JPS63213677A - Adhesive for electroless plating - Google Patents
Adhesive for electroless platingInfo
- Publication number
- JPS63213677A JPS63213677A JP62045159A JP4515987A JPS63213677A JP S63213677 A JPS63213677 A JP S63213677A JP 62045159 A JP62045159 A JP 62045159A JP 4515987 A JP4515987 A JP 4515987A JP S63213677 A JPS63213677 A JP S63213677A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- nbr
- phenol resin
- contg
- electroless plating
- 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.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 45
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 45
- 238000007772 electroless plating Methods 0.000 title claims abstract description 16
- 239000005011 phenolic resin Substances 0.000 claims abstract description 31
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 28
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002989 phenols Chemical class 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 6
- 229920003986 novolac Polymers 0.000 claims abstract description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012790 adhesive layer Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000011787 zinc oxide Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000000945 filler Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000013405 beer Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、無電解めっき用の接着剤に係り、特には、無
電解めっきにより印刷配線板の製造に際して用いるアク
リロニトリルブタジェンゴム（以下ｒＮＢＲＪ という
）とフェノール樹脂とを含有する無電解めっき用接着剤
に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an adhesive for electroless plating, and particularly to acrylonitrile butadiene rubber (hereinafter referred to as rNBRJ) used in the production of printed wiring boards by electroless plating. ) and a phenolic resin.
［従来の技術］
無電解めっきによる印刷配線板の製造は、一般には、接
着剤を樹脂或いは金属等の基板上に塗布し、これを乾燥
・硬化させて接着剤付基板とした後、この接着剤の表面
を化学的に粗化し、次いで無電解めっき触媒を乗せ１回
路を形成する部分以外の箇所を無電解めっきレジストで
被覆して無電解めっきを行い、回路を形成する方法が採
用されている。[Prior Art] Generally, in manufacturing printed wiring boards by electroless plating, adhesive is applied onto a resin or metal substrate, dried and cured to form an adhesive-coated substrate, and then this adhesive is applied. The method used is to chemically roughen the surface of the agent, then place an electroless plating catalyst on it, cover the parts other than the parts that form one circuit with an electroless plating resist, and perform electroless plating to form a circuit. There is.
かかる方法において、従来、上記基板上に塗布する接着
剤としてＮＢＲとレゾール型フェノール樹脂を含有した
もの（特開昭５８−１５７８７７号公報）、ＮＢＲ、フ
ェノール樹脂、エポキシ樹脂及びエチレン酢酸ビニル共
重合体を含有したもの（特開昭６０−６８９３５号公報
）、ＮＢＲ、エポキシ樹脂及びフェノール変性キシレン
樹脂を含有したもの（特開昭６０−１８９９８７号公報
等が提案さ九でいる。In this method, conventionally, adhesives containing NBR and resol type phenolic resin (JP-A-58-157877), NBR, phenol resin, epoxy resin, and ethylene-vinyl acetate copolymer have been used as adhesives to be applied onto the substrate. (Japanese Unexamined Patent Publication No. 60-68935), and those containing NBR, epoxy resin, and phenol-modified xylene resin (Japanese Unexamined Patent Publication No. 60-189987) have been proposed.
［発明が解決しようとする問題点コ
ところで、このような接着剤は、基板に対する接着力が
強くなければならないことは言うまでもなく、電子部品
等を半田付けする際の高温にも充分耐える必要があり、
さらには接着剤を基板に塗布したときに接着剤層中に気
泡が残存しないものでなければならない。[Problems to be solved by the invention] By the way, it goes without saying that such an adhesive must have strong adhesion to the board, and must also be able to withstand the high temperatures that occur when soldering electronic components, etc. ,
Furthermore, it is necessary that no air bubbles remain in the adhesive layer when the adhesive is applied to the substrate.
上記従来の接着剤では、接着力、耐熱性については満足
するものの、接着剤の粘度が高く基板に塗布した後の接
着剤層中に気泡が残存し、無電解めっきを行なったとき
、めっきが来らず断線の原因となったり、又、印刷配線
板表面に凹凸が生じ電子部品の固定が不安定なる等の問
題点を有していた。Although the above conventional adhesives are satisfactory in terms of adhesive strength and heat resistance, the viscosity of the adhesive is high and air bubbles remain in the adhesive layer after it is applied to the substrate, resulting in poor plating when electroless plating is performed. There have been other problems, such as failure to come through, causing wire breakage, and unevenness on the surface of the printed wiring board, which makes the fixation of electronic components unstable.
本発明者らは、上記問題を解決すべく鋭意検討した結果
、ＮＢＲのうちでも、極高ニトリル含有のものを、また
フェノール樹脂のうちでも、ヘキサメチレンテトラミン
を硬化剤としたノボラック型未変性フェノール樹脂を用
いることにより、接着力、耐熱性が優れるとともに接着
剤の粘度を低下させ、塗布後の接着剤層中に気泡が残存
しないことを見い出した。As a result of intensive studies to solve the above-mentioned problems, the present inventors found that among NBRs, those containing extremely high nitrile, and among phenolic resins, novolak-type unmodified phenol using hexamethylenetetramine as a curing agent. It has been found that by using a resin, the adhesive strength and heat resistance are excellent, the viscosity of the adhesive is lowered, and no air bubbles remain in the adhesive layer after application.
本発明は、かかる知見に基づいてなされたもので、本発
明の目的は、接着力、耐熱性に優れるとともに、塗布後
の接着剤層中に気泡が残存しない無電解めっき用接着剤
を提供することにある。The present invention was made based on this knowledge, and an object of the present invention is to provide an adhesive for electroless plating that has excellent adhesive strength and heat resistance, and does not leave any air bubbles in the adhesive layer after application. There is a particular thing.
［問題点を解決するための手段］
本発明は、アクリロニトリルブタジェンゴムとフェノー
ル樹脂とを含有する無電解めっき用接着剤において、前
記アクリロニトリルブタジェンゴムとして当該アクリロ
ニトリルブタジェンゴム中の結合アクリロニトリル量が
４２重量％以上のものを用い、かつ前記フェノール樹脂
として、ノボラック型未変性フェノール樹脂を用いるこ
とから成る無電解めっき用接着剤である。[Means for Solving the Problems] The present invention provides an adhesive for electroless plating containing acrylonitrile butadiene rubber and a phenolic resin, in which the amount of bound acrylonitrile in the acrylonitrile butadiene rubber is This is an adhesive for electroless plating, which uses a novolak type unmodified phenol resin as the phenol resin, and uses a novolak type unmodified phenol resin as the phenol resin.
上記４２重量％以上の結合アクリロニトリルを有するＮ
ＢＲとはいわゆる極高ニトリルのＮＢＲで、結合アクリ
ロニトリル量が６０重量％以下のものが、溶剤への溶解
性等の理由から好ましい。N having the above 42% by weight or more of bound acrylonitrile
BR is so-called extremely high nitrile NBR, and it is preferable that the amount of bound acrylonitrile is 60% by weight or less for reasons such as solubility in solvents.
一方、フェノール樹脂としては、ヘキサメチレンテトラ
ミンを硬化剤としたノボラック型未変性フェノール樹脂
以外のノボラック型変性フェノール樹脂は１本発明の目
的を達成することができない。On the other hand, as a phenol resin, novolak-type modified phenol resins other than novolak-type unmodified phenol resins using hexamethylenetetramine as a curing agent cannot achieve the object of the present invention.
上記ＮＢＲの配合量は、ＮＢＲとフェノール樹脂との和
を１００重量部したとき、５０〜７５重量部とすること
が好ましい、上記ＮＢＲの量を５０重量部以下とすると
、室温での密着力が低下し、又、７５重量％とすると高
温時の密着力が低下して好ましくない。The amount of NBR blended is preferably 50 to 75 parts by weight when the sum of NBR and phenol resin is 100 parts by weight.If the amount of NBR is 50 parts by weight or less, the adhesion strength at room temperature is Moreover, if it is set to 75% by weight, the adhesion strength at high temperatures will decrease, which is not preferable.
又、このＮＢＲ及びフェノール樹脂の量は、接着剤中１
５〜２５重量％とすることが好ましい。１５重量％以下
とすると接着力が低下し、又、２５重量％以上とすると
接着剤の粘度が高くなり、塗工性の上で好ましくない。Also, the amount of NBR and phenol resin in the adhesive is 1
The content is preferably 5 to 25% by weight. When the amount is less than 15% by weight, the adhesive strength decreases, and when it is more than 25% by weight, the viscosity of the adhesive becomes high, which is not preferable in terms of coatability.
尚、この接着剤には、上記ＮＢＲ及びフェノール樹脂の
他に、無機充填剤として、炭酸カルシウム、炭酸マグネ
シウム等の炭酸塩粉末や酸化亜鉛、酸化チタン、二酸化
硅素等の酸化物粉末及び硫黄粉東等を加えることができ
る。これらの無機充填剤は、塗膜強度を向上させるとと
もに塗工性をも向上させるが、配合は接着剤量に対し３
０重量％以下とすることが好ましい。In addition to the above-mentioned NBR and phenol resin, this adhesive also contains carbonate powders such as calcium carbonate and magnesium carbonate, oxide powders such as zinc oxide, titanium oxide, and silicon dioxide, and sulfur powder as inorganic fillers. etc. can be added. These inorganic fillers improve coating strength as well as coating properties, but the blending ratio is 3% to the amount of adhesive.
The content is preferably 0% by weight or less.
３０重量％以上とすると接着力の低下が生じるので好ま
しくない。If it exceeds 30% by weight, the adhesive strength will decrease, which is not preferable.
以上のような、ＮＢＲ、フェノール樹脂、無機充填剤は
有機溶媒と混合されるが、この場合の有機溶媒としては
メチルエチルケトン、メチルイソブチルケトン、シクロ
ヘキサノン等のケトン類、エチルベンゼン、キシレン等
の芳香族類等、ＮＢＲ及びフェノール樹脂に対し溶解力
或いは膨潤力を有する溶媒を用いることができる。As mentioned above, NBR, phenolic resin, and inorganic filler are mixed with an organic solvent. In this case, organic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and aromatics such as ethylbenzene and xylene. , NBR and phenol resin can be used.
接着剤の作成に当っては、先ず、所定割合で配合したＮ
ＢＲと無機充填剤とをロール等で充分に混練した後に、
有機溶媒を添加して溶解しこれに、フェノール樹脂の有
機溶媒溶液を加えることが簡便で好ましい。When creating an adhesive, first, N mixed in a predetermined ratio is used.
After thoroughly kneading BR and inorganic filler with a roll etc.,
It is convenient and preferable to add and dissolve an organic solvent and then add a solution of the phenol resin in the organic solvent.
以上の接着剤は、先ず、基板上にフローコート、浸漬等
の方法により塗布され、室温〜５０℃の温度で風乾した
後１５０〜１８０℃の温度で加熱して基板上に接着、硬
化させる。このようにして得られた基板は、硬化した接
着剤の表面を無水クロム酸及び硫酸、或いはホウフッ化
水素酸及び重クロム酸塩等をベースとした粗化液で化学
的に粗化され、パラジウム及び錫を含有する液に浸漬し
て、その表面に触媒を着け。The above adhesive is first applied onto a substrate by a method such as flow coating or dipping, air-dried at a temperature of room temperature to 50°C, and then heated at a temperature of 150 to 180°C to bond and harden the adhesive onto the substrate. In the thus obtained substrate, the surface of the cured adhesive is chemically roughened with a roughening solution based on chromic anhydride and sulfuric acid, or fluoroboric acid and dichromate, etc. and immersed in a liquid containing tin to coat the surface with a catalyst.
無電解めっきに供される。Subjected to electroless plating.
［作 用コ
以上のような本発明は、ＮＢＲとして極高ニトリル含量
のものを用い、さらに、フェノール樹脂としてヘキサメ
チレンテトラミンを硬化剤としたノボラック型未変性の
フェノール樹脂を用いたため接着剤の粘度を下げ、塗布
後の接着剤層に気泡を残存させることのない作用を有す
るとともに優れた接着力及び耐熱性を付与する作用を有
する。[Function] In the present invention as described above, NBR with extremely high nitrile content is used, and the phenol resin is a novolac type unmodified phenol resin with hexamethylenetetramine as a curing agent, so that the viscosity of the adhesive is reduced. It has the effect of reducing the amount of air bubbles remaining in the adhesive layer after application, and also has the effect of imparting excellent adhesive strength and heat resistance.
［実施例］
ＮＢＲ５７重量部、炭酸カルシウム１５重量部、二酸化
硅素６重量部、酸化亜鉛２重量部。[Example] 57 parts by weight of NBR, 15 parts by weight of calcium carbonate, 6 parts by weight of silicon dioxide, 2 parts by weight of zinc oxide.
硫黄１重量部を、二本ロールミルにより混練した後、エ
チルベンゼン６０ｆｆｉ量部、キシレン５８重量部、メ
チルイソブチルケトン１４６重量部、シクロへキサノン
８８重量部からなる溶剤に十分混合攪拌した。これに第
１表に示したフェノール樹脂４３重量部、シクロへキサ
ノン８８重量部からなる溶液１３１重量部を加え十分混
合攪拌し、無電解めっき用接着剤とした後、Ｅ型粘度計
にて２５℃の温度での粘度を測定した。第１表に使用し
たＮＢＲ及びフェノール樹脂を示す。次に、この接着剤
を難燃性紙フエノール樹脂積層板に乾燥後の膜厚が約３
０μｍとなるよう塗布し、室温で十分風乾した後、１６
５℃の温度で１１０分間加熱して接着剤を硬化し接着剤
付基板とした。One part by weight of sulfur was kneaded using a two-roll mill, and then thoroughly mixed and stirred into a solvent consisting of 60 parts by weight of ethylbenzene, 58 parts by weight of xylene, 146 parts by weight of methyl isobutyl ketone, and 88 parts by weight of cyclohexanone. To this was added 131 parts by weight of a solution consisting of 43 parts by weight of phenolic resin and 88 parts by weight of cyclohexanone shown in Table 1, and the mixture was sufficiently mixed and stirred to form an adhesive for electroless plating. The viscosity was measured at a temperature of °C. Table 1 shows the NBR and phenolic resins used. Next, apply this adhesive to a flame-retardant paper phenolic resin laminate with a dry film thickness of approximately 3.
After applying it to a thickness of 0 μm and thoroughly air-drying it at room temperature,
The adhesive was cured by heating at a temperature of 5° C. for 110 minutes to obtain an adhesive-attached substrate.
次にこの接着剤付基板をクロム酸混液（Ｃｒ０３６５ｇ
、濃硫酸２３０ｍＬを水で稀釈して全体をＩＱとする）
に４５℃の温度で５分間浸漬して化学的粗化処理を行な
い、水洗した。次に、これを６ｇ／ΩのＮａＯＨ水溶液
中に１０分間浸漬し、その後水洗し、引き続き、１８％
ＨＣＬ中に１分間浸漬した後、ＰｄＣｌ２．５ｎＣ１゜
を含む塩酸酸性水溶液から成る化学めっき用触媒液（日
本鉱業（株）製ＮＣ−３）に５分間浸漬した。次いで、
これをシュウ酸を含む塩酸酸性水溶液に５分間浸漬し、
水洗して、室温で風乾した後、１２０℃の温度で２０分
間の乾燥を行なった。この後、この基板を７２℃の温度
に保った無電解鋼めっき液（日本鉱業（株）製ＫＣ−１
０）に浸漬し、約３０μｍの厚さの銅暎を得た。十分に
水洗し、１６０℃の温度で４０分間乾燥した。このもの
の常態ビール強度と半田耐熱秒数（２６０℃に於る）を
測定した。この結果を第２表に示す。 （
以下余白）以上の結果から明らかなように、本発明の一
実施態様である実施例１〜２は、粘度が３００ｃｐと低
く、又、常態ビール強度が２．ＯＯに２７口以上、半田
耐熱秒数３０秒以上と接着力、耐熱性に優れていること
が分かる。これに対して、フェノール樹脂としてヘキサ
メチレンテトラミンを硬化剤としたノボラック型未変性
フェノール樹脂以外の樹脂を用いた比較例では、常態ビ
ール強度が低く、接着力に劣り、又、結合アクリロニト
リル量の低いＮＢＲを用いた比較例４は、粘度が高く接
着剤を塗布するに際し、気泡が残存した。Next, apply this adhesive-coated substrate to a chromic acid mixture (Cr0365g).
, dilute 230 mL of concentrated sulfuric acid with water and use the total as IQ)
The material was chemically roughened by immersing it in water at a temperature of 45° C. for 5 minutes, and then washed with water. Next, this was immersed in a 6 g/Ω NaOH aqueous solution for 10 minutes, then washed with water, and then 18%
After being immersed in HCL for 1 minute, it was immersed for 5 minutes in a chemical plating catalyst solution (NC-3 manufactured by Nippon Mining Co., Ltd.) consisting of an acidic hydrochloric acid aqueous solution containing 2.5 nCl of PdCl. Then,
This was immersed in a hydrochloric acid aqueous solution containing oxalic acid for 5 minutes,
After washing with water and air drying at room temperature, drying was performed at a temperature of 120° C. for 20 minutes. After that, this substrate was coated with an electroless steel plating solution (KC-1 manufactured by Nippon Mining Co., Ltd.) kept at a temperature of 72°C.
0) to obtain a copper strip with a thickness of about 30 μm. It was thoroughly washed with water and dried at a temperature of 160° C. for 40 minutes. The normal beer strength and soldering heat resistance seconds (at 260°C) of this product were measured. The results are shown in Table 2. (
As is clear from the above results, Examples 1 and 2, which are embodiments of the present invention, have a low viscosity of 300 cp and a normal beer strength of 2.5 cp. It can be seen that it has excellent adhesive strength and heat resistance, with an OO of 27 or more holes and a soldering heat resistance of 30 seconds or more. On the other hand, in comparative examples using resins other than novolak-type unmodified phenolic resins using hexamethylenetetramine as a curing agent as phenolic resins, the normal beer strength was low, the adhesive strength was poor, and the amount of bound acrylonitrile was low. In Comparative Example 4 using NBR, the viscosity was high and bubbles remained when the adhesive was applied.
［発明の効果］
以上のような本発明の接着剤は、接着力、耐熱性に優れ
るとともに粘度を低くすることができるため、基板に接
着剤を塗布するときに塗布された接着剤層中に気泡が残
存することがなく、最終製品である印刷配線板に断線が
起ったり、当該板表面に凹凸が生じ電子部品の固定が不
安定になることがない等の格別の効果を奏する。[Effects of the Invention] The adhesive of the present invention as described above has excellent adhesive strength and heat resistance, and can have a low viscosity. There are no air bubbles left behind, and the printed wiring board, which is the final product, is free from wire breakage and unevenness on the surface of the board, which prevents the fixation of electronic components from becoming unstable.
Claims (1)
を含有する無電解めっき用接着剤において、前記アクリ
ロニトリルブタジエンゴムとして当該アクリロニトリル
ブタジエンゴム中の結合アクリロニトリル量が４２重量
％以上のものを用い、かつ前記フェノール樹脂として、
ヘキサメチレンテトラミンを硬化剤としたノボラック型
未変性フェノール樹脂を用いることを特徴とする無電解
めっき用接着剤。In an adhesive for electroless plating containing an acrylonitrile butadiene rubber and a phenolic resin, an acrylonitrile butadiene rubber having a bound acrylonitrile content of 42% by weight or more in the acrylonitrile butadiene rubber, and as the phenol resin,
An adhesive for electroless plating characterized by using a novolak type unmodified phenol resin with hexamethylenetetramine as a curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62045159A JPS63213677A (en) | 1987-03-02 | 1987-03-02 | Adhesive for electroless plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62045159A JPS63213677A (en) | 1987-03-02 | 1987-03-02 | Adhesive for electroless plating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63213677A true JPS63213677A (en) | 1988-09-06 |
Family
ID=12711486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62045159A Pending JPS63213677A (en) | 1987-03-02 | 1987-03-02 | Adhesive for electroless plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63213677A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010065078A (en) * | 2008-09-08 | 2010-03-25 | Nitto Denko Corp | Thermosetting adhesive composition, thermosetting adhesive tape or sheet, and flexible circuit board |
| WO2010145945A1 (en) * | 2009-06-17 | 2010-12-23 | Tesa Se | Use of heat-activated adhesive tape for the adhesion of flexible circuit boards |
-
1987
- 1987-03-02 JP JP62045159A patent/JPS63213677A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010065078A (en) * | 2008-09-08 | 2010-03-25 | Nitto Denko Corp | Thermosetting adhesive composition, thermosetting adhesive tape or sheet, and flexible circuit board |
| WO2010145945A1 (en) * | 2009-06-17 | 2010-12-23 | Tesa Se | Use of heat-activated adhesive tape for the adhesion of flexible circuit boards |
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