JPS6067145A - Manufacture of copper lined laminated board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention provides a copper-clad 1 with excellent silver migration durability.
The present invention relates to a method for manufacturing a laminate.

[Technical costs of inventions and their problems]

Paper phenolic resin copper-clad laminates are widely used in relatively inexpensive consumer electronic devices, and their uses are becoming more diverse year by year, and they are increasingly being used in harsh environments. One of these uses is print 1 to wiring base for printing resistors. Printed resistors are usually composed of silver paste through holes, silver base 1 circuits, and carbon resistors, but with the demand for higher circuit densities, high-vidity resistors, which narrow the pitch between silver through holes, are also being developed. There is C. .

If a voltage is applied to such a high-pitched circuit for a long period of time, silver micro-migration (migration) will occur between the silver through-holes, causing deterioration of the printed wiring board and resulting in a J3 pattern short circuit. This is due to moisture and electrolysis, and is noticeable in materials that have high hygroscopicity or have a surface that has a strong affinity for moisture. 4 from fish like this
] It is desired to develop a laminate that is moisture resistant and does not cause migration without damaging the 1f#L.

[Purpose of the invention]

The present invention has been made in view of the above-mentioned drawbacks, and provides a method for manufacturing a copper-clad laminate that has excellent moisture resistance, electrical properties, and soldering heat resistance without impairing punching workability, and does not cause silver migration. ° The purpose is to

(11!ll Requirements of the Invention) As a result of intensive research aimed at achieving the above object, the present invention has been developed to provide a laminated layer with excellent silver migration resistance without impairing punchability by using the resin composition described below. It was discovered that a board can be obtained.

That is, the present invention provides (A) resol type oil-modified aromatic hydrocarbon phenol resin 1001i! A resin composition is obtained by blending 5 to 6 parts of (B) resol type 71-nol modified polybutadiene resin to 1 part of J, and a plurality of prepregs are prepared by impregnating the resin composition into a paper heat shield. There is a manufacturing method T'' for copper-clad laminates, which is characterized by integrally laminating prepregs under heat and pressure.

The (△) resol type oil-modified aromatic hydrocarbon phenol resin used in the present invention includes xylene formaldehyde resin and medicylene formaldehyde resin, such as dicanol 1-1 and dicanol M (both trade names manufactured by Mitsubishi Gas Chemical Co., Ltd.). ), AB resin (product name manufactured by Toho Chemical Co., Ltd.) and other aromatic hydrocarbon formaldehyde resins are used as starting materials, and to this, a drying oil selected from tung oil, dehydrated castor oil, and linseed oil, phenol, and budelphenol are added. It is obtained by reacting phenols selected from cresol with formaldehyde. There are four reaction methods as follows: ■ After reacting aromatic hydrocarbon formaldehyde resin and phenols under acidic conditions Then, drying oil and formaldehyde are reacted in an Alno J finish. (2) Aromatic hydrocarbon formaldehyde resin and phenols are reacted under acidic conditions, followed by reaction with drying oil under acidic conditions, and then reacted with formaldehyde under alkaline conditions. (2) Aromatic hydrocarbon formaldehyde resin, phenols, and drying oil are reacted under acidic conditions, followed by reaction with formaldehyde under alkaline conditions. - Phenols and drying oil are first reacted under acidic conditions, and then aromatic hydrocarbon formaldehyde resin is reacted under acidic conditions.
Thereafter, the alkaline handcarrier aluminum reacts with humans. Either one is 6. These resins can be used alone or 2M! A mixture of the above is used.

The resol-type phenol-modified polybutadiene resin (B) used in the present invention is obtained by adding polybutadiene and phenols, reacting in the presence of an acid catalyst in a nitrogen atmosphere, and then performing resolization by adding a resolization catalyst and formaldehyde. It is something that can be done. The polybutadiene resin used here (for example, Nisso PQlooo.2
000.

3000, '400, l) C-1000.2000 (trade name manufactured by Kuchiki Kodatsu Co., Ltd.), Nippon-h volbutazine B-1000
．． 2000. 3000. 4 000 (product name manufactured by El Kimo Yukagaku Co., Ltd.), Sumika Mail #5o.

#150 (trade name manufactured by Sumitomo Chemical Co., Ltd.) and the like.

The blending ratio of (A) resol-type oil-modified aromatic hydrocarbon phenol resin and (B) resol-type phenol-modified polybutazine resin is as follows: (A) 100 parts by weight, (
B) It is preferable to mix 5 to 60 parts by weight. (I3
) is less than 5 parts by weight (. has no effect on anti-silver migration, and if it exceeds 60 parts by weight, the compatibility of the resin is poor and the impregnation of the resin composition into the paper base material is poor.Rough punching) This is not preferable as it also deteriorates processability.Therefore, it is limited to the range shown in 1 above.

A material containing cellulose as a main component is used as a material for laminated boards, such as Kotsuichi paper, linter paper, or kraft paper. It is also possible to use these substrates that have been previously treated, for example, treated with a water-illuminated, low-molecular-weight phenolic resin or a methamine resin.

Next, to manufacture a copper-clad laminate, (A>resol type oil-modified aromatic hydrocarbon phenol resin and (B) resol type phenol-modified polybutadiene resin are blended in a predetermined ratio and added to the resin solution. immersed in the resin and coated with resin.
Next, C-drying is performed to create a prepreg. After that, the required number of prepreg sheets and copper foil are stacked together and heated and pressed under molding conditions of, for example, 160° C. humidity, 80 kg/cm' pressure, and 1 hour to form the desired copper clad laminate. can get.

〔Effect of the invention〕

The copper clad laminate machine that has been properly operated in this way can produce copper clad laminates that have excellent punchability, good moisture resistance, electrical properties, semi-Ill heat resistance, and no J3 silver migration. Due to circumstances, I send 9F to consumer electronic devices, etc.b
There is a C.

(Example of 5R, Ming) The present invention will be explained in detail with reference to 1. Examples below.

Example xyleneform I\aldehyde resin (Mitsubishi m 1lli Chemical Co., Ltd. dicanol l-(-80) 2000 liters and 71 g, -l 2700 g, baratol earth sulfone g 6.5
In the presence of -e 90 to 95°C and reacted for 90 minutes, and then added tung oil to this acid compound for 2000! l from 90 to 95
Incubate for 90 minutes at °C. Next, 37% formalin aqueous solution 219°, 1-liethanolamine 70Q
was added and reacted at 96°C for 3 hours. Dehydrated and concentrated under reduced pressure, 1 heluene/methanol-1:1i#! I! A resol-type oil-modified xylene resin varnish (T) with a resin content of 50% was obtained.

Next, N15so PB-200 () (product name manufactured by Fi1 Tsujine 1) 1000g, phenol 600g, Para 1
- Add 2.5 liters of 1Nol 1200 (1,, 37% formalin aqueous solution 1850
(J, Add 35G of 40%-E tumedelamine aqueous solution (96℃ ZnrI reaction), further dehydrate and concentrate under reduced pressure, dilute with toluene/methanol = 1 = 1 solvent, resin content 5
A 0% resol type]-f-nol modified polytazine resin Sonis (11) was obtained.

The solid content ratio of varnish (it) and varnish (II) was 70:3.
A prepreg with a resin content of 55% was made by impregnating two-inch paper with this mixture so that the resin content was 0.

Stack 8 sheets of this prepreg and use adhesive (;J35μ
A copper clad laminate having a thickness of 1.6 Il+m was manufactured by stacking copper foils and heating and press-forming them at T 160° C. and 80 ka/cm for 2.60 minutes.

The obtained laminate was tested for silver migration properties, insulation resistance, water absorption, soldering heat resistance, and punching properties. Show me.

Silver Migracie 1 Bamboo evaluation was conducted between 2.5n+m pitch silver through holes using a predetermined silver through hole pattern for 5R-value at 40°C in a 90% R1-1 environment l)C!
A voltage of IOV was applied, and changes in insulation resistance between silver through-hole pitches were measured. This is shown in Figure 1.

In FIG. 1, the curve a is for the copper-clad laminate of the present invention, and the curve a is for the copper-clad laminate of the comparative example. It can be seen that the copper-clad laminate of the present invention is superior with less decrease in insulation resistance.

Comparative example: 1000 (l) of tung oil, 1500 g of Kaminol and 1 Paratol
sulfonic acid 2. ! Add ill and 90~bU, then add 37% ij-runlin aqueous solution 1800 (+ and 40% t
Add 30g of methylamine aqueous solution and add 96"C (21
The reaction mixture was subjected to an IAI reaction of 1 liter, then dehydrated and concentrated under reduced pressure, and diluted with a 1:1 methanol/1:1 solvent to obtain a resol type oil denaturation with a resin content of 50%.

Using varnish (1), prepare prepreg is obtained in the same manner as in the example, and then a copper-clad laminate is made! l! ! I made it.

The same tests as in the Examples were conducted on this copper-clad laminate, and the results are shown in FIG. 1 and Table 1.

Measured according to Table 1 J 15-C-6481 Table 1 and Figure M1 show that the copper-clad laminate of the present invention has excellent properties, particularly good moisture resistance and silver migration properties.

[Brief explanation of drawings]

FIG. 1 is a small graph showing the change in insulation resistance between silver through-holes.

Claims (1)

[Claims] 1. Prepare a resin composition by blending 5 to 60 parts by weight of (B) resol type phenol-modified polybutadiene resin to 100 parts of (A) resol type oil-modified aromatic hydrocarbon phenol resin. Prepreg, which is made by stacking multiple sheets of prepreg made by impregnating paper base material with
1. A method for manufacturing a copper-clad GI laminate, which comprises integrally laminating and molding a GI layer by heating.