JPS5981370A - Adhesive for electric circuit laminate - Google Patents

Abstract

PURPOSE:To provide the titled adhesive which gives sufficient adhesion between a laminate and a circuit metal in the additive method, by using a silicone-modified epoxy resin and NBR as main components and adding an arom. polyamine as a hardener and a curing accelerator thereto. CONSTITUTION:NBR is blended with a silicone-modified epoxy resin, both ingredients being used as main components for adhesive, and an arom. polyamine as a hardener, a curing accelerator and optionally an inorg. filler and a solvent are added thereto to prepare the titled adhesive. The silicone-modified epoxy resin is one obtd. by adding polysiloxane as side chain to the main chain of a bisphenol A type epoxy resin, and those having an epoxy equivalent of 500- 2,500 and a silicone component content of 5-20% are preferred. Examples of the curing accelerators are boron trifluoride/amine complexes.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to an adhesive used for bonding an electric circuit formed of a metal layer in an electric circuit laminate to a panel on the laminate.

Electrical circuit f* laminates include paper-based paulownia phenolic resin laminated boards, paper-based evo+shi resin laminated boards, and glass cloth-based ehoshi resin laminates, etc.Copper with copper foil bonded under pressure to insulating substrates Clad laminates (CCL) are common, and the laF air circuit is formed by etching away the copper foil leaving the circuit pattern behind. Conventional adhesives have been used, and the heel properties of the copper foil when heated are not sufficient.

In addition, in CCL, the copper foil and gold edges of the anti-freezing parts are removed to form circuits, so there is the problem of saving energy and soil.Additionally, from the viewpoint of simplifying the process and increasing the thickness of the circuit pattern, the aditipu method has recently been adopted. It has been extensively refined and is now in practical use. As is well known, the additive construction method involves forming electrical circuits using only electroless copper plating on the laminate (full additive method), or forming a thin layer of electroless copper plating on the laminate. In this method, an electric path is formed in one go by applying current to the conductive layer in all parts other than the circuit, and the conductive layer other than the electric path is removed by soft etching (seven-day tape method). However, in the adipure method, there was a problem with the adhesion between the circuit and the laminate because the circuit was formed on the laminate with a metal glue. M) fr: Use the mixture, apply this adhesive to the laminate, harden it at B stage, and then etch the surface of this adhesive with a liquid containing chromium #. Tangent by All
The surface of the adhesive is roughened by dissolving the butashikonin component in it, and the anchoring effect of Metsushi metal on the rough surface is used to create a heel characteristic between the circuit and the laminate [Ikura Mukai] I was trying to force him to do it. However, in this case, the waste liquid from the etching treatment containing muric acid will be discharged, which will cause major problems in terms of the working environment and pollution. Although it is possible to roughen the surface of the adhesive by physical polishing such as polishing with ω1 polishing paper, it is possible to roughen the surface by etching, which completely forms a rough surface with unevenness created by deep micro-holes. In contrast, physical polishing does not produce such a rough surface, and surface roughening using large anchors is often used. Even if the i, +: y solidification process is performed using this adhesion construction method, the circuit is formed on the laminate using metallurgy, so the heel strength between the circuit and the laminate is not as strong as CCL. It is.

The present invention has been made in view of the above points, and has excellent adhesion between the laminate and the circuit metal. The object of the present invention is to provide an adhesive for electrical circuit laminates that can provide sufficient adhesion to the electrical circuit laminate.

However, the present invention combines the silicone modified Evo + Geo seal and N
The above object has been achieved by an adhesive for electrical circuit laminates, which is characterized in that it contains B as a main ingredient, an aromatic polyamine as a curing agent, and a curing accelerator. Detailed explanation of.

The present invention is first characterized in that a silicone-modified epoxy resin is used as an adhesive component. As shown in the following structural formula, silicone-modified epoxy resin is a hisphenol A-type epoxy resin with a side chain added to the main chain of the epoxy resin, and the epoxy equivalent is 500
/-2500, preferably containing 5 to 20% silicon component.
○) is preferable, R is an aromatic or aliphatic group 1 hydrocarbon, and R is preferably an aliphatic group, particularly preferably an ethyl group.

``NBR is blended with the silicone-modified Eho + Si resin described in Section 2, and both are used as the main ingredients of the adhesive, and in addition, a curing agent, a curing accelerator, an inorganic photonic agent, and a solvent are further blended as necessary. And the glue? It is manufactured by A. Aromatic polyamines are used as curing agents, and such aromatic polyamines include m-phenylenediamine, cyanodiphenyl ether, cyanodiphenyl sulfone, etc.
Examples include benzidine and m-aminepenzylamine. Further, a boron trifluoride amine complex is used as a curing accelerator, and examples of the boron trifluoride amine complex include boron trifluoride-aniline, boron trifluoride-nonuratoidine, and boron trifluoride-nonuratoidine. Benzylamine, boron trifluoride-1~
Examples include reethanolamine, boron trifluoride-hyberidine, and the like. Furthermore, as an inorganic photoresist, C
aC0,,,A403,Zr(Sins)3.5iO3
L, kaolin, etc., oxides, silicates, carbonates, nitrides,
Various materials such as carbides can be used, and those having a particle size of -J: 0.1-10μ are preferable. Solvents include 1-luene, isop-D alcohol, azetone, M
E K s Cyclohe Jusatsushi etc. can be used alone or in combination of two or more.

The blending ratio is 30 to 20 parts of NBR to 100 parts of silicon-modified resin, and θ of the inorganic brightening agent.
It is preferable to use 1 part by weight of ~500, and 400 to 700 parts by weight of the solvent, and the curing agent and curing accelerator may be blended in appropriate amounts depending on the usage conditions of the adhesive. A suitable amount of the accelerator is about 0.2 to 2 parts by weight.

The adhesive according to the present invention obtained as described above is used for bonding between a laminate and a metal circuit in the CCL or Ajiitei construction method, and an outline of its usage will be explained below. First, C
In the case of CL, an adhesive is applied to the copper foil to a thickness of about 20 to 30 microns, and this is pre-dried to a B-stage state for about 150'0.2 minutes. Then, this copper foil was layered on a Zurizuref obtained by impregnating a paper base paulownia or Nocorus cloth base material with 9 varnish such as phenol resin or Epo Toshiwa J resin and drying it.
By carrying out hot press molding for 90 minutes at a pressure of about 120 kg/7, a CCL is obtained in which a laminate, which is a cured laminate of Laliprej, is covered with copper foil via an adhesive. In the case of the adjoining method, adhesive is applied to the surface of the laminate to a thickness of about 30 μm or more, first preheated to a B-stage state, and then the surface of the adhesive is physically polished. Physical polishing can be carried out by manually handling abrasive paper, using an abrasive belt machine, using a lidoplast method, or by transferring a rough surface from a rough sheet. In this manner, the surface of the adhesive is roughened by physical polishing to a roughness of approximately 0.2 to 1.0 microns (preferably 05 to 0.75 microns). Next, a circuit is formed on the rough surface of the adhesive using a conventional technique such as that of a masked or electrician, and after the circuit is formed in this manner, the adhesive is completely cured.

Here, the second feature of the present invention is that an aromatic polyamine is used as a curing agent and boron trifluoride Amicion Durex is used as a curing accelerator in curing the silicone-modified EVO+Si resin. By using such a curing agent and curing accelerator, it is possible to improve the heel characteristics of the adhesive between the laminate and the metal circuit. This is clearly confirmed in the graph of FIG. In other words, N in the rough seam in Figure 1
o, 1~No, 6id silicon modified resin + resin 100
This graph shows the relationship between heel strength and temperature when curing agents and curing accelerators are blended in the proportions shown in Table 1 to 106 parts by weight of NBR. Adhesive that uses Horia 3-J (rare trinodiphenyl sulfone) in combination with the curing accelerator boron trifluoride hiberidine / Adhesive A61% that does not use the curing accelerator boron trifluoride piperidine in 162, 4, and 6 /168.
It is confirmed that the heel strength is greatly improved compared to 765.

1 Table 1 (parts by weight) As mentioned above, the adhesive according to the present invention is based on silicone-modified epoxy resin and NBR, and further contains an aromatic polyamine as a curing agent. CCLK is used in combination with a curing accelerator, and can improve the adhesion between the laminate and the metal circuit due to the adhesive action of the silicone-modified epoxy resin. It should be able to improve the heel % property, prevent the metal circuit from peeling off from the A-layer board during soldering, and increase the soldering heat resistance. Due to the excellent adhesion of the silicone-modified Evo+ resin, even if the adhesive surface is roughened due to physical polishing, the metal circuit can be bonded well with Metsu+, making the laminate KM thin and providing high heel characteristics. There is no need to roughen the surface by etching with a chromic acid solution. In terms of electrical properties, the adhesive of the present invention has the same properties as conventional adhesives.

Next, the present invention will be explained by examples.

Evo + Shi equivalent weight is 1100-1300 and silicon content is 1
5%, 100 parts by weight of silicone-modified epoxy resin in which R in the structural formula is an ethyl group, NBR (N1po11072
106 parts by weight of Nippon Zeon), 6 parts by weight of cyanodiphenylsulfone as a curing agent, 1 part by weight of boron trifluoride piperidine as a curing accelerator, TeC as a filler.
An adhesive was prepared by mixing 94M parts of aCO3 (#'2000), 4 parts by weight of Aerosil R972 as a stabilizer, 506 parts by weight of toluene as a solvent, 40 parts by weight of Schiff D + linone, and isopropyl alcohol. did.

This adhesive was applied to a paper cyan clad laminate to a coating thickness of 50 μm, and then heated under conditions of 130° and 0.60 min to primary cure the adhesive to B-stage state K. Next, the surface of this adhesive was polished 30 times vertically and horizontally with 600φ" abrasive paper, and then 50 times vertically and horizontally with Scotchprite UF manufactured by Sumitomo 3M, so that the surface was roughened to a roughness of 05μ. Processed.

A circuit was formed on the roughened adhesion-treated laminate obtained as described above by an additive method. First of all, Shirazurei + Setara Lip 404 270jj/'l
Aqueous solution (80±10'O) was applied to the rough surface of the adhesive and treated for 5 to 6 minutes to complete the acid treatment, and then 270jj/
1. *Filling liquid and Shipley's medium 1 lid posi 44-3
A mixed solution with 0 cc/l water chick liquid was prepared at 30±1°0, applied to the rough surface of the adhesive, and treated for 5 to 6 minutes to carry out catalyst treatment. Next, after washing with water, a 6-fold diluted aqueous solution (3
0±10'O) was applied to the rough surface of the adhesive and treated for 5 to 6 minutes, and then treated overnight. After carrying out the pretreatment in this way, sulfuric acid copper (2-8g1lc copper content), HoIb? Su: 15/-9g/13. ED
An electroless II copper methane bath consisting of an aqueous solution containing TA...2Na 2 og/l and a small amount of stabilizer was prepared at 80±1° OVC, and the laminate was immersed in this electroless copper methane bath for 5 to 10 minutes. By doing so, a thin copper plating layer was formed on the rough surface of the adhesive using electroless copper metal. Next, after washing with water, the parts that would become circuits were left on the surface of the thin copper methane layer and masked by coating and curing etching resist U R-450B manufactured by Tamura Kaken.
A circuit pattern is formed on the thin copper foil layer by immersing the laminate in an electrolytic copper foil bath prepared with an aqueous solution containing a small amount of brightener and performing electric foil bathing for 8 A, /d+n2.60 minutes at room temperature. Metsuushida. Thereafter, the above etching resist was removed with a 5% NaOH aqueous solution, and then dichloride dichloride was added.
The thin copper plating layer other than the circuit was removed by light etching using an iron solution.

Furthermore, this laminated board was 100”0×60 minutes, 160°
An electric circuit laminate was obtained by secondarily curing the adhesive by heating under conditions of 6θ.

Regarding the electrical circuit laminate obtained as described above, the heel strength between the metal circuit and the laminate and the heat resistance (measured at 260'O) were measured by floating the electrical circuit laminate in a solder bath. The heel strength at normal state was 450 to 4.80 m/m, and the heel strength at 150°○ was 1.06 to +. to ky/α, which is 260
'O-ken heat resistance was 81 seconds.

When the relationship between the heel strength and temperature of the example is qualitatively shown in a graph, it is as shown in the accompanying diagram. Here, in the accompanying graph, Comparative Example 1 is the electrical circuit laminate, and Comparative Example 2 is the conventional paper ejector + cyan clad laminate using a mixed adhesive of phenol resin and butyral resin as the adhesive. This graph shows the relationship between the heel strength of CCLK and temperature.From this graph, it can be seen that the heel strength of the previous example is much higher than that of the Aditipue method of comparative example 1.
Confirmed to be better than others.

[Brief explanation of the drawing]

FIGS. 1 and 2 are graphs showing the relationship between heel strength and temperature. Agent Patent Attorney Ishi 1) Chief Seventh Procedural Amendment (spontaneous) December 20, 1980 Mr. Commissioner of the Japan Patent Office 1, Indication of Case 1988 Patent Application No. 191871 2, Name of Issue 1 Electrical Circuit Adhesive for laminates 3, Person making the amendment (Relationship with 'l Patent Applicant Place
1048 Bold Kadoma, Kadoma City, Osaka Prefecture Name (583)
) Matsushita Electric Nichoji Co., Ltd. Representative Iku Kobayashi 4 Agent postal code 530 5 Date of amendment order 6 Reduction in the number of inventions increased by amendment 1'1 Application number 1 Patent application 1977- 19137]ke1, '13
14 Hosoridge 5th line from negative to 4th line from the bottom
1 to 4, m = ' 3 to 8 (4 to 6 in width) - j all deleted, [n - 2 to 20 (more conveniently 4 to 7), m''1 to
8 (J-Rishunsuku-2~4) Insert once and enjoy. 2 Same as above @7 negative] 5th line [20~・3011.7ψ
Delete "degree" and r 20 / A thick ladle! Insert knee 1 completely. 8 Same page 1, page 12, lines 14 to 16, delete 1-1 and insert ``Immersed in water for 6 minutes''. 4.Delete all "process this for minutes" in lines 19 and 20 of the same as above, and insert "Soak seedlings for 5 to 6 minutes-1". 5. Lines 2 to 2 of page 13 of the same In line 3, 1'--Delete all of ``Adhesive/minute treatment'' and insert all of ``UVC for 5 to 6 minutes and residue''.

Claims (1)

[Scope of Claims] (1) An electric circuit 811-layer board characterized by comprising a Silico'J-modified epoxy resin, NBR, a base agent, an aromatic polyamine as a curing agent, and a curing accelerator. Adhesive for use. (2) The adhesive for electrical circuit laminates according to claim 1, wherein the curing accelerator is a boron trifluoride trifluoride complex. (8) Special feature i characterized by containing a filler
fFMg The adhesive for electrical circuit laminates according to item 1 or 2.