JP2018001764A - Metal-clad laminate and method for manufacturing the same, method for manufacturing printed wiring board, and method for manufacturing multilayer printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal-clad laminate which reduces warpage and is less likely to cause a defect in a mounting step.SOLUTION: A metal-clad laminate 5 is obtained by heating and pressing a metallic foil 4 while overlapping a prepreg 3 obtained by impregnating a resin composition 2 containing a thermosetting resin with an opened glass cloth base material and semi-curing the resin composition, and curing the resin composition 2. A dimension of a laminate 6 after subjected to an etching treatment of removing the metallic foil 4 of the metal-clad laminate 5 increases compared to a dimension of the metal-clad laminate 5 before subjected to the etching treatment. The dimension of the laminate 6 after subjected to an aging treatment of heating at 150°C for 30 minutes after subjected to the etching treatment increases compared to the dimension of the metal-clad laminate 5 before subjected to the etching treatment.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metal-clad laminate used for the production of printed wiring boards and the like, a method for producing the same, a method for producing a printed wiring board produced using the metal-clad laminate, and a method for producing a multilayer printed wiring board. .

  Conventionally, as a metal-clad laminate, a flexible metal-clad laminate obtained by bonding a metal foil to an adhesive film is known (for example, see Patent Document 1). In particular, the adhesive film described in Patent Document 1 is a film in which a polyimide film is provided with an adhesive layer containing a thermoplastic polyimide, and the polyimide film is a film obtained by partially imidizing a precursor polyamic acid. Is obtained by heating and stretching. Thus, the occurrence of dimensional change can be suppressed.

JP 2004-338160 A

  The above-mentioned flexible metal-clad laminate does not include a base material inside, but recently, a rigid metal-clad laminate including a base material inside is also flexible metal in order to cope with downsizing and thinning. Similar to the tension laminate, it is required to suppress the occurrence of dimensional changes. Hereinafter, a rigid metal-clad laminate including a base material inside is simply referred to as a metal-clad laminate.

  FIG. 6B shows a dimensional change rate (+ is elongation and − is shrinkage) after etching and aging of a general metal-clad laminate. The etching process corresponds to a conductor pattern forming process, and the aging process corresponds to a heating process when forming a resist for protecting the conductor pattern. As shown in FIG. 6B, when the dimension after molding is used as a reference, the dimension after the etching process slightly shrinks, and the dimension after the aging process shrinks significantly. As described above, generally, when a conductor pattern is formed and then greatly contracted, the warpage tends to increase, and when the warpage increases, the possibility of occurrence of a defect in the component mounting process increases. In recent years, with the progress of miniaturization and thinning of substrates and difficulty in mounting, suppression of dimensional changes with respect to the substrate has been demanded.

  The present invention has been made in view of the above points, a metal-clad laminate capable of reducing warpage and making it difficult to cause defects in the mounting process, a method for manufacturing the same, a method for manufacturing a printed wiring board, and a multilayer It aims at providing the manufacturing method of a printed wiring board.

  The metal-clad laminate according to the present invention is obtained by laminating a metal foil on a prepreg that is semi-cured by impregnating a spread glass cloth substrate with a resin composition containing a thermosetting resin, and is heated and pressurized. A metal-clad laminate in which the resin composition is cured, and the dimension of the laminate after performing the etching treatment to remove the metal foil of the metal-clad laminate is the metal-clad laminate before the etching treatment is performed. The dimension of the laminated sheet after the etching process is performed, and after the etching process is performed, the dimension of the laminated sheet after performing the aging process of heating at 150 ° C. for 30 minutes is the dimension of the metal-clad laminate before the etching process. Increased compared to

  The metal-clad laminate according to the present invention is obtained by laminating a metal foil on a prepreg that is semi-cured by impregnating a spread glass cloth substrate with a resin composition containing a thermosetting resin, and is heated and pressurized. A metal-clad laminate in which the resin composition is cured, and the dimension of the laminate after performing the etching treatment to remove the metal foil of the metal-clad laminate is the metal-clad laminate before the etching treatment is performed. The size of the laminated board after the etching process is further increased to the dimension of the laminated board after performing the aging process of heating at 150 ° C. for 30 minutes after the etching process. Compared to decrease.

  The method for producing a metal-clad laminate according to the present invention includes a step of impregnating a spread glass cloth substrate with a resin composition containing a thermosetting resin, and a step of semi-curing the resin composition to form a prepreg. And a step of curing the resin composition by heating and pressurizing the metal foil on the prepreg, and removing the metal foil of the metal-clad laminate An aging treatment in which the dimension of the laminate after the etching process is increased as compared with the dimension of the metal-clad laminate before the etching process is performed, followed by heating at 150 ° C. for 30 minutes after the etching process is performed. The dimension of the laminated board after performing increases compared with the dimension of the metal-clad laminated board before performing the said etching process.

  The method for producing a metal-clad laminate according to the present invention includes a step of impregnating a spread glass cloth substrate with a resin composition containing a thermosetting resin, and a step of semi-curing the resin composition to form a prepreg. And a step of curing the resin composition by heating and pressurizing the metal foil on the prepreg, and removing the metal foil of the metal-clad laminate An aging treatment in which the dimension of the laminate after the etching process is increased as compared with the dimension of the metal-clad laminate before the etching process is performed, followed by heating at 150 ° C. for 30 minutes after the etching process is performed. The dimension of the laminated board after performing decreases compared with the dimension of the laminated board after performing the said etching process.

  A method for producing a printed wiring board according to the present invention is a method for producing a printed wiring board in which a conductive pattern is formed on both sides or one side of an insulating layer impregnated with a resin composition in a glass cloth substrate and cured. A step of forming the conductor pattern by removing unnecessary portions of the metal foil of the metal-clad laminate.

  A method for producing a multilayer printed wiring board according to the present invention is a method for producing a multilayer printed wiring board having three or more layers of conductor patterns, by removing unnecessary portions of the metal foil of the metal-clad laminate. And a step of forming the conductor pattern.

  According to the present invention, it is possible to reduce the warpage and make it difficult to cause defects in the mounting process.

1 shows an example of a metal-clad laminate according to the present invention, where (a) is a cross-sectional view of a double-sided metal-clad laminate, (b) is a cross-sectional view of a single-sided metal-clad laminate, and (c) is an entire surface of a metal foil. Sectional view of the removed laminated board, (d) is a sectional view of the metal-clad laminated board with the inner layer circuit, and (e) is a laminated board with the inner layer circuit from which the metal foil has been completely removed. An example of the manufacturing process of a double-sided metal clad laminated board is shown, (a) (b) is sectional drawing. An example of the manufacturing process of a single-sided metal-clad laminated board is shown, (a) (b) is sectional drawing. An example of the manufacturing process of the metal-clad laminated board containing an inner layer circuit is shown, (a)-(c) is sectional drawing. It is a top view which shows an example of the sample for a dimensional change rate measurement. (A) is a graph which shows an example of the dimensional change rate after the etching process of the metal-clad laminated board which concerns on this invention, and after an aging process, (b) is after the etching process of an ordinary metal-clad laminated board, and an aging process. It is a graph which shows an example of the subsequent dimensional change rate.

  Embodiments of the present invention will be described below.

  As shown in FIGS. 2 to 4, the metal-clad laminate 5 according to the present invention is formed by heating and pressing the metal foil 4 on both sides or one side of the prepreg 3 and used as a printed wiring board material. In the metal-clad laminate 5, the prepreg 3 is cured to form an insulating layer 30 having electrical insulation. FIG. 1 (a) shows a double-sided metal-clad laminate. FIG. 1B shows a single-sided metal-clad laminate. FIG. 1C shows the laminate 6 after the metal foil 4 of the metal-clad laminate 5 has been completely removed. FIG. 1 (d) shows the metal-clad laminate 5 with the inner layer circuit 7 having the inner layer circuit 7 inside the insulating layer 30. FIG. 1 (e) shows the laminated board 6 with the inner layer circuit 7 after the metal foil 4 of the metal-clad laminated board 5 with the inner layer circuit 7 is completely removed.

  Here, as the metal foil 4, for example, a copper foil, an aluminum foil, a stainless steel foil or the like can be used. Although the thickness of the metal foil 4 is 2-70 micrometers, for example, it is not limited to this.

  The prepreg 3 is formed by impregnating the base material 1 with the resin composition 2 and heating and drying it until it is in a semi-cured state (B stage state).

  It is preferable that said resin composition 2 contains a thermosetting resin and a filler.

  Here, as a thermosetting resin, an epoxy resin, a phenol resin, cyanate resin, a melamine resin, an imide resin etc. can be used, for example. In particular, as the epoxy resin, for example, a polyfunctional epoxy resin, a bisphenol type epoxy resin, a novolac type epoxy resin, a biphenyl type epoxy resin, or the like can be used.

  Examples of the filler that can be used include silica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, talc, and alumina.

  Moreover, it is preferable that 50-80 mass% of fillers are contained with respect to the resin composition 2 whole quantity. Thus, when the content of the filler is 50% by mass or more, the dimensional change from after forming the metal-clad laminate 5 to after the etching treatment and the dimensional change from after the etching treatment to after the aging treatment are further increased. It can be made smaller. Moreover, if content of a filler is 80 mass% or less, a resin composition 2 can be made to contain a filler, suppressing a raise of a viscosity.

  Moreover, the resin composition 2 may contain a hardening | curing agent and a hardening accelerator.

  Here, as a hardening | curing agent, a phenol type hardening | curing agent, a dicyandiamide hardening | curing agent, etc. can be used, for example.

  Moreover, as a hardening accelerator, imidazoles, a phenol compound, amines, organic phosphines, etc. can be used, for example.

  In addition to the above thermosetting resin, if necessary, the resin composition 2 can be prepared by blending a filler, a curing agent, and a curing accelerator, and the resin composition is further diluted with a solvent. A varnish of product 2 can be prepared. As the solvent, for example, methyl ethyl ketone, toluene, styrene, methoxypropanol or the like can be used.

  As the base material 1, for example, a material made of inorganic fibers such as glass cloth, glass paper, glass mat, or a material made of organic fibers such as aramid cloth can be used. Although the thickness of the base material 1 is 20-200 micrometers, for example, it is not limited to this.

  In manufacturing the prepreg 3, first, the base material 1 is impregnated with the resin composition 2. Next, the prepreg 3 can be obtained by drying by heating until it is in a semi-cured state. The heating temperature at this time is, for example, 100 to 200 ° C., and the heating time is, for example, 1 to 10 minutes, but is not limited thereto. Moreover, it is preferable that content (resin content) of the resin composition 2 is 40-75 mass% with respect to the prepreg 3 whole quantity.

  The metal-clad laminate 5 according to the present invention is formed as follows.

  That is, the metal-clad laminate 5 which is a double-sided metal-clad laminate is formed by laminating the metal foil 4 on both sides of the prepreg 3 as shown in FIGS. In this case, the metal foil 4 may be laminated and molded on both sides of one prepreg 3, or a plurality of prepregs 3 may be laminated and the metal foil 4 may be laminated on both sides. The thickness of the metal-clad laminate 5 is preferably 0.2 mm or less (the lower limit is 0.015 mm). As a result, the printed wiring board can be reduced in size and thickness.

  Moreover, the metal-clad laminate 5 which is a single-sided metal-clad laminate is formed by laminating a metal foil 4 on one side of the prepreg 3 as shown in FIGS. In this case, the metal foil 4 may be laminated and formed on one side of one prepreg 3, or a plurality of prepregs 3 may be laminated and the metal foil 4 may be laminated and formed on one side. The thickness of the metal-clad laminate 5 is preferably 0.2 mm or less (the lower limit is 0.015 mm). As a result, the printed wiring board can be reduced in size and thickness. The single-sided metal-clad laminate may be formed by removing the entire surface of the metal foil 4 on one side of the double-sided metal-clad laminate.

  Further, the metal-clad laminate 5 with the inner layer circuit 7 is manufactured by first manufacturing the core material 8 shown in FIG. 4A, and then, as shown in FIGS. 4B and 4C, one of the prepregs 3 described above. The core material 8 is formed on this surface, and the metal foil 4 is laminated on the other surface. The core material 8 is manufactured, for example, by providing a conductor pattern on one side of a double-sided metal-clad laminate by a subtractive method, or by providing a conductor pattern on a surface without a metal foil 4 of a single-sided metal-clad laminate. Or can be manufactured. The conductor pattern thus provided is embedded in the insulating layer 30 to form the inner layer circuit 7. In the above case, the prepreg 3 sandwiched between the core material 8 and the metal foil 4 may be one sheet or a plurality of sheets, but the thickness of the metal-clad laminate 5 containing the inner layer circuit 7 is 0.2 mm or less. (The lower limit is preferably 0.015 mm). As a result, the printed wiring board can be reduced in size and thickness.

  Moreover, each said lamination molding can be performed by heat-pressing using a multistage vacuum press, a double belt press, a linear pressure roll, a vacuum laminator etc., for example. In this case, the rate of temperature increase during heating and pressing is preferably 200 ° C./min or more. Thereby, the metal-clad laminated board 5 which shows the characteristic dimensional change behavior like FIG. 6 (a) mentioned later can be obtained easily. The upper limit of the heating rate is 350 ° C./min, but is not limited to this. The peak temperature during lamination molding is preferably 140 to 350 ° C., the molding pressure is 0.5 to 6.0 MPa, and the molding time is preferably 1 to 240 minutes.

  About the metal-clad laminated board 5 manufactured as mentioned above, the behavior of a dimensional change is as follows. FIG. 6A shows the dimensional change rate (+ is stretched and − is shrunk) after the etching process and after the aging process of the metal-clad laminate 5 according to the present invention.

As shown in FIG. 6A, when the dimension of the metal-clad laminate 5 after forming, that is, the dimension of the metal-clad laminate 5 before performing the etching process is used as a reference, the laminate after the etching process is performed. The size of 6 tends to increase. Thereby, the distortion inside the laminated board 6 can be removed. Since the etching process corresponds to a conductor pattern forming process, it means that the strain inside the laminated plate 6 can be removed when the conductor pattern is formed. The dimensional change rate at this time can be calculated according to, for example, JIS C 6481. First, an interval between any two points on the surface of the metal-clad laminate 5 before the etching treatment is measured, and this is defined as _L0 . Next, an etching process was performed by removing the entire surface of the metal foil 4 of the metal-clad laminate 5 using an etchant mainly composed of cupric chloride, and the distance between the two points was measured again. This is referred to as _{L 1} Te. Then, it is possible by the following equation (1) to calculate the dimensional change rate S ₁ after the etching treatment.

S ₁ = (L ₁ −L ₀ ) × 100 / L ₀ (%) (1)
When the dimensional change rate of the laminated plate 6 after the etching process is specifically calculated by the above formula (1), the dimensional change rate of the metal-clad laminate 5 according to the present invention exceeds 0% and is 0. It tends to be less than 1%. Thus, the distortion inside the laminated board 6 can be removed with a minimum dimensional change.

Further, as shown in FIG. 6A, when the dimension of the laminated board 6 after the etching process is used as a reference, the dimension of the laminated board 6 after the aging process after the etching process hardly changes. The dimensional change rate at this time can also be calculated in accordance with, for example, JIS C 6481. After the aging treatment by heating for 30 minutes the laminate 6 after the etching treatment at 0.99 ° C., which is referred to as L ₂ by measuring the distance between two points in the re. Then, it is possible to calculate the dimensional change rate S ₂ after aging treatment by the following equation (2).

S ₂ = (L ₂ −L ₁ ) × 100 / L ₁ (%) (2)
When the dimensional change rate of the laminate 6 after the aging treatment is specifically calculated by the above formula (2), the dimensional change rate of the metal-clad laminate 5 according to the present invention is ± 0.03%. Within range. Thus, even if the metal-clad laminate 5 according to the present invention is subjected to an aging process after the etching process, the dimensions hardly change. This aging treatment corresponds to a heating process at the time of forming a resist for protecting a conductor pattern, but the warpage can be reduced after the completion of such a heating process, resulting in problems in the subsequent component mounting process. It can be made difficult.

  The printed wiring board according to the present invention is formed by providing a conductor pattern on both sides or one side of the metal-clad laminate 5. The conductor pattern can be formed by, for example, a subtractive method or an additive method.

  The multilayer printed wiring board according to the present invention is formed by providing at least three conductor pattern layers using the above-described printed wiring board. The printed wiring board usually has two or less conductor pattern layers, but a multilayer printed wiring board having three or more conductor pattern layers can be produced as follows.

  That is, although not shown in the drawings, the multilayer printed wiring board according to the present invention has the metal foil 4 laminated on both sides or one side of the printed wiring board via the prepreg 3, and unnecessary portions of the metal foil 4. And a conductor pattern layer can be formed. In this case, the prepreg 3 is preferably used, but other prepregs 3 may be used. Moreover, as the metal foil 4, the thing similar to the above can be used. Lamination molding and molding conditions are the same as in the case of manufacturing the metal-clad laminate 5 described above. The conductor pattern can be formed in the same manner as when a printed wiring board is manufactured. That is, when the metal foil 4 is present, the conductor pattern layer can be formed by a subtractive method, and when the metal foil 4 is not present, the conductor pattern layer can be formed by an additive method. Alternatively, a multilayer printed wiring board may be manufactured by forming a conductor pattern layer on both surfaces of the metal-clad laminate 5 containing the inner layer circuit 7 shown in FIG. 1D by a subtractive method. In the multilayer printed wiring board, the number of layers of the conductor pattern is not particularly limited.

  Hereinafter, the present invention will be specifically described by way of examples.

Example 1
“HP9500” and “N540” manufactured by DIC Corporation were used as thermosetting resins.

  Further, “YC100C-MLE” and “S0-25R” manufactured by Admatechs Co., Ltd., which are silica, were used as fillers.

  As a curing agent, “TD2090” manufactured by DIC Corporation, which is a phenolic curing agent, was used.

  In addition, “2E4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., which is imidazole, was used as a curing accelerator.

  Further, as the substrate 1, “1037 cloth” (thickness 29 μm) manufactured by Nitto Boseki Co., Ltd., which is a glass cloth, was used.

  And said thermosetting resin ("HP9500": 46.51 mass parts, "N540": 19.94 mass parts), filler ("YC100C-MLE": 50 mass parts, "S0-25R": 250 mass) Part), a curing agent (“TD2090”: 33.55 parts by mass), a curing accelerator (“2E4MZ”: 0.05 parts by mass), and further diluted with a solvent (methyl ethyl ketone). A varnish was prepared.

  Next, the base material 1 was impregnated with the above varnish, and the prepreg 3 was produced by heating and drying in a drying furnace at 150 ° C. for 3 minutes until it became a semi-cured state. The content (resin content) of the resin composition 2 is 59% by mass with respect to the total amount of the prepreg 3.

Next, two prepregs 3 are stacked, and copper foil ("3EC-VLP" manufactured by Mitsui Metal Mining Co., Ltd., 500 mm x 500 mm x thickness 18 m) is laminated and molded on both sides as metal foil 4 As the metal-clad laminate 5, a double-sided metal-clad laminate (thickness: 0.096 mm) as shown in FIG. The above lamination molding was performed by heating and pressing using a multistage vacuum press. The heating rate during heating and pressing is 250 ° C./min, the peak temperature is 250 ° C., the molding pressure is 3.9 MPa (40 kgf / cm ² ), and the molding time is 5 minutes.

Next, the metal-clad laminate 5 is cut into a 50 mm square, and this is used as a sample for measuring the dimensional change rate, and between any two points in two orthogonal directions (X direction and Y direction) on the surface of the sample. Were measured as L ₀ (X) and L ₀ (Y), respectively (see FIG. 5).

Next, the etching process is performed by removing the entire surface of the metal foil 4 of the metal-clad laminate 5 using an etchant mainly composed of cupric chloride and the like, and then the distance between the two points in the above two directions. Were measured again to be L ₁ (X) and L ₁ (Y), respectively. Then, to calculate the rate of dimensional change after etching _S 1 (X) and _S 1 (Y) by the above equation (1). The results are shown below.

S ₁ (X) = + 0.03%
S ₁ (Y) = + 0.03%
Next, after performing the aging treatment by heating the laminated plate 6 after the etching treatment at 150 ° C. for 30 minutes, the distance between the two points in the two directions is measured again, and these are respectively expressed as L ₂ (X) And L ₂ (Y). Then, the dimensional change rates S ₂ (X) and S ₂ (Y) after the aging treatment were calculated by the above formula (2). The results are shown below.

S ₂ (X) = + 0.01%
S ₂ (Y) = + 0.01%
Then, the laminate 6 was placed on a surface plate in a no-load state with the convex surface facing upward, and the maximum warpage amount of the laminate 6 was measured by a stationary method according to JIS C 6481. As a result, the maximum warpage amount was 1.1 mm.

(Example 2)
“EPPN502H” manufactured by Nippon Kayaku Co., Ltd. was used as the thermosetting resin.

  Further, “YC100C-MLE”, “S0-25R” and “S0-C6” manufactured by Admatechs Co., Ltd., which are silica, were used as fillers.

  In addition, “MEH7600” manufactured by Meiwa Kasei Co., Ltd., which is a phenolic curing agent, was used as the curing agent.

  In addition, “2E4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., which is imidazole, was used as a curing accelerator.

  Further, as the substrate 1, “1037 cloth” (thickness 29 μm) manufactured by Nitto Boseki Co., Ltd., which is a glass cloth, was used.

  And said thermosetting resin ("EPPN502H": 62.83 mass parts), filler ("YC100C-MLE": 50 mass parts, "S0-25R": 100 mass parts, "S0-C6": 50 masses) Part), a curing agent ("MEH7600": 37.17 parts by mass), a curing accelerator ("2E4MZ": 0.05 parts by mass), and further diluted with a solvent (methyl ethyl ketone) A varnish was prepared.

  Next, a prepreg 3 (resin content: 59 mass%) was produced in the same manner as in Example 1 except that the above varnish was used, and a metal-clad laminate 5 was produced using the prepreg 3.

Next, the dimensional change rates S ₁ (X) and S ₁ (Y) after the etching treatment were calculated in the same manner as in Example 1. The results are shown below.

S ₁ (X) = + 0.02%
S ₁ (Y) = + 0.02%
Next, the dimensional change rates S ₂ (X) and S ₂ (Y) after the aging treatment were calculated in the same manner as in Example 1. The results are shown below.

S ₂ (X) = + 0.03%
S ₂ (Y) = + 0.03%
And the maximum curvature amount of the laminated board 6 was measured like Example 1. FIG. As a result, the maximum warpage amount was 1.3 mm.

(Example 3)
As the base material 1, “1036 cloth” (28 μm thickness) manufactured by Nitto Boseki Co., Ltd., which is a glass cloth, was used.

  A varnish of the resin composition 2 was prepared in the same manner as in Example 1.

  Next, a prepreg 3 (resin content: 51 mass%) was produced in the same manner as in Example 1 except that the varnish and the substrate 1 were used, and the metal-clad laminate 5 was produced using the prepreg 3. Manufactured.

Next, the dimensional change rates S ₁ (X) and S ₁ (Y) after the etching treatment were calculated in the same manner as in Example 1. The results are shown below.

S ₁ (X) = + 0.03%
S ₁ (Y) = + 0.03%
Next, the dimensional change rates S ₂ (X) and S ₂ (Y) after the aging treatment were calculated in the same manner as in Example 1. The results are shown below.

S ₂ (X) = + 0.02%
S ₂ (Y) = + 0.01%
And the maximum curvature amount of the laminated board 6 was measured like Example 1. FIG. As a result, the maximum warpage amount was 0.9 mm.

Example 4
By laminating and forming a copper foil ("3EC-VLP" manufactured by Mitsui Metal Mining Co., Ltd., 500 mm x 500 mm x thickness 18 m) as a metal foil 4 on both sides of one prepreg 3 similar to that in Example 1, A double-sided metal-clad laminate (thickness 0.066 mm) was produced as the metal-clad laminate 5. The above lamination molding was performed by heating and pressing using a multistage vacuum press. The heating rate during heating and pressing is 250 ° C./min, the peak temperature is 250 ° C., the molding pressure is 3.9 MPa (40 kgf / cm ² ), and the molding time is 5 minutes.

  Next, a conductor pattern was provided on one side of the double-sided metal-clad laminate by a subtractive method to manufacture the core material 8.

  Next, the core material 8 is laminated on one surface of one prepreg 3 similar to the above, and the metal foil 4 is laminated on the other surface to form the metal-clad laminate 5 with the inner layer circuit 7 (thickness). 0.120 mm) was manufactured. The above lamination molding was performed in the same manner as the production of the double-sided metal-clad laminate.

Next, the dimensional change rates S ₁ (X) and S ₁ (Y) after the etching treatment were calculated in the same manner as in Example 1. The results are shown below.

S ₁ (X) = + 0.02%
S ₁ (Y) = + 0.02%
Next, the dimensional change rates S ₂ (X) and S ₂ (Y) after the aging treatment were calculated in the same manner as in Example 1. The results are shown below.

S ₂ (X) = + 0.03%
S ₂ (Y) = + 0.03%
And the maximum curvature amount of the laminated board 6 was measured like Example 1. FIG. As a result, the maximum warpage amount was 3.1 mm.

(Comparative Example 1)
Two prepregs 3 similar to those in Example 1 are stacked, and copper foil (“3EC-VLP” manufactured by Mitsui Mining & Smelting Co., Ltd., 500 mm × 500 mm × thickness 18 μm) is laminated and molded on both sides as metal foil 4. Thus, a double-sided metal-clad laminate (thickness 0.096 mm) was produced as the metal-clad laminate 5. The above lamination molding was performed by heating and pressing using a multistage vacuum press. The heating rate during heating and pressurization is 3 ° C./min, the peak temperature is 220 ° C., the molding pressure is 3.9 MPa (40 kgf / cm ² ), and the molding time is 80 minutes.

Next, the dimensional change rates S ₁ (X) and S ₁ (Y) after the etching treatment were calculated in the same manner as in Example 1. The results are shown below.

S ₁ (X) = + 0.01%
S ₁ (Y) = + 0.01%
Next, the dimensional change rates S ₂ (X) and S ₂ (Y) after the aging treatment were calculated in the same manner as in Example 1. The results are shown below.

S ₂ (X) = − 0.05%
S ₂ (Y) = − 0.05%
And the maximum curvature amount of the laminated board 6 was measured like Example 1. FIG. As a result, the maximum warpage amount was 2.5 mm.

(Comparative Example 2)
“HP9500” and “N540” manufactured by DIC Corporation were used as thermosetting resins.

  Further, “S0-25R” manufactured by Admatechs Co., Ltd., which is silica, was used as the filler.

  As a curing agent, “TD2090” manufactured by DIC Corporation, which is a phenolic curing agent, was used.

  In addition, “2E4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., which is imidazole, was used as a curing accelerator.

  Further, as the substrate 1, “1036 cloth” (28 μm thickness) manufactured by Nitto Boseki Co., Ltd., which is a glass cloth, was used.

  And said thermosetting resin ("HP9500": 46.51 mass parts, "N540": 19.94 mass parts), a filler ("S0-25R": 300 mass parts), a hardening | curing agent ("TD2090": 33.55 parts by mass), a curing accelerator (“2E4MZ”: 0.05 part by mass), and further diluted with a solvent (methyl ethyl ketone), a varnish of the resin composition 2 was prepared.

  Next, a prepreg 3 (resin content: 72 mass%) was produced in the same manner as in Comparative Example 1 except that the varnish and the substrate 1 were used, and the metal-clad laminate 5 was produced using this prepreg 3. Manufactured.

Next, the dimensional change rates S ₁ (X) and S ₁ (Y) after the etching treatment were calculated in the same manner as in Example 1. The results are shown below.

S ₁ (X) = − 0.02%
S ₁ (Y) = − 0.02%
Next, the dimensional change rates S ₂ (X) and S ₂ (Y) after the aging treatment were calculated in the same manner as in Example 1. The results are shown below.

S ₂ (X) = − 0.06%
S ₂ (Y) = − 0.06%
And the maximum curvature amount of the laminated board 6 was measured like Example 1. FIG. As a result, the maximum warpage amount was 3.7 mm.

DESCRIPTION OF SYMBOLS 1 Base material 2 Resin composition 3 Prepreg 4 Metal foil 5 Metal-clad laminated board 6 Laminated board

Claims (15)

A metal-clad laminate in which a resin composition containing a thermosetting resin is impregnated into a spread glass cloth base material and semi-cured, and a metal foil is laminated and heated and pressed to cure the resin composition. A board,
The size of the laminate after performing the etching treatment to remove the metal foil of the metal-clad laminate is increased compared to the size of the metal-clad laminate before the etching treatment,
After performing the etching process, the dimension of the laminate after performing the aging process of heating at 150 ° C. for 30 minutes increases compared to the dimension of the metal-clad laminate before performing the etching process,
Metal-clad laminate. The size of the laminate after the aging treatment is reduced as compared to the size of the laminate after the etching treatment,
The metal-clad laminate according to claim 1. A metal-clad laminate in which a resin composition containing a thermosetting resin is impregnated into a spread glass cloth base material and semi-cured, and a metal foil is laminated and heated and pressed to cure the resin composition. A board,
The size of the laminate after performing the etching treatment to remove the metal foil of the metal-clad laminate is increased compared to the size of the metal-clad laminate before the etching treatment,
The size of the laminate after performing the aging treatment of heating at 150 ° C. for 30 minutes after the etching treatment is reduced as compared with the size of the laminate after the etching treatment,
Metal-clad laminate. When the dimension of the laminate after performing the etching treatment is a standard, the dimensional change rate of the laminate after the aging treatment is within a range of ± 0.03%.
The metal-clad laminate according to any one of claims 1 to 3. The resin composition contains a filler,
The metal-clad laminate according to any one of claims 1 to 4. The filler contains 50-80% by mass of the filler in the resin composition,
The metal-clad laminate according to claim 5. A step of impregnating a spread glass cloth base material with a resin composition containing a thermosetting resin;
Semi-curing the resin composition to form a prepreg;
A step of curing the resin composition by superposing a metal foil on the prepreg and applying heat and pressure, and a method for producing a metal-clad laminate,
The size of the laminate after performing the etching treatment to remove the metal foil of the metal-clad laminate is increased compared to the size of the metal-clad laminate before the etching treatment,
After performing the etching process, the dimension of the laminate after performing the aging process of heating at 150 ° C. for 30 minutes increases compared to the dimension of the metal-clad laminate before performing the etching process,
A method for producing a metal-clad laminate. The size of the laminate after the aging treatment is reduced as compared to the size of the laminate after the etching treatment,
The method for producing a metal-clad laminate according to claim 7. A step of impregnating a spread glass cloth base material with a resin composition containing a thermosetting resin;
Semi-curing the resin composition to form a prepreg;
A step of curing the resin composition by superposing a metal foil on the prepreg and applying heat and pressure, and a method for producing a metal-clad laminate,
The size of the laminate after performing the etching treatment to remove the metal foil of the metal-clad laminate is increased compared to the size of the metal-clad laminate before the etching treatment,
The size of the laminate after performing the aging treatment of heating at 150 ° C. for 30 minutes after the etching treatment is reduced as compared with the size of the laminate after the etching treatment,
A method for producing a metal-clad laminate. When the dimension of the laminate after performing the etching treatment is a standard, the dimensional change rate of the laminate after the aging treatment is within a range of ± 0.03%.
The manufacturing method of the metal-clad laminated board of any one of Claims 7-9. Containing a filler in the resin composition,
The manufacturing method of the metal-clad laminated board of any one of Claims 7-10. Containing 50-80% by mass of the filler in the resin composition,
The method for producing a metal-clad laminate according to claim 11. The temperature increase rate during the heating and pressing in the step of curing the resin composition by heating and pressing the metal foil on the prepreg is 200 ° C./min or more,
The manufacturing method of the metal-clad laminated board of any one of Claims 7-12. A method for producing a printed wiring board in which a conductive pattern is formed on both sides or one side of an insulating layer impregnated with a resin composition on a glass cloth substrate and cured,
Including a step of forming the conductor pattern by removing unnecessary portions of the metal foil of the metal-clad laminate according to any one of claims 1 to 6.
Manufacturing method of printed wiring board. A method for producing a multilayer printed wiring board having three or more layers of conductor patterns,
Including a step of forming the conductor pattern by removing unnecessary portions of the metal foil of the metal-clad laminate according to any one of claims 1 to 6.
A method for producing a multilayer printed wiring board.

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