KR100791353B1 - Method of Forming Permanent Protective Film and Printed Circuit Board thereof - Google Patents

Abstract

A method of forming a permanent protective film and a printed circuit board on which a permanent protective film is formed are disclosed.

Laminating the thermosetting resin composition filling the conductor circuit to the printed circuit board, curing the thermosetting resin composition, and removing the thermosetting resin composition from 20% to 100% of the height of the conductor circuit so that a part of the conductor circuit The method of forming a permanent protective film and the printed circuit board manufactured by the method and the printed circuit board produced by the permanent protective film is easy to work and the thickness variation of the inner and outer sides of the permanent protective film is less, so there is little warpage or warpage and the surface smoothness is excellent. In addition to less peeling of the conductor circuit, the bonding property is good, and the heat resistance and moisture resistance after moisture absorption are excellent.

Permanent protective film, thermosetting resin, printed circuit board

Description

Method of forming a permanent protective film and a printed circuit board having a permanent protective film {Method of Forming Permanent Protective Film and Printed Circuit Board}

1 is a flow chart showing a method of forming a permanent protective film according to a first embodiment of the present invention.

2 is a cross-sectional view showing a state in which a thermosetting resin composition layer is formed on a printed circuit board in the method for forming a permanent protective film according to the first embodiment of the present invention.

3 is a cross-sectional view showing a state in which the thermosetting resin composition layer of FIG. 2 is removed at the same height as the conductor circuit.

Figure 4 is a flow chart showing a permanent protective film forming method according to a second embodiment of the present invention.

5 is a cross-sectional view showing a state in which a thermosetting resin composition and a film are placed on a printed circuit board in a method of forming a permanent protective film according to a second embodiment of the present invention.

6 is a cross-sectional view showing a state in which a thermosetting resin is filled between the conductor circuits by thermally compressing the film of FIG. 5.

7 is a cross-sectional view showing a state in which a part of the film of FIG. 6 is removed.

8 is a cross-sectional view showing a state in which the thermosetting resin of FIG. 7 is removed to the same height as the conductor circuit.

9 is a cross-sectional view showing a state in which a film remaining in FIG. 8 is removed.

10 is a flowchart illustrating a method of forming a permanent protective film according to a third embodiment of the present invention.

11 is a cross-sectional view showing a state in which a thermosetting resin composition and a metal foil are placed on a printed circuit board in a method of forming a permanent protective film according to a third embodiment of the present invention.

FIG. 12 is a cross-sectional view illustrating a state in which a thermosetting resin is filled between the conductor circuits by thermally compressing a metal foil in FIG. 11.

13 is a cross-sectional view showing a state in which a part of the metal foil is removed in FIG. 12.

14 is a cross-sectional view showing a state in which the thermosetting resin is removed to a height slightly higher than the conductor circuit in FIG.

15 is a cross-sectional view showing a state in which a metal foil remaining in FIG. 14 is removed.

16 is a cross-sectional view showing a state in which the thermosetting resin is removed to the same height as the conductor circuit height in FIG.

17 is a flowchart illustrating a method of forming a permanent protective film according to a fourth embodiment of the present invention.

18 is a cross-sectional view showing a state in which a thermosetting resin composition is formed on a printed circuit board in a method of forming a permanent protective film according to a fourth embodiment of the present invention.

FIG. 19 is a cross-sectional view illustrating a state in which a thermosetting receiving composition sheet is laminated in FIG. 18. FIG.

20 is a cross-sectional view showing a state in which a part of the release film is removed from FIG. 19.

FIG. 21 is a cross-sectional view illustrating a state in which a thermosetting resin composition is removed to a height of a conductor circuit in FIG. 20. FIG.

22 is a flow chart showing a permanent protective film forming method according to a fifth embodiment of the present invention.

FIG. 23 is a cross-sectional view illustrating a state in which a thermosetting resin composition is formed on a printed circuit board in a method of forming a permanent protective film according to a fifth embodiment of the present invention. FIG.

FIG. 24 is a cross-sectional view illustrating a state in which a thermosetting resin composition sheet is stacked in FIG. 23. FIG.

25 is a cross-sectional view illustrating a state in which a part of the metal foil is removed in FIG. 24.

FIG. 26 is a cross-sectional view illustrating a state in which the thermosetting resin composition is removed to slightly above the height of the conductor circuit in FIG. 25. FIG.

FIG. 27 is a cross-sectional view illustrating a state in which a metal foil remaining in FIG. 26 is removed. FIG.

28 is a cross-sectional view showing a state removed to the height of the conductor circuit of the thermosetting resin composition in FIG.

29 is a flowchart illustrating a method of forming a permanent protective film according to a sixth embodiment of the present invention.

30 is a flowchart illustrating a method of forming a permanent protective film according to a seventh embodiment of the present invention.

FIG. 31 is a cross-sectional view showing a state in which a permanent protective film is formed on a portion other than the wire bonding pad portion of a printed circuit board in the method of forming a permanent protective film according to the seventh embodiment of the present invention. FIG.

32 is a cross-sectional view illustrating a state in which a thermosetting resin composition is injected onto a wire bonding pad part of a printed circuit board in FIG. 31.

FIG. 33 is a cross-sectional view of a protective resin composition layer laminated on portions other than the wire bonding pad portion of the printed circuit board of FIG. 32;

FIG. 34 is a cross-sectional view illustrating a state in which a conductor circuit is exposed by removing the thermosetting resin composition of the wire bonding pad unit in FIG. 33. FIG.

35 is a cross-sectional view showing a state in which the protective resin composition layer is removed in FIG.

The present invention relates to a method of forming a permanent protective film of a printed circuit board and a printed circuit board on which a permanent protective film is formed, and more particularly, to form a permanent protective film having excellent reliability by filling a thermosetting resin up to 20% to 100% of a conductor circuit height. A method and a printed circuit board having a permanent protective film formed thereon.

As printed circuit boards become thinner and shorter, the width of the conductor circuit and the distance between the conductor circuits are 50 µm or less, and further, 25 µm or less. Under these fine conditions, the peeling of the conductor circuit occurs in the machining process, resulting in a drop in yield, and in thin plates, problems such as bending and warping occur. Moreover, various reliability problems, such as migration resistance and heat resistance after moisture absorption, arise.

In order to solve this problem, a permanent protective film was formed on the surface of a printed circuit board through a screen printing method using a thermosetting resin composition for a solder resist. However, the screen printing method has a bad position by printing on a printed circuit board having a fine circuit, and the resin solution overflows and adheres to the bonding pads, resulting in poor gold plating resulting in poor semiconductor chip bonding.

In addition, since conventional solution solder resists have irregularities that follow the conductor circuits, surface irregularities are large after drying, and negative film followability is poor, causing eccentricity after exposure and development. In addition, solvent type solder resists need to be double-coated to solve this problem because air bubbles remain in the holes when filling through holes and blind via holes (BVH) drilled in a printed circuit board. Bad sex and many bad. In addition, problems such as large deviations in the thickness of the permanent protective film between the inside and the outside, and the warpage and inaccuracy were increased.

In order to solve the problems of the solder resist as described above, UV (Ultra violet) selective thermosetting resists have been used in recent years. However, UV selective thermosetting resists contain many acrylic resins, unsaturated group-containing polycarboxylic acid resins, defoamers, leveling agents, photopolymerization initiators, and photosensitizers for exposure and development. There is a problem that falls in the solder resist of the thermosetting resin composition.

The present invention is derived to solve the problems of the prior art as described above,

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a permanent protective film having an easy forming process and excellent workability and a printed circuit board having a permanent protective film formed thereon.

Another object of the present invention is to provide a method for forming a permanent protective film having excellent filling property of resin into a through hole or blind via hole of a printed circuit board, and a printed circuit board having a permanent protective film formed thereon.

Another object of the present invention is to provide a permanent protective film forming method and a printed circuit board on which a permanent protective film is formed since the thickness variation of the inner and outer sides of the permanent protective film is small.

Still another object of the present invention is to provide a method for forming a permanent protective film having excellent surface smoothness and no circuit peeling and a printed circuit board having a permanent protective film formed thereon.

Still another object of the present invention is to provide a method of forming a permanent protective film having excellent bonding properties, excellent heat resistance and reliability after moisture absorption, and a printed circuit board having a permanent protective film formed thereon.

The present invention is implemented by the embodiment having the following configuration in order to achieve the above object.

The method of forming a permanent protective film according to the first embodiment of the present invention comprises the steps of laminating a thermosetting resin composition filling the conductive circuit on a printed circuit board, curing the thermosetting resin composition, and the thermosetting resin composition to the conductor circuit height Removing 20% to 100% of the portion so that a portion of the conductor circuit is exposed to the outside. The permanent protective film forming method according to the first embodiment of the present invention is easy to work and less thickness variation between the inside and the outside of the permanent protective film is less warpage or warpage and excellent surface smoothness. In addition, it is possible to form a permanent protective film having a low peeling of the conductor circuit and a good bonding property and excellent heat resistance and reliability after moisture absorption.

The thermosetting resin composition may be formed from a resin in which one or two or more selected from epoxy resins, cyanic acid ester resins, bismaleed resins, polyimide resins, functional group-containing polyphenylene ether resins, and cyanic acid ether resins are combined. In addition, the thermosetting resin composition is preferably formed of cyanic acid ester resin to prevent migration of the conductor circuit. It is preferable to add a non-halogen type flame retardant to the thermosetting resin composition. In addition, it is preferable to increase the curing rate by adding a curing agent or a thermosetting catalyst to the thermosetting resin composition. The thermosetting resin composition may be added one selected from the group consisting of an inorganic base, an organic base, and a mixed yarn mixed with an inorganic base and an organic base.

The thermosetting resin composition is removed by laser, router and plasma or a combination thereof.

The permanent protective film forming method according to the second embodiment of the present invention, the step of placing the thermosetting resin composition and the film filling the conductor circuit on the printed circuit board, and the step of curing the thermosetting resin composition by thermocompression bonding the film And removing a portion of the film, removing the thermosetting resin composition by 20% to 100% of the height of the conductor circuit so that a portion of the conductor circuit is exposed to the outside, and removing the remaining film. . As the film, a release film or a heat-resistant organic film may be used.

The release film is preferably a film that can be developed with UV exposure and dilute alkali solution. Moreover, it is preferable that a heat resistant organic film is a liquid crystal polyester resin film. The film is preferably removed to be somewhat smaller than the removal area of the thermosetting resin composition.

The permanent protective film forming method according to the second embodiment of the present invention is easy to work and excellent in filling of the resin into the hole. In addition, since the thickness variation between the inner and outer sides of the permanent protective film is small, the warpage and the warpage are small and the surface smoothness is excellent, so that the peeling of the conductor circuit can be reduced. In addition, it is possible to form a permanent protective film having good bonding properties and excellent heat resistance and reliability after moisture absorption.

The permanent protective film forming method according to the third embodiment of the present invention, the step of placing the thermosetting resin composition and the metal foil on the printed circuit board to fill the conductor circuit, and the step of curing the thermosetting resin composition by the metal foil thermocompression bonding And removing a portion of the metal foil, removing the thermosetting resin composition to a little above the conductor circuit, removing the remaining metal foil, and removing the thermosetting resin composition from 20% to 100% of the conductor circuit height. It includes a step.

The thermosetting resin composition is removed by plasma treatment. The B stage thermosetting resin composition is cured by thermocompression bonding the film in a vacuum state using a flat plate. The metal foil can be removed by etching.

The permanent protective film forming method according to the fourth embodiment of the present invention comprises the steps of forming a thermosetting resin composition filling the conductor circuit on the printed circuit board, and attaching the thermosetting resin composition to the release film to form a thermosetting resin composition sheet Manufacturing, laminating the thermosetting resin composition sheet on the printed circuit board coated with the thermosetting resin composition, removing a part of the release film, and setting the thermosetting resin composition to 20% to 100% of the height of the conductor circuit. Removing a portion of the conductor circuit to the outside and removing the remaining release film.

The permanent protective film forming method according to the fifth embodiment of the present invention comprises the steps of forming a thermosetting resin composition filling the conductor circuit on the printed circuit board, and attaching the thermosetting resin composition to the metal foil to produce a thermosetting resin composition sheet Laminating the thermosetting resin composition sheet on the printed circuit board to which the thermosetting resin composition has been applied, removing a portion of the metal foil, removing the thermosetting resin composition to slightly above the conductor circuit, and Removing the metal foil; and removing the thermosetting resin composition to 20% to 100% of the height of the conductor circuit.

In the fourth to fifth embodiments of the present invention, it is preferable that the thermosetting resin composition is treated by plasma. And the thermosetting resin composition sheet | seat can be manufactured by affixing the thing which formed the thermosetting resin composition on both surfaces of a heat resistant organic film to metal foil or a release film. It is preferable to include an organic fiber cloth base material or an inorganic fiber cloth base material in the thermosetting resin of a thermosetting resin composition sheet. And it is preferable that a thermosetting resin composition has non-halogen and flame retardancy.

The permanent protective film forming method according to the sixth embodiment of the present invention comprises the steps of laminating a thermoplastic resin composition having a melting point of 270 ℃ or more on a printed circuit board, filling the conductor circuit, curing the thermoplastic resin composition, thermoplastic resin Removing the composition by 20 to 100% of the height of the conductor circuit to expose a portion of the conductor circuit to the outside. The thermoplastic resin composition may be a liquid crystal polyester resin composition. And the thermoplastic resin composition is preferably non-halogen and flame retardant.

The permanent protective film forming method according to the seventh embodiment of the present invention comprises the steps of forming a permanent protective film on the portion other than the wire bonding pad portion of the printed circuit board, and injecting the thermosetting resin composition into the wire bonding pad portion on the printed circuit board And then curing or semi-curing, and removing the thermosetting resin composition to expose the conductor circuit.

After curing or semi-curing the thermosetting resin composition may further comprise the step of laminating a protective resin composition layer on a portion other than the wire bonding pad portion of the printed circuit board, and exposing the conductor circuit and removing the protective resin composition layer. have.

It is preferable that a protective resin composition layer is a resin composition which can be photo-exposed and can develop alkali, and it is preferable that it is a cyanic acid ester resin composition specifically ,.

In the method of forming a permanent protective film according to the eighth embodiment of the present invention, in the seventh embodiment, the thermosetting resin composition is filled to 25 to 100% of the height of the conductor circuit.

Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings, in the following description with reference to the accompanying drawings, the same or corresponding components are given the same reference numerals regardless of the reference numerals and Duplicate explanations will be omitted.

1 is a flowchart of a method for forming a permanent protective film according to a first embodiment of the present invention. As shown in Figure 1, the permanent protective film forming method of the present invention comprises the steps of forming a thermosetting resin composition layer on a printed circuit board (S11), curing the thermosetting resin composition layer (S13), and a thermosetting resin composition Removing the layer to 20% to 100% of the height of the conductor circuit (S15).

2 is a cross-sectional view showing a state in which the thermosetting resin composition layer 15 is formed on the printed circuit board 11 in step S11. As shown in FIG. 2, the printed circuit board 11 is formed with a conductor circuit 13 having a constant width and spacing. In addition, a hole such as a through hole, a blind via hole, or the like may be formed in the printed circuit board 11. The permanent protective film forming method of the present invention is suitable for use in a printed circuit board having a width and a spacing of the conductor circuit 13 of 25 µm or less.

The method of forming the thermosetting resin composition layer 15 in the step S11 is formed by applying the thermosetting resin composition on one or both sides of the printed circuit board or printing by screen printing, and then curing the thermosetting resin composition. The height of the thermosetting resin composition layer 15 is formed somewhat higher than the height of the conductor circuit 13. Although the thickness of the thermosetting resin composition layer 15 is not particularly limited, 20 μm to 100 μm is suitable, and a thickness sufficient to bury the conductor circuit 13 is sufficient. The thickness of the thermosetting resin composition layer 15 may be appropriately selected depending on the thickness of the conductor circuit 13 and the copper residual ratio.

The thermosetting resin composition 15 has a composition in which resins such as epoxy resins, cyanic acid ester resins, bismaleimide resins, polyimide resins, and functional group-containing polyphenylene ether resins are used alone or in combination. Cyanic acid ester resin is suitable for preventing migration between the conductor circuits 13. Moreover, what flame-retarded resin with bromine can also be used.

The thermosetting resin composition 15 may be cultured various additives. For example, various additives such as thermoreversible resins, organic fillers, inorganic fillers, dyes, pigments, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, brightening agents, polymerization initiators, thixotropic agents, and the like are added according to the purpose and use. In addition, a flame retardant, flame retardant with bromine, non-halogen (non-halogen) type of flame retardant may be used, and non-flame retardant may be used. The printed circuit board 11 and the thermosetting resin composition layer 15 used as a permanent protective film may be formed of a non-halogen flame-retardant UV94V-0 printed circuit board by using a non-halogen type UL94V-0. . A non-halogen flame retardant can use a well-known thing. In addition, the non-halogen standard preferably has a content of bromine and chlorine of less than 900 ppm.

The thermosetting resin composition layer 15 is cured by heating itself, but a hardening agent or a thermosetting catalyst may be added to the thermosetting resin composition layer 15 in order to increase the curing rate and improve productivity.

A reinforcing base may be added to the thermosetting resin composition layer 15. As the reinforcing base material, organic or inorganic base materials can be used. As the organic substrate, a woven fabric, a nonwoven fabric, or the like produced using fibers such as polyoxazole fiber, wholly aromatic polyamide fiber, liquid crystalline polyester fiber, or the like can be used. As an inorganic base material, well-known glass fiber woven fabrics, nonwoven fabrics, such as E, S, T, NE, and D glass are mentioned. In addition, a mixed cloth of organic and inorganic substrates may be used. Generally the thickness of an organic base material or an inorganic base material is 10 micrometers-100 micrometers. It is suitable that the organic base material and the inorganic base material have been treated to improve the adhesion with the thermosetting resin. By adding organic or inorganic intercalation to the thermosetting resin composition layer 15, the overall strength of the printed circuit board can be increased and the hygroscopicity from the surface can be reduced, thereby improving reliability.

The method of attaching the organic base material and the inorganic base material and the thermosetting resin is made by continuously passing the substrate in the thermosetting resin composition solution, impregnating the thermosetting resin composition, and then passing it through a heating furnace to dry and wet the stage.

A protective film such as a polypropylene film or a heat resistant organic film may be laminated on the thermosetting resin composition. A polyimide film, a polyoxadiazole film, a wholly aromatic polyamide film, a liquid crystalline polyester film, etc. can be used as a heat resistant organic film. There is no restriction on the thickness of the protective film or the heat-resistant organic film, but in general, the thickness is preferably 10 μm to 70 μm.

3 is a cross-sectional view illustrating a state in which the top surface of the conductor circuit 13 is exposed to the outside by removing the thermosetting resin composition layer 15 by the step S15. The thermosetting resin composition layer 15 may be removed by machining, such as a laser or a router, or may be removed by plasma processing. In particular, plasma processing has the advantage that the thermosetting resin composition layer 15 can be precisely processed to a desired height.

The thermosetting resin composition layer 15 is removed until it becomes 20% to 100% of the height of the conductor circuit 13. The height of the thermosetting resin composition layer 15 is preferably the same as the height of the conductor circuit (13). When the height of the thermosetting resin composition layer 15 is less than 20%, the likelihood of peeling of the conductor circuit 13 increases, and when 100% or more, precious metal plating such as gold and nickel may be performed on the conductor circuit 13. It becomes impossible. The thermosetting resin composition layer 15 filled between the conductor circuits 13 does not cause peeling of the conductor circuits 13 even in a microcircuit having a circuit width and a circuit spacing (L / S) of 25 μm, respectively. .

4 is a flowchart illustrating a method of forming a permanent protective film according to a second embodiment of the present invention. In the method of forming a permanent protective film according to a second embodiment of the present invention, the step of placing the thermosetting resin composition and the film on a printed circuit board (S17), and curing the film by laminating the thermosetting resin composition by thermocompression bonding the film ( S19), removing a portion of the film (S21), removing the thermosetting resin composition from 20% to 100% of the height of the conductor circuit (S23), and removing the remaining film (S25). .

5 is a cross-sectional view illustrating a step S17 of sequentially placing the film 17 and the thermosetting resin composition 15 on one surface of the printed circuit board 11. The thermosetting resin composition 15 and the film 17 are sequentially positioned on the printed circuit board 11. The thickness of the thermosetting resin composition 15 is greater than the height of the conductor circuit 13.

The components of the thermosetting resin composition 15 and additives such as a flame retardant, a curing agent, and a reinforcing base are as described above. The film 17 may be a release film or a heat-resistant organic film.

As the release film, a polyethylene terephthalate film, a polybutylene terephthalate film, or the like is used. The surface of the release film can be used both untreated and release agent treated. There is no particular limitation on the thickness of the release film, but generally 10 μm to 50 μm are suitable. When the release film is used as the film 17, a film-based reinforcement base may be used for the thermosetting resin composition 15. As such a reinforcing base material, heat-resistant films, such as a polyimide film, a polyoxazole film, a wholly aromatic polyamide film, and a liquid crystalline polyester film, are mentioned. In order to facilitate the removal of the release film, an etching film which can be developed with a dilute aqueous alkali solution while being capable of UV exposure may be used.

As the heat-resistant organic film, a polyimide film, a polyoxazole film, a wholly aromatic polyamide film, a liquid crystal polyester film, or the like can be used. There is no particular limitation on the thickness of the heat-resistant organic film, but generally 10 μm to 100 μm is used. The heat-resistant organic film can also be subjected to surface treatment for improving adhesion with the resin. As the heat-resistant organic film, it is preferable to use liquid crystalline polyester which can improve reliability because it is excellent in moisture permeability and can reduce moisture absorption from the surface.

6 is a cross-sectional view showing a state of curing by laminating the thermosetting resin composition 15 by thermocompression bonding the film 17 by the step S19. The thermosetting resin composition 15 is laminated and cured by heating and compressing the film 17 by a smooth plane. The heating temperature and pressure may vary depending on the type and flowability of the thermosetting resin composition, but are generally cured for about 1 to 120 minutes in a vacuum at a temperature of 100 ° C. to 300 ° C. and a pressure of 1 kgf / cm 2 to 50 kgf / cm 2. If the degree of curing is appropriately treated by plasma treatment or the like, curing is performed to such an extent that no defects are generated. In the case of semi-hardening, it is processed by plasma etc. and then post-heat-hardened.

Since the thermosetting resin composition 15 is thermocompressed by a smooth flat plate, the present invention is excellent in workability and also excellent in filling property for the energizing hole and the blind via hole. In addition, since the pressure is uniformly transmitted to the entire thermosetting resin composition 15 by the flat plate, the thickness variation between the inside and the outside of the permanent protective film can be reduced, and the bending and warping of the permanent protective film can be prevented. We can plan. In addition, since the thermocompression and curing are performed in a vacuum state, bubbles are not generated in the energizing hole or the blade via hole.

7 is a cross-sectional view showing a state in which a part of the film 17 is removed by the step S21. As the method of removing the film 17, various methods such as machining or plasma processing by a router or a laser may be used. When the film 17 is an etching film, it can be removed by exposing and developing a negative film, and when the film 17 is difficult to dissolve, such as polyethylene terephthalate, it can be machined using a laser or a router. Can be. When the film 17 is a heat-resistant organic film, a flat plate (not shown) having an upper portion of the noble metal plating portion of the printed circuit board may be closely adhered or temporarily bonded to the heat-resistant organic film, and may be plasma-treated or sandblasted. It can also be processed by laser or router machining. At this time, the heat-resistant organic film and the thermosetting resin composition 15 may be simultaneously processed.

8 is a cross-sectional view illustrating a state in which the conductor circuit 13 is exposed to the outside by removing the thermosetting resin composition 15 by the step S23. The thermosetting resin composition 15 may be removed by various methods such as machining or plasma processing by a router, a laser and a sand blast. And a combination of machining and plasma reaction may be used. In particular, in the case of using a plasma process, there is an advantage in that the thermosetting resin composition layer 15 can be accurately removed to a desired height. The thermosetting resin composition 15 is removed from 20% to 100% of the height of the conductor circuit 13. In particular, when the thickness of the thermosetting resin composition 15 is equal to the height of the conductor circuit 13, the reinforcing effect of the thermosetting resin composition 15 on the conductor circuit 13 is increased, so that the separation of the conductor circuit 13 is prevented. You can eliminate it.

9 is a cross-sectional view showing a state in which the film 17 is removed by the step S25. After the processing for the thermosetting resin composition 15 is finished, the remaining film 17 is removed. Of course, the film 17 may be completely removed before machining such as a router, it is preferable to process with the film attached in order to prevent adhesion or contamination of the processing debris. Thereafter, the exposed conductor circuit 13 is subjected to nickel or gold plating.

10 is a flowchart illustrating a method of forming a permanent protective film according to a third embodiment of the present invention. The permanent protective film forming method according to the third embodiment of the present invention comprises the steps of placing the thermosetting resin composition and the metal foil on the printed circuit board (S27), the step of curing while laminating the thermosetting resin composition by thermocompression bonding the metal foil (S29), Removing a portion of the metal foil (S31), removing the thermosetting resin composition up to slightly above the conductor circuit (S33), removing the remaining metal foil (S35), and removing the thermosetting resin composition from 20% of the height of the conductor circuit. Removing up to 100%.

FIG. 11 is a cross-sectional view illustrating the step S27 of sequentially placing the thermosetting resin composition 15 and the metal foil 19 on the printed circuit board 11. The thermosetting resin composition 15 and the metal foil 19 are sequentially stacked on one or both surfaces of the printed circuit board 11.

As the metal foil 19, an electrolytic copper foil, a rolled copper foil, nickel foil, iron foil, aluminum foil and an alloy of these metals are used. There is no particular limitation on the thickness, but it is better to have a thinner thickness in order to finally remove the melt. Generally 3 micrometers-18 micrometers are used. In the case where the metal foil 19 is thin, since the carrier foil and the like are adhered to each other, the price is high, and therefore, 9 μm to 12 μm without the carrier foil is preferable.

As a method of attaching the thermosetting resin composition 15 to the metal foil 19 to form a sheet, for example, a roll coater is used to continuously apply and dry the thermosetting resin composition to form a B stage. There is a way to make it. When the thermosetting resin composition 15 is attached to an organic or inorganic fiber substrate, the substrate is continuously passed through the thermosetting resin composition to impregnate the thermosetting resin composition, followed by drying in a heating furnace to make a B stage. Produced by Finally, when it is finally taken out of the drying furnace, it may be wound as it is.The protective film, for example, a polypropylene film or the like, is press-bonded to the thermosetting resin composition and integrated to cover the B-stage thermosetting resin composition with a protective film. You can also

In order to attach the metal foil 19 to the film base material, a sheet having a B-stage thermosetting resin composition attached thereto is disposed on the metal foil 19, and on the opposite side, the B-stage thermosetting resin is disposed on one side of a release film such as a PET film. The method which arrange | positions the sheet | seat with a composition, laminates it with a press roll, and integrates is used. The thickness of the thermosetting resin composition 15 adhered to both surfaces is preferably a thickness capable of filling the conductor circuit 13, but preferably 20 µm to 100 µm. Then, the thickness of the thermosetting resin composition layer is selected according to the thickness of the conductor circuit and the copper residual ratio. The metal foil 19 is disposed outward so that the PET film is peeled off and the thermosetting resin composition 15 faces the printed circuit board 11 on the surface of the printed circuit board 11 on which the conductor circuit 13 is formed. After lamination. Lamination conditions are selected according to the kind, flowability, etc. of the thermosetting resin composition 15. Generally, the temperature is 100 ° C. to 300 ° C., and the pressure is 1 kgf / cm 2 to 50 kgf / cm 2, and cured by thermocompression bonding for 1 to 120 minutes in vacuum, if possible, for 2 to 90 minutes.

Figure 13 is a short shave showing a state in which a part of the metal foil 19 in accordance with step S31 is removed. The metal foil 19 on the conductor circuit 13 which performs noble metal plating among the metal foils 19 is removed through exposure and development using an etching film. In addition, the metal foil 19 may be removed through a machining process such as a router or a laser.

14 is a cross-sectional view showing a state in which the thermosetting resin composition 15 is removed to a position slightly higher than the conductor circuit 13 through the portion where the metal foil 19 is removed by the step S33. The thermosetting resin composition 15 is removed to a little above the conductor circuit 13 by a plasma, a router, a sandblaster, or the like. This is to prevent the exposed conductor circuit 13 from being damaged by etching when etching to remove the remaining metal foil 19. The method of removing the thermosetting resin composition 15 may be a router, a laser, a sand blast, and a plasma method. Since the method has already been described, a detailed description thereof will be omitted.

15 is a cross-sectional view showing a state in which the metal foil 19 remaining in the step S35 is removed through etching. The metal foil 19 is removed by etching. At this time, since the conductor circuit 13 is protected by the thermosetting resin composition 15, the etching solution does not damage the conductor circuit 13.

FIG. 16 is a cross-sectional view illustrating a state in which the thermosetting resin composition 15 is removed to the same height as the conductor circuit 13 after the metal foil 19 is completely removed by the step S37. The thermosetting resin composition 15 is removed from 20% to 100% of the height of the conductor circuit 13, preferably 100% for the reinforcement of the conductor circuit 13 by the thermosetting resin composition 15. Since the method of removing the thermosetting resin composition 15 has already been described, a detailed description thereof will be omitted.

When the thermosetting resin composition 15 is removed by a plasma process, the size of the portion from which the metal foil 19 and the thermosetting resin composition 15 is removed is made somewhat smaller than the size of the portion to be actually processed. This is because, when the plasma process processes the thermosetting resin composition 15 in the depth direction, the machining proceeds in the transverse direction at the same time. In the case of machining by a router or the like, it is preferable to add an inorganic filler to the thermosetting resin composition 15. In addition, when the area to be processed is large, it is preferable to use a plasma or a router, and when the area is small, a laser is used to reduce the positional difference as much as possible. Nickel or gold plating is applied to the exposed conductor circuit 13.

17 is a flowchart illustrating a method of forming a permanent protective film according to a fourth embodiment of the present invention. As shown in FIG. 17, in the method of forming a permanent protective film according to the present invention, the thermosetting resin composition 15 is formed on the printed circuit board 11 (S39), and the thermosetting resin composition 15 is formed on the release film 21. ) Attaching the thermosetting resin composition sheet 23 to (S41), laminating the thermosetting resin composition sheet 23 on the printed circuit board 11 (S43), the release film 21 Removing a portion of (S45), removing the thermosetting resin composition 15 to 20 to 100% of the height of the conductor circuit 13 (S47) and removing the remaining release film 21 (S49) ).

Hereinafter, a permanent protective film forming method according to a fourth embodiment of the present invention will be described in more detail with reference to FIGS. 18 to 21.

FIG. 18 is a cross-sectional view illustrating a state in which the thermosetting resin composition 15 is formed on the printed circuit board 11. Since the type and formation method of the printed circuit board 11 and the thermosetting resin composition 15 are the same as in the above-described embodiment, a detailed description thereof will be omitted. In addition, the organic or inorganic substrate may be added to the thermosetting resin composition 15 as in the present embodiment.

The thermosetting resin composition 15 is applied slightly higher than the conductor circuit 13. As a coating method, a printed circuit board is first manufactured and subjected to known treatments such as black copper oxide treatment, oxidation treatment such as brown copper oxide treatment, and surface unevenness forming chemical treatment such as Cc treatment of Mec Corporation. Then, the solution of the moderate viscosity melt | dissolved in the liquid thermosetting resin composition or solvent of 100% of solid content on both surfaces is apply | coated by well-known methods, such as the screen printing method and the curtain court method. After that, when heated and the solvent is contained, it is blown to make B stage.

FIG. 19 is a cross-sectional view illustrating a state in which the thermosetting resin composition sheet 23 is laminated in FIG. 18. Since the release film 21 or the thermosetting resin composition 15 of the thermosetting resin composition sheet 23 is the same as in the present embodiment, a detailed description thereof will be omitted.

The thermosetting resin composition sheet 23 is to attach the thermosetting resin composition 15 to the release film. As a method of manufacturing the thermosetting resin composition sheet 23, a generally known method may be used. For example, when continuously applying a thermosetting resin composition solution in a roll coater and attaching it to an inorganic or organic fiber cloth substrate, the substrate is continuously passed through a thermosetting resin composition solution to impregnate the resin composition and then passed through a heating furnace. It is made by the method of making it dry and heat-stage. Finally, when the drying furnace is released, it can be wound as it is, and the protective film, for example, polypropylene film, is pressed onto the thermosetting resin composition to laminate and integrated, and the thermosetting resin composition is coated with the protective film. It is also possible.

When the thermosetting resin composition 15 is attached to the heat-resistant organic film substrate, a sheet having a thermosetting resin composition attached to one side of a release film or a metal foil on one side thereof, and the other side of the thermosetting resin composition on one side of the release film A well-known method can be used, such as arrange | positioning this attached sheet, laminating | stacking with a heating roll, and integrally manufacturing. The thickness of the thermosetting resin composition layer to be attached is not particularly limited, and the best thickness is 10 to 100 μm, and the thickness of the thermosetting resin composition layer may be determined by the thickness of the conductor circuit and the copper residual ratio. Choose appropriately. In the case of use, the release film or the protective film is peeled off, and then the release film is placed outward so that the thermosetting resin composition faces the printed circuit board on the surface of the printed circuit board on which the conductor circuit is formed. Are bonded under heating, pressurization and vacuum. Moreover, it is also possible to apply a smooth hot plate directly, and to apply | coat and harden under pressurization and a vacuum. In this case, although the surface does not need to be smooth, a smooth flat plate is preferable also in appearance and prevention of subsequent outflow of resin. In addition, underfill resin flows uniformly in a flip chip mounted printed circuit board.

When the thermosetting resin composition sheet 23 is thermally laminated and pressed onto the printed circuit board 11, there is no special lamination condition, and it is selected according to the type of resin, flowability, or the like. In general, the temperature is preferably 100 to 300 ° C. under pressure of 1 to 50 kgf / cm ² under vacuum for 1 to 120 minutes and 2 to 90 minutes to be integrated to form a substrate.

FIG. 20 is a cross-sectional view illustrating a state in which the release film 21 of the portion of the printed circuit board 11 of FIG. 19 to be plated is removed. The release film is removed by a plasma, a laser, a router, and the like, as described above in the embodiments described above, so a detailed description thereof will be omitted.

FIG. 21 is a cross-sectional view illustrating a state in which the release film 21 is removed after removing the thermosetting resin composition 15 to the same height as the conductor circuit 13 in FIG. 20. As the method of removing the thermosetting resin composition 15, a known method such as a plasma, a router, a laser, and the like described above is used. And the method of removing the release film 21 is also as described above.

22 is a flowchart illustrating a method of forming a permanent protective film according to a fifth embodiment of the present invention. The method of forming a permanent protective film as shown in Figure 22 is a step of forming a thermosetting resin composition filling the conductor circuit on the printed circuit board (S51), by attaching the thermosetting resin composition to the metal foil to produce a thermosetting resin composition sheet Step (S53), the step of laminating the thermosetting resin composition sheet on a printed circuit board coated with a thermosetting resin composition (S55), removing a portion of the metal foil (S57), the thermosetting resin composition slightly above the conductor circuit Removing (S59), removing the remaining metal foil (S61), the step of removing the thermosetting resin composition to 20% ~ 100% of the height of the conductor circuit (S63).

Hereinafter, the steps S51 to S61 will be described with reference to FIGS. 23 to 28.

FIG. 23 is a cross-sectional view illustrating a state in which the thermosetting resin composition 15 is formed on the printed circuit board 11 in the method of forming a permanent protective film according to the fifth embodiment. Since the method of manufacturing the printed circuit board 11 and the thermosetting resin composition 15 and the method of applying the thermosetting resin composition 15 are the same as in the fourth embodiment, detailed description thereof will be omitted.

FIG. 24 shows the curable resin composition sheet 23 'made of the metal foil 19 and the thermosetting resin composition 15 in FIG. 23, on the printed circuit board 11 to which the thermosetting resin composition 15 is applied. Indicates the state according to the stage.

The metal foil 19 is not particularly limited, and generally known ones can be used. Specifically, electrolytic copper foil, rolled copper foil, nickel foil, iron foil, aluminum foil, etc. Furthermore, these alloy foils can be used. The thickness is not particularly limited, but the thickness is preferably thinner because it is finally dissolved and removed. Generally 3-18 micrometers is used. In the case of being thin, since carrier foil etc. are adhered and a unit price rises, 9-12 micrometers with no carrier foil is most preferable.

Since the bonding method between the metal foil 19 and the thermosetting resin composition 15 and the laminating method of the thermosetting resin composition sheet 23 ′ are the same as in the above-described fourth embodiment, a detailed description thereof will be omitted.

FIG. 25 is a cross-sectional view taken along the step S57 showing a state in which a portion of the metal foil 19 of a portion where a noble metal is to be formed is removed in FIG. 24. The metal foil 19 is removed by etching or the like, and the detailed description thereof is the same as in the present embodiment.

FIG. 26 is a cross-sectional view taken along the step S59 in which the thermosetting resin composition 15 of the portion where the metal foil 19 is removed in FIG. 25 is removed to slightly above the conductor circuit 15. The remaining metal foil 19 is later removed by etching or the like, in which part of the thermosetting resin composition 15 is removed. Therefore, the thermosetting resin composition 15 is preferably removed to a little above the conductor circuit (13).

FIG. 27 is a cross-sectional view according to the step S61 showing the state in which the metal foil 19 is removed from FIG. 26, and FIG. 28 shows the state in which the thermosetting resin composition 15 is removed to the same height as the conductor circuit 13 in FIG. 27. Sectional drawing in accordance with step S63. 27 and 28, the metal foil 19 and the thermosetting resin composition 15 are removed as described above.

28 is a flow diagram illustrating a method of forming a permanent protective film according to a sixth embodiment of the present invention. As shown in FIG. 28, the method for forming a permanent protective film according to the sixth embodiment of the present invention comprises the steps of laminating a thermoplastic resin composition having a melting point of 270 ° C. or more on a printed circuit board (S65), and stacking the laminated thermoplastic resin composition. Curing step (S67) and removing the thermoplastic resin composition to 20 ~ 100% of the height of the conductor circuit.

The thermoplastic resin may be generally known. Specifically, known thermoplastic resin compositions having a melting point of 270 ° C. or higher, such as liquid crystalline polyester resins and polyphenylene ether resins, are used alone or in combination of two or more thereof. Moreover, what mix | blended various well-known additives with resin is generally used as a resin composition. For example, various additives, such as a small amount of thermosetting resins, well-known inorganic fillers, dyes, pigments, and a defoaming agent, are added according to a purpose and a use. In addition, flame retardants such as flame retardant, bromine flame retardant and non-halogen flame retardant can be used, and any non-flame retardant can be used, but it can be used as printed circuit board and permanent protective film. The thermoplastic resin composition can be made non-halogen and flame retardant UL94V-0 printed circuit board by using non-halogen flame retardant or possibly UL94V-0. As a non-halogen flame retardant, a well-known thing can be used. In addition, the non-halogen standard should be less than 900ppm of bromine and chlorine in the IPC and JPCA standards, so that the value is satisfied.

The thermoplastic resin of the present invention uses a melting point of 270 占 폚 or higher, or possibly 280-310 占 폚. This is to prevent defects such as softening, dropping, and scratching of the thermoplastic resin composition during component mounting. If the temperature is high, the resin may decompose the constituents, thereby causing defects. This is determined by looking at the heat resistance of the resin composition to be used. A thermoplastic resin composition makes it easy to use by defining molecular weight, melting | fusing point, viscosity, etc. by an additive. The thermoplastic resin composition to be used may be any of a solution dissolved in a solvent, a solvent-free flake, and a sheet, but a sheet is more suitable.

There is no restriction | limiting in particular in the manufacturing method, The thing manufactured by a well-known method is used. The thickness of the thermoplastic resin composition is not particularly limited, but the thickness is preferably 20 to 100 μm, and the thickness of the conductor circuit and the hole can be filled, and the thickness is appropriately selected according to the thickness of the conductor circuit, copper residual ratio, hole size, and number. .

Thereafter, the release film on the outside is placed on the surface of the printed circuit board on which the conductor circuit is formed, and a flat plate with a smooth surface is placed on the outside to be bonded under heating, pressure, and vacuum. Alternatively, the heat plate may be directly bonded to the hardened plate under pressure and vacuum.

When the lamination and curing of the thermoplastic resin composition are completed by the steps S65 and S67, the thermoplastic resin composition is removed by 20 to 100% of the height of the conductor circuit by the step S69. The removal method is not particularly limited, and for example, a plate having a noble metal plating conductor circuit can be adhered or temporarily adhered to the substrate to be processed and removed by plasma treatment, sand blasting, or machining such as laser or luther. And a method of processing and removing the same by a combination thereof, but are not limited thereto. In this case, in the thin wire circuit, the thermoplastic resin composition is processed to a surface of the conductor circuit by plasma or the like, and the inter-circuit portion is filled with resin.

The height is preferably 20 to 100% of the height of the conductor circuit, more preferably about the same level. In this case, in the case of an ultrafine circuit, the conductor circuit peeling in the process is eliminated. Of course, the height of the thermoplastic resin composition layer between the circuits may be less than 20% of the circuit height, but if possible, the reinforcing effect of the circuit is increased by making the height of the thermoplastic resin composition layer 20 to 100% of the height of the thin wire conductor circuit or about the same height. It can eliminate the peeling defect. Part of the circuit that exposes the flip chip bumps on the solder ball pad or the surface of the back is plasma or laser, but it is sufficient to expose the circuit surface when not processing the thermoplastic resin composition layer around the circuit. Do. In addition, when the thermosetting resin composition is protruded out of the circuit and processed, the thermoplastic resin composition layer is preferably 20 to 100% of the height of the conductor circuit, and the best is almost the same height. By doing so, it is possible to obtain a strong solder ball lateral shear strength attached to an increasingly smaller solder ball pad.

30 is a flowchart illustrating a method of forming a permanent protective film according to a seventh embodiment of the present invention. In the method of forming a permanent protective film as shown in FIG. 30, the step of forming a permanent protective film on a portion other than the wire bonding pad portion of the printed circuit board (S71), injecting the thermosetting resin composition into the wire bonding pad portion on the printed circuit board After curing or semi-curing (S73), laminating a protective resin composition layer on a portion other than the wire bonding pad portion (S75), removing the thermosetting resin composition to expose the conductor circuit (S77) and protective resin Removing the composition layer (S79).

Hereinafter, a method of forming a permanent protective film according to a seventh embodiment of the present invention will be described with reference to FIGS. 31 to 35.

FIG. 31 is a cross-sectional view showing a state where the permanent protective film 25 is formed on portions other than the wire bonding pad portions of the printed circuit board 11. As the permanent protective film 25, a known one such as a thermosetting resin composition, a thermoplastic resin composition or a photoselective resin composition may be used. These can be applied by screen printing or the like on a solution, drying, curing, heat pressing on a sheet, then exposure, developing, thermosetting, heat pressing on a sheet having a bonding pad removed in advance. Finally, all of the wire bonding pad portions of the printed circuit board 11 are opened to have a concave shape.

The permanent protective film 25 may be a resin composition alone, but may contain a reinforcement base therein. Examples of the substrate include organic and inorganic substrates. These are not particularly limited, and for example, organic substrates include polyoxazole fibers, wholly aromatic polyamide fibers, wholly aromatic polyamide fibers, liquid crystalline polyester fibers, and the like. A well-known glass fiber woven fabric and nonwoven fabric, such as E, S, T, N, E, D glass, are mentioned. Moreover, these mixed cloths are mentioned. Moreover, a well-known thing can be used as a film-form base material, For example, heat resistant films, such as a polyimide film, a polyoxazole film, a wholly aromatic polyamide film, and a liquid crystalline polyester film, can be used. However, release films, such as PET film, are not used. It is suitable that these base materials gave well-known treatment to the surface of a base material in order to improve adhesiveness with resin. As the thermoplastic resin composition, a liquid crystal polyester sheet or the like is used.

FIG. 32 is a cross-sectional view illustrating a state in which the thermosetting resin composition 15 is injected into the wire bonding pad part on the printed circuit board 11 of FIG. 31 and then cured.

The thermosetting resin composition 15, such as a cyanic acid ester resin composition, is filled between the conductor circuits 13 of the wire bonding pad portion to be cured or cured. In the case of a solution, it flows, it is dried by heating, and a post-cure is carried out after blowing a solvent. In addition, in the case of a solvent-free, it flows as it is, and semi-hardens or hardens. In this case, it is cured after degassing in a vacuum so that bubbles do not enter the resin composition.

The method of injecting the thermosetting resin composition 15 is not particularly limited, but may be injected into a dispenser or the like so as not to adhere to the permanent protective film 25. The filling height is not particularly limited, but is preferably lower than that of the permanent protective film 25. In addition, it is charged to be slightly higher than the height of the conductor circuit (13).

There is no particular limitation on the degree of curing of the thermosetting resin composition 15 injected therein, and the degree of curing is easy to be processed by processing such as plasma and laser. In the case of semi-hardening, the said thermosetting resin composition 15 is post-cured and hardened | cured after processing.

Although no treatment may be required on the surface of the conductor circuit 13 of the wire bonding pad portion, a best known chemical treatment, for example, black copper oxide treatment, brown, is used to improve adhesion of the thermosetting resin composition 15. It is preferable to perform surface uneven | corrugated formation chemical treatment, such as oxidation treatment, such as copper oxide treatment, and Cb treatment of Mec Corporation.

FIG. 33 is a cross-sectional view illustrating a state in which the protective resin composition layer 27 is laminated on portions other than the wire bonding pad portion in the printed circuit board 11 of FIG. 32.

As the protective resin composition layer 27, generally known ones such as a sheet having a resin composition having an adhesive property attached to one side of a release film such as a PET film, a liquid photoselective thermosetting resist, and this sheet type can be used. It is preferable to use a photoselective thermosetting resist as a coating for protection from the viewpoint of workability, position accuracy, adhesion of a printed circuit board having a permanent protective coating, peeling property, and the like. The thickness is not particularly limited, but in general, 10 to 50 μm is used as the surface layer. At the time of processing, the part which inject | poured the said thermosetting resin composition 15 removes the protective resin composition layer 27. The protective resin composition layer 27 is peeled off after processing the bonding pad part by plasma. When a photoselective thermosetting resist is used as a protective film, it is dissolved and removed by the aqueous alkali solution.

FIG. 34 is a cross-sectional view illustrating a state in which a part of the conductor circuit 13 is removed by removing the thermosetting resin composition 15 from FIG. 33. The thermosetting resin composition 15 is removed to 20 to 100% of the height of the conductor circuit 13, preferably the same as the height of the conductor circuit (13). The method of removing the thermosetting resin composition 15 is the same as the above-described embodiment. FIG. 35 is a cross-sectional view showing a state in which the protective resin composition layer 27 is removed in FIG. 34.

According to the eighth embodiment of the present invention, in the seventh embodiment, when the thermosetting resin composition 15 is filled in the wire bonding pad portion of the printed circuit board, the height of the thermosetting resin composition 15 is increased in the conductor circuit 13. It is preferable to make it 25 to 100% of. Thereafter, the thermosetting resin composition 15 is removed to expose a portion of the conductor circuit 13. As the method of removing the thermosetting resin composition 15, a known one may be used, and in particular, UV laser or plasma treatment may be used. And the thermosetting resin composition may be cyanic acid ester resin.

Hereinafter, the first to third embodiments will be described in more detail with reference to experimental and comparative examples. "Part" described below shows a weight part unless there is particular notice.

Experiment 1 : In the first embodiment  According Permanent protective coating  Characteristic experiment

Experimental Example  1-1

450 parts of 2,2, -bis (4-cyanatophenyl) propane monomers were melted and stirred at 160 degreeC, and they were made to react for 4.5 hours, and the mixture of a monomer and a prepolymer was obtained. After dissolving this in methyl ethyl ketone, 200 parts of bisphenol A type epoxy resin (brand name: Epicoat 1001, Japan epoxy resin), a phenol novolak type epoxy resin (brand name: N-700, Daekyo Ink Chemical Co., Ltd.) ) 250 parts, cresol novolak type epoxy resin (trade name: ESCN-220F, Sumitomo Chemical Co., Ltd.) 200 parts are blended, 0.5 parts of phthalocyanine blue is added as an adhesive, and 0.25 parts of zinc octylate as a curing catalyst is added to methyl ethyl ketone. It was added, stirred and mixed to form varnish A having a high viscosity.

In addition, a double-sided copper clad laminate (trade name: CCL-HL832HS, Mitsubishi Chemical Co., Ltd.) having an insulating layer thickness of 0.4 mm and an electrolytic copper foil thickness of 12 µm was used as a printed circuit board. A phosphor conductor was formed. Then, Mec CZ8100 + CZ8300 treatment was performed to prepare a substrate B having a surface irregularity of 2 μm. Screen printing was performed on one surface of the substrate B using a screen having a screen of 100 µm, followed by drying and semi-curing. Furthermore, after printing and drying on the back surface of the board | substrate B, the film was formed on both surfaces of the printed circuit board. The thermosetting resin composition layer on the upper surface of the printed circuit board where the conductive circuit for noble metal plating was formed was processed with a router, and the processing was stopped when the thermosetting resin composition layer had a thickness of 2 μm to 5 μm on the upper portion of the conductor circuit. In addition, the back surface of the board | substrate B processed and removed the thermosetting resin composition layer of the solder ball pad part with the carbon dioxide laser. At this time, the remaining thermosetting resin composition layer has a thickness of 1 μm to 2 μm. Subsequently, the thin thermosetting resin composition layer remaining on the conductor circuit in the plasma apparatus is processed and removed, leaving a layer of the thermosetting resin composition between the conductor circuits, and processed to a height of 92% to 99% of the height of the conductor circuit. Exposed. The solder ball pads on the back side of the substrate B exposed the copper foil. Thereafter, nickel plating and gold plating were used to make a printed circuit board. Table 1 shows the characteristics test results for the printed circuit board manufactured according to the Experimental Example 1-1.

Experimental Example  1-２

400 parts of bis (4-cyanatophenyl) ether monomer and 50 parts of bis (4 maleimide phenyl) ether monomers were melted at 150 ° C and reacted for 4 hours with stirring to obtain a mixture of monomer and prepolymer. After dissolving this in a mixed solvent of methyl ethyl ketone and N, N'-dimethylformamide, 200 parts of bisphenol A epoxy resin (trade name: Epicoat 1001, Japan Epoxy Resin Co., Ltd.), phenol novolak epoxy resin (brand name: DEN-431, Dow Chemical Co., Ltd. 150 parts, Cresol novolak-type epoxy resin (brand name: ESCN-220F, Sumitomo Chemical Co., Ltd.), liquid epoxidized polybutadiene (brand name: E-1000-8.0, Nihon Seki Oil Co., Ltd. was blended with 100 parts, and 0.5 part of phthalocyanine blue was added as a colorant, and 0.2 part of acetylacetone iron was dissolved in methyl ethyl ketone using a thermosetting catalyst, and stirred and mixed to prepare varnish C. Varnish C was continuously impregnated and dried in a 30 μm thick liquid crystalline polyester nonwoven fabric to prepare a prepreg D having a gel time of 135 seconds at a thickness of 45 μm and 170 ° C. At the time of preparation of the prepreg D, Temperature 80 Heating roll 5kgf / cm in linear pressure of the laminate adhered to a release PET film having a thickness of 25㎛ on both surfaces of the sheet to prepare a three-layer structure of E.

On the other hand, the printed circuit board was made of a double-sided copper clad laminate (trade name: CCL-HL832HS, Mitsubishi Gas Chemical Co., Ltd.) having an insulating layer thickness of 0.4 mm and an electrolytic copper foil thickness of 12 μm. / S) to form a conductor circuit. Then, Mec CZ8100 + CZ8300 treatment was performed to give a surface roughness of 2 μm. The PET film on both sides of the three-layer structure sheet E was peeled off, and one sheet was placed inside and outside the printed circuit board. Furthermore, a liquid crystal polyester film having a thickness of 25 μm on both sides and a plasma treatment was disposed to increase surface adhesion, and was continuously laminated in a vacuum of 5 mmHg or less at a temperature of 120 ° C. and a linear pressure of 10 kgf / cm. Thereafter, the mixture was heated and cured at 150 ° C. for 90 minutes, at 190 ° C. for 100 minutes, and cooled to prepare a substrate F.

The substrate F was processed in the same manner as in Experimental Example 1-1, and the surface was such that the height of the thermosetting resin composition layer was 93% to 100% of the height of the conductor circuit. The solder ball pads on the back exposed copper foil. After that, the printed circuit board was manufactured by nickel plating and gold plating. Table 1 shows the results of the characteristics test on the printed circuit board manufactured by Experimental Example 1-2.

Experimental Example 1 -3

1300 parts of aluminum hydroxide (average particle diameter: 2.0 µm), zinc-supported molybdate zinc (TALK) 911C, average particle diameter of 4.1 µm, 19% by weight of zinc molybdate, Shawin Williams Co., Ltd. in varnish A of Experimental Example 1-1. 100 parts, hydroxy zinc stannate (brand name: ZHS, JOSEPH STOREY & CO. LTD) 20 parts were added, and subsequently impregnated and dried on an inorganic E-Glass fiber woven fabric having a thickness of 10 µm to prepare a prepreg (gel time 127 seconds) G having a thickness of 30 µm.

On the other hand, a printed circuit board which processed a double-sided non-halogen copper clad laminate (trade name: CCL-HL832NB, Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 0.4 mm and a thickness of 12 μm of an electrolytic copper foil in the same manner as in Experimental Example 1-1. By using, each of the above prepregs G was disposed one by one. Then, a release PET film having a thickness of 25 μm was placed on both sides, and the laminate was continuously bonded and taken out in a vacuum of 5 mmHg or less at a temperature of 120 ° C. and a linear pressure of 8 kgf / cm, 60 minutes at 140 ° C., 60 minutes at 160 ° C., The substrate H was prepared by heat curing at 190 ° C. for 100 minutes. The thermosetting resin composition layer containing the base material of the board | substrate H was processed by the router until the edge of the conductor circuit for wire bonding exposed, and the height of the conductor circuit and the thermosetting resin composition layer was made the same height. In addition, the back side was exposed to the circuit by removing the thermosetting resin composition layer containing the substrate on the solder ball bonding circuit with a UV-YAG laser. After that, nickel plated and gold plated to manufacture a printed circuit board. Table 1 shows the characteristics test results for the printed circuit board manufactured according to Experimental Example 1-3.

Comparative example 1-1

In Experimental Example 1-1, UV selective thermosetting resist (trade name: PSR4000AUS5, manufactured by Taiyo Ink Co., Ltd.) was applied, dried, exposed to light, and developed by screen printing to obtain the same thickness, followed by thermosetting at 150 ° C for 60 minutes. Then, nickel plated and gold plated to manufacture a printed circuit board. Table 1 shows the characteristics test results for the printed circuit board manufactured by Comparative Example 1-1.

Comparative Example 1 -2

Varnish C was used in Experimental Example 1-2, and the printed circuit board was printed on a printed circuit board using a screen having a thickness of 100 μm, except for a portion where precious metal plating was performed. After evaporating the solvent at 80 ° C. for 30 minutes, heat curing at 150 ° C. for 60 minutes and heating at 190 ° C. for 60 minutes was carried out using nickel plating and gold plating to prepare a printed circuit board. Table 1 shows the characteristics test results for the printed circuit board manufactured by Comparative Example 1-2.

How to measure

(1) Bad circuit peeling

On a printed circuit board, 25 L / S bonding pads are manufactured in 25 µm / 25 µm packages within a 250 x 250 mm work size. The number of circuits peeled from each package of the printed circuit board after the production of 100 panels was passed to the end, and was expressed as% (number of occurrences / 2500) 500100 (%).

(2) Smeared bonding pad

It was observed whether the resin came out to the bonding pad part by 100 micrometers or more with the magnifying glass.

(3) migration resistance

In each experiment and comparative example, connect 100 fabricated nozzle type patterns with L / S of 25 µm / 25 µm on the printed circuit board, and insulate between terminals by applying 85 ° C / 85% RH / 100VDC. The resistance value was measured.

(4) solder heat resistance

The printed circuit board is cut to 50x50 (mm), treated in PCT (Pressure Cooker Test) for 4 hours at 121 ℃ and 203kPa, then taken out for 30 seconds during 260 ℃ soldering, and cooled for abnormality. Observed visually.

(5) flame resistance

The board | substrate was produced with the same structure, without using copper foil, it was cut | disconnected by the UL-94 test piece, and tested according to UL94.

Experiment result

Item Experimental Example 1-1 Experimental Example 1-2 Experimental Example 1-3 Comparative Example 1-1 Comparative Example 1-2 Defective circuit (%) 0 0 0 19.2 11.6 Smeared Bonding Pad none none none none has exist   My migration characteristic (Ω) condition 5 × 10 ¹³ 6 × 10 ¹³ 4 × 10 ¹³ 5 × 10 ¹³ 5 × 10 ¹³ 200hrs. 2 × 10 ¹¹ 1 × 10 ¹² 1 × 10 ¹¹ 7 × 10 ⁹ 2 × 10 ¹¹ 500hrs. 3 × 10 ¹⁰ 5 × 10 ¹⁰ 6 × 10 ⁹ <10 ⁸ 1 × 10 ¹⁰ Heat resistance (expansion yumu) none none none has exist none Flame Retardant (UL-94) HB HB V-0 HB HB

As can be seen from Table 1, the printed circuit board manufactured by the method for forming a permanent protective film according to the first embodiment of the present invention is excellent in reliability because no defective circuit peeling, no spreading of the bonding pads, and no expansion occurs. It can be seen. And it can be seen that the migration characteristics are also superior to the conventional permanent protective film forming method.

Experiment 2 : Using release film In the second embodiment  According Protective film  Characteristic experiment

Experimental Example  2-1

450 parts of 2,2, -bis (4-cyanatophenyl) propane monomers were melted at 160 degreeC and reacted for 4.5 hours, stirring, and the mixture of a monomer and a polymer was obtained. After dissolving this in methyl ethyl ketone, 100 parts of bis phenol A type epoxy resin (brand name: Epicoat 1001, product made by Japan Epoxy Resin Co., Ltd.), phenol novolak type epoxy resin (product name: DEN-431, product of Dow Chemical Co., Ltd.), 200 parts of cresol novolak-type epoxy resins (trade name: ESCN-220F, manufactured by Sumitomo Chemical Co., Ltd.) and 100 parts of liquid epoxidized polybutadiene resin (trade name: E-1000-8.0, manufactured by Nippon Petroleum Co., Ltd.) were blended. 0.5 parts of rocyanine blue was added and 0.2 parts of zinc octylate as a curing catalyst was dissolved in methyl ethyl ketone, followed by stirring and mixing to make varnish A. The varnish A was continuously applied to a cross section of a PET film having a thickness of 50 µm. B stage thermosetting resin composition sheet B (gelling time: 170 seconds at 170 ° C.) having a release film having a thickness of 31 μm of resin composition layer after drying was produced at a temperature of 80 ° C. An etching film having a thickness of 25 μm was laminated on a heating roll of 5 kgf / cm to prepare a sheet C having a three-layer structure.

As a printed circuit board, a double-sided copper clad laminate (trade name: CCL-HL832HS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having an insulating layer thickness of 0.4 mm and a copper foil thickness of 12 µm was used. 20,000 drilled holes in the work size After electroless copper plating 0.7 μm and electrocopper plating 15 μm, a circuit having an L / S = 25/25 (μm) was formed thereon and subjected to Mec CZ8100 + CZ8300 treatment to give surface irregularities of 2 μm. Then, the PET film of the sheet C of the three-layer structure is peeled off, and the B-stage thermosetting resin composition is disposed on both sides thereof so as to face the printed circuit board, and placed in a press device at 100 ° C. and 40 kgf / cm ^2. And laminated molding for 15 minutes in a vacuum state of 5mmHg or less and then cooled. Thereafter, a negative film was placed on the etching film of the surface layer to perform exposure and development to remove the etching film of the portion where the precious metal plating was carried out on the printed circuit board. This was placed in a plasma apparatus to remove the thermosetting resin composition which is modified to 90 to 98% of the circuit height. And the solder ball pad part of the back surface exposed the copper foil surface simultaneously. Thereafter, the etching film was dissolved in 1% aqueous sodium carbonate solution, and after heat curing at 190 ° C. for 1 hour, nickel plating and gold plating were performed to make a printed circuit board. Table 2 shows the characteristics test results for the printed circuit board manufactured by Experimental Example 2-1.

Experimental Example  2-2

400 parts of bis (4-cyanatophenyl) ether monomers and 50 parts of bis (4 maramide phenyl) ether were melted at 150 degreeC, and it stirred for 4 hours, stirring, and obtained the mixture of a monomer and a prepolymer. After dissolving this in a mixed solvent of methyl ethyl ketone and N, N'-dimethylformamide, 200 parts of bisphenyl A type epoxy resin (trade name: Epicoat 1001, manufactured by Japan Epoxy Resin Co., Ltd.), phenol novolak type epoxy resin (brand name) ： 150 parts of DEN-431, Dow Chemical Co., Ltd., 100 parts of cresol novolak type epoxy resin (brand name: ESCN-220F, product of Sumitomo Chemical Industries, Ltd.), liquid epoxidized polybutadiene resin (brand name: E-1000-8.0, Japan) 100 parts of Petroleum Co., Ltd. was combined. 0.5 parts of phthalocyanine blue was added as a colorant, and acetylacetone iron was dissolved in 0.2 parts of methyl ethyl ketone as a curing catalyst, and then stirred and mixed to prepare varnish D. This varnish D was continuously impregnated and dried in a 30 탆 thick all aromatic polyamide nonwoven fabric to prepare a prepreg E having a thickness of 45 탆 and a gel time of 100 seconds. At the time of preparation of the prepreg E, a release PET film having a thickness of 50 μm was laminated on both surfaces with a linear pressure of 5 kgf / cm on a heating roll having a temperature of 80 ° C. to prepare a sheet F having a three-layer structure.

On the other hand, a double-sided copper clad laminate (trade name: CCL-HL832HS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having an insulating layer thickness of 0.4 mm and a copper foil thickness of 12 µm was used as a printed circuit board. 20,000 holes in size. After carrying out electroless copper plating 0.7 micrometer and electrocopper plating 15 micrometers, the L / S circuit was formed like the Experimental example 2-1 by the regular method, the CZ8100 + CZ8300 process of Mec Corporation was performed, and surface unevenness was made into 2 micrometers. Thereafter, the PET film on one side of the three-layer structure sheet F was peeled off and placed on both sides so that the B-stage thermosetting resin composition layer faced the printed circuit board, and then placed in a press apparatus at 190 ° C., 30 kgf / cm ^{2 ,} Substrate G was made by lamination for 90 minutes in a vacuum state of 10 mmHg or less. The PET film on the bonding pad part which performs noble metal plating of the surface of this board | substrate G was removed with the UV-YAG laser. Then, the cured thermosetting resin composition was removed until it became 96% to 100% of the height of the conductor circuit. In addition, the solder ball pad portion of the surface was directly irradiated with a UV-YAG laser on the release film to remove the thermosetting resin composition layer to copper foil, and then nickel plated and gold plated to produce a printed circuit board. Table 2 shows the characteristics test results for the printed circuit board manufactured by Experimental Example 2-2.

Experimental Example  2-3

90 degreeC heating roll after arrange | positioning so that the resin composition surface of B stage thermosetting resin composition sheet B which the mold release PET film of Experimental Example 2-1 may adhere to both sides of the liquid-crystal polyester film of thickness 25micrometer may face a liquid-crystalline polyester film. B stage sheet H was produced by laminating at a pressure of 5 kgf / cm at. The PET film of one side was peeled off and placed on both sides of the printed circuit board treated in Experimental Example 2-1, and the substrate I was manufactured by laminating at 190 ° C., 30 kgf / cm ² , and vacuum degree of 5 mmHg or less for 90 minutes. The PET film on the part to which the noble metal plating of this board | substrate I is performed was removed by UV-YAG laser. Thereafter, the cured thermosetting resin composition was removed using a plasma process until it became 96% to 100% of the height of the conductor circuit. And the solder ball pad part of the inner side exposed the copper foil surface. Thereafter, nickel plated and gold plated to make a printed circuit board. A characteristic test result for the printed circuit board manufactured by Experimental Example 2-3 is shown in FIG. 2.

Experimental Example  2-４

1300 parts of aluminum hydroxide (average particle diameter: 2.0 µm), zinc molybdate-supported talc (brand name: KEMGARD911C, average particle diameter of 4.1 µm, 19 mol% of zinc molybdate supported) in varnish A of Experimental Example 2-1, 100 parts of Sherwin Williams Co., Ltd., 20 parts of hydroxy zinc stannate (trade name: ZHS, JOSEPH STOREY & CO., LTD) were added, and impregnated and dried on an inorganic E glass fiber cloth having a thickness of 10 μm in succession to a prepreg having a thickness of 30 μm. Gelation time 127 seconds) J was produced. On the other hand, using a printed circuit board manufactured by the same method as Experimental Example 2-1 using a double-sided halogen-free copper clad laminate (trade name: CCL-HL832NB, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 0.4 mm and a copper foil of 12 µm, Each prepreg J is placed one by one so that the resin composition layer faces the printed circuit board, and a PET film having a thickness of 25 μm is disposed on both sides thereof, and laminated for 120 minutes in a vacuum of 220 ° C., 35 kgf / cm 2, and 5 mm Hg or less. The substrate K was formed by molding. The PET film and the thermosetting resin composition layer of the part which carries out the noble metal plating of this board | substrate K were removed using the router until it became 99%-100% of the height of a conductor circuit. In addition, the inner surface was exposed to the circuit by removing the PET film and the thermosetting resin composition layer on the surface of the solder ball bonding circuit with a UV-YAG laser. Thereafter, nickel plating and gold plating were performed to complete the printed circuit board. Table 2 shows the characteristics test results for the printed circuit board manufactured by Experimental Example 2-4.

Comparative example  2-1

A commercially available UV selective thermosetting resist (trade name: PSR4000AUS5, manufactured by Taityo Ink Co., Ltd.) was applied by the screen printing method without using the B stage resin composition sheet with a release film as in Experimental Example 2-1-1. After drying, exposure and development to heat curing, nickel plating, gold plating were performed to make a printed circuit board. Table 2 shows the characteristics test results for the printed circuit board manufactured by Comparative Example 2-1.

Comparative example  2-2

In Comparative Example 2-1-1, the UV resist was applied twice to fill the hole and processed the same to prepare a printed circuit board.

Comparative example  2-３

Varnish A of Experimental Example 2-1 was screen printed on a printed circuit board except for a portion where noble metal plating was carried out using a screen having a mesh of 100. Thereafter, the solvent was evaporated at a temperature of 80 ° C. for 30 minutes and then cured by heating at 150 ° C. for 90 minutes. And nickel plated and gold plated to make a printed circuit board. Table 2 shows the characteristics test results for the printed circuit board manufactured by the above method.

Comparative example  2-４

In Experimental Example 2-1-1, instead of the release film, an electrolytic copper foil having a thickness of 18 μm was laminated and post-cured in the same manner to prepare a substrate M. After laminating an etching film having a thickness of 25 占 퐉 on the substrate M, the negative film is placed, exposed and developed, and the upper film subjected to noble metal plating of the printed circuit board is dissolved and removed with an aqueous 1% sodium carbonate solution, followed by etching the copper foil. Removed to create an opening in the surface. After dissolving and removing the etching film, plasma was irradiated to remove the thermosetting resin composition in the opening portion, and the surface of the conductor circuit portion was exposed in the same manner as in Comparative Examples 2-1 to 2-1. Thereafter, the copper foils on the front and back were etched away to perform nickel plating and gold plating, to form a printed circuit board. In this case, the circuit of the printed circuit board was also etched away and thinned, and the height was 16 µm to 20 µm lower than that of the resin. Table 2 shows the characteristics test results for the printed circuit board manufactured by the above method.

The measurement method for poor circuit peeling, spreading to the bonding pad portion, solder heat resistance and migration resistance is the same as the measurement method of Experiment 1. The measurement method for the new evaluation item is as follows.

How to measure

(1) Bubbles in the energizing hall

The hole generation number was measured by observing 10,000 holes under a microscope.

(2) concave

The cross section of 100 holes was observed and the maximum value of the concave part was measured.

(3) Bad wire bonding

100 wire bondings were each carried out on a printed circuit board. In Comparative Examples 2-1 to 203, those having no circuit peeling failure were selected and carried out. Bonding defects were observed.

(4) bending and twisting

The printed circuit board, which was subjected to gold plating with a work size of 250 × 250 (mm), was placed on a plate and the maximum value thereof was measured.

(5) Cold and heat shock resistance

After performing 200 cycles with 30 minutes at -55 degreeC and 30 minutes at 150 degreeC as 1 cycle, the cross section of the 100-hole through-hole part was observed, and the presence of crack was confirmed.

(6) heat resistance

The board | substrate was produced with the same structure, without using copper foil, and it cut | disconnected by the UL-94 test piece and tested according to UL94.

Experiment result

Item Experimental Example 2-1 Experimental Example 2-2 Experimental Example 2-3 Experimental Example 2-4 Comparative Example 2-1 Comparative Example 2-2 Comparative Example 2-3 Comparative Example 2-4 Bubble in energizing hall 0 0 0 0 521 401 778 0 Through Hole Concave (㎛) 6.5 <3 <3 <3 53 21 79 6.2 Circuit surface unevenness (㎛) <5 <5 <5 <5 17.3 8.8 21 <5 Defective circuit (%) 0 0 0 0 18.9 24.5 11.0 0 Bending / Twisting (mm) <2 <2 <2 <2 4.0 5.1 4.2 <2 Smear to Bonding Pad none none none none none none has exist none Bad wire bonding connection none none none none none none has exist has exist Solder heat resistance clear clear clear clear Some air bubbles Some air bubbles clear clear   Migration resistance (Ω) condition 3 × 10 ¹³ 5 × 10 ¹³ 4 × 10 ¹³ 5 × 10 ¹³ 5 × 10 ¹³ 5 × 10 ¹³ 4 × 10 ¹³ 3 × 10 ¹³ 200hrs. 3 × 10 ¹¹ 1 × 10 ¹¹ 1 × 10 ¹² 8 × 10 ¹¹ 7 × 10 ⁹ 8 × 10 ⁹ 2 × 10 ¹¹ 1 × 10 ¹¹ 500hrs. 2 × 10 ¹⁰ 1 × 10 ¹⁰ 2 × 10 ¹¹ 7 × 10 ¹⁰ <10 ⁸ <10 ⁸ 1 × 10 ¹⁰ 2 × 10 ¹⁰ Cold shock resistance none none none none has exist has exist has exist none Flame Retardant (UL-94) HB HB HB V-0 HB HB HB HB

As can be seen in Table 2, the printed circuit board manufactured by the second embodiment using the release film can be seen that the performance is improved in the resin fillability to the holes, irregularities and circuit peeling of the surface portion. In addition, it can be seen that not only the bending / twist of the conductor circuit is reduced, but also the performance is improved in bonding pad part bleeding, solder heat resistance, migration resistance, and cold shock resistance.

Experiment 3 : Heat-resistant organic film In the second embodiment  According Permanent protective coating  Characteristic experiment

Experimental Example  3-1

450 parts of 2,2, -bis (4-cyanatophenyl) propane monomers were melted at 160 degreeC, and it reacted for 4.5 hours, stirring, and obtained the mixture of a monomer and a polymer. After dissolving the mixture in methyl ethyl ketone, 100 parts of bisphenol A epoxy resin (trade name: Epicoat 1001, manufactured by Japan Epoxy Resin Co., Ltd.), phenol novolak-type epoxy resin (trade name: DEN-431, manufactured by Dow Chemical Co., Ltd.) 150 parts, cresol novolak-type epoxy resin (trade name: ESCN-220F, manufactured by Sumitomo Chemical Co., Ltd.) and 200 parts of liquid epoxidized polybutadiene resin (trade name: E-1000-8.0, manufactured by Nippon Petroleum Co., Ltd.) were blended. , 0.5 parts of phthalocyanine blue as a colorant and 0.2 parts of methyl octylate as a curing catalyst were dissolved, added, stirred, and mixed to form a varnish A. The varnish A was continuously PET film having a thickness of 50 μm. After applying and drying the cross-section to produce a B-stage thermosetting resin composition sheet B (gelling time at 170 ° C .: 90 sec) with a release film having a thickness of 31 μm of resin composition, and then using a heating roll having a temperature of 80 ° C. An adhesive film having a thickness of 25 μm was laminated on the substrate at a pressure of 5 kgf / cm to prepare a sheet C having a three-layer structure.

As a printed circuit board, a double-sided copper clad laminate (trade name: CCL-HL832HS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having an insulating layer thickness of 0.4 mm and a copper foil thickness of 12 µm was used. In full bloom. After electroless copper plating 0.7 탆 and electro copper plating 15 탆, a circuit having an L / S of 25/25 탆 was formed by a regular method, and CZ8100 + CZ8300 treatment made by Mec was applied to make the surface irregularities 2 탆. Peel off the PET film of the sheet C of the structure and place it on both sides so that the B-stage thermosetting resin composition faces the printed circuit board, and put it in a press device, and laminate it for 90 minutes at 190 ° C and 30 kgf / cm ² under a vacuum of 5 mmHg or less. It was. After cooling the printed circuit board, a 1mm-thick stainless steel plate in which the noble metal plating portion of the printed circuit board is cut on the liquid crystal polyester film of the surface layer is pressed against the inside and the outside, and then pressed into a plasma apparatus, followed by thermosetting resin composition. The thermosetting resin composition was removed until the layer was 92% to 99% of the height of the conductor circuit. Then, nickel plating and gold plating were performed to make the printed circuit board. Thus, the results of the characteristics test for the printed circuit board manufactured by Experimental Example 3-1 is shown in Table 3.

Experimental Example  3-2

400 parts of bis (4-cyanatophenyl) ether monomers and 50 parts of bis (4 maleimide phenyl) ether monomers were reacted for 4 hours, melting and stirring at 150 degreeC, and the mixture of a monomer and a prepolymer was obtained. The mixture was dissolved in a mixed solvent of methyl ethyl ketone and N, N'-dimethylformamide, and then 200 parts of bisphenyl A type epoxy resin (trade name: Epicoat 1001, manufactured by Japan Epoxy Resin Co., Ltd.), and phenol novolak type. 150 parts of epoxy resin (brand name: DEN-431, Dow Chemical Co., Ltd.), 100 parts of cresol novolak type epoxy resin (brand name: ESCN-220F, Sumitomo Chemical Co., Ltd.), liquid epoxidized polybutadiene resin (brand name: E-1000 -8.0, manufactured by Japan Petroleum Co., Ltd.), 100 parts were blended. Then, 0.5 parts of phthalocyanine blue as a coloring agent and acetylacetone iron were dissolved in 0.2 parts of methyl ethyl ketone as a curing catalyst, and then stirred and mixed to form varnish D. This varnish D was continuously impregnated and dried to a 30 μm-thick all aromatic polyamide nonwoven fabric to prepare a prepreg E having a thickness of 45 μm and a gelation time (at170 ° C.) of 133 seconds. On both sides of the prepreg E, a release PET film having a thickness of 25 μm was laminated on both sides with a linear pressure of 5 kgf / cm on a heating roll having a temperature of 80 ° C. to prepare a sheet F having a three-layer structure.

On the other hand, a double-sided copper clad laminate (trade name: CCL-HL832HS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with an insulating layer thickness of 0.4 mm and a copper foil thickness of 12 μm was used as a printed circuit board, and through a metal drill, 20,000 through holes with a hole diameter of 250 μm were drilled into the work size. . Then, electroless copper plating 0.7 탆 and electro copper plating 15 탆 were carried out, and circuits were formed in the same L / S width as in Experimental Example 3-1 by the same method, followed by treatment of CZ8100 + CZ8300 manufactured by Mec. It was. The three-layer structure sheet F on which the PET film on both sides was peeled was placed on both sides of the printed circuit board thus manufactured. In order to increase the surface adhesion on both sides of the substrate, a 25 μm thick liquid crystal polyester film was disposed, and laminated at 90 ° C. under 30 kgf / cm ² and 5 mmHg for 90 minutes, and then taken out and cooled. Made. The substrate G was processed in the same manner as in Experimental Example 3-1, and the processing was completed when the height of the thermosetting resin composition layer became 94% to 100% of the respective circuit heights exposed. Thereafter, nickel plating and gold plating were performed to make a printed circuit board. Table 3 shows the characteristics test results for the printed circuit board manufactured by Experimental Example 3-2.

Experimental Example  3-3

1300 parts of aluminum hydroxide (average particle diameter: 2.0 µm), zinc molybdate-supported talc (trade name: KEMGARD911C, average particle diameter of 4.1 µm, 19 mol% of zinc molybdate supported) in varnish A of Experimental Example 3-1-1. 100 parts of Sherwin Williams Co., Ltd. and 20 parts of hydroxy zinc stannate (trade name: ZHS, JOSEPH STOREY & CO., LTD) are blended, and then continuously coated and dried on an inorganic E glass fiber cloth having a thickness of 10 μm, and then 30 μm thick. Prepreg (gelling time 121 seconds) H was produced. On the other hand, the printed circuit board which processed the double-sided halogen free copper clad laminated board (brand name: CCL-HL832NB, Mitsubishi Gas Chemical Co., Ltd.) of 0.4 mm thickness and 12 micrometers of copper foils in the same manner as Experimental example 3-1 was used. And each of the prepreg H on the both sides so that the resin composition layer toward the printed circuit board, each one, and then placed on the outer side of the 25㎛ thick all aromatic polyamide film 220 ℃, 35kgf / ㎠, 5mmHg Substrate I was produced by laminating for 120 minutes in the following vacuum state. After removing the wholly aromatic polyamide film on the surface of the substrate I where the noble metal plating is carried out with a UV-YAG laser, the thermosetting resin composition is processed and removed by a router to expose the circuit and at the same time 98% to 100 of the circuit height. %. Moreover, the surface removed the wholly aromatic polyamide film and the thermosetting resin composition layer on the solder ball bonding circuit with UV-YAG laser, and exposed the circuit. Thereafter, nickel plating and gold plating were performed to make a printed circuit board. Table 3 shows the results of the characteristics test on the printed circuit board manufactured by the above method.

Comparative example  3-1

A commercially available UV selective thermosetting resist (trade name: PSR4000AUS5, manufactured by Taityo Ink Co., Ltd.) was applied by screen printing without using the B stage resin composition sheet with a release film as in Experimental Example 3-1. After drying, exposure and development to heat curing, nickel plating, gold plating were performed to make a printed circuit board. Table 3 shows the characteristics test results for the printed circuit board manufactured by Comparative Example 3-1.

Comparative example  3-2

In Comparative Example 3-1, the UV resist was first applied twice to fill the hole, and then the same process was performed to fabricate a printed circuit board. Table 3 shows the results of the characteristics test on the printed circuit board manufactured as described above.

Comparative example  3-3

Varnish A of Experimental Example 3-1 was printed on a printed circuit board except for a portion where noble metal plating was performed using a screen having a mesh of 100. Then, the solvent was evaporated at 80 ° C. for 30 minutes, heat-cured at 150 ° C. for 90 minutes, and nickel plated and gold plated to form a printed circuit board. Table 3 shows the results of the characteristics test on the printed circuit board manufactured as described above.

Experiment result

Item Experimental Example 3-1 Experimental Example 3-2 Experimental Example 3-3 Comparative Example 3-1 Comparative Example 3-2 Comparative Example 3-3 Bubble in energizing hall 0 0 0 521 401 778 Through Hole Concave (㎛) 6.5 <3 <3 53 21 79 Circuit surface irregularities (㎛) <5 <5 <5 17.3 8.8 21 Deletion of circuit (%) 0 0 0 18.9 24.5 11.0 Bending / Twisting (mm) <2 <2 <2 4.0 5.1 4.2 Smeared Bonding Pad none none none none none has exist Bad wire bonding connection none none none none none has exist Solder heat resistance clear clear clear Some bubbles Some bubbles clear   Migration resistance (Ω) condition 3 × 10 ¹³ 5 × 10 ¹³ 4 × 10 ¹³ 5 × 10 ¹³ 5 × 10 ¹³ 4 × 10 ¹³ 200hrs. 3 × 10 ¹¹ 1 × 10 ¹² 4 × 10 ¹¹ 7 × 10 ⁹ 8 × 10 ⁹ 2 × 10 ¹¹ 500hrs. 2 × 10 ¹⁰ 5 × 10 ¹⁰ 6 × 10 ⁹ <10 ⁸ <10 ⁸ 1 × 10 ¹⁰ Cold shock resistance none none none has exist has exist has exist Flame Retardant (UL-94) HB HB V-0 HB HB HB

As can be seen from Table 3, the printed circuit board fabricated by the second embodiment of the present invention using a heat-resistant organic film is improved in the resin filling ability to the holes, irregularities in the surface portion and circuit peeling. have. In addition, it can be seen that not only the bending / twist of the conductor circuit is reduced, but also the performance is improved in bonding pad part bleeding, solder heat resistance, migration resistance, and cold shock resistance.

Experiment 4 3rd room In the city  According Permanent protective coating  Characteristic experiment

Experimental Example  4-1

450 parts of 2,2,-screw (4-cyanaphenyl) propane monomers were dissolved at 160 ° C and reacted for 4.5 hours to obtain a mixture of monomers and preformima. After dissolving this mixture in methyl ethyl ketone, 100 parts of bisphenol-A epoxy resin (brand name: Epicoat 1001, Japan epoxy resin Co., Ltd.), a phenol novolak-type epoxy resin (brand name: DEN-431, Dow Chemical Co., Ltd.) 150 parts, cresol novolak-type epoxy resin (brand name: ESCN-220F, Sumitomo Chemical Co., Ltd.) 200 parts, liquid epoxidized polybutadiene resin (brand name: E-1000-8.0, Nippon Petroleum Co., Ltd.) 100 parts were combined. Vise A was prepared by mixing 0.5 parts of phthalocyanine blue as a colorant and 0.2 parts of methyl ethyl ketone as octylate as a curing catalyst. This varnish A was continuously applied and dried on one side of a 25-micrometer-thick PET film to prepare a B-stage thermosetting resin composition sheet B (gelling time at 170 ° C: 92 seconds) with a release film having a resin composition layer thickness of 30 micrometers. . And the 12-micrometer-thick electrolytic copper foil was laminated on the heating roll of the temperature of 80 degreeC by the linear pressure of 5 kgf / cm, and the sheet | seat C of the three-layer structure was produced.

Meanwhile, as a printed circuit board, a double-sided copper clad laminate (trade name: CCL-HL832HS, Mitsubishi Gas Chemical Co., Ltd.) having an insulating layer thickness of 0.4 mm and a copper foil thickness of 3 µm was used. 20,000 pieces were formed in the work size. After attaching 0.4 탆 of electroless copper plating and 1 탆 of electroplated copper, a plating resistor was attached, followed by exposure and development to leave a resist having a space of 30 탆 and a resist width of 20 탆. After attaching 25 탆 thick copper electroplating, the plating resistor was peeled off, and a circuit having a L / S of 25/25 (탆) and a circuit of L / S of 70/70 (탆) were formed on the outside in flash etching. It was. And CZ8100 + CZ8300 process of Mack Corporation was performed, and the board | substrate D whose surface asperity is 2 micrometers was produced. On this, the PET film of the sheet C of the three-layer structure was peeled off, and the B-stage thermosetting resin composition was disposed on both sides thereof so as to face the printed circuit board. Thereafter, in a press apparatus, the laminate was molded for 90 minutes in a vacuum state of 190 ° C, 30 kgf / cm 2, and 5 mmHg or less, followed by cooling. And after attaching the etching film of thickness 25micrometer on the double-sided copper foil in a surface layer by lamination, it exposed, developed, and etched using the negative film on this. And after removing the copper foil of the range on the conductor circuit which performs noble metal plating of a printed circuit board, the etching film was dissolved and removed and the board | substrate E was produced. This was placed in a plasma apparatus to treat and remove the thermosetting resin composition layer so that the thermosetting resin composition had a thickness of 4 to 7 µm on the upper portion of the conductor circuit. Thereafter, after removing the copper foil of the surface layer, the thermosetting resin composition remaining in the plasma apparatus was processed and removed, and the processing was terminated when the thermosetting resin composition layer became 92 to 99% of the height of the conductor circuit. At the same time, the copper foil surface of the circuit board for handball pads on the back side was exposed. Thereafter, nickel plating and gold plating were performed to obtain a printed circuit board. Table 4 shows the characteristics test results for the printed circuit board manufactured by Experimental Example 4-1.

Experimental Example  4-2

400 parts of screw (4-cyanaphthyl) ether monomers and 50 parts of screw (4 marimidphenyl) ethers were dissolved and stirred at 150 ° C., and then reacted for 4 hours to obtain a mixture of monomers and preformima. After dissolving this mixture in the mixed solvent of methyl ethyl ketone and N, N'-dimethyl formamide, 200 parts of bisphenol-A epoxy resins (brand name: Epicoat 1001, Japan Epoxy Resin Co., Ltd.), a phenol novolak-type epoxy resin (Brand name: DEN-431, Dow Chemical Co., Ltd.) 150 parts, cresol novolak type epoxy resin (brand name: ESCN-220F, Sumitomo Chemical Co., Ltd.) 100 parts, liquid epoxidized polybutadiene resin (brand name) : 100 parts of E-1000-8.0 and Nippon Petroleum Co., Ltd. were mix | blended. And varnish F was produced by melt | dissolving 0.5 part of phthalocyanine blue as a coloring agent, and 0.2 part of acecile acetone iron as a curing catalyst, in methyl ethyl ketone, and mixing. This varnish F was continuously impregnated and dried to a 30-micrometer-thick wholly aromatic polyamide nonwoven fabric, and the prepreg G of thickness 45micrometer and gelation time (at170 degreeC) 100 second was produced. When prepreg G was produced, the release PET film of thickness 25micrometer was laminated on both surfaces by the heating roll of temperature 80 degreeC by the linear pressure of 5 kgf / cm, and the sheet | seat H of 3 layer structure was produced.

On the other hand, as a printed circuit board, the PET film of both sides of the sheet H of the said three-layer structure was peeled off to the board | substrate D of Experimental Example 4-1, and it arrange | positions one sheet each on both sides of a printed circuit board, and has a thickness of 9 micrometers on it. The electrolytic copper foil was arrange | positioned. Subsequently, the substrate I was fabricated by laminating for 90 minutes in a vacuum state of 190 ° C., 30 kgf / cm 2, and 10 mmHg or less using a press device. The metal foil of the part which performs noble metal plating on the surface of the printed circuit board of this board | substrate I was removed like Experimental example 4-1. Then, the thermosetting resin composition layer was treated and removed by using a plasma so that the thickness of the thermosetting resin composition layer was 2 μm to 5 μm on the upper portion of the conductor circuit. Thereafter, after the copper foil of the surface layer was etched away, the thermosetting resin composition was removed until it was put in a plasma apparatus again to 95% to 100% of the height of the conductor circuit. At the same time, the copper foil surface of the circuit for handball pads on the back side was exposed. Thereafter, nickel plating and gold plating were performed to fabricate a printed circuit board. Table 4 shows the characteristics test results for the printed circuit board manufactured by Experimental Example 4-2.

Experimental Example  4-3

On one surface of the liquid crystal polyester film having a thickness of 25 µm, the B stage with the release PET film of Experimental Example 4-1 was disposed so that the resin composition surface of the thermosetting resin composition sheet B faced the liquid crystal polyester film, and the copper foil B was placed on the opposite side. The PET film of the stage thermosetting resin composition sheet C was peeled off, and it arrange | positioned. And it laminate-bonded by the linear pressure of 5 kgf / cm by the 90 degreeC heating roll, and produced B-stage thermosetting resin composition sheet J with copper foil. After peeling the PET film on both sides of the printed circuit board treated in the same manner as in Experimental Example 4-1, a substrate K was manufactured by laminating and molding at 190 ° C., 30 kgf / cm 2, and vacuum degree of 5 mmHg or less for 90 minutes. After etching away copper foil on the conductor circuit for noble metal plating of the substrate K as in Experimental Example 4-1, the thermosetting resin composition layer was treated and removed in the plasma apparatus, and the thickness of the thermosetting resin composition layer on the conductor circuit. Was 2-4 micrometers. The copper foil on the surface layer was etched away, and then plasma treated to remove the thermosetting resin composition layer until it became 96% to 100% of the height of the conductor circuit. Moreover, the copper foil surface of the circuit for handball pads on the back surface was exposed. Thereafter, nickel plating and gold plating were performed to fabricate a printed circuit board. Table 4 shows the characteristics test results for the printed circuit board manufactured by Experimental Example 4-3.

Experimental Example  4-4

1300 parts of aluminum hydroxide (average particle diameter: 2.0 µm), zinc molybdate-supported talc (brand name: KEMGARD911C, average particle diameter of 4.1 µm, 19% by weight of molybdate zinc oxide, Shawin Williams) in varnish A of Experimental Example 4-1 Note) 100 parts and 20 parts of hydroxy zinc stannate (trade name: ZHS, JOSEPH STOREY & CO., LTD) were added, and then impregnated and dried in a glass cloth having a thickness of 10 µm and then dried on a B stage thermosetting resin composition (170 ° C, A prepreg L having a thickness of 30 μm with a gelation time of 125 seconds) was prepared. On the other hand, after processing the non-halogen copper clad laminated board (brand name: CCL-HL832NB, Mitsubishi Gas Chemical Co., Ltd.) of 0.4 mm in thickness and 3 micrometers of copper foil thicknesses in the same manner as Experimental Example 4-1, the B-stage resin composition sheet was formed on both sides. Each of L was placed, and an electrolytic copper foil having a thickness of 12 µm was placed on the outside thereof, and laminated substrate was formed for 120 minutes in a vacuum state of 220 ° C, 35 kgf / cm 2, or 5 mmHg or less to obtain a substrate M. Then, the whole copper foil located in the surface layer was etched away uniformly, and the board | substrate N with a copper foil thickness of 3 micrometers was produced. The copper foil on the conductor circuit which performs noble metal plating of the printed circuit board of this board | substrate N was etched away similarly to Experimental Example 4-1. And the thermosetting resin composition layer of the bonding pad part was processed and removed by the router, and 1 micrometer-3 micrometers of the thermosetting resin composition layer were left on the conductor circuit. Thereafter, a carbon dioxide laser was irradiated to remove the thermosetting resin composition and the glass woven fabric, leaving 0.5 to 2 µm of the thermosetting resin composition layer on the conductor circuit. Thereafter, the copper foil of the surface layer was etched away, the substrate was subjected to desmia treatment, and the residual resin on the circuit was processed and removed, and the surface bonding pad circuit portion was removed from the thermosetting resin composition layer so as to be 95 to 99% of the circuit height. And the back surface melt | dissolved the thermosetting resin composition layer to the handball copper foil surface. Thereafter, nickel plating and gold plating were performed to obtain a printed circuit board. Table 4 shows the characteristics test results for the printed circuit board manufactured by Experimental Example 4-4.

Comparative example  4-1

Without using the B-stage resin composition sheet with copper foil of Experimental Example 4-1, the UV selective thermosetting resistor (brand name: PSR4000AUS5, Taiyo Ink Co., Ltd.) currently marketed is apply | coated by the screen printing method so that it may become the same thickness. After drying, exposing, developing, and thermosetting, nickel and gold plating were used to fabricate a printed circuit board. Table 4 shows the characteristics test results for the printed circuit board manufactured as described above.

Comparative example  4-2

In Comparative Example 4-1, the UV register was applied twice to fill the hole, and then processed in the same manner to prepare a printed circuit board. Table 4 shows the characteristics test results for the printed circuit board formed by Comparative Example 4-2.

Comparative example   4-3

In Experimental Example 4-1, this was printed using varnish A on a printed circuit board on a portion where the mesh was subjected to precious metal plating using a screen having a thickness of 100 µm. Then, the solvent was blown at 80 ° C. for 30 minutes, heat-cured at 150 ° C. for 90 minutes, and then nickel-plated and gold-plated to prepare a printed circuit board. Table 4 shows the characteristics test results for the printed circuit board manufactured by the above method.

Comparative example  4-4

Substrate E of Experimental Example 4-1 was placed in a plasma apparatus, and the plasma was irradiated to remove the thermosetting resin composition of the opening portion at once. And the surface conductor circuit was exposed. In addition, the copper foil of the surface layer was etched and removed to perform nickel plating and gold plating to prepare a printed circuit board. In this case, the conductor circuit of the printed circuit board was also etched away and thinned, resulting in a height of 10 to 13 mu m lower than that of the resin. Table 4 shows the characteristics test results for the printed circuit board manufactured by the above method.

Experiment result

Item Experimental Example 4-1 Experimental Example 4-2 Experimental Example 4-3 Experimental Example 4-4 Comparative Example 4-1 Comparative Example 4-2 Comparative Example 4-3 Comparative Example 4-4 Bubble in energizing hall 0 0 0 0 525 398 750 0 Through Hole Concave (㎛) 6.1 <3 <3 <3 52 22 76 6.2 Circuit surface irregularities (㎛) <5 <5 <5 <5 17.0 8.7 21 <5 Defective circuit (%) 0 0 0 0 19.1 24.5 11.0 0 Bending / Twisting (mm) <2 <2 <2 <2 4.2 5.1 4.2 <2 Smear to Bonding Pad none none none none none none has exist has exist Bad wire bonding connection none none none none none none has exist has exist Solder heat resistance clear clear clear clear Some air bubbles clear Some air bubbles Some air bubbles Migration resistance (Ω) condition 5 × 10 ¹³ 4 × 10 ¹³ 4 × 10 ¹³ 4 × 10 ¹³ 5 × 10 ¹³ 5 × 10 ¹³ 4 × 10 ¹³ 3 × 10 ¹³ 200hrs. 2 × 10 ¹¹ 9 × 10 ¹⁰ 2 × 10 ¹² 1 × 10 ¹¹ 7 × 10 ⁹ 8 × 10 ⁹ 2 × 10 ¹¹ 1 × 10 ¹¹ 500hrs. 2 × 10 ¹⁰ 1 × 10 ¹⁰ 1 × 10 ¹¹ 6 × 10 ¹⁰ <10 ⁸ <10 ⁸ 1 × 10 ¹⁰ 2 × 10 ¹⁰ Cold shock resistance none none none none has exist has exist has exist has exist Flame Retardant (UL-94) HB HB HB V-0 HB HB HB HB

As can be seen in Table 4, it can be seen that the printed circuit board manufactured by the third embodiment of the present invention using the metal foil has improved performance in resin filling property to holes, irregularities in surface portions, and circuit peeling. In addition, it can be seen that not only the bending / twist of the conductor circuit is reduced, but also the performance is improved in bonding pad part bleeding, solder heat resistance, migration resistance, and cold shock resistance.

Experiment 5: the fourth Example  According Permanent protective coating  Characteristic experiment

Experimental Example 5-１

450 parts of 2,2, -bis (4-cyanaphenyl) propane monomers were melted at 160 degreeC, and it reacted for 4.5 hours, mixing, and obtained monomer and a prepolymer mixture. This is dissolved in methyl ethyl ketone, and bisphenol A type epoxy resin is here .: Epicoat 1001, Japan Epoxy Resin Co., Ltd. 100 parts, phenol novolak type epoxy resin 150 parts, cresol noborac epoxy resin (trade name: ESCN-220F, manufactured by Sumitomo Chemical Industries, Ltd.), 200 parts, liquid epoxidized polybutadiene resin (trade name: E-1000-8.0, manufactured by Nihon Sekiyu Co., Ltd.) 0.5 parts of phthalocyanine blue was added as a coloring agent, zinc octylate was dissolved in 0.2 parts of methyl ethyl ketone by the curing catalyst, and the varnish A was prepared. The varnish A was continuously applied to a PET film having a thickness of 25 µm and dried to produce a B-stage thermosetting resin composition sheet B (170 ° C Gel Time: 92 seconds) having a resin composition layer of 30 µm in thickness. 5 kgf / cm linear pressure and 18 micrometers thick electrolytic copper foil were laminated | stacked with the temperature 80 degreeC heating roll, and the sheet | seat C which is three layers structure was produced.

The printed circuit board is a double-sided copper clad laminate (trade name: CCL-HL832HS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having an insulating layer thickness of 0.4 mm and a copper foil thickness of 12 µm. 20,000 holes were drilled into the work size, and electroless copper plating 0.7 µm and electroplating 15 µm were attached to each other, and a line / space = 15/15 circuit was formed by a regular method, and Mec's CZ8100 + CZ8300 treatment was used to form surface irregularities A substrate D was fabricated with a thickness of 2 μm. The varnish A was printed on a cross-section of the substrate D by 100 mesh screen and placed in a vacuum dryer at 120 ° C. to blow off the solvent, and at the same time, to stage B (170 ° C. Gel Time: 162 seconds). The substrate E was formed by forming a 7-16 탆 resin layer on the PCB surface layer, in which case the surface irregularities were large and the thermosetting resin composition was not filled very much in the through hole, resulting in large irregularities. Structural sheet C Peel off the PET film and place it on both sides so that the B-stage thermosetting resin composition layer side faces the PCB side, and place a smooth surface 1.5mm stainless plate on the outer side and put it in the press device at 5 ℃ or less at 190 ℃ and 30kgf / cm ² After the laminate was formed for 90 minutes under vacuum, cooled, and then cooled, a 25 μm thick etching film was laminated on the copper foils on both sides of the surface layer, and the negative film was placed thereon to expose, develop and etch the printed circuit board. The copper foil was removed, and the etching film was dissolved to remove a substrate F. When the precious metal plating of the printed circuit board was carried out in a plasma apparatus, the thermosetting resin composition layer was treated and removed to form a thermosetting resin composition layer on the printed circuit board conductor circuit. The thickness is left to ˜7 μm. After that, the surface copper foil is etched away and once again placed in a plasma apparatus, the remaining thermosetting property The resin composition layer was removed, and the processing was terminated when the height of the conductor circuit reached 95 to 99%, and the surface of the copper foil for solder ball pads was exposed at the same time, after which the PCB was fabricated by nickel plating and gold plating. The evaluation results are shown in Table 5.

Experimental Example  5-２

400 parts of bis (4-cyanatphenyl) ether monomer and 50 parts of bis (4 maleimide phenyl) ether were melted at 150 ° C and reacted for 4 hours while mixing well to obtain a monomer and prepolymer mixture. This was dissolved in a mixed solvent of methyl ethyl ketone and N, N'-diethyl formamide, and 200 parts of bisphenol A epoxy resin (trade name: Epicoat 1001, manufactured by Nippon Epoxy Resin Co., Ltd.) and phenol novolak epoxy resin ( Product Name: DEN-431, Dow Chemical Co., Ltd.) 150 parts, Cresol novolak-type epoxy resin (Product Name: ESCN-220F, Sumitomo Chemical Co., Ltd.) 1000-8.0, manufactured by Nihon Seki Oil Co., Ltd.) was added, 0.5 parts of phthalocyanine blue was added as a colorant, acetylacetone iron was dissolved in 0.2 parts of methyl ethyl ketone as a curing catalyst, and mixed well to prepare varnish G. This varnish G was continuously impregnated with 30 mu m thick non-aromatic polyamide nonwoven fabric and dried to prepare Prepreg H having a thickness of 45 mu m and Gel Time (at 170 deg. C) for 100 sec. Release PET with linear pressure of 25㎛ To laminate the adhesive to flow on both sides to prepare a three-layer structure sheet I.

On the other hand, the printed circuit board is prepared by using the substrate E of Experimental Example 5-1-1, peeling the single-sided PET film of the three-layer structure sheet I on it, and placing one sheet each so that the Prepreg H faces both sides of the printed circuit board. The surface smooth stainless steel plate of thickness 1.5mm was arrange | positioned at the outer side, it put into the press apparatus, laminated | stacked and formed for 90 minutes under the vacuum of 10 mmHg or less at 190 degreeC and 30 kgf / cm <^2> for 90 minutes, and produced the board | substrate J. Remove the release PET film on the surface where the precious metal plating on the surface of the substrate J is carried out with a UV-YAG laser and insert it into a plasma device to remove the cured thermosetting resin composition layer and to treat the thermosetting resin composition layer on the conductor circuit. The process was finished when the thermosetting resin composition layer became 96-100% in height of the conductor circuit. At the same time, the surface of the circuit copper foil for the solder ball pads was exposed. After that, the release PET film was peeled off and nickel plated and gold plated to manufacture a printed circuit board. The evaluation results are shown in Table 5.

Experimental Example  5-３

In Experimental Example 5-1, the B-stage thermosetting resin composition surface of the B-stage thermosetting resin composition sheet B having the release PET film attached to the cross-section of the liquid crystal polyester film having a thickness of 25 μm was disposed so as to face the liquid crystal polyester film side, and the opposite side thereof. Thereafter, the PET film of the B-stage thermosetting resin composition sheet C with copper foil was peeled and placed, and laminated at 5 kgf / cm linear pressure with a 90 ° C. heating roll to produce the B-stage thermosetting resin composition sheet K with copper foil. The PET film was peeled and placed on both sides of the substrate E treated in Experimental Example 5-1, and the substrate L was prepared by stacking and removing the film at 190 ° C and 30 kgf / cm ² for 90 minutes under a vacuum degree of 5 mmHg. The copper foil on the circuit of the precious metal plating on the PCB of the substrate L was etched and removed as in Experimental Example 5-1, placed in a plasma apparatus, and the thermosetting resin composition layer cured by plasma was treated to remove the thermosetting resin composition layer on the conductor circuit. After etching away the copper foil of the surface layer leaving 2 to 5 µm, the remaining thermosetting resin composition layer was processed and removed by plasma treatment to treat 90-95% of the exposed conductor circuit height, respectively. At the same time, the surface of the circuit copper foil for the solder ball pads was exposed. After that, nickel plated and gold plated were used to fabricate the printed circuit board. The evaluation results are shown in Table 5.

Experimental Example  5-４

1300 parts of aluminum hydroxide (average particle diameter: 2.0 µm), tar molybdenum-supported tar on the varnish A (brand name: KEMGARD911C, average particle diameter of 4.1 µm, 19 mol% of zinc molybdate supported), Shawin Williams (Note) Varnish M was prepared by adding 100 parts of zinc hydroxytinate (trade name: ZHS, JOSEPH STOREY & CO., LTD). This was impregnated and dried on a glass cloth substrate having a thickness of 10 μm to prepare a 30 μm Prepreg N to which a B stage thermosetting resin composition (170 ° C. Gel Time 125 seconds) was attached. On the other hand, a non-halogen copper clad laminate (trade name: CCL-HL832NB, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a thickness of 0.4 mm and a copper foil of 12 µm on both sides was formed in the same manner as in Experimental Example 5-1, and the surface treatment was performed. Varnish M was applied and dried on both surfaces in the same manner, to prepare a substrate O having a B stage thermosetting resin composition layer having a Gel Time of 148 seconds. Each of Prepreg N was placed on both sides of the substrate O, and an electrolytic copper foil having a thickness of 12 µm was placed on the outer side thereof, and the substrate P was laminated for 120 minutes under vacuum at 220 ° C, 35 kgf / cm ² and 5 mmHg or less. . The whole front and back copper foil was etched away uniformly, and the board | substrate Q of 3 micrometers of copper foil thickness was produced. The thermosetting resin composition layer and the glass woven fabric on the bonding pad conductor circuit of the printed circuit board noble metal plating surface of this board | substrate Q were processed and removed by luther, and the thermosetting resin composition layer on the conductor circuit was left to 2-5 micrometers. In addition, the PET film and the thermosetting resin composition layer on the solder ball pad part on the back side were irradiated with a carbon dioxide laser to remove the thermosetting resin composition and the glass woven fabric, and the thermosetting resin composition layer was exposed on the conductor circuit by 0.5 to 1 μm. The desmearing process exposed the conductor circuit, and the surface of the thermosetting resin composition layer was 95-99% of the height of the conductor circuit, and the copper foil surface of the solder ball pad was exposed on the reverse side. After that, nickel plated and gold plated were used to fabricate the printed circuit board. The evaluation results are shown in Table 5.

Comparative example  5-１

UV-selective thermosetting resist (trade name: PSR4000AUS5, manufactured by Taiyo Ink Co., Ltd.), commercially available without using the B-stage resin composition sheet with copper foil in Experimental Example 5-1, was applied and dried by screen printing. After exposure, development and thermosetting, nickel plating and gold plating were used to produce a printed circuit board. The evaluation results are shown in Table 5.

Comparative example  5-２

In Comparative Example 5-1-1, the UV resist was repeatedly applied twice, filled in the hole, and processed in the same manner to prepare a printed circuit board. The evaluation results are shown in Table 5.

Comparative example  5-３

In Experimental Example 5-1-1, Varnish A was used to print through a precious metal plating area using a screen with a mesh of 100 mesh on a printed circuit board, which was then blown at 80 ° C. for 30 minutes, and then heated at 150 ° C. for 60 minutes. Then, the substrate was heat-cured at 190 ° C. for 60 minutes and nickel plated and gold plated to manufacture a printed circuit board. The evaluation results are shown in Table 5.

Comparative example  5-４

In Experimental Example 5-1-1, the substrate D was used and placed in a plasma apparatus, the plasma was irradiated thereon to remove the thermosetting resin composition of the opening at once, exposing the conductor circuit on the surface to make the height of the thermosetting resin composition layer the same. . Subsequently, the copper foil of the surface layer was etched away and nickel plated and gold plated to manufacture a printed circuit board. In this case, the printed circuit board circuit was also etched away, becoming thinner and 16 to 19 mu m lower than the resin. The evaluation results are shown in Table 5.

Experiment Result 5

Item Experimental Example 5-1 Experimental Example 5-2 Experimental Example 5-3 Experimental Example 5-4 Comparative Example 5-1 Comparative Example 5-2 Comparative Example 5-3 Comparative Example 5-4 Bubble in energizing hall 0 0 0 0 525 398 750 0 Through hole irregularities (㎛) <3 <3 <3 <3 52 22 76 6.4 Circuit surface irregularities (㎛) <5 <5 <5 <5 17.0 8.7 21 <5 Bad circuit (%) 0 0 0 0 19.1 24.5 11.0 0 Bending / Twisting (mm) <3 <3 <3 <3 4.2 5.1 4.2 <3 Smeared Bonding Pad none none none none none none has exist none Bad wire bonding connection none none none none none none has exist has exist Solder heat resistance clear clear clear clear Some bloating Some bloating clear clear Migration resistance (Ω) condition 5 × 10 ¹³ 4 × 10 ¹³ 4 × 10 ¹³ 4 × 10 ¹³ 5 × 10 ¹³ 5 × 10 ¹³ 4 × 10 ¹³ 3 × 10 ¹³ 200hrs. 3 × 10 ¹¹ 9 × 10 ¹⁰ 2 × 10 ¹² 1 × 10 ¹¹ 7 × 10 ⁹ 8 × 10 ⁹ 2 × 10 ¹¹ 1 × 10 ¹¹ 500hrs. 4 × 10 ¹⁰ 5 × 10 ¹⁰ 1 × 10 ¹¹ 1 × 10 ¹⁰ <10 ⁸ <10 ⁸ 1 × 10 ¹⁰ 3 × 10 ¹⁰ Cold shock resistance none none none none has exist has exist has exist none Flame Retardant (UL-94) HB HB HB V-0 HB HB HB HB

As can be seen from Table 5, it can be seen that the printed circuit board manufactured by the fourth embodiment of the present invention has improved performance in resin fillability to holes, irregularities in surface portions, and circuit peeling. In addition, it can be seen that not only the bending / twist of the conductor circuit is reduced, but also the performance is improved in bonding pad part bleeding, solder heat resistance, migration resistance, and cold shock resistance.

Experiment 6: fifth Example  According Permanent Protective Film  Performance experiment

Experimental Example 6-1

As a printed circuit board, a double-sided copper clad laminated board (trade name: CCL-HL832NB, Mitsubishi Gas Chemical Co., Ltd.) having an insulating layer thickness of 0.4 mm and a copper foil thickness of 12 µm was used. 20,000 pieces were drilled into the workpiece size, and 0.7 µm of electroless copper plating and 15 µm of electroplated copper were attached to each other. 2 micrometers of unevenness | corrugation is arrange | positioned each liquid crystal polyester resin film (brand name: FA film, melting | fusing point 280 degreeC, Kuraray) of 25 micrometers on both surfaces, and the 50-micrometer-thick fluororesin on the outside. The film was placed, and a 2 mm thick surface smooth stainless steel plate was placed on the outside thereof, mounted on a press device, laminated at a temperature of 295 ° C. and 20 kgf / cm ² for 10 minutes under vacuum of 5 mmHg, and then taken out. After cooling, foil the fluororesin film On the liquid crystal polyester film of the surface layer, a stainless steel plate having a thickness of 1 mm is formed on the liquid crystal polyester film of the printed circuit board. The resin composition layer was treated to remove the front and back circuits, and the processing was completed at the time when the height became 92 to 99% of the height of the circuits. Thereafter, nickel plating and gold plating were used to make a printed circuit board. The evaluation results are shown in Table 6.

Comparative example  6-１

In Experimental Example 6-1, commercially available UV selective thermosetting resists (trade name: PSR4000AUS5, manufactured by Taiyo Ink Co., Ltd.) were applied, dried, and exposed to light, without using a liquid crystal polyester resin film. After developing and thermosetting, nickel plating and gold plating were used to make a printed circuit board. The evaluation results are shown in Table 6.

Comparative example  6-２

In Comparative Example 6-1, the UV resist was applied twice, the holes were filled, and the same process was performed to produce a printed circuit board. The evaluation results are shown in Table 6.

Comparative example  6-３

450 parts of 2,2, -bis (4-cyanatophenyl) propane monomers were melted at 160 degreeC, and it was made to react for 4.5 hours, stirring, and the monomer and prepolymer mixture were obtained. This was dissolved in methyl ethyl ketone and thus bisphenol A epoxy resin (brand name: Epicoat 1001, Japan Epoxy Resin Co., Ltd.) 100 parts, phenol novolak type epoxy resin (brand name: DEN-431, Dow Chemical Co., Ltd.) 150 Part: 200 parts of cresol noborac epoxy resin (trade name: ESCN-220F, manufactured by Sumitomo Chemical Co., Ltd.), 100 parts of liquid epoxidized polybutadiene resin (brand name: E-1000-8.0, Nippon Petroleum Co., Ltd.) Then, 0.5 part of phthalocyanine blue was added as a coloring agent, zinc octylate was melt | dissolved in 0.2 part methyl ethyl ketone as a hardening catalyst, it added, it stirred well, it was made into varnish A. This varnish A was used to make a 100-mesh screen on the printed circuit board of Experimental Example 6-1. The precious metal plating part was printed using a mesh screen to penetrate the precious metal plating part and the solvent was heated at 80 ° C. Was blown for 30 minutes, heat-cured at 150 ° C. for 60 minutes, and at 190 ° C. for 60 minutes. Then, nickel plating and gold plating were used to form a printed circuit board. The evaluation results are shown in Table 6.

Experiment result

Item Experimental Example 6-1 Comparative Example 6-1 Comparative Example 6-2 Comparative Example 6-3 Bubble in energizing hall 0 521 401 778 Through hole irregularities (㎛) 3.5 53 21 79 Circuit surface irregularities (㎛) <5 17.3 8.8 21 Bad circuit (%) 0 18.9 24.5 11.0 Bending / Twisting (mm) <2 4.0 5.1 4.2 Smeared Bonding Pad none none none Bad wire bonding connection none none none has exist Solder heat resistance clear Some bloating Some bloating Some bloating    Migration resistance (Ω) condition 3 × 10 ¹³ 5 × 10 ¹³ 5 × 10 ¹³ 4 × 10 ¹³ 200hrs. 1 × 10 ¹¹ 7 × 10 ⁹ 8 × 10 ⁹ 2 × 10 ¹¹ 500hrs. 8 × 10 ⁹ <10 ⁸ <10 ⁸ 9 × 10 ⁹

Cold shock resistance none has exist has exist has exist Flame Retardant (UL-94) HB HB HB V-0

As can be seen from Table 6, it can be seen that the printed circuit board manufactured by the fifth embodiment of the present invention has improved performance in resin filling property to holes, irregularities in surface portions, and circuit peeling. In addition, it can be seen that not only the bending / twist of the conductor circuit is reduced, but also the performance is improved in bonding pad part bleeding, solder heat resistance, migration resistance, and cold shock resistance.

Experiment 7: 6th Example  According Permanent protective coating  Performance experiment

Experimental Example  7-１

450 parts of 2,2, -bis (4-cyanatophenyl) propane monomer were melted at 160 degreeC, and it reacted for 4.5 hours, mixing well, and obtained the monomer and prepolymer mixture. This was dissolved in methyl ethyl ketone, and 150 parts of bisphenol-A epoxy resin (trade name: Epicoat 1001, manufactured by Japan Epoxy Resin Co., Ltd.), phenol nobolo-type epoxy resin (trade name: DEN-431, Dow Chemical Co., Ltd.) 200 parts of cresol novolent-type epoxy resin (trade name: ESCN-220F, manufactured by Sumitomo Chemical Co., Ltd.). 0.5 parts of Pigment Blue 15: 3) and 0.5 parts of Yellow (CI Pigment® Yellow 151) were added to the mixture, and green pigment was added. Zinc octylate was dissolved in 0.2 parts of methyl ethyl ketone as a curing catalyst, and stirred and mixed to prepare varnish A. .

On the other hand, a double-sided copper clad laminate (trade name: CCL-HL832HS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) with an insulating layer thickness of 0.4 mm and a copper foil thickness of 3 μm was used as a printed circuit board. The hole was drilled into 20,000 holes in the work size, and 0.4 µm of electroless copper plating and 1 µm of electroplated copper were deposited to attach, expose, and develop a plating resist, leaving a resist having a space of 30 µm and a resist width of 20 µm. After the thickness was deposited, the plating resist was stripped, and then flash etched to finally form a line / space = 25/25 μm circuit in the bonding range, and a line / space = 70/70 μm circuit on the outer side to form Mec CZ8100 + CZ8300. After the treatment, the surface irregularities were set to 1 µm, and the noble metal plating permanent protection solder resist (trade name: PSR4000AUS5, manufactured by Taiyo Inky Co., Ltd.) was coated and dried to have a thickness of 20 µm. The temporary film was placed on the inside and outside, and exposed, developed, and post-cured to cover the surface with a permanent protective film, leaving the range of wire bonding pads on the surface and the solder ball pads on the back. Then, the varnish A was injected into the wire bonding pad range with a dispenser, dried under vacuum at 60 ° C. and 60 mm Hg to blow off the solvent to uniformly fill the resin within the wire bonding pad range to produce 5 to 9 μm in the conductor circuit. did. After heating and semi-curing at 150 ° C. for 60 minutes, a UV selective thermosetting resist was applied to the entire surface by a caten coat method, and a negative film was applied to the surface to expose and develop a resin composition in the range of wire bonding pads. Thereafter, the resultant was placed in a plasma apparatus, and processed so that the thermosetting resin composition layer of the opening was 90 to 95% of the height of the wire bonding pad conductor circuit. Subsequently, after curing at 160 ° C. for 60 minutes, nickel plated and gold plated were used to fabricate a printed circuit board. The semiconductor chip was bonded to the surface by silver paste, and then encapsulated with a mold resin after wire bonding. Made. The evaluation results are shown in Table 7.

Comparative example  7-１

In Experimental Example 7-1, between the wire bonding conductor circuits was processed without filling with a thermosetting resin composition, and the semiconductor plastic package was produced similarly. The evaluation results are shown in Table 7.

Comparative example  7-2

In Experimental Example 1, Varnish A was printed on a printed circuit board using 100 mesh screen, except where precious metal plating was applied. The solvent was blown at 80 ° C. for 30 minutes, heat cured at 150 ° C. for 90 minutes, and then nickel The printed circuit board was manufactured by plating and gold plating. The evaluation results are shown in Table 7.

Comparative example  7-３

Except for injecting the acrylic solder resist used in Experimental Example 7-1 in the bonding pad range in Experimental Example 7-1, the printed circuit board was manufactured. The evaluation results are shown in Table 7.

Experiment result

Item Experimental Example 7-1 Comparative Example 7-1 Comparative Example 7-2 Comparative Example 7-3 Bad circuit (%) 0 22.1 14.9 0 Smeared Bonding Pad none none has exist none Bad wire bonding connection none none has exist none    Migration resistance (Ω) condition 3 × 10 ¹³ 5 × 10 ¹³ 5 × 10 ¹³ 4 × 10 ¹³ 200hrs. 6 × 10 ¹¹ 8 × 10 ⁹ 4 × 10 ⁹ 8 × 10 ⁸ 700hrs. 5 × 10 ¹⁰ 1 × 10 ⁹ 8 × 10 ⁸ <10 ⁸

As can be seen from Table 7, the printed circuit board manufactured according to the sixth embodiment of the present invention not only reduced the circuit peeling defect and the bending / twisting of the conductor circuit, but also the performance in the bleeding and migration of the bonding pad part. It can be seen that this improvement.

Experiment 8: 7th Example  According Permanent protective coating  Performance experiment

Experimental Example  8-１

450 parts of 2,2, -bis (4-cyanatophenyl) propane monoma were melted at 160 degreeC, and it stirred for 45 hours, stirring well, and obtained the monomer and prepolymer mixture. This is dissolved in methyl ethyl ketone, and bisphenol A epoxy resin (trade name: Epicoat 1001, manufactured by Japan Epoxy Resin Co., Ltd.) 150 parts, phenol novolak type epoxy resin (trade name: DEN-431, Dow Chemical Co., Ltd.) 200 parts of cresol novolak type epoxy resin (trade name: ESCN-220F, manufactured by Sumitomo Chemical Co., Ltd.) is blended with copper phthalocyanine blue KRO (CI) as a colorant. 0.5 parts of Pigment® Blue 15: 3) and 0.5 parts of Yellow (C.I. Pigment® Yellow 151) were added, green pigment was added, zinc octylate was dissolved in 0.5 parts of methyl ethyl ketone as a curing catalyst, added, and the varnish A was prepared.

On the other hand, using a double-sided copper clad laminate (trade name: CCL-HL832HS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) having an insulating layer thickness of 0.4 mm and a copper foil thickness of 3 µm as a printed circuit board, a metal drill penetrates a hole diameter of 250 µm. 20,000 holes were processed in the work size, and after the desmearing treatment, 0.4 µm of electroless copper plating and 1 µm of electroplated copper were attached, and a plating resist was attached, exposed and developed to leave a 30 µm space and a 20 µm resist width. . The copper copper plating was deposited to a thickness of 25 μm, and after the plating resist was peeled off, a flash etching was used to finally form a line / space = 25/25 μm circuit in the bonding range, and outside the line / space = 60/60 μm circuit. The surface was uneven | corrugated to 1 micrometer by the CZ8100 + CZ8300 process of Mec Co., Ltd., and apply | coated and dried so that the noble metal plating permanent protection soldering resist (brand name: PSR4000AUS5, the Taiyo Inky Co., Ltd. make) may be set to 20 micrometers. Was placed on the front and back, exposed, developed, and post-cured, and the substrate B was manufactured by covering the entire surface with a permanent protective film, leaving the surface wire bonding pad range including the semiconductor chip-mounted metal foil portion and the solder ball pad portion on the back side. Then, the varnish A was injected into the wire bonding pad range with a dispenser, dried under vacuum at 60 ° C. and 60 mmHg to blow off the solvent, and the resin was uniformly filled in the wire bonding pad range, which was then heated at 150 ° C. for 60 minutes. The substrate C was obtained by setting it as a semi-hardening machine so that the height might be 95 to 99% of the conductor circuit height. At this time, the thermosetting resin composition is attached to the wire bonding pad conductor circuit 3 ~ 5㎛. The thermosetting resin composition adhered on the wire bonding pad conductor circuit was processed and removed by UV-YAG laser, after which it was post-cured at 160 ° C. for 60 minutes, and nickel plated and gold plated to manufacture a printed circuit board. The semiconductor chip was bonded to this surface by silver paste, connected to the wire bonding pad by wire bonding, and molded with a molding resin to produce a semiconductor plastic package. The evaluation results are shown in Table 8.

Example  8-２

Using the substrate C of Example 8-1, as a protective coating resin composition, a UV selective thermosetting resist was applied to the entire surface by a caten coat method, and the film was exposed and developed by coating a film on the surface to obtain a metal foil for semiconductor chip mounting. The resin composition of the wire bonding pad range to include was developed and removed. Then, it put into a plasma apparatus and processed, and it processed so that the thermosetting resin composition of an opening part might be 89 to 93% of the height of a wire bonding pad conductor circuit. Thereafter, the substrate was post-cured at 160 ° C. for 60 minutes, nickel plated, and gold plated to produce a printed circuit board. The semiconductor chip was bonded to this surface by silver paste, connected to the wire bonding pad by wire bonding, and molded into a molding resin to produce a semiconductor plastic package. The evaluation results are shown in Table 8.

Comparative example  8-1

In Experimental Example 8-1, a printed circuit board was produced without filling the wire bonding conductor circuit with the thermosetting resin composition, and a semiconductor plastic package was produced in the same manner. The evaluation results are shown in Table 8.

Comparative example  8-２

In Experimental Example 8-1, using varnish A, it was printed using a 100 mesh screen on a printed circuit board, punched out of the metal-plated part, and the solvent was blown at 80 ° C. for 30 minutes, followed by heat curing at 150 ° C. for 90 minutes. Then, nickel plated and gold plated were used to produce a printed circuit board, and then a semiconductor plastic package was produced. The evaluation results are shown in Table 8.

Comparative example  8-３

In Experimental Example 8-1, except that the acrylic solder resist used in Experimental Example 8-1 was injected into the bonding pad range, a printed circuit board was produced in the same manner to produce a semiconductor plastic package. The evaluation results are shown in Table 8.

Experiment result

Item Experimental Example 8-1 Experimental Example 8-1 Comparative Example 8-1 Comparative Example 8-2 Comparative Example 8-3 Bad circuit (%) 0 0 22.1 14.9 0 Smeared Bonding Pad none none none has exist none Bad wire bonding connection none none none has exist none    Migration resistance (Ω) condition 3 × 10 ¹³ 4 × 10 ¹³ 5 × 10 ¹³ 5 × 10 ¹³ 4 × 10 ¹³ 200hrs. 7 × 10 ¹¹ 5 × 10 ¹¹ 8 × 10 ⁹ 4 × 10 ⁹ 8 × 10 ⁸ 700hrs. 6 × 10 ¹⁰ 4 × 10 ¹⁰ 1 × 10 ⁹ 8 × 10 ⁸ <10 ⁸

As can be seen from Table 8, the printed circuit board manufactured according to the seventh embodiment of the present invention not only reduced the circuit peeling defect and the bending / twisting of the conductor circuit, but also performed the performance in bleeding and migration of the bonding pad part. It can be seen that this improvement.

Although the technical spirit of the present invention has been described in detail according to the above-described embodiments, the above-described embodiments are for the purpose of description and not of limitation, and a person of ordinary skill in the art will appreciate It will be understood that various embodiments are possible within the scope.

The present invention can achieve the following effects by the above configuration.

The present invention can provide a permanent protective film forming method and a printed circuit board on which a permanent protective film is formed, which is easy to form and process and has excellent workability.

The present invention has an effect of providing a method for forming a permanent protective film having excellent filling properties of resin into a through hole or blind via hole of a printed circuit board, and a printed circuit board having a permanent protective film formed thereon.

The present invention can achieve the effect of providing a permanent protective coating method and a printed circuit board having a permanent protective coating because the thickness variation of the inner and outer sides of the permanent protective coating is small.

The present invention can achieve the effect of providing a method for forming a permanent protective film having excellent surface smoothness and low circuit peeling and a printed circuit board having a permanent protective film formed thereon.

The present invention has the effect of providing a method of forming a permanent protective film having excellent bonding properties, excellent heat resistance and reliability after moisture absorption, and a printed circuit board having a permanent protective film formed thereon.

Claims (37)

Stacking a thermosetting resin composition filling the conductor circuit on the printed circuit board; Curing the thermosetting resin composition; And removing the thermosetting resin composition to remain at 20% to 100% of the height of the conductor circuit so that a part of the conductor circuit is exposed to the outside.  The method of claim 1, The thermosetting resin composition is a permanent protective film forming method to which a non-halogen type flame retardant is added.  The method of claim 1, The thermosetting resin composition is a permanent protective film forming method is added one selected from the group consisting of an inorganic base, an organic base and a mixed yarn mixed with an inorganic base and an organic base.  The method of claim 1, And the thermosetting resin composition is removed by one or a combination thereof selected from the group selected from laser, router and plasma. Placing a thermosetting resin composition and a film filling the conductor circuit on the printed circuit board; Curing the film by laminating the thermosetting resin composition by thermocompression bonding the film; Removing a portion of the film; Removing the thermosetting resin composition to remain at 20% to 100% of the height of the conductor circuit so that a part of the conductor circuit is exposed to the outside; Permanent protective film forming method comprising the step of removing the remaining film. The method of claim 5, The film is a permanent protective film forming method of the release film. The method of claim 5, The film is a heat-resistant organic film permanent protective film forming method. Sequentially placing the thermosetting resin composition and the metal foil filling the conductor circuits on the printed circuit board; Curing the metal foil by laminating the thermosetting resin composition by thermocompression bonding the metal foil; Removing a portion of the metal foil; Removing the thermosetting resin composition slightly above the conductor circuit; Removing the remaining metal foil; Permanent protective film forming method comprising the step of removing the thermosetting resin composition to remain to 20% ~ 100% of the height of the conductor circuit.  The method according to any one of claims 5 to 8, The deteriorated resin composition is a non-halogen type flame retardant is added permanent protective film forming method.  The method according to any one of claims 5 to 8, The thermosetting resin composition is a permanent protective film forming method is added one selected from the group consisting of an inorganic base, an organic base and a mixed yarn mixed with an inorganic base and an organic base.  The method according to any one of claims 5 to 8, The thermosetting resin composition is a permanent protective film forming method that is removed by a plasma treatment.  The method according to any one of claims 5 to 8, The thermosetting resin composition is a permanent protective film forming method which is cured by thermal compression of the film in a vacuum state by using a flat plate.  The method of claim 6, The release film is a permanent protective film forming method that is a film that can be developed with UV exposure and dilute alkali solution.  The method of claim 7, wherein The heat-resistant organic film is a liquid crystal polyester resin film permanent protective film forming method.  The method of claim 8, And the metal foil is removed by etching.  The method of claim 11, And the film is removed to be somewhat smaller than the removal area of the thermosetting resin composition. (a) forming a thermosetting resin composition filling the conductor circuits on the printed circuit board; (b) attaching the thermosetting resin composition to the release film to produce a thermosetting resin composition sheet; (c) laminating the thermosetting resin composition sheet on the printed circuit board to which the thermosetting resin composition is applied; (d) removing a portion of the release film; (e) removing the thermosetting resin composition to remain at 20% to 100% of the height of the conductor circuit so that a part of the conductor circuit is exposed to the outside; (f) forming a permanent protective film comprising the step of removing the remaining release film. The method of claim 17, In the step (e), the thermosetting resin composition is a permanent protective film forming method that is treated by a plasma. The method of claim 17, In the step (b), the thermosetting resin composition sheet forms the thermosetting resin composition on both sides of the heat resistant organic film, and the permanent protective film forming method attached to the release film. The method of claim 17, The thermosetting resin of the thermosetting resin composition sheet in the step (b) comprises an organic fiber cloth base material or an inorganic fiber cloth base material. The method according to any one of claims 17 to 20, The thermosetting resin composition is a non-halogen and flame-retardant method of forming a permanent protective film. (a) forming a thermosetting resin composition filling the conductor circuits on the printed circuit board; (b) attaching the thermosetting resin composition to the metal foil to prepare a thermosetting resin composition sheet; (c) laminating the thermosetting resin composition sheet on the printed circuit board to which the thermosetting resin composition is applied; (d) removing a portion of the metal foil; (e) removing the thermosetting resin composition slightly above the conductor circuit; (f) removing the remaining metal foil; (g) removing the thermosetting resin composition so as to remain at 20% to 100% of the height of the conductor circuit. The method of claim 22, In the step (e) and (g) the thermosetting resin composition is a permanent protective film forming method which is treated by a plasma. The method of claim 22, In the step (b), the thermosetting resin composition sheet forms the thermosetting resin composition on both sides of the heat resistant organic film, wherein the permanent protective film is formed on the metal foil. The method of claim 22, The thermosetting resin of the thermosetting resin composition sheet in the step (b) comprises an organic fiber cloth base material or an inorganic fiber cloth base material. The method according to any one of claims 22 to 25, The thermosetting resin composition is a non-halogen and flame-retardant method of forming a permanent protective film. (a) laminating a thermoplastic resin composition having a melting point of at least 270 ° C. on a printed circuit board, which is filled between conductor circuits; (b) curing the thermoplastic resin composition; (c) removing the thermoplastic resin composition so as to remain at 20 to 100% of the height of the conductor circuit so that a part of the conductor circuit is exposed to the outside. The method of claim 27, The thermoplastic resin composition is a permanent protective film forming method of the liquid crystal polyester resin composition. The method of claim 27, The thermoplastic resin composition is non-halogen and flame retardant permanent protective film forming method. (a) forming a permanent protective film on a portion of the printed circuit board other than the wire bonding pad portion; (b) injecting a thermosetting resin composition into a wire bonding pad portion on the printed circuit board and curing or semi-curing the resin; (c) removing the thermosetting resin composition to expose the conductor circuit. The method of claim 30, Laminating a protective resin composition layer on a portion other than the wire bonding pad portion of the printed circuit board after the step (b); Permanent protective film forming method further comprising the step of removing the protective resin composition layer after the step (c). The method of claim 31, wherein The protective resin composition layer is a method of forming a permanent protective film is a resin composition capable of photoexposure and develop a rare alkali. The method of claim 32, The protective resin composition layer is a cyanic acid ester resin composition permanent protective film forming method. The method of claim 30, In the step (b), the thermosetting resin composition is a permanent protective film forming method of injecting to be 25 to 100% of the height of the conductor circuit. A printed circuit board filled with a thermosetting resin composition between 20 and 100% of the height of the conductor circuit between the conductor circuits. 36. The method of claim 35 wherein The thermosetting resin composition is a printed circuit board to which a non-halogen type flame retardant is added 36. The method of claim 35 wherein The thermosetting resin composition is a printed circuit board to which one selected from the group consisting of an inorganic substrate, an organic substrate and a mixed yarn mixed with an inorganic substrate and an organic substrate is added.

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