JPH08290527A - Continuous manufacture of laminated sheet - Google Patents

Abstract

PURPOSE: To obtain a laminated sheet, in which warp and twist are small, by a method wherein a laminated body is formed by passing a plurality of resin-impregnated base materials, each of which is prepared by infiltrating a thermosetting resin liquid in the base material, and then precured so as to reduce the fluidity of the thermosetting resin and, after being piled up with metal foil, passed between laminating rolls. CONSTITUTION: A plurality of continuous band-like base materials 3 are continuously delivered from states being wound on base material rolls 6 and immersed in a dipping tank 7 filled with a thermosetting resin liquid 8 so as to infiltrate the resin liquid in a plurality of the base materials 3. A plurality of the base materials 3 impregnated with the thermosetting resin liquid 8 are fed to squeeze rolls 9 so as to squeeze excess resin liquid in order to pile up and integrate the base materials together for forming the laminated body. And, after the thermosetting resin liquid 8 in the laminated body is precured, the laminated body is fed to laminating rolls 11 so as to be piled up with continuous metal foil 4 for laminating and, at the same time, controlling the thickness of the laminated body in order to be continuously conveyed to a curing over for obtaining the laminated sheet by hot curing the resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for continuously producing a laminated board used as a material for a printed wiring board used in electronic and electric devices.

[0002]

2. Description of the Related Art In recent years, in order to meet the demand for lighter, thinner, shorter and smaller electronic devices, techniques for directly mounting and high-density mounting semiconductor components on a printed wiring board have been developed. with this,
The quality required for printed wiring boards on which semiconductor components are mounted has also increased.

Conventionally, as shown in FIG. 2, a long base material 3 is used.
Is impregnated with the thermosetting resin liquid 8 and a plurality of the resin-impregnated base materials are stacked to form a laminated body 1. The laminated body 1 is heated without pressurizing to harden the resin liquid 8 and continuously laminated. Continuous production of plates is practiced.

In the above-mentioned manufacturing method, each long substrate 3 to be conveyed is filled with a thermosetting resin 8 in a dip tank 7
The base material 3 is impregnated with the resin liquid 8 and the base material 3 impregnated with the resin liquid 8 is superposed and passed between a pair of squeeze rolls 9 to remove excess surplus material adhering to the base material 3. The resin liquid 8 is squeezed out to form the integrated laminate 1.
Further, the metal foil 4 coated with the resin liquid 8 is superposed on the laminated body 1 and laminated by a laminating roll 11 and heated to cure the resin liquid 8 to manufacture a laminated plate.

However, according to the above manufacturing method, the squeezed amount of the excess resin liquid adhering to the base material depends on the viscosity of the resin liquid and the excess resin amount of the base material one by one.
The amount of resin between each substrate is not constant. Further, even when the metal foil is attached, since the resin liquid between the base materials and the resin liquid of the metal foil have fluidity, the resin liquid may move due to the contact pressure of the rolls, and the base material may be stressed. .

[0006] As described above, when the amount of resin between the base materials is different or when the resin liquid moves and stresses the base material, residual stress is accumulated in the manufactured laminated plate, which causes warpage and twisting. Was becoming.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for manufacturing a laminated board with less warpage and twist.

[0008]

A method for continuously manufacturing a laminated plate according to the present invention is a method in which a plurality of resin-impregnated base materials in which a base material 3 is impregnated with a thermosetting resin liquid 8 are continuously integrated by a sandwiching roll 2. By making the laminate 1 into a laminated body 1 and pre-curing the laminated body 1 to reduce the fluidity of the thermosetting resin, further stacking the metal foil 4 on the laminated body 1 and passing it between the laminating rolls 11. It is characterized in that a laminated plate is formed.

Further, the resin-impregnated base material forming the laminate 1 is passed between the squeeze rolls 9 to squeeze out the excess resin, and then superposed and sent to the sandwiching roll 2.

As a method for pre-curing the thermosetting resin liquid of the laminate 1, pre-curing is performed by at least one of electron beam, hot air, dielectric heating and ultraviolet rays. Curing degree of liquid is 15% to 90%
It is characterized in that it is pre-cured until.

The metal foil 4 is characterized by being either a copper foil or an aluminum foil coated with a thermosetting resin.

Further, the thermosetting resin is characterized by being at least either an unsaturated polyester resin or an epoxy resin.

The present invention will be described in more detail below. FIG.
FIG. 4 is a process diagram of a method for continuously manufacturing laminated plates showing an embodiment of the present invention.

As shown in FIG. 1, a plurality of long strips of base material 3 are continuously wound around a base material roll 6 and are dipped in a dip tank 7 containing a thermosetting resin liquid 8. Thus, the plurality of base materials 3 are impregnated with the resin liquid. A plurality of base materials 3 thus impregnated with the thermosetting resin liquid 8
Is fed to the squeeze roll 9, and the excess resin liquid is squeezed to be superposed and integrated to form a laminated body 1.

Then, after the thermosetting resin liquid 8 of the laminated body 1 is pre-cured, the laminated body 1 is laminated with a laminating roll 11
Then, the long metal foils 4 are superposed on each other, and while being adjusted in thickness, superposed and laminated, and continuously conveyed to the curing furnace 10 to heat and cure the above resin to obtain a laminated plate.

In this continuous manufacturing method, when the metal foil is provided on only one side, the other side is covered with a sheet material of, for example, a polyester film to form a laminated plate, which is cured by heating and then peeled off. As described above, the metal foil may be a metal foil of copper, aluminum, iron, nickel, zinc or the like alone or an alloy thereof depending on the intended use of the laminate, and may be used on one or both surfaces of the laminate as necessary. When used on one side, a release film such as a polyester film is used on the other side.

Further, as the base material in the above continuous production method,
A glass woven fabric, a glass non-woven fabric, or a combination thereof is used, and the kind thereof is not particularly limited.

Further, there are a series of impregnating devices such as a base material roll 6 and a dip tank 7 for impregnating the base material 3 with the thermosetting resin liquid 8 according to the number of the base materials 3 to be stacked.
As the impregnating device, the one in which the base material is immersed in the thermosetting resin liquid in this way, the one in which the thermosetting resin liquid is dropped on the upper surface of the base material, and the thermosetting resin liquid on the lower surface of the base material There is something that contacts the liquid surface of.

In the present invention, the type of resin impregnated in the substrate is not particularly limited, and examples include epoxy resin and
Any of thermosetting resins such as unsaturated polyester resin, vinyl ester resin, phenol resin, polyimide resin, and polyphenylene ether resin can be used alone, as a modified product or as a mixture, and preferably an epoxy resin or an unsaturated polyester resin. Is used. The resin composition, if necessary, aluminum hydroxide in the above resin,
Clay, talc, silica, alumina, magnesium carbonate, calcium carbonate, fillers such as synthetic resin powder and hollow bodies, and further, a curing agent, a curing accelerator, a coloring agent, etc. are added and mixed according to the characteristics of the resin. It can also be used.

Further, as a method for pre-curing the laminate, ultraviolet rays, electron beams, hot air, dielectric heating, etc. are used.
A method capable of heating without touching the laminate is preferable.
By this preliminary curing, the thermosetting resin liquid has a curing degree of 15% to
Curing is performed in the range of 90%, and if the curing degree is 15% or less, the fluidity of the resin liquid is high, and the resin liquid moves during lamination, which causes internal stress. Also,
When the curing degree is 90% or more, the resin liquid is cured, the adhesiveness with the metal foil attached by the laminating roll is reduced, and the adhesion between the laminate and the metal foil is reduced.

The continuously produced laminated plate is cut into a predetermined size by the cutting device 12, and is then subjected to the curing furnace again if necessary.

Next, the present invention will be described with reference to Examples and Comparative Examples. Of course, the present invention is not limited to the following examples.

(Examples 1 to 4 and Comparative Examples 1 and 2) Example 1 100 parts by weight of a vinyl ester resin (R-806DA manufactured by Showa High Polymer Co., Ltd.) as a thermosetting resin, 25 parts by weight of aluminum hydroxide, and heat. 1 part by weight of di-t-butyl peroxide as a polymerization initiator, a photopolymerization initiator (manufactured by Merck: DA
1 part by weight of ROCURE 1173) was added to refine the vinyl ester resin composition, and as shown in FIG.
mm long and 1050 mm wide long glass woven fabric (manufactured by Nitto Boseki Co., Ltd.) is continuously impregnated. Excess resin liquid of the base material impregnated with this resin is squeezed out by a squeeze roll 9 and adjusted to a thickness of 0.25 mm so that the resin amount becomes 42%.

Then, the obtained three vinyl ester resin-impregnated glass woven fabric base materials were overlapped with each other, and a clearance of 0.
By passing between 72 mm3 nip rolls 2,
The excessively impregnated resin composition is squeezed to form an integrated laminate 1. This laminated body 1 is irradiated with ultraviolet rays of 800 mj / cm ² to cure the vinyl ester resin by 70% to obtain a semi-cured resin-impregnated glass woven fabric substrate.

Furthermore, a copper foil 4 having a thickness of 35 μm is formed on both sides of the copper foil 4.
50 g / m ² of a vinyl ester resin composition is applied to, and the scissors are continuously sandwiched between a pair of laminating rolls 11 having a clearance of 0.8 mm to be laminated, and further fed into a curing chamber 10 at 150 ° C. for 15 Heat cure in minutes,
After that, after-curing was performed at 170 ° C. for 30 minutes to obtain a copper-clad laminate.

Example 2 100 parts by weight of vinyl ester resin (R-806DA manufactured by Showa High Polymer Co., Ltd.) as a thermosetting resin, 25 parts by weight of aluminum hydroxide, and 1 part by weight of di-t-butyl peroxide as a thermal polymerization initiator. The vinyl ester resin composition was refined by blending parts, and as shown in FIG. 1, the thickness was 0.2 mm and the width was 10 mm.
A 50 mm long glass woven fabric (manufactured by Nitto Boseki Co., Ltd.) is continuously impregnated.

Thereafter, in the same manner as in Example 1 above, the obtained three vinyl ester resin-impregnated glass woven fabric base materials were laminated to form a laminate 1, and the laminate 1 was formed with 6 Mrad.
60% of the above vinyl ester resin by irradiating
It is cured to obtain a semi-cured resin-impregnated glass woven fabric substrate.

Furthermore, a copper foil 4 having a thickness of 35 μm is formed on both sides of the copper foil 4.
50 g / m ² of the vinyl ester resin composition is applied to the film, and the film is continuously sandwiched between a pair of laminating rolls 11 having a clearance of 0.8 mm for lamination, and further fed into the curing chamber 10 at 150 ° C. for 15 Heat cure in minutes,
After that, after-curing was performed at 170 ° C. for 30 minutes to obtain a copper-clad laminate.

Example 3 Epoxy resin (YD-produced by Tohto Kasei Co., Ltd.) as a thermosetting resin
128) 100 parts by weight, 70 parts by weight of methyl tetrahydrophthalic anhydride, and 0.8 parts by weight of benzyldimethylamine were mixed to purify the epoxy resin composition, and a glass woven fabric substrate was prepared in the same manner as in Example 1 above. After being impregnated with the epoxy resin composition, three epoxy resin-impregnated glass woven fabric substrates are laminated to form a laminated body 1.
Heat for 3 minutes with hot air at 0 ° C,
It is cured by 5% to obtain a semi-cured resin impregnated glass woven fabric substrate.

Further, a copper foil 4 having a thickness of 35 μm is formed on both sides of the copper foil 4.
50g / m of epoxy resin composition ²Apply and clearer
Between a pair of laminating rolls 11 with a thickness of 0.8 mm.
Continue to scissor and laminate, and then in the curing chamber 10.
Send in, heat cure at 150 ° C for 15 minutes, then
After-curing at 170 ℃ for 30 minutes, copper clad laminate
Got

Example 4 The same as Example 3 except that instead of curing the laminate 1 with hot air in Example 3, 40% of the epoxy resin was cured by a high frequency electromagnetic field with an alternating current of 20 MHz by a dielectric heating device. A copper clad laminate was obtained by the method described in 1.

Comparative Example 1 A copper clad laminate was obtained in the same manner as in Example 2 except that the resin was not cured by irradiating the laminate 1 with an electron beam in Example 2 above.

Comparative Example 2 A copper clad laminate was obtained by the same method as in Example 2 except that the resin was not cured by hot air in the laminate 1 in Example 3 above.

First, the copper clad laminates obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated for quality.

Regarding warping and twisting, the obtained copper clad laminate was cut into a size of 250 mm × 250 mm to give a test piece, the copper foil of the test piece was removed by etching the entire surface, and then passed through a reflow furnace. The sample copper clad laminate was preheated at 150 ° C for about 3 minutes, and then heated at 230 ° C, 20 ° C.
After passing through the reflow furnace for 2 seconds, each test piece was placed on a glass flat plate, and the distances from the glass flat plate at the four corners of the test piece were measured with a JIS class 1 metal gauge to determine the maximum value.

Further, the thickness of the resin between the base materials of the test piece,
And the thickness of the resin between the copper foil and the substrate was measured.

The results of the above measurements are shown in Table 1.

[0038]

[Table 1] From Table 1, the laminated plates produced in Examples 1 to 4 were able to obtain excellent results in terms of warpage and twist as compared with Comparative Examples 1 and 2, respectively. It was also confirmed that the thickness of the interlayer resin did not change according to the method for continuously producing a laminated board of the present invention.

[0039]

According to the method for continuously producing a laminated plate according to the present invention, a plurality of resin-impregnated base materials impregnated with a thermosetting resin liquid are continuously integrated by a sandwiching roll to form a laminated body. Is pre-cured, and further, a metal foil is superposed on this laminate to pass between the laminating rolls to form a laminated plate, so that the resin liquid impregnated into the base material does not flow out much, and the thickness of the interlayer resin and the base material are reduced. The thickness between the metal foil and the metal foil can be kept substantially constant, residual stress can be reduced, and a laminated plate with less warp and twist can be obtained.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a continuous manufacturing method of laminated plates according to the present invention.

FIG. 2 is an explanatory view showing a conventional continuous manufacturing method of laminated plates.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Laminated body 2 Clamping roll 3 Base material 4 Metal foil 5 Precuring device 6 Base material roll 7 Dip tank 8 Thermosetting resin liquid 9 Squeeze roll 10 Curing chamber 11 Laminating roll

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location B32B 27/38 B32B 27/38

Claims (6)

[Claims] 1. A laminate (1) in which a plurality of resin-impregnated base materials in which a base material (3) is impregnated with a thermosetting resin liquid (8) are continuously integrated by a holding roll (2) to obtain a laminate (1). The laminate (1) is pre-cured to reduce the fluidity of the thermosetting resin, and
A method for continuously producing a laminated sheet, comprising forming a laminated sheet by laminating a metal foil (4) on the laminated body (1) and passing it between laminating rolls (11). 2. The resin-impregnated base material constituting the laminate (1) is passed between squeeze rolls (9) to squeeze out excess resin, and then superposed and sent to a sandwiching roll (2). The continuous manufacturing method of a laminated board according to claim 1. 3. A method of pre-curing the thermosetting resin liquid of the laminate (1) includes ultraviolet ray, electron beam, hot air, dielectric heating,
The method for continuously producing a laminated plate according to claim 1 or 2, wherein the method is pre-cured by at least one of the above methods. 4. The method for continuously producing a laminated plate according to claim 1, wherein the thermosetting resin liquid of the laminate (1) is pre-cured to a curing degree of 15% to 90%. 5. The method for continuously producing a laminated board according to claim 1, wherein the metal foil (4) is either a copper foil coated with a thermosetting resin or an aluminum foil. 6. The method for continuously producing a laminated board according to claim 1, wherein the thermosetting resin is at least one of unsaturated polyester resin and epoxy resin.