JP2007262198A - Resin composition and laminate for printed circuit board - Google Patents
Resin composition and laminate for printed circuit board Download PDFInfo
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本発明は，樹脂組成物およびそれを用いたプリント配線板用積層板に関するものである。 The present invention relates to a resin composition and a laminate for a printed wiring board using the same.
火災や発火を防止し，安全性を保つという観点から，電気・電子機器に使用されるプリント配線板には難燃性が要求される。この難燃性を確保するために一般には，ハロゲン元素を含む難燃剤，特に臭素系難燃剤が用いられてきた。しかし，最近の地球環境の保全・悪化防止の観点から，毒性の強いダイオキシン類，ベンゾフラン等を発生させる恐れのあるハロゲン元素を含有せず難燃化する技術が要求されている。 From the standpoint of preventing fire and fire and maintaining safety, printed wiring boards used in electrical and electronic equipment are required to be flame retardant. In general, flame retardants containing halogen elements, particularly brominated flame retardants, have been used to ensure this flame retardancy. However, from the viewpoint of the recent conservation of the global environment and prevention of deterioration, there is a demand for technology that makes flame retardant without containing halogen elements that may generate highly toxic dioxins, benzofuran, and the like.
プリント配線板用材料としては，フェノール樹脂，エポキシ樹脂，ポリイミド樹脂等が主に使用されているが，近年の電子機器の発達はめざましく，携帯電話やノートパソコン等携帯端末の普及により，小型化，高密度化が急速に進んでいる。これらの用途には，多層高密度化が可能で，高いガラス転移温度（以下Ｔｇと称す）による高信頼性等の点でガラス布基材，エポキシ樹脂金属箔張積層板やガラス布基材，ポリイミド樹脂金属箔張積層板等が用いられているが，コストの点で，一般的にはエポキシ樹脂が多く使用されている。 Phenol resin, epoxy resin, polyimide resin, etc. are mainly used as materials for printed wiring boards, but the development of electronic devices has been remarkable in recent years. Densification is progressing rapidly. For these applications, it is possible to increase the density of the multilayer, and in terms of high reliability due to the high glass transition temperature (hereinafter referred to as Tg), glass cloth substrates, epoxy resin metal foil-clad laminates and glass cloth substrates, A polyimide resin metal foil-clad laminate or the like is used, but in general, epoxy resin is often used in terms of cost.
しかしながら前述のハロゲンフリー材は一般的に難燃化が難しいため，エポキシ樹脂よりも難燃性に優れている樹脂をエポキシ樹脂と併用する方法が提案されている。例えば特開平２−６９５６７号公報，特開平７−３１２１号公報などに開示されているように，フェノール類とアミン類とホルムアルデヒドから得られるジヒドロベンゾオキサジン環を有する化合物を主材に用いる方法であるが，難燃性に優れているジヒドロベンゾオキサジン環を有する樹脂を用いても，それ単体ではプリント配線板に要求される難燃性ＵＬ９４Ｖ−０を実現することは難しいため，リン化合物を併用する等の手法が提案されている（特開２００２−２４９６３９号公報）。特に前述のジヒドロベンゾオキサジン環を有する化合物は窒素を含有しており，リン化合物と併用することで高い難燃性を付与することができる。その機構は，窒素化合物がリン化合物の分解および熱縮合によるポリリン酸の生成を促進し，そのポリリン酸が表面に皮膜を生成し，断熱効果，酸素遮断効果を生じその結果燃焼を防ぐというものである。 However, since the above-mentioned halogen-free materials are generally difficult to flame retardant, a method has been proposed in which a resin that is superior in flame retardancy than an epoxy resin is used in combination with an epoxy resin. For example, as disclosed in JP-A-2-69567, JP-A-7-3121, etc., it is a method using a compound having a dihydrobenzoxazine ring obtained from phenols, amines and formaldehyde as a main material. However, even if a resin having a dihydrobenzoxazine ring having excellent flame retardancy is used, it is difficult to achieve the flame retardancy UL94V-0 required for a printed wiring board alone, so a phosphorus compound is used in combination. Have been proposed (Japanese Patent Laid-Open No. 2002-249639). In particular, the above-mentioned compound having a dihydrobenzoxazine ring contains nitrogen, and high flame retardancy can be imparted by using it together with a phosphorus compound. The mechanism is that the nitrogen compound promotes the decomposition of the phosphorus compound and the formation of polyphosphoric acid by thermal condensation, and the polyphosphoric acid forms a film on the surface, resulting in an adiabatic effect and an oxygen blocking effect, thereby preventing combustion. is there.
難燃化のために用いられるリン化合物としては主にトリフェニルフォスフェートやクレジルジフェニルフォスフェート等のリン酸エステル類が用いられてきたが，これらをエポキシ樹脂等に添加した場合，これらの化合物の可塑性によって，樹脂のガラス転移点が大幅に低下するという欠点が生じる。これらのリン酸エステル類はエポキシ樹脂の骨格と共有結合を生じておらず，リン化合物同士の相互作用が，リン化合物と樹脂骨格との相互作用よりも大きい。このため，これらのリン酸エステルを樹脂に添加しプリプレグを作製した場合，一定時間経過後，リン酸エステル類が容易に結晶化し，プリプレグ表面に析出するため使用できなくなるという問題が生じる。また，リン化合物は加水分解しやすいため，多量に配合する場合，プリント配線板製造工程内で使用される薬液に溶解し易く（主にアルカリ溶液），また，耐湿耐熱性の低下を招くものが多い。 Phosphoric esters such as triphenyl phosphate and cresyl diphenyl phosphate have been mainly used as the phosphorus compounds used for flame retardancy. When these are added to epoxy resins, these compounds are used. Due to the plasticity, the glass transition point of the resin is greatly lowered. These phosphate esters do not form a covalent bond with the epoxy resin skeleton, and the interaction between the phosphorus compounds is larger than the interaction between the phosphorus compound and the resin skeleton. For this reason, when these phosphoesters are added to a resin to produce a prepreg, the phosphoric acid esters easily crystallize after a certain period of time and precipitate on the prepreg surface, resulting in a problem that they cannot be used. In addition, since phosphorus compounds are easily hydrolyzed, they are easily dissolved in chemicals used in the printed wiring board manufacturing process (mainly alkaline solutions) when they are blended in large quantities, and those that cause a decrease in moisture resistance and heat resistance. Many.
そこでリン化合物を樹脂骨格に組み込むことができれば，樹脂のガラス転移点の大幅な低下や，リン化合物のプリプレグ表面への析出，加水分解性，耐熱性の低下という問題を解決できると考えられる。リン化合物を樹脂骨格に組み込む手法としてはＪｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ，Ｖｏｌ．６１，ｐ１７８１−１７９６（１９９６）などに記載が見られるが，合成に多大な費用を有する欠点がある。 Therefore, if the phosphorus compound can be incorporated into the resin skeleton, it is considered that the problems of a significant decrease in the glass transition point of the resin, precipitation of the phosphorus compound on the surface of the prepreg, degradation in hydrolyzability, and heat resistance can be solved. As a method for incorporating a phosphorus compound into a resin skeleton, Journal of Applied Polymer Science, Vol. 61, p 1781-1796 (1996), etc., but there is a drawback that the synthesis is expensive.
本発明はかかる状況を鑑みてなされたものであり，ハロゲンを使用せずに高度な難燃性を有し，長期間にわたって樹脂組成物やプリプレグの特性が変化せず，大幅なガラス転移点の低下や，耐熱性の低下を招かない樹脂組成物，およびプリント配線板用積層板を提供するものである。 The present invention has been made in view of such circumstances, has high flame retardancy without using halogen, does not change the properties of the resin composition or prepreg over a long period of time, and has a significant glass transition point. It is an object of the present invention to provide a resin composition and a printed wiring board laminate that do not cause a decrease or a decrease in heat resistance.
本発明は、以下に関する。
１．（ａ）分子中にジヒドロベンゾオキサジン環を有する化合物、（ｂ）フェノール類とトリアジン環を有する化合物とアルデヒド類の重縮合物、（ｃ）エポキシ樹脂、（ｄ）下記式（１）に示すリン化合物である９，１０−ジヒドロ−９−オキサ−１０−（２，５−ジオクソテトラヒドロ−３−フラニルメチル）−１０−ホスファフェナントレン−１０−オキシド、（ｅ）無機充填剤を含む樹脂組成物であって、
（ａ），（ｂ）及び（ｃ）の有機固形分の総量中、（ａ）３５〜７５重量％、（ｂ）１０〜２５重量％、（ｃ）１０〜４５重量％を含み，
且つ（ｄ）リン化合物を、（ａ），（ｂ）及び（ｃ）の有機固形分の総量１００重量部に対し、５〜３５重量部含み，
且つ（ｅ）無機充填剤を，（ａ），（ｂ），（ｃ）および（ｄ）の有機固形分の総量１００重量部に対し，３０〜１００重量部含み，使用する全ての材料のハロゲン含有量が０．１重量％以下であることを特徴とする樹脂組成物。
The present invention relates to the following.
1. (A) a compound having a dihydrobenzoxazine ring in the molecule, (b) a polycondensate of a phenol and a triazine ring and a aldehyde, (c) an epoxy resin, (d) a phosphorus represented by the following formula (1) 9,10-dihydro-9-oxa-10- (2,5-dioxotetrahydro-3-furanylmethyl) -10-phosphaphenanthrene-10-oxide which is a compound, (e) a resin composition containing an inorganic filler Because
(A) 35 to 75% by weight, (b) 10 to 25% by weight, (c) 10 to 45% by weight in the total amount of organic solids of (a), (b) and (c),
And (d) 5 to 35 parts by weight of the phosphorus compound with respect to 100 parts by weight of the total organic solids of (a), (b) and (c),
And (e) 30 to 100 parts by weight of an inorganic filler with respect to 100 parts by weight of the total organic solid content of (a), (b), (c) and (d), and halogens of all materials used Content is 0.1 weight% or less, The resin composition characterized by the above-mentioned.
２．項１記載の樹脂組成物をワニスとし，このワニスを基材に含浸乾燥してなるプリプレグを所定枚数重ね合わせ、その両面または片面に金属箔を構成後，加熱成形して得られるプリント配線板用積層板。 2. Item 1. A printed wiring board obtained by using a resin composition according to Item 1 as a varnish, superposing a predetermined number of prepregs obtained by impregnating and drying the varnish on a base material, forming a metal foil on both sides or one side, and then heat-molding Laminated board.
ハロゲンを使用せずに高度な難燃性を有し，長期間にわたって樹脂組成物やプリプレグの特性が変化せず，大幅なガラス転移点の低下や，耐熱性の低下を招かない樹脂組成物，およびプリント配線板用積層板を提供することが可能となった。 Resin composition that has high flame resistance without using halogen, does not change the properties of the resin composition or prepreg over a long period of time, and does not cause a significant decrease in glass transition point or heat resistance, And it became possible to provide the laminated board for printed wiring boards.
前述のリン酸エステルにより生じる問題点に対し，９，１０−ジヒドロ−９−オキサ−１０−（２，５−ジオクソテトラヒドロ−３−フラニルメチル）−１０−ホスファフェナントレン−１０−オキシドはエポキシ基と反応するためエポキシ樹脂骨格に容易に組み込むことができる。ただし，酸無水物であるため，アミン類との併用は困難であり，窒素成分を含有するジヒドロベンゾオキサジン環を有する化合物以外に窒素系難燃成分を樹脂骨格中に組み込むことが困難である。そこでトリアジン変性フェノールノボラック樹脂はフェノール水酸基をもち，しかも窒素をもつため窒素系難燃剤として有用である。 9,10-Dihydro-9-oxa-10- (2,5-dioxotetrahydro-3-furanylmethyl) -10-phosphaphenanthrene-10-oxide is an epoxy group for the problem caused by the above-mentioned phosphate ester. Can be easily incorporated into the epoxy resin skeleton. However, since it is an acid anhydride, it is difficult to use it together with amines, and it is difficult to incorporate a nitrogen-based flame retardant component into a resin skeleton in addition to a compound having a dihydrobenzoxazine ring containing a nitrogen component. Therefore, triazine-modified phenol novolak resin has a phenolic hydroxyl group and also has nitrogen, so it is useful as a nitrogen-based flame retardant.
以上のように本発明においては，ジヒドロベンゾオキサジン環を有する化合物とエポキシ樹脂を主剤として用い，トリアジン変性フェノールノボラック樹脂を硬化剤として用い，難燃剤として９，１０−ジヒドロ−９−オキサ−１０−（２，５−ジオクソテトラヒドロ−３−フラニルメチル）−１０−ホスファフェナントレン−１０−オキシドを用いることで，窒素とリンの相乗効果を発現させて高度な難燃性を有しつつ，樹脂骨格にリン化合物を取り込むことで，長期間にわたって樹脂組成物やプリプレグの特性が変化せず，大幅なガラス転移点の低下や，耐熱性の低下を招かない樹脂組成物を得るものである。 As described above, in the present invention, a compound having a dihydrobenzoxazine ring and an epoxy resin are used as main components, a triazine-modified phenol novolak resin is used as a curing agent, and 9,10-dihydro-9-oxa-10- is used as a flame retardant. By using (2,5-dioxotetrahydro-3-furanylmethyl) -10-phosphaphenanthrene-10-oxide, a resin skeleton is produced while exhibiting a synergistic effect of nitrogen and phosphorus and having high flame retardancy. By incorporating a phosphorus compound into the resin composition, the resin composition and prepreg characteristics do not change over a long period of time, and a resin composition that does not cause a significant decrease in glass transition point or heat resistance is obtained.
本発明で使用する，（ａ）ジヒドロベンゾオキサジン環を有する化合物としては，ジヒドロベンゾオキサジン環を有し，ジヒドロベンゾオキサジン環の開環反応により硬化する樹脂であれば特に限定されるものではなく，例えばフェノール性水酸基を有する化合物，ホルマリン，１級アミンから下記反応式（２）により合成される。 The compound having (a) dihydrobenzoxazine ring used in the present invention is not particularly limited as long as it is a resin having a dihydrobenzoxazine ring and cured by a ring-opening reaction of the dihydrobenzoxazine ring. For example, it is synthesized by the following reaction formula (2) from a compound having a phenolic hydroxyl group, formalin, and a primary amine.
フェノール性水酸基を有する化合物として，多官能フェノール，ビフェノール化合物，ビスフェノール化合物，トリスフェノール化合物，テトラフェノール化合物，フェノール樹脂があげられる。多官能フェノールとしてはカテコール，ヒドロキノン，レゾルキノールがあげられる。ビスフェノール化合物としてはビスフェノールＡ，ビスフェノールＦ及びその位置異性体，ビスフェノールＳがあげられる。また，フェノール樹脂としてはレゾール樹脂，フェノールノボラック樹脂，フェノール変性キシレン樹脂，アルキルフェノール樹脂，メラミンフェノール樹脂，ベンゾグアナミンフェノール樹脂，フェノール変性ポリブタジエン等があげられる。 Examples of the compound having a phenolic hydroxyl group include polyfunctional phenols, biphenol compounds, bisphenol compounds, trisphenol compounds, tetraphenol compounds, and phenol resins. Polyfunctional phenols include catechol, hydroquinone, and resorquinol. Examples of the bisphenol compound include bisphenol A, bisphenol F and its positional isomer, and bisphenol S. Examples of the phenol resin include resole resin, phenol novolac resin, phenol-modified xylene resin, alkylphenol resin, melamine phenol resin, benzoguanamine phenol resin, and phenol-modified polybutadiene.
１級アミンとしては，具体的にメチルアミン，シクロヘキシルアミン，アニリン，置換アニリン等があげられる。 Specific examples of the primary amine include methylamine, cyclohexylamine, aniline, and substituted aniline.
本発明においてフェノール性水酸基を有する化合物と１級アミンとの混合物を、例えば７０℃以上に加熱したアルデヒド中に添加して，７０〜１１０℃，好ましくは９０〜１００℃で２０〜１２０分反応させ，その後１２０℃以下の温度で減圧乾燥することにより，合成することができる。 In the present invention, a mixture of a compound having a phenolic hydroxyl group and a primary amine is added to, for example, an aldehyde heated to 70 ° C. or more, and reacted at 70 to 110 ° C., preferably 90 to 100 ° C. for 20 to 120 minutes. Then, it can be synthesized by drying under reduced pressure at a temperature of 120 ° C. or lower.
本発明の成分（ｂ）フェノール類とトリアジン環を有する化合物とアルデヒド類の重縮合物を得るために，使用するフェノール類としては，フェノール又はビスフェノールＡ，ビスフェノールＦ等の多価フェノール類やアルキルフェノール類，アミノフェノール，フェニルフェノール等が挙げられ１種類又は２種類以上併用することができる。 In order to obtain a polycondensate of component (b) phenols, a compound having a triazine ring and aldehydes of the present invention, the phenols used include polyhydric phenols such as phenol or bisphenol A, bisphenol F, and alkylphenols. , Aminophenol, phenylphenol and the like can be used alone or in combination of two or more.
また，トリアジン環を有する化合物としては，メラミンまたはベンゾグアナミン，アセトグアナミン等のグアナミン誘導体，シアヌル酸又はメチルシアヌレート，エチルシアヌレート等のシアヌル酸誘導体や，イソシアヌル酸又はメチルイソシアヌレート，エチルシアヌレート等のイソシアヌル酸誘導体等が挙げられる。耐燃性が良好であり，かつ低価格なメラミンが適しており，トリアジン環を有する化合物の種類及び使用量を目的に合せて選定する。 The compounds having a triazine ring include guanamine derivatives such as melamine or benzoguanamine and acetoguanamine, cyanuric acid or cyanuric acid derivatives such as methyl cyanurate and ethyl cyanurate, isocyanuric acid or methyl isocyanurate and ethyl cyanurate. Examples include isocyanuric acid derivatives. Melamine with good flame resistance and low cost is suitable, and the type and amount of the compound having a triazine ring are selected according to the purpose.
アルデヒド類としては特に制限はないが一般的にホルムアルデヒドが使用される。
本発明で使用する変性フェノール樹脂の合成方法は，前記フェノール類，トリアジン環類を有する化合物，アルデヒド類の主材料を所定の窒素含有量，水酸基当量になる配合で，触媒下にて反応させる。このときの触媒としては，トリアジン環を有する化合物の溶解性が良好であることから塩基性触媒が好ましく，中でも金属類が触媒残として残ると電気絶縁材料として好ましくないため，アミン類が好ましい。反応の順序は制限されず，主原料全てを同時でも，２種の主原料を先に選択的に反応させることもできる。アセトン，メチルエチルケトン等の各種溶剤下の存在下で反応させることにより安定制御が可能となるので好ましい。反応物は中和，水洗，加熱処理，蒸留等を常法に従って行い，未反応のフェノール類，アルデヒド類，溶媒を除去して、本発明で使用する変性フェノール樹脂を得ることができる。
Although there is no restriction | limiting in particular as aldehydes, Formaldehyde is generally used.
In the method for synthesizing the modified phenolic resin used in the present invention, the main materials of the phenols, compounds having triazine rings, and aldehydes are reacted under a catalyst with a predetermined nitrogen content and a hydroxyl group equivalent. As the catalyst at this time, a basic catalyst is preferable since the solubility of the compound having a triazine ring is good. Among them, amines are preferable because metals are not preferable as an electrically insulating material when the catalyst remains. The order of the reaction is not limited, and all the main raw materials can be reacted simultaneously or the two main raw materials can be selectively reacted first. It is preferable to carry out the reaction in the presence of various solvents such as acetone, methyl ethyl ketone, and the like because stability control can be performed. The reaction product can be neutralized, washed with water, heat-treated, distilled, etc. in accordance with conventional methods to remove unreacted phenols, aldehydes, and solvent to obtain the modified phenol resin used in the present invention.
上記において，フェノール類に対するアルデヒド類のモル比は，特に限定されるものではないが，０．２〜１．５が好ましく，０．４〜０．８がより好ましい。また，フェノール類に対するトリアジン環を有する化合物の重量比は樹脂化と難燃効果の両方を考慮すると１０〜９８：９０〜２であることが好ましく，５０〜９５：５０〜５であることがより好ましい。 In the above, the molar ratio of aldehydes to phenols is not particularly limited, but is preferably 0.2 to 1.5, more preferably 0.4 to 0.8. The weight ratio of the compound having a triazine ring to phenols is preferably 10 to 98:90 to 2 and more preferably 50 to 95:50 to 5 in consideration of both resinification and flame retardancy. preferable.
また成分（ｂ）は，各々の成分の反応における比率及び熱硬化反応性を考慮すると，本発明の組成物中に，成分（ａ），（ｂ）及び（ｃ）の有機固形分の総量当り，１０〜２５重量％，好ましくは１５〜２０重量％含まれる。 In addition, the component (b) is based on the total amount of organic solids of the components (a), (b) and (c) in the composition of the present invention in consideration of the reaction ratio of each component and the thermosetting reactivity. , 10 to 25% by weight, preferably 15 to 20% by weight.
本発明に使用される，成分（ｃ）エポキシ樹脂としては，ビスフェノールＡ型エポキシ樹脂，ビスフェノールＦ型エポキシ樹脂，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，環状脂肪族エポキシ化合物，複素環式エポキシ化合物，ジグリシルエステル系エポキシ化合物等が挙げられるが，特に制限されない。単独でまたは２種以上組合わせて用いることができる。 Component (c) epoxy resin used in the present invention includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin, cycloaliphatic. An epoxy compound, a heterocyclic epoxy compound, a diglycyl ester epoxy compound and the like can be mentioned, but there is no particular limitation. It can be used alone or in combination of two or more.
また成分（ｃ）は，各々の成分の反応性及び硬化物特性を考慮すると，成分（ａ），（ｂ）及び（ｃ）の有機樹脂固形分の総量当り，１０〜４５重量％含まれる。成分（ｄ）のリン化合物（９，１０−ジヒドロ−９−オキサ−１０−（２，５−ジオクソテトラヒドロ−３−フラニルメチル）−１０−ホスファフェナントレン−１０−オキシド）は，難燃性を向上させるものであり，難燃性向上の効果と耐湿耐熱性及びＴｇの両方を考慮すると，成分（ａ），（ｂ）及び（ｃ）の有機樹脂固形分１００重量部に対し、５〜３５重量部であり、５〜２０重量部が好ましい。 The component (c) is contained in an amount of 10 to 45% by weight based on the total amount of the organic resin solids of the components (a), (b) and (c) in consideration of the reactivity and cured product characteristics of each component. The phosphorus compound (9,10-dihydro-9-oxa-10- (2,5-dioxotetrahydro-3-furanylmethyl) -10-phosphaphenanthrene-10-oxide) of component (d) has flame retardancy. Considering both the effect of improving flame retardancy and moisture and heat resistance and Tg, it is 5 to 35 with respect to 100 parts by weight of the organic resin solid content of components (a), (b) and (c). Parts by weight, preferably 5 to 20 parts by weight.
（ｅ）無機充填剤としては，公知の材料を用いることができ，特に限定されず，使用する目的に応じ選択することができる。水酸化アルミニウム，水酸化マグネシウム，ゼオライトやハイドロタルサイト等の無機水和物，クレー，タルク，ワラストナイト，マイカ，炭酸カルシウム，炭酸マグネシウム，アルミナ，シリカ，ガラス粉等の汎用に使用されている無機充填剤，ホウ酸亜鉛，スズ酸亜鉛，ヒドロキシスズ酸亜鉛等のＢ又はＳｎ系充填剤，酸化亜鉛，酸化スズ等の金属酸化物等が挙げられる。 (E) As an inorganic filler, a well-known material can be used, It does not specifically limit and can be selected according to the purpose to be used. Used for general purposes such as aluminum hydroxide, magnesium hydroxide, inorganic hydrates such as zeolite and hydrotalcite, clay, talc, wollastonite, mica, calcium carbonate, magnesium carbonate, alumina, silica, glass powder, etc. Examples include inorganic fillers, B or Sn-based fillers such as zinc borate, zinc stannate, and zinc hydroxystannate, and metal oxides such as zinc oxide and tin oxide.
また，無機充填剤は，シランカップリング剤，チタネートカップリング剤，モリブデン酸亜鉛等によりコーティング又は表面処理して，有機成分との接着性を向上させることが好ましい。成分（ｅ）無機充填剤は、成分（ａ），（ｂ），（ｃ）および（ｄ）の固形分の総量１００重量部に対し，３０〜１００重量部である。 The inorganic filler is preferably coated or surface-treated with a silane coupling agent, titanate coupling agent, zinc molybdate or the like to improve the adhesion with the organic component. The component (e) inorganic filler is 30 to 100 parts by weight with respect to 100 parts by weight of the total solid content of the components (a), (b), (c) and (d).
本発明のプリント配線板用積層板は、前記の樹脂組成物をワニスとし，このワニスを基材に含浸乾燥してなるプリプレグを所定枚数重ね合わせ、その両面または片面に金属箔を構成後，加熱成形して得られる。プリプレグを作製する際に使用する基材、好ましくはガラス繊維基材としては，Ｅガラス，Ｃガラス，Ｄガラス，Ｓガラスなどを使用した織布が挙げられる。本発明のガラス繊維織物は，通常シランカップリング剤で表面処理が施されている。表面処理に用いるシランカップリング剤は任意であり，従来公知のものが使用できる。これらを配合したワニスは従来と同様に，前記記載の基材に含浸させてプリプレグを製造する。 The laminate for a printed wiring board of the present invention uses the above resin composition as a varnish, superposes a predetermined number of prepregs obtained by impregnating and drying the varnish on a base material, forms a metal foil on both sides or one side, and then heats Obtained by molding. Examples of the base material used when preparing the prepreg, preferably a glass fiber base material, include woven fabrics using E glass, C glass, D glass, S glass, and the like. The glass fiber fabric of the present invention is usually surface-treated with a silane coupling agent. The silane coupling agent used for the surface treatment is arbitrary, and conventionally known silane coupling agents can be used. The varnish blended with these is impregnated into the base material described above to produce a prepreg as in the conventional case.
以上の発明の手段をとることにより，内層銅箔との接着性，吸湿はんだ耐熱性，及び難燃性が良好である多層プリント配線板用プリプレグ及びプリント配線板用積層板が完成した。 By taking the above-described means, a multilayer printed wiring board prepreg and a printed wiring board laminate having good adhesion to the inner layer copper foil, moisture-absorbing solder heat resistance, and flame retardancy were completed.
以下に本発明を、実施例を用いて詳細に説明するが，本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
（実施例１〜４，比較例１〜２）
下記表１に示した固形分配合の樹脂組成物を作製した。なお、表１中の配合単位は重量部であり、下記に使用した各成分の合成例、特性、名称等を示した。
(Examples 1-4, Comparative Examples 1-2)
A resin composition having a solid content shown in Table 1 below was prepared. In addition, the compounding unit in Table 1 is parts by weight, and synthesis examples, characteristics, names, and the like of the respective components used below are shown.
［１］ジヒドロベンゾオキサジン環を有する樹脂の合成
ビスフェノールＦ１０００ｇとメタノール９２０ｇを加え攪拌溶解した。ここに，パラホルムアルデヒド６５２ｇを加えた。攪拌しながらアニリン９３０ｇを１時間かけて滴下し，１時間後に７８〜８０℃になるようにした。還流下７時間反応させた後，３６０ｍｍＨｇで減圧濃縮を開始した。この減圧度を保ったまま，濃縮を継続し１１０℃になった地点で，減圧度を９０ｍｍＨｇにした。流出液がなくなったことを確認した後，樹脂をバットに取り出した。以上により，樹脂の軟化点が７８℃のジヒドロベンゾオキサジン環を主成分とする熱硬化性樹脂を得た。
[1] Synthesis of resin having dihydrobenzoxazine ring 1000 g of bisphenol F and 920 g of methanol were added and dissolved by stirring. To this, 652 g of paraformaldehyde was added. While stirring, 930 g of aniline was added dropwise over 1 hour, and after 1 hour, the temperature was adjusted to 78 to 80 ° C. After reacting for 7 hours under reflux, concentration under reduced pressure was started at 360 mmHg. While maintaining this reduced pressure, the concentration was continued and the reduced pressure was set to 90 mmHg at the point where the temperature reached 110 ° C. After confirming that the effluent was gone, the resin was taken out into the vat. As a result, a thermosetting resin mainly composed of a dihydrobenzoxazine ring having a softening point of 78 ° C. was obtained.
［２］フェノール類とトリアジン環を有する化合物とアルデヒド類との重縮合物の合成例
フェノール９４重量部に４１．５％ホルマリン２９重量部，およびトリエチルアミン０．４７重量部を加え，８０℃にて３時間反応させた。メラミンを１９重量部加えさらに１時間反応させた後，常圧下にて水を除去しながら１２０℃まで昇温し，温度を保持したまま２時間反応させた。次に常圧下にて水を除去しながら１８０℃まで昇温し，減圧下にて未反応のフェノールを除去し，軟化点１３６℃のフェノールとメラミンの重縮合物を得た（以下，トリアジン変性フェノール樹脂と呼ぶ）。
[2] Example of synthesis of polycondensation product of phenols, compound having triazine ring and aldehydes 29 parts by weight of 41.5% formalin and 0.47 parts by weight of triethylamine were added to 94 parts by weight of phenol at 80 ° C. The reaction was performed for 3 hours. After adding 19 parts by weight of melamine and further reacting for 1 hour, the temperature was raised to 120 ° C. while removing water under normal pressure, and the reaction was continued for 2 hours while maintaining the temperature. Next, the temperature was raised to 180 ° C. while removing water under normal pressure, and unreacted phenol was removed under reduced pressure to obtain a polycondensate of phenol and melamine having a softening point of 136 ° C. (hereinafter referred to as triazine modification). Called phenolic resin).
［３］ フェノールノボラック型エポキシ樹脂
ＹＤＰＮ−６３８Ｐ （東都化成株式会社製）
[3] Phenol novolac type epoxy resin YDPN-638P (manufactured by Toto Kasei Co., Ltd.)
［４］ リン化合物
９，１０−ジヒドロ−９−オキサ−１０−（２，５−ジオクソテトラヒドロ−３−フラニルメチル）−１０−ホスファフェナントレン−１０−オキシド
[4] Phosphorus compound 9,10-dihydro-9-oxa-10- (2,5-dioxotetrahydro-3-furanylmethyl) -10-phosphaphenanthrene-10-oxide
［５］ 水酸化アルミニウム
電子材料用に一般的に用いられている残留イオン等の少ないもので，粒子径が３μｍ〜５μｍのものを使用した。
[5] Aluminum hydroxide A small amount of residual ions or the like generally used for electronic materials and having a particle diameter of 3 μm to 5 μm was used.
内層用積層板として絶縁層厚さ０．２ｍｍ，銅箔厚さ３５μｍの両面銅張積層板（日立化成製ＭＣＬ−ＢＥ−６７Ｇ）を用い，回路加工し，内層粗化処理として黒化処理を行った。表１に示した固形分配合の樹脂組成物をメチルエチルケトンに溶解させ，不揮発分を７５重量％になるように調整し，ワニスを作製した。これをＩＰＣ品番＃７６２９のガラスクロスに含浸し，乾燥，半硬化させてプリプレグを得た。このプリプレグの樹脂分は５０重量％とした。 A double-sided copper-clad laminate (MCL-BE-67G manufactured by Hitachi Chemical Co., Ltd.) with an insulation layer thickness of 0.2mm and a copper foil thickness of 35μm is used as the inner layer laminate, and the blackening treatment is performed as the inner layer roughening treatment. went. The resin composition containing the solid content shown in Table 1 was dissolved in methyl ethyl ketone, and the non-volatile content was adjusted to 75% by weight to prepare a varnish. This was impregnated into a glass cloth of IPC product number # 7629, dried and semi-cured to obtain a prepreg. The resin content of this prepreg was 50% by weight.
上記内層用積層板とプリプレグを用いて圧力２．９ＭＰａ，温度１９０℃９０分間加熱加圧して一体化し４層板を作製した。下記に示す特性評価を行なった。結果を下記表２に示した。
（１）耐燃焼性：ＵＬ９４に準拠する。
（２）Ｔｇ：ＴｈｅｒｍｏＭｅｃｈａｎｉｃａｌ Ａｎａｌａｙｚｅｒ（Ｄｕ Ｐｏｎｔ社製ＴＡ２１００）によりＴｇを測定した。
（３）はんだ耐熱性：１２１℃，２１３０ｈＰａのプレッシャークッカー処理装置内に１〜２時間保持後の試験片を，２６０℃に加熱された、はんだ槽に３０秒間沈め，ふくれ及びミーズリングの発生の有無を肉眼にて観察した。表中の各記号は，○：変化なし，△：ミーズリングまたは目浮き発生，×：ふくれ発生を意味する。
（４）耐薬品性：１０％ＮａＯＨ（６０℃）溶液に５分間浸漬させ，浸漬前後の重量差から，重量減少率を計算。
（５）２５℃±２℃の環境下で１０日間保存し，プリプレグ表面の状態を観察した。
The inner layer laminate and the prepreg were integrated by heating and pressing at a pressure of 2.9 MPa and a temperature of 190 ° C. for 90 minutes to prepare a four-layer plate. The following characteristic evaluation was performed. The results are shown in Table 2 below.
(1) Combustion resistance: Conforms to UL94.
(2) Tg: Tg was measured by ThermoMechanical Analyzer (TA2100 manufactured by Du Pont).
(3) Solder heat resistance: 121 ° C. and 2130 hPa pressure cooker processing specimen held for 1 to 2 hours, submerged in a solder bath heated to 260 ° C. for 30 seconds, causing blistering and measling The presence or absence was observed with the naked eye. Each symbol in the table means ◯: no change, △: occurrence of messling or floating eyes, ×: occurrence of blistering.
(4) Chemical resistance: Immerse in a 10% NaOH (60 ° C.) solution for 5 minutes, and calculate the weight reduction rate from the weight difference before and after immersion.
(5) It preserve | saved for 10 days in 25 degreeC +/- 2 degreeC environment, and observed the state of the prepreg surface.
表２の結果から，本発明のリン化合物を添加した実施例１〜４は従来用いられてきたリン化合物を添加した比較例１，２に比べて，ガラス転移点の低下，耐熱性の低下，アルカリ水溶液への溶出が少なく，且つ長期間保管した際のリン化合物の結晶析出がないことが確認された。 From the results of Table 2, Examples 1 to 4 to which the phosphorus compound of the present invention was added had a lower glass transition point, lower heat resistance than Comparative Examples 1 and 2 to which a conventionally used phosphorus compound was added. It was confirmed that there was little elution into the alkaline aqueous solution and there was no crystal precipitation of phosphorus compounds when stored for a long time.
以上の説明および表１〜２から明らかなように，ベンゾオキサジン環状有する化合物およびエポキシ樹脂を主剤とし，トリアジン変性フェノールノボラック樹脂を硬化剤とした樹脂組成物を主成分とする従来からのハロゲンフリーＦＲ−４用樹脂組成物に式（１）に示すリン化合物を添加することにより，ガラス転移点の低下，耐熱性の低下，アルカリ水溶液への溶出が少なく，且つ長期間保管した際のリン化合物の結晶析出がない難燃性の良好なプリント配線板への適用可能な材料の提供が可能となった。
As is apparent from the above description and Tables 1 and 2, a conventional halogen-free FR mainly composed of a resin composition mainly composed of a benzoxazine cyclic compound and an epoxy resin and a triazine-modified phenol novolac resin as a curing agent. By adding the phosphorus compound represented by the formula (1) to the resin composition for -4, the glass transition point is lowered, the heat resistance is reduced, the elution into the alkaline aqueous solution is small, and the phosphorus compound when stored for a long time It has become possible to provide a material that can be applied to a printed wiring board having good flame retardancy without crystal precipitation.
Claims (2)
（ａ），（ｂ）及び（ｃ）の有機固形分の総量中、（ａ）３５〜７５重量％、（ｂ）１０〜２５重量％、（ｃ）１０〜４５重量％を含み，
且つ（ｄ）リン化合物を、（ａ），（ｂ）及び（ｃ）の有機固形分の総量１００重量部に対し、５〜３５重量部含み，
且つ（ｅ）無機充填剤を，（ａ），（ｂ），（ｃ）および（ｄ）の有機固形分の総量１００重量部に対し，３０〜１００重量部含み，使用する全ての材料のハロゲン含有量が０．１重量％以下であることを特徴とする樹脂組成物。
(A) 35 to 75% by weight, (b) 10 to 25% by weight, (c) 10 to 45% by weight in the total amount of organic solids of (a), (b) and (c),
And (d) 5 to 35 parts by weight of the phosphorus compound with respect to 100 parts by weight of the total organic solids of (a), (b) and (c),
And (e) 30 to 100 parts by weight of an inorganic filler with respect to 100 parts by weight of the total organic solid content of (a), (b), (c) and (d), and halogens of all materials used Content is 0.1 weight% or less, The resin composition characterized by the above-mentioned.
A printed wiring board obtained by using the resin composition according to claim 1 as a varnish, superposing a predetermined number of prepregs obtained by impregnating and drying the varnish on a base material, forming a metal foil on both sides or one side, and then thermoforming. Laminated board.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015532673A (en) * | 2012-08-31 | 2015-11-12 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ．ＫＧａＡ | Benzoxazine-containing flame retardant composition |
| JP2022166005A (en) * | 2017-11-09 | 2022-11-01 | ブルー キューブ アイピー エルエルシー | Phosphorated anhydride-containing epoxy resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000239491A (en) * | 1999-02-16 | 2000-09-05 | Sumitomo Bakelite Co Ltd | Flame-retardant resin composition, and prepreg and laminate made by using it |
| JP2003246844A (en) * | 2002-02-26 | 2003-09-05 | Hitachi Chem Co Ltd | Flame-retardant thermosetting resin composition, and prepreg and laminated board for electrical wiring board using the same |
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2006
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000239491A (en) * | 1999-02-16 | 2000-09-05 | Sumitomo Bakelite Co Ltd | Flame-retardant resin composition, and prepreg and laminate made by using it |
| JP2003246844A (en) * | 2002-02-26 | 2003-09-05 | Hitachi Chem Co Ltd | Flame-retardant thermosetting resin composition, and prepreg and laminated board for electrical wiring board using the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015532673A (en) * | 2012-08-31 | 2015-11-12 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ．ＫＧａＡ | Benzoxazine-containing flame retardant composition |
| JP2022166005A (en) * | 2017-11-09 | 2022-11-01 | ブルー キューブ アイピー エルエルシー | Phosphorated anhydride-containing epoxy resin |
| JP7394930B2 (en) | 2017-11-09 | 2023-12-08 | ブルー キューブ アイピー エルエルシー | Epoxy resin containing phosphorylated anhydride |
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