1-cyanoethyl-2-phenylimidazole (2PZ- CN), 1-cyanoethyl- 2-ethyl-4-methylimidazolium trimellitate (2E4MZ-CNS), 1-cyanoethyl-2-undecylimidazolium trimellitate (C11Z-CNS), 1-cyanoethyl-2-phenylimidazolium trimellitate ( 2PZ-CNS), 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine (2MZ-A), 2,4-diamino-6- (2′-un) Decylimidazolyl) -ethyl-s-triazine (C11Z-A), 2,4-diamino-6- (2′-ethyl-4-methylimidazolyl- (1 ′))-ethyl-s-triazine (2E4MZ-A) 2,4-diamino-6- (2′methylimidazolyl- (1 ′))-ethyl-striazine isocyanuric acid adduct (2MA-OK), 2-pheni Imidazole isocyanuric acid adduct (2PZ-OK), 2-methylimidazole isocyanuric acid adduct (2MZ-OK), 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ), 2-phenyl-4-methyl-5 Hydroxymethylimidazole (2P4MHZ), 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole (2PHZ-CN), 2-methylimidazoline (2MZL-F), 2-phenylimidazoline (2PZL) ), 1-dodecyl-2-methyl-3-benzylimidazolium chloride (SFZ), 1-benzyl-2-phenylimidazole hydrochloride (1B2PZ-HCL), 1-benzyl-2-phenylimidazolium trimellitate ( 1B2PZ-S), 2,4-diamy -6-vinyl-s-triazine (VT), 2,4-diamino-6-methacryloyloxy-s-triazine (MAVT), 2,4-diamino-6-vinyl-1,3,5-triazine isocyanuric acid addition Product (VT-OK), 2,4-diamino-6-methacryloyloxy-1,3,5-triazine isocyanuric acid adduct or organic acid salts thereof. The names in parentheses are product names manufactured by Shikoku Kasei Kogyo Co., Ltd.
イミダゾール系化合物(B)のソルダーレジスト組成物中の含有率は、組成物の全固形分100質量部を基準として、好ましくは0.1〜10質量%であり、より好ましくは0.2〜7質量%である。 The content of the imidazole compound (B) in the solder resist composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 7 based on 100 parts by mass of the total solid content of the composition. % By mass.
なお、本発明においては、エポキシ硬化触媒として上記イミダゾール系化合物以外にも、例えば、トリエチルアミン、トリブチルアミン、ジメチルベンジルアミン、ジエチルベンジルアミン、4−(ジメチルアミノ)−N,N−ジメチルベンジルアミン、4−メトキシ−N,N−ジメチルベンジルアミン、4−メチル−N,N−ジメチルベンジルアミンなどの第3級アミン、ベンジルトリメチルアンモニウムクロライド、ベンジルトリエチルアンモニウムクロライドなどの4級アンモニウム塩、トリエチルホスフィン、トリフェニルホスフィンなどのホスフィン類、n−ブチルトリフェニルホスホニウムブロマイドなどのホスホニウム塩、有機酸塩類、アセトグアナミン、ベンゾグアナミン等のグアナミン類などを用いることができ、これらと共にアミン類、酸無水物、アミノポリアミド樹脂、ポリスルフィド樹脂、三弗化ホウ素アミンコンプレックス、ノボラック樹脂、ジシアンジアミド、酸ヒドラジド、カルボキシル基含有化合物などを組み合わせて使用することができる。 In the present invention, in addition to the above-mentioned imidazole compound as an epoxy curing catalyst, for example, triethylamine, tributylamine, dimethylbenzylamine, diethylbenzylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4 Tertiary amines such as -methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, triethylphosphine, triphenyl Phosphines such as phosphine, phosphonium salts such as n-butyltriphenylphosphonium bromide, organic acid salts, guanamines such as acetoguanamine, benzoguanamine, etc. can be used. Both amines, acid anhydrides, aminopolyamide resin, polysulfide resin can be used in combination boron trifluoride amine complexes, novolac resins, dicyandiamide, acid hydrazides, and the like carboxyl group-containing compound.
具体例としては、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、メタキシリレンジアミン、メタフェニレンジアミン、パラフェニレンジアミン、4,4′−ジアミノジフェニルメタン、4,4′−ジアミノジフェニルスルホン、4,4′−ジアミノジフェニエーテル、アニリン−ホルマリン樹脂などのアミン類、無水フタル酸、無水ヘキサヒドロフタル酸、ナジック酸無水物、メチルナジック酸無水物、トリメリット酸無水物、ピロメリット酸無水物、ベンゾフェノンテトラカルボン酸無水物などの酸無水物、ダイマー酸とジエチレントリアミン、トリエチレンテトラミン等との縮合物であるアミノポリアミド樹脂、メルカプタン基を末端に持つポリスルフィド樹脂、三弗化ホウ素とアニリン、ベンジルアミン、エチルアミンなどとの三弗化ホウ素アミンコンプレックス、フェノール、クレゾール、キシレノール、レゾルシンなどとホルマリンの縮合反応により得られるノボラック樹脂、ジシアンジアミド、アジピン酸ジヒドラジド、セバシン酸ヒドラジド等の潜在性硬化剤が挙げられる。その他、カルボキシル基含有化合物、例えばジョンソンポリマー社製のジョンクリル−68などの(メタ)アクリル酸共重合物等も用いることもできる。これらを単独で、又は2種以上を組合せて使用することができるが、より好ましくはイミダゾールを必須とし、イミダゾールと他の硬化触媒を併用することである。 Specific examples include diethylenetriamine, triethylenetetramine, isophoronediamine, metaxylylenediamine, metaphenylenediamine, paraphenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diamino. Amines such as diphenyl ether, aniline-formalin resin, phthalic anhydride, hexahydrophthalic anhydride, nadic acid anhydride, methyl nadic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid Acid anhydrides such as anhydrides, aminopolyamide resins that are condensates of dimer acid and diethylenetriamine, triethylenetetramine, etc., polysulfide resins terminated with mercaptan groups, boron trifluoride and aniline, benzylamine, Such as a boron trifluoride amine complex triethanolamine, phenol, cresol, xylenol, etc. and formalin condensation reaction by novolak resin obtained resorcin, dicyandiamide, adipic acid dihydrazide include latent curing agents such as sebacic acid hydrazide. In addition, a carboxyl group-containing compound such as a (meth) acrylic acid copolymer such as John Cryl-68 manufactured by Johnson Polymer Co., Ltd. can also be used. These can be used alone or in combination of two or more. More preferably, imidazole is essential, and imidazole and another curing catalyst are used in combination.
(C)着色剤
本発明のソルダーレジスト組成物は、着色剤(C)を含有してもよい。
特に保色性を要求される白色ソルダーレジストの着色剤としては、C.I.ピグメントホワイト4に示される酸化亜鉛、C.I.ピグメントホワイト6に示される酸化チタン、C.I.ピグメントホワイト7に示される硫化亜鉛があげられるが、着色力と無毒性という点から特に好ましいのは酸化チタンであり例えば、富士チタン工業(株)製TR−600、TR−700、TR−750、TR−840、石原産業(株)R−550、R−580、R−630、R−820、CR−50、CR−60、CR−90、チタン工業(株)製KR−270、KR−310、KR−380等のルチル型酸化チタン、富士チタン工業(株)製TA−100、TA−200、TA−300、TA−500、石原産業(株)製A100、A220、チタン工業(株)製KA−15、KA−20、KA−35、KA−90等のアナターゼ型酸化チタンがあげられる。
(C) Colorant The solder resist composition of the present invention may contain a colorant (C).
In particular, as a colorant for a white solder resist that requires color retention, zinc oxide shown in CI Pigment White 4, titanium oxide shown in CI Pigment White 6, and zinc sulfide shown in CI Pigment White 7 can be mentioned. Particularly preferred from the standpoint of coloring power and non-toxicity is titanium oxide, for example, TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industry Co., Ltd., R-550, Ishihara Sangyo Co., Ltd. , R-580, R-630, R-820, CR-50, CR-60, CR-90, Rutile type titanium oxide such as KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd., Fuji TA-100 manufactured by Titanium Industry Co., Ltd. TA-200, TA-300, TA-500, A100, A220 manufactured by Ishihara Sangyo Co., Ltd., KA-15 manufactured by Titanium Industry Co., Ltd. KA-20, KA-35, anatase type titanium oxide such as KA-90 and the like.
白色以外の着色剤としては、色相的に限定されるものではなく、例えば、ペリレン、ペリノン、キナクリドン、キナクリドンキノン、アントラキノン、アントアントロン、ベンズイミダゾロン、ジスアゾ縮合、ジスアゾ、アゾ、インダントロン、フタロシアニン、トリアリールカルボニウム、ジオキサジン、アミノアントラキノン、ジケトピロロピロール、チオインジゴ、イソインドリン、イソインドリノン、ピラントロンもしくはイソビオラントロン化合物、またはそれらの混合物などが挙げられる。 The colorant other than white is not limited in hue. And triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compounds, or a mixture thereof.
着色剤(C)のソルダーレジスト組成物中の含有率は、熱硬化に影響しないため特に厳密な範囲はないが、印刷性、密着性を考慮し、組成物の全固形分100質量部を基準として、好ましくは0〜50質量%であり、より好ましくは1〜40質量%である。 The content of the colorant (C) in the solder resist composition is not particularly limited because it does not affect thermosetting, but the printability and adhesion are taken into consideration, and the total solid content of the composition is 100 parts by mass. As, it is 0-50 mass% preferably, More preferably, it is 1-40 mass%.
(D)体質顔料
本発明のソルダーレジスト組成物は、体質顔料(D)を含有してもよい。体質顔料(D)を含有させることは、印刷性、鉛筆硬度、耐熱性、密着性向上の観点から好ましい。
体質顔料(D)としては、例えば、シリカ、硫酸バリウム、タルク、クレー、酸化アルミニウム、水酸化アルミニウム、炭酸カルシウム、などの公知慣用の無機充填剤が挙げられ、これらを単独で、又は2種以上を組合せて使用することができる。
体質顔料(D)のソルダーレジスト組成物中の含有率は、組成物中の全固形分を基準として、好ましくは10〜60質量%であり、より好ましくは10〜40質量%である。
(D) Extender The solder resist composition of the present invention may contain extender (D). The inclusion of the extender pigment (D) is preferable from the viewpoints of printability, pencil hardness, heat resistance, and adhesion.
Examples of the extender pigment (D) include known and commonly used inorganic fillers such as silica, barium sulfate, talc, clay, aluminum oxide, aluminum hydroxide, and calcium carbonate. These may be used alone or in combination of two or more. Can be used in combination.
The content of the extender pigment (D) in the solder resist composition is preferably 10 to 60% by mass, more preferably 10 to 40% by mass, based on the total solid content in the composition.
(E)有機溶剤
本発明のソルダーレジスト組成物は、組成物の調製や粘度調整のために用いられる有機溶剤(E)を含有し得る。有機溶剤(E)としては、例えば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2種類以上を組み合わせて用いることができる。
(E) Organic solvent The solder resist composition of the present invention may contain an organic solvent (E) used for preparing the composition and adjusting the viscosity. Examples of the organic solvent (E) include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methylcellosolve, butylcellosolve, carbitol, methylcarbitol, butylcarbitol, Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; 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 acetate Tate, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and organic solvents such as petroleum-based solvents such as solvent naphtha may be used. These organic solvents can be used alone or in combination of two or more.
(F)他の添加剤
本発明のソルダーレジスト組成物は、更に必要に応じて、有機ベントナイト、モンモリロナイトなどの公知慣用の増粘剤、シリコーン系、フッ素系、高分子系などの消泡剤及び/又はレベリング剤、チアゾール系、トリアゾール系等のシランカップリング剤などのような公知慣用の添加剤類を配合することができ、また本発明の熱硬化性樹脂組成物の白色を損なわない範囲において着色剤を配合することができる。
(F) Other Additives The solder resist composition of the present invention may further comprise, as necessary, known and commonly used thickeners such as organic bentonite and montmorillonite, silicone-based, fluorine-based, polymer-based antifoaming agents, and the like. In the range which does not impair the white color of the thermosetting resin composition of the present invention, and / or can be blended with known and commonly used additives such as leveling agents, thiol- and triazole-based silane coupling agents, etc. Coloring agents can be blended.
(硬化物の形成)
本発明のソルダーレジスト組成物は、前記有機溶剤で塗布方法に適した粘度に調整し、基材上に、スクリーン印刷法等の方法により塗布する。塗布後、例えば140℃〜180℃の温度に加熱して熱硬化させることにより、硬化塗膜を得ることができる。
(Formation of cured product)
The solder resist composition of the present invention is adjusted to a viscosity suitable for the coating method with the organic solvent, and coated on the substrate by a method such as a screen printing method. After application, for example, a cured coating film can be obtained by heating to a temperature of 140 ° C. to 180 ° C. and thermosetting.
次に実施例を示して本発明について具体的に説明するが、本発明が以下の実施例に限定されるものでないことはもとよりである。
表1に従って各成分を3本ロールミルで混練し、各熱硬化性ソルダーレジスト組成物(組成物例1〜22)を得た。表中の数字は、質量部を表す。
Each component was kneaded with a three-roll mill according to Table 1, and each thermosetting solder resist composition (Composition Examples 1 to 22) was obtained. The numbers in the table represent parts by mass.
性能評価:
(評価基板の作製)
上記熱硬化性ソルダーレジスト組成物1〜22を、それぞれ銅張り基板上にスクリーン印刷により特定パターンに塗布し、熱風循環式乾燥炉において150℃で30分硬化した。得られた硬化塗膜を以下の各評価方法において使用した。
Performance evaluation:
(Production of evaluation board)
The said thermosetting soldering resist compositions 1-22 were apply | coated to the specific pattern by screen printing, respectively on the copper-clad board | substrate, and were hardened | cured for 30 minutes at 150 degreeC in the hot air circulation type drying furnace. The obtained cured coating film was used in the following evaluation methods.
(1)耐薬品性
硬化塗膜を10vol%HClに20℃で60分浸漬させた後、すぐにテープピールテストを行い、レジスト層の膨れ・剥がれについて評価した。
(1) Chemical resistance After the cured coating film was immersed in 10 vol% HCl at 20 ° C. for 60 minutes, a tape peel test was immediately performed to evaluate the swelling and peeling of the resist layer.
○:膨れ、剥がれなし。 ○: No swelling or peeling.
△:ほんの僅かに剥がれあり。 Δ: Slightly peeled off.
×:塗膜の大きな剥がれあり。 X: There is a large peeling of the coating film.
(2)耐熱性
硬化塗膜を、260℃のはんだに30秒フローさせテープピールテストを行い、レジスト層の膨れ・剥がれについて評価した。
(2) Heat resistance The cured coating film was allowed to flow in 260 ° C. solder for 30 seconds to perform a tape peel test, and the swelling and peeling of the resist layer were evaluated.
○:膨れ、剥がれなし。 ○: No swelling or peeling.
△:ほんの僅かに剥がれあり。 Δ: Slightly peeled off.
×:塗膜の大きな剥がれあり。 X: There is a large peeling of the coating film.
(3)鉛筆硬度
硬化塗膜をJIS C 5400の試験方法に従って試験し、塗膜に傷のつかない最も高い硬度を観測した。
(3) Pencil hardness The cured coating film was tested according to the test method of JIS C 5400, and the highest hardness at which the coating film was not damaged was observed.
(4)保色性
硬化塗膜を金めっき工程に流した後、触媒の吸着の有無を変色具合から観測した。
(4) Color retention After passing the cured coating film through the gold plating step, the presence or absence of catalyst adsorption was observed from the color change.
○:変色なし。 ○: No discoloration.
△:ほんの僅かに変色あり。 Δ: Slightly discolored.
×:大部分に変色あり。 X: Mostly discolored.
(5)密着性
硬化塗膜に巾1mmで10×10のクロスカットを入れ、テープピーリングで剥離テストを行い剥がれの状態を目視確認した。
(5) Adhesiveness A 10 × 10 crosscut with a width of 1 mm was put into the cured coating film, and a peeling test was performed by tape peeling to visually check the peeling state.
○:剥がれなし。 ○: No peeling.
△:1〜10箇所に剥がれあり。 Δ: Peeled off at 10 to 10 locations.
×:10箇所以上剥がれあり。 X: Ten or more places peeled off.
(6)印刷性
上記熱硬化性ソルダーレジスト組成物1〜22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特定パターンに塗布し、かすれ、にじみ、レベリング性を確認した。
(6) Printability Each of the thermosetting solder resist compositions 1 to 22 was applied to a specific pattern by screen printing on a printed wiring board on which a circuit was formed, and it was blurred, smudged, and leveled.
○:かすれ、にじみ、レベリング性に問題なく塗布可能。 ○: Can be applied without any problem in fading, bleeding and leveling.
△:ほんの僅かに印刷後のかすれが発生。 Δ: Slight fading occurred after printing.
×:全体的にかすれ、レベリング性不良。 X: Overall is faint and leveling property is poor.
(8)電気特性
上記熱硬化性ソルダーレジスト組成物1〜22を、IPCくし型Bパターンに塗布、硬化し、90%RH、25〜65℃、DC100Vに印加にて168時間加湿後、DC500Vにて1分値の絶縁抵抗値を観測した。
(8) Electrical characteristics The above thermosetting solder resist compositions 1-22 are applied to an IPC comb B pattern, cured, and humidified for 168 hours by applying to 90% RH, 25-65 ° C., DC 100V, and then to DC 500V. The insulation resistance value of 1 minute was observed.
(9)動的粘弾性試験
試験方法:塗膜作製方法
上記熱硬化性ソルダーレジスト組成物1〜22のソルダーレジスト組成物をスクリーン印刷法により、25〜50μm(ドライ)になるようにフィルム上に塗布し、熱風循環式乾燥炉において150℃×30分硬化させ、評価フィルムを作製した。フィルムから塗膜を採取し測定機器にセットした。
(9) Dynamic viscoelasticity test Test method: Coating film preparation method The solder resist composition of the above thermosetting solder resist compositions 1-22 is formed on a film so as to be 25-50 μm (dry) by screen printing. The film was applied and cured at 150 ° C. for 30 minutes in a hot air circulating drying oven to prepare an evaluation film. A coating film was collected from the film and set on a measuring instrument.
測定装置/セイコーインスツルメンツ社製
形式:DMS6100
測定条件/測定温度:20〜300℃
昇温速度:5℃/分
周波数:1、10Hz
変形モード:引っ張り・正弦波モード
測定塗膜サイズ:10mm×5mm
JIS K7244−4に記載の試験方法により動的粘弾性試験を行い、E’(貯蔵弾性率)、E”(損失弾性率)を得、これらから上述した手法に従い本発明の架橋密度(n)、およびガラス転移温度(Tg)を求めた。
Measuring device / Seiko Instruments
Format: DMS6100
Measurement conditions / temperature: 20 to 300 ° C
Temperature increase rate: 5 ° C / min
Frequency: 1, 10Hz
Deformation mode: Pull / Sine wave mode
Measurement film size: 10 mm x 5 mm
A dynamic viscoelasticity test is performed by the test method described in JIS K7244-4 to obtain E ′ (storage elastic modulus) and E ″ (loss elastic modulus), and the crosslinking density (n) of the present invention is obtained from these according to the above-described method. And the glass transition temperature (Tg).
結果を表2に示す。
表2に示された結果から明らかなように、本発明のソルダーレジスト組成物は、プリント配線板用ソルダーレジスト層に一般的に要求される諸特性を満たしつつ、印刷性及び保色性にも優れることがわかる。 As is apparent from the results shown in Table 2, the solder resist composition of the present invention satisfies various properties generally required for a printed wiring board solder resist layer, and also has good printability and color retention. It turns out that it is excellent.
Claims (3)
n=E’min/3ΦRT (1)
式中、nは架橋密度、E’minは貯蔵弾性率E’の最小値、Φはフロント係数(Φ≒1)、Rは気体定数8.31451(J/mol・K)、TはE’minの絶対温度を表わす。 (A) A thermosetting solder resist composition containing an epoxy compound having 3 or more nuclei and (B) an imidazole compound, wherein the crosslinking density after curing calculated by the formula (1) is 30000 mol / and the m 3 or more, thermosetting solder resist composition having a glass transition temperature of 0.99 ° C. or higher.
n = E'min / 3ΦRT (1)
In the formula, n is the crosslink density, E′min is the minimum value of the storage elastic modulus E ′, Φ is the front coefficient (Φ≈1), R is the gas constant 8.31451 (J / mol · K), and T is E ′. Represents the absolute temperature of min.
n=E’min/3ΦRT (1)
式中、nは架橋密度、E’minは貯蔵弾性率E’の最小値、Φはフロント係数(Φ≒1)、Rは気体定数8.31451(J/mol・K)、TはE’minの絶対温度を表わす。 (A) A solder resist layer comprising a cured product of a thermosetting solder resist composition containing an epoxy compound having three or more nuclei and (B) an imidazole compound, and is calculated by the formula (1). A solder resist layer comprising a cured product having a crosslinking density after curing of 30000 mol / m 3 or more and a glass transition temperature of 150 ° C. or more.
n = E'min / 3ΦRT (1)
In the formula, n is the crosslink density, E′min is the minimum value of the storage elastic modulus E ′, Φ is the front coefficient (Φ≈1), R is the gas constant 8.31451 (J / mol · K), and T is E ′. Represents the absolute temperature of min.
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