JP2006310788A - Method of manufacturing resin-filled substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a resin-filled substrate which can prevent unfilling of an opening and roll-in of a void and has small polishing load (excellent in productivity). <P>SOLUTION: The method of manufacturing a resin-filled substrate is used which includes a process of rotating non-contact roll (R) at a circumferential velocity (v) (mm/sec.) so that the rotation direction of a portion of a substrate from a rotation axis is opposite to a moving direction while linearly moving the non-contact roll (R) at a moving velocity (i) (mm/sec.) in a direction horizontal to a substrate face and a direction vertical to the rotation axis of the (R), and filling a resin paste (J) having a loss elasticity (G") of 50-100,000 Pa into the opening provided on the substrate. In this method, the moving velocity (i) and the circumferential velocity (v) are in a relation of v≥10×i. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a resin-filled substrate. More specifically, the present invention relates to a method for manufacturing a resin-filled substrate in which openings (such as recesses and through-holes) provided in a substrate such as a printed wiring board and a silicone wafer are filled with a resin paste.

As a method for manufacturing a resin-filled substrate, a manufacturing method using a screen printing method (Patent Document 1), a manufacturing method using a method of press-fitting with a roll (Patent Document 2), and the like are known.

JP 2001-177254 A JP 2001-358433 A

In the conventional manufacturing method, the ratio of the depth of the opening to the square root of the opening area (the depth of the opening / the square root of the opening area) among the various openings (recesses, through-holes, etc.) provided in the substrate is If it exceeds 5, there is a problem that an unfilled opening is generated. In particular, this problem becomes prominent when a high-viscosity filling resin paste is used to prevent sagging of the resin and dents in the filling portion.
Further, in the conventional manufacturing method, it is necessary to print through a print mask corresponding to the position and size of the opening provided in the substrate during printing in order to prevent the filling portion from being dented. For this reason, when filling an opening with a small opening area, it is necessary to align the printing mask with high accuracy (if the printing mask is displaced, unfilling or void entrainment occurs in the opening). is there. Further, it is necessary to polish a portion corresponding to the thickness of the printing mask after filling the resin, and there is a problem that the substrate warps due to a load during polishing.
An object of the present invention is to provide a method for producing a resin-filled substrate that is free from unfilled openings or voids and has a small polishing load (excellent productivity).

The inventor of the present invention has reached the present invention as a result of intensive studies to solve the above problems. That is, in the method for producing a resin-filled substrate of the present invention, the non-contact roll (R) is moved in the horizontal direction with respect to the substrate surface and in the direction perpendicular to the rotation axis of (R) (i) (mm / second). ) And rotating (R) at a peripheral speed (v) (mm / sec) so that the rotation direction of the portion on the substrate side from the rotation axis of (R) is opposite to the movement direction,
Including a filling step of filling a resin paste (J) having a loss elastic modulus (G ″) of 50 to 100,000 Pa into an opening provided in the substrate, and the moving speed (i) and the peripheral speed (v) are v> 10. The point is that there is a relationship of xi.
Here, the linear movement of the non-contact roll (R) may be performed by relatively linearly moving the non-contact roll (R) and the substrate. Accordingly, the non-contact roll (R) may move with respect to the stopped substrate, or the substrate moves with respect to the non-contact roll (R) that is stopped (rotating). Good.

  In the manufacturing method of the present invention, unfilled or void entrainment occurs even in a substrate having a large ratio of the depth of the opening to the square root of the opening area (depth of the opening / square root of the opening area) (greater than 5). It is easy to fill the recesses and through holes with the filling resin. Further, even if the printing mask is not used, the filling portion does not dent, and it is possible to reduce the alignment process of the printing mask and to prevent the warpage of the substrate due to the reduction of the polishing load.

  The loss elastic modulus (G ″) (unit: Pa) of the resin paste (J) used in the present invention is preferably from 50 to 100,000, more preferably from 60 to 100,000, from the viewpoint of fillability (easy to fill). 10000, particularly preferably 80 to 5000, and most preferably 100 to 2000. Within this range, the occurrence of unfilled or void entrainment can be further suppressed.

The loss elastic modulus (G ″) (unit: Pa) in the present invention is “Rheological engineering and its applied technology”, Fuji Techno System Co., Ltd., published on January 12, 2001, first edition, pages 204-206. It is a value measured at the same temperature as that at the time of filling using a viscoelasticity measuring device (for example, Rheostress RS75 manufactured by HAAKE, Inc.) that can be measured by the stress control method described in 1. and is obtained as follows.
A measurement sample is sandwiched between measurement jigs {between the upper cone disk and the lower flat disk (see FIG. 1, the arrow in FIG. 1 indicates the direction of sinusoidal vibration)}, and is perpendicular to the upper surface of the upper cone disk Strain is generated by applying stress (σ) (unit: Pa) to the measurement sample by sine vibration while changing the angular velocity (ω) (unit: rad / sec) about the central axis. (Unit: rad) and phase angle (δ) (unit: rad) are measured.
Then, in accordance with JIS K7244-1: 1998 “Plastics—Test Method for Dynamic Mechanical Properties Part 1: General Rules”, the complex elastic modulus is calculated from the ratio (σ / ε) of stress (σ) to strain (ε). After calculating (G ^* = σ / ε) (unit: Pa), the loss elastic modulus (G ″) is calculated from the formula {G ″ = G ^* × sinδ} as the imaginary part of the complex elastic modulus (G ^* ). To do.
From the “angular velocity-loss elastic modulus curve” obtained by plotting the calculation result, the loss elastic modulus at the angular velocity (ω) corresponding to the peripheral velocity (v) of the non-contact roll (R) used at the time of filling is read. The peripheral speed (v) and the angular speed (ω) are converted by the following equation.
Angular velocity (ω) = circumferential velocity (v) / radius (r) of roll (R)

The measurement conditions are shown below.
Measuring device: Dynamic viscoelasticity measuring device (for example, Rheostress RS75 manufactured by HAAKE)
Measuring jig: 20mm diameter aluminum disk (upper cone disk angle 2 degrees)
Sample volume: 0.5mL
Rotational shear stress: 10Pa
Measurement temperature: Same temperature as filling (usually 20-30 ° C)
Angular velocity: 0.628-628 rad / sec

  In the conventional manufacturing method, the filling property of the resin paste is often specified by the viscosity, but the viscosity is measured under a constant stress condition and a time condition using a rotary viscometer. In the present invention, it is not suitable for measurement corresponding to a change in speed, and it is difficult to prescribe with a rotational viscometer the filling property by roll rotation in which the shearing force against the resin paste and the flow rate of the resin paste always change. Defines the resin paste (J) in terms of loss elastic modulus (G ″).

As the resin paste (J), a mixture of a filler (F) and a curable resin and / or a thermoplastic resin is used.
As the filler (F), known inorganic fillers and organic fillers can be used.
Inorganic fillers include oxides {silica (silicon oxide), titania (titanium oxide), alumina (aluminum oxide), zirconia (zirconium oxide), barium titanate, etc.}, carbonate {calcium carbonate, etc.}, sulfate {sulfuric acid Barium etc.}, metal {gold, platinum, copper, silver, nickel, tin, iron, etc., and composites thereof (including mixed formed bodies and solid solutions)}. Of these, silica, copper and silver are preferred.
Examples of the organic filler include acrylic resin powder, epoxy resin powder, fluororesin powder, polyether sulfone resin powder, silicone resin, and nylon resin powder. Of these, acrylic resin powder is preferred.

The content (% by weight) of the filler (F) is preferably 30 to 95, more preferably 50 based on the total weight of the filler (F), the curable resin, and the thermoplastic resin from the viewpoint of the thermal expansion coefficient. ˜90, particularly preferably 60˜85. Within this range, the unfilled opening and the generation of voids are further suppressed.
The volume average particle diameter (μm) of the filler (F) is preferably 0.1 to 30, more preferably 0.5 to 20, and particularly preferably 1.0 to 10. Within this range, the unfilled opening and the generation of voids are further suppressed.
The volume average particle size is a laser diffraction type particle size distribution measuring device having a measurement principle based on JIS Z8825-2: 2001 “Particle size analysis—laser diffraction method” (for example, trade name SALD-1100 manufactured by Shimadzu Corporation). Measured in

  The shape of the filler (F) is spherical, teardrop-shaped, angular, dendritic, flaky, granular, irregular, needle-like, fibrous (JIS Z2500: 2000 “Powder and Gold Terms”) 4. Terms and Definitions 4) Particle shape of powder) may be used, but spherical, teardrop-like, flake-like, and granular are preferable, and spherical is more preferable from the viewpoint of filling of the opening.

  Although a filler (F) may be used independently, you may use it in combination of 2 or more type. For example, a combination of spherical silica, dendritic copper powder, and granular calcium carbonate.

Examples of the curable resin include a thermosetting resin and an active energy ray curable resin.
As the thermosetting resin, an epoxy resin or a polyimide resin described in JP-A-2004-149758 can be used.
Examples of the active energy ray-curable resin include an epoxy resin described in JP-A No. 2004-149758, a compound having a polymerizable double bond described in JP-A No. 2001-330951, and a photo radical generator. Things can be used.

Of the thermosetting resins, a liquid epoxy resin (consisting of a liquid epoxide and a curing agent) is preferable.
The liquid epoxide means an epoxide that is liquid at 25 ° C., but also includes an epoxide that is liquid at 25 ° C. together with a liquid epoxide that becomes liquid as a whole. Of the liquid epoxides, bisphenol F-type epoxides, bisphenol A-type epoxides and glycidylamine-type epoxides are preferred, bisphenol F-type epoxides and bisphenol A-type epoxides are more preferred, and bisphenol F-type epoxides are particularly preferred. These liquid epoxides may be one kind or a mixture of two or more kinds.
Of the curing agents, phenol compounds, organic acid anhydrides and amine compounds, dicyandiamide, imidazole compounds, organic acid hydrazide compounds, and solid dispersed amine adducts (latent curing agents) are preferred, and phenol compounds and organic acid anhydrides are more preferred. An imidazole compound. These curing agents may be used alone or in combination of two or more.

The active energy ray-curable resin is preferably a composition comprising a compound having a polymerizable double bond and a photo radical generator.
Among compounds having a polymerizable double bond, an ester of polyhydric alcohol or an alkylene oxide adduct of polyhydric alcohol and (meth) acrylic acid {dipentaerystol hexa (meth) acrylate, ethoxylated trimethylolpropane tri ( Meth) acrylate, etc.}, urethane (meth) acrylate {isocyanatoethyl (meth) acrylate, reaction product of polyisocyanate and (meth) acrylate having an active hydrogen-containing group (hydroxy group, carboxy group, amino group, etc.): Reactants of hexamethylene diisocyanate and hydroxyethyl acrylate} and epoxy (meth) acrylate {reaction product of polyfunctional epoxide and (meth) acrylic acid: bisphenol A diglycidyl ether di (meth) acrylate and phenol novolak ( Data) acrylate} is preferably an ester of more preferably a polyhydric alcohol or an alkylene oxide adduct of polyhydric alcohol and (meth) acrylic acid.
These compounds having a polymerizable double bond may be used alone or in combination of two or more.
In the present invention, “... (Meth) acryl ...” means “... acrylic ...”, “... metacri ...”.

  Examples of the photo radical generator include diphenyl- (2,4,6-triethylbenzoyl) phosphine oxide, 2,2-dimethoxy-2-phenylacetophenone, dimethylhydroxyacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one are preferred. These photo radical generators may be used alone or in combination of two or more.

These curable resins may be used alone or in combination of two or more.
In the case of using a curable resin, the content (% by weight) of the curable resin is preferably 5 to 233, more preferably 11 to 100, and particularly preferably 18 to 67, based on the weight of the filler (F). . Within this range, unfilled recesses and voids are further suppressed. Within this range, the unfilled opening and the generation of voids are further suppressed.

  As the thermoplastic resin, polyethylene, polypropylene, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, polyamide, polyurethane, phenoxy resin, and the like can be used. The thermoplastic resin is dissolved in a solvent (water, organic solvent, etc.) to be liquefied, and after filling, the solvent is distilled off to form a solid or at the temperature above its melting point during filling. It is melted and liquefied, and solidified by returning to room temperature (about 25 ° C.) after filling. Therefore, in the latter case, if this melting point is too high, there are concerns about problems such as resin degradation and heat resistance of the apparatus. Therefore, the melting point (° C.) of the thermoplastic resin is preferably 100 to 250, more preferably 120 to 200, particularly preferably 140 to 180. On the other hand, in the former case, the melting point of the thermoplastic resin is not limited, and those having a high melting point can be used.

  When a thermoplastic resin is used, the content (% by weight) of the thermoplastic resin is preferably 5 to 233, more preferably 11 to 100, and particularly preferably 18 to 67, based on the weight of the filler (F). . Within these ranges, unfilled recesses and generation of voids are further suppressed. Within this range, the unfilled opening and the generation of voids are further suppressed.

  When using a curable resin and a thermoplastic resin, the content (% by weight) of the curable resin is preferably 40 to 99, more preferably 50 to 95, based on the total weight of the curable resin and the thermoplastic resin. Especially preferably, it is 60-90. Within this range, the unfilled opening and the generation of voids are further suppressed. In this case, the content (% by weight) of the thermoplastic resin is preferably 1 to 60, more preferably 5 to 50, and particularly preferably 10 to 40 based on the total weight of the curable resin and the thermoplastic resin. It is. Within these ranges, the unfilled opening and the generation of voids are further suppressed.

  The resin paste (J) may be further added with a commonly used additive {antifoaming agent, dispersing agent, organic / inorganic colorant, flame retardant and / or thixotropic agent}. When the antifoaming agent is added, the content (% by weight) is preferably 0.05 to 5, more preferably 0.5 based on the total weight of the filler (F), the curable resin and the thermoplastic resin. -3, particularly preferably 1-2. In the case of adding a dispersant, the content (% by weight) is preferably 0.01 to 5, more preferably 0.03 to 2, based on the total weight of the filler (F), the curable resin and the thermoplastic resin. Especially preferably, it is 0.05-1. When the organic / inorganic colorant is added, the content (% by weight) is preferably 0.01 to 5, more preferably 0, based on the total weight of the filler (F), the curable resin, and the thermoplastic resin. 0.03 to 2, particularly preferably 0.05 to 1. When the flame retardant is added, the content (% by weight) is preferably 0.5 to 10, more preferably 0.8 to, based on the total weight of the filler (F), the curable resin, and the thermoplastic resin. 8, particularly preferably 1-5. When the thixotropic agent is added, the content (% by weight) is preferably 0.01 to 5, more preferably 0.03, based on the total weight of the filler (F), the curable resin and the thermoplastic resin. ˜2, particularly preferably 0.05˜1.

The resin paste (J) may further contain a solvent. However, when a vacuum is applied at the time of filling, the volatile matter contained in (J) at the degree of vacuum and temperature at the time of filling is 10% by weight or less in order to prevent generation of voids. It is preferably 5% by weight or less, more preferably 0.5% by weight or less. The volatile content is measured in accordance with JIS K0067-1992, “Chemical Product Weight Loss and Residual Test Method”. As such a solvent, a hydrocarbon solvent (such as toluene and xylene), a glycol ether solvent (such as diethylene glycol monoethyl ether acetate and triethylene glycol dimethyl ether) and a ketone solvent (such as methyl ethyl ketone and methyl isobutyl ketone) can be used.
When the solvent is contained, the content (% by weight) of the solvent is preferably 0.1 to 10, more preferably 0.1 to 5, particularly preferably 0.1 based on the weight of the resin paste (J). ~ 1.

  The loss elastic modulus (G ″) of the resin paste (J) can be adjusted by the content of the filler (F), the volume average particle size and / or shape, etc., but the curable resin, additive (particularly thixotropic agent) and It can also be adjusted by the type and content of the solvent.

  Resin paste (J) is commercially available, Nopcocure SVC-710 (thermosetting filling resin paste), Nopcocure SVC-712 (thermosetting filling resin paste), Nopcocure SVC-720 (thermosetting) manufactured by San Nopco Co., Ltd. Copper paste); DD paste AE3030 (conductive copper paste) manufactured by Tatsuta System Electronics Co., Ltd., DD paste AE1125HD (thermosetting copper paste); TK paste CT-1129 (conductive silver paste) manufactured by Kaken Tech Co., Ltd. And YSM2002 (filled hole and solder resist) manufactured by Wise Techno Inc.

  As a substrate applicable to the production method of the present invention, a copper-clad laminate for printed wiring boards (glass cloth base epoxy resin, glass cloth base as defined in JIS C6480-1994 “General Rules for Copper-clad Laminates for Printed Wiring Boards”) (Polyimide resin, glass cloth base material bismaleimide / triazine / epoxy resin, etc.) are preferable, but it can also be applied to base materials such as those mixed with thermoplastic resins such as polyphenylene ether and inorganic fillers such as silica, and silicon wafers. it can. Further, the present invention can also be applied to a core substrate for a printed wiring board in which a circuit is formed or an insulating layer is formed using a copper clad laminate.

  An opening is a through-hole (so-called through-hole) formed on the substrate using a drill or a carbon dioxide laser, or a bottomed hole (so-called via hole) on the substrate, or a circuit is formed on the substrate. It means a concave portion formed by scraping a concave portion between subsequent circuits or a part of the substrate.

In the production method of the present invention, the non-contact roll (R) is linearly moved at a moving speed (i) (mm / sec) in a direction horizontal to the substrate surface and in a direction perpendicular to the rotation axis of (R). Rotating (R) at a peripheral speed (v) (mm / sec) so that the rotation direction of the portion on the substrate side from the rotation axis is opposite to the moving direction, the resin paste (J) is applied to the substrate. Including a filling step of filling the provided opening, and the moving speed (i) and the peripheral speed (v) are preferably in a relationship of v> 10 × i, more preferably 50 × i>v> 10 ×. i, particularly preferably 30 × i>v> 10 × i, and most preferably 20 × i>v> 10 × i.
When the peripheral speed (v) is in the above relationship, the occurrence of unfilling and void entrainment can be further suppressed. That is, it is preferable to increase the filling force by increasing the peripheral speed (v) with respect to the moving speed (i).

  The non-contact roll (R) is not limited in speed as long as it can move linearly while keeping the rotation axis horizontal to the substrate surface, but the linear movement speed (i) (mm / sec) of the non-contact roll (R). Is preferably 5 to 100, more preferably 10 to 70, and particularly preferably 20 to 50. Within this range, the occurrence of unfilled or void entrainment can be further suppressed.

The movement direction of the non-contact roll (R) is perpendicular to the rotation axis of (R), but the angle between the movement direction and the rotation axis is not limited to 90 ° but includes 60 to 120 °. It is a waste.
The rotation direction of the non-contact roll (R) is a direction in which the rotation direction of the portion on the substrate side with respect to the rotation axis is opposite to the movement direction, that is, the rotation direction so that the non-contact roll (R) rolls in the linear movement direction. is there. This opposite direction (the direction in which the rotation direction of the portion closer to the substrate than the rotation axis is the same as the movement direction, that is, the non-contact roll (R) rotates so that the non-contact roll (R) rolls in the direction opposite to the linear movement direction) The object of the present invention cannot be achieved.

  The peripheral speed (v) (mm / second) of the non-contact roll (R) is represented by {Roll angular velocity (ω)} × {(Roll radius (r)}, and a range satisfying the formula (1) is preferable. More preferably, it is a range satisfying the formula (2) The peripheral speed when a roll having a diameter of 50 mm makes one revolution per second is 25 mm × 6.28 rad / sec = 157 mm / sec.

The non-contact roll (R) is preferably provided with a doctor {resin paste (J) scraping squeegee}. The doctor is arranged on the side opposite to the moving direction of the non-contact roll (R) so as to come into contact with the non-contact roll (R) and moves linearly with the non-contact roll (R). Moreover, it is preferable to have a plane having an angle of 5 to 45 ° with respect to the substrate on the moving direction side of the distal end portion of the doctor, and the angle is more preferably about 15 ° (see FIGS. 7 and 8). .
The presence of this doctor further reduces unfilled openings and void entrainment. That is, the doctor has a function of moving the resin paste (J) collected by the rotation of the non-contact roll (R) in the moving direction together with (R) {no resin paste (J) is left on the substrate surface}. Further, the resin paste (J) scraped between the doctor, the non-contact roll (R), and the substrate has a function of maintaining a pressurized state {pressed by the rotation of the non-contact roll (R). This pressurized state generates an action of pushing the resin paste (J) into the opening}.

  The maximum value (t) (mm) of the depth of the opening is the substrate thickness when the opening is a through-hole, and is usually about 0.4 to 1.6, but in some cases less than 0.4 ( The present invention can also be applied to a thin plate substrate of 0.1 or less, a thick plate substrate of 1.6 or more (3.0 or more), and the like. On the other hand, when the opening is a recess such as a via hole or a circuit, the maximum depth (t) (mm) of the opening is often 0.1 or less. The maximum value (t) of the depth of the opening means the maximum value among the depths measured in accordance with JIS C5012-1993 “Printed Wiring Board Test Method”.

The minimum value (S) (mm ² ) of the area of the opening is about 0.002 to 0.2 mm ² because the hole diameter is about 0.05 to 0.5 mm when the opening is a through hole or via hole. It is. If the opening is such as recesses between circuits, the order of the circuit interval 0.01 to 1 mm, a 0.01～100Mm ² about Since circuit length is about 1 mm to 100 mm. The minimum area (S) of the opening is measured according to JIS C5012-1993 “Printed Wiring Board Test Method”. The areas of a plurality of openings existing on a single substrate are measured based on the above, and the minimum value of these areas is defined as the minimum value (S) of the area of the openings.

  The shortest distance (mm) between the substrate surface and the non-contact rotating roll surface is preferably 0.1 to 5, more preferably 0.3 to 3, particularly preferably 0.5 to 1. 5. Within this range, the occurrence of unfilled or void entrainment is further suppressed.

  The filling step is preferably a step of simultaneously filling openings having different opening areas and / or depths, and simultaneously filling openings having different opening areas and / or depths and forming a resin layer on the substrate surface. More preferably, it is a process.

The step of simultaneously filling openings having different opening areas and / or depths is a step of simultaneously filling a plurality of through holes (such as Sulu holes) having different opening areas, through holes and bottomed holes (via holes, for mounting components) A plurality of through holes having different opening areas and a plurality of bottomed holes at the same time, and a plurality of through holes having different opening areas and a plurality of different opening areas. It means a step of filling the bottomed holes at the same time.
And if the opening area is different, from the group consisting of open area 0.002 mm ² (circuit between the recess distance 5mm length 500 mm) (diameter 50 [mu] m), the opening area 19.7 mm ² (diameter 5000 .mu.m), and the opening area 2500 mm ² Examples include at least two combinations selected.
The case where the depths are different includes, for example, a combination of a recess (via hole) having a depth of 30 μm and a through hole having a depth of 3.2 mm.

In the step of simultaneously filling openings having different opening areas and / or depths and forming a resin layer on the substrate surface, a method of filling with spacers on the substrate surface and filling in the same manner as described above or doctor {resin paste (J ) A method of filling with a constant distance between the tip portion of the scraping squeegee} and the substrate surface can be applied.
As the spacer, a metal mask (such as a stainless metal mask), a resin film (such as a polyester film), a screen mesh (such as a polyester screen mesh or a stainless screen mesh), or the like can be used.
The thickness of the spacer and the distance between the tip of the doctor and the substrate surface (μm) are preferably 5 to 500, more preferably 10 to 200, and particularly preferably 20 to 100. This thickness is the thickness of the resin layer to be formed. In addition, it is preferable that the space | interval of the front-end | tip of a doctor and a substrate surface is smaller than the space | interval of a non-contact roll (R) and a board | substrate from a viewpoint of control of the film thickness of a resin layer, etc. This process of forming the resin layer is useful for simultaneously forming the insulating layer and the solder resist layer simultaneously with filling of the through hole, via hole, and inter-circuit recess in the printed wiring board manufacturing process.

The filling step preferably includes a step (a) of filling under a pressure of 10 to 10000 Pa, and a step (b) performed after the step (a) and filling under atmospheric pressure, more preferably. Between the step (a) and the step (b), a temporary curing step (c) of the resin paste (J) is included.
The atmospheric pressure (Pa) in the filling step (a) is preferably 10 to 10,000, more preferably 50 to 5000, and particularly preferably 100 to 1000 from the viewpoint of filling properties. Within this range, the occurrence of unfilled or void entrainment is further suppressed.

When the resin paste filled in the filling step (a) is returned to the atmospheric pressure, a dent may be generated due to the volume reduction. In order to fill the dent, the step of filling under the atmospheric pressure (b) Is preferably provided.
Step (a) may be performed a plurality of times (preferably 2 to 4 times, more preferably 2 or 3 times) on the same substrate surface. By performing the step (b) after performing the step (a) a plurality of times, the occurrence of unfilling and void entrainment is further suppressed.
It is preferable to provide a temporary curing step (c) of the resin paste (J) between the step (a) and the step (b) because a dent due to curing shrinkage can be eliminated.

The temporary curing step (c) is achieved by heat treatment when the resin paste is a thermosetting resin, irradiation treatment with active energy rays such as ultraviolet rays when the resin paste is an active energy ray curable resin, and cooling treatment when the resin paste is a thermoplastic resin. Is done. In the temporary curing step (c), when polishing is performed in the next flattening step, it is preferable that the resin paste be in a semi-cured state in order to reduce the polishing load. For example, when the resin paste is a thermosetting resin and is completely cured at 150 ° C. with an energy of 30 minutes, the temporary curing step (c) is heated at 150 ° C. for about 10 minutes. Alternatively, when the resin paste contains an active energy ray-curable resin and a thermosetting resin and is completely cured by 1 J / cm ² of ultraviolet irradiation and 150 ° C. for 30 minutes, the temporary curing step (c) is 1 J / cm. Only ² UV irradiation.

The ratio (t / √S) of the square root between the depth (t) and the minimum area (S) is preferably 0.1 to 30, more preferably 1 to 25, particularly preferably 1.5 to 20, and most preferably. Is 2-15. In addition, when filling the opening part containing a through-hole whose t / √S is 15 or more, before the step (a), the resin is used under the atmospheric pressure with respect to the substrate surface opposite to the step (a). It is preferable to include a temporary curing step (f) of the resin paste (J) after the step (e) of filling the paste (J) and the step (e).
If the steps (e) and (f) are included, the occurrence of unfilling and void entrainment is further suppressed.
The step (e) may be the same method as the previous filling step, or a normal filling method other than this method (screen printing method, roll printing method, etc.).
That is, after all the through holes are converted into bottomed holes by the steps (e) and (f), the step (a) is performed. The resin paste filled in the step (e) and the resin paste filled in the step (a) may be the same or different. For example, a conductive resin paste may be used in steps (e) and (f), and an insulating resin paste may be used in steps (a) and (b).
In the pre-curing step (f), when the resin paste is a thermosetting resin, the thermoplastic resin is similarly treated by heat treatment. Similarly, when the resin paste is an active energy ray-curable resin, by irradiation treatment with active energy rays such as ultraviolet rays, In this case, the resin paste may be cured by a cooling process. The conditions for the temporary curing step (f) may be the same as those for the temporary curing step (c).

It is preferable to provide a temporary curing step (d) after the filling step. The conditions of the provisional curing step (d) are the same as those of the provisional curing step (c). For example, when the polishing step is not performed later or when the polishing property is less affected, the complete curing may be performed. After the temporary curing step (d), the thin film residue of the cured resin remaining on the surface of the substrate is polished and removed, and when the resin layer is formed, the unevenness of the resin layer is eliminated and the film thickness is reduced. In order to make it uniform, a planarization step (g) may be provided. According to the conventional manufacturing method, since a resin having a film thickness of about 10 to 100 μm corresponding to the thickness of the printing mask to be used remains on the substrate surface, a strong polishing force such as a belt sander or a ceramic roll buff is used in the planarization process. However, in the case of the production method of the present invention, only a thin resin layer having a film thickness of several μm remains on the substrate surface, and therefore, non-woven cloth roll buff polishing, desmear treatment (permanganic acid) Flattening is possible only by weak polishing such as salt treatment and plasma treatment. Therefore, when flattening with a strong polishing force as in the conventional manufacturing method, there is a problem that the substrate is stretched due to the load, and the substrate is warped or deformed. However, the manufacturing method of the present invention is weak. Since planarization can be performed with the polishing force, warpage and deformation of the substrate can be prevented, and reduction of defective products can be achieved. Furthermore, according to the manufacturing method of the present invention, reduction of process time and the like can be achieved.
When the resin paste (J) needs to be completely cured after the planarization step (g), a main curing step (h) may be further provided. The main curing step (h) is carried out in order to completely cure, for example, when the semi-cured state is set in the temporary curing step in order to reduce the polishing load in the flattening step.

When there are low holes (via holes or the like) on both sides of the substrate, the substrate surface opposite to the filled substrate surface is filled in the same manner.
By laminating insulating layers and / or wiring layers (alternately) on the resin-filled substrate obtained by the production method of the present invention (the above filling step may be further provided if necessary), a so-called build-up multilayer A printed wiring board can be obtained.
For example, the wiring layer is filled with resin paste (J) in the opening, cured (including the case where a resin layer is formed on the substrate surface), roughened by desmear treatment, etc., and electroless plated (copper Etc.) and electrolytic plating (copper or the like) or the like, and a conductive layer is formed by removing unnecessary portions by etching or the like.
In the manufacturing method of the present invention, since the opening after filling with the resin paste (J) has excellent flatness (since no dent is generated), a wiring layer having a uniform conductor thickness and width can be easily formed.

  The manufacturing method of the present invention can be filled without using a printing mask, but if there is an opening that you do not want to fill, or if you want to create a discharge part such as an electrode bump on the substrate, print at the time of filling. A mask may be used. The printing mask is not limited as long as it is placed on the substrate, has a through hole at a position corresponding to the opening that needs filling, and covers a portion that does not need filling. As the printing mask, a stainless steel metal mask plate, a resin film such as polyester, a screen plate, a photosensitive film, and the like can be used.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.
A resin-filled substrate was manufactured using the following filling device, resin paste, and substrate.
<Filling device (see FIGS. 2 to 5, 11 and 12)>
In the filling apparatus, a substrate fixing base (4), a doctor (7), a non-contact roll (8) and a guard (14) are arranged in a vacuum chamber (3). The doctor (7), the non-contact roll (8), and the guard (14) are integrated with each other so as to move in the horizontal direction with respect to the substrate surface and in the direction perpendicular to the rotation axis of the non-contact roll (8) (i ) (Mm / sec) can be moved linearly.
The doctor (7) can scrape excess resin paste remaining on the substrate after the opening of the substrate is filled with the resin paste (9). The doctor (7) is made of polyurethane resin having a hardness of 80 degrees, and has a width of 70 mm, a thickness of 20 mm, and a length of 510 mm, and the tip has the shape shown in FIG.
The guard (14) can prevent the resin paste (J) from protruding from both ends of the doctor (7) and the non-contact roll (8). The guard (14) is a polyacetal plate (height 80 mm, width 100 mm, thickness 20 mm) provided with a through hole with a diameter of 51 mm at the center (the through hole is a non-contact roll (8) and a substrate fixing base). It exists in the position which becomes 0.1 mm between (4)}. And the terminal part of a non-contact roll (8) is inserted in this hole. The guard (14) is in contact with the upper surface of the substrate fixing base (4) and both end portions of the doctor (7).
The inside of the vacuum chamber (3) can be depressurized.
Further, the non-contact roll (8) is such that the rotation direction of the substrate side portion with respect to the rotation axis of the non-contact roll (8) is opposite to the movement direction of the doctor (7) and the non-contact roll (8). {Because it rolls forward in the direction of linear movement of the non-contact roll (8)}, it can be rotated at a peripheral speed (v) (mm / sec). In FIG. 3, the rotation direction of the non-contact roll (R) is indicated by an arrow 26.
The surface material of the non-contact roll (8) is made of stainless steel, and its size is 100 mm in diameter and 550 mm in length.

<Resin paste>
With composition and use amount (parts by weight) shown in Table 1, with a planetary mixer (trade name “PLM-50”, manufactured by Inoue Seisakusho, revolution speed: 20 rpm, temperature: 22 ° C., time: 30 minutes) After premixing, the resin paste J1 is kneaded with three rolls (trade name “HHC-178X356”, manufactured by Inoue Seisakusho, pressure between rolls: 3 MPa, temperature: 22 ° C., number of passes: 2 times). ~ J10 was obtained.
The loss elastic moduli (G ″) of the resin pastes J1 to J10 were measured at 23 ° C. (filling operation temperature) using a viscoelasticity measuring apparatus (Rheostress RS75 manufactured by HAAKE). “Angular velocity-loss elastic modulus curve” Got. Subsequently, the loss elastic modulus at the angular velocity (Tables 3 to 6) 0.628, 3.14, 6.28, 31.4, 62.8 corresponding to the peripheral velocity of the non-contact roll (8) used at the time of filling is read. The results are shown in Table 1.

Silica: TH6R (volume average particle size 6 μm spherical silica) manufactured by Tatsumori Co., Ltd.
Copper powder: SRC-Cu15 (volume average particle diameter 12 μm spherical copper powder) manufactured by Fukuda Metal Foil Powder Co., Ltd.
Silver powder: manufactured by Fukuda Metal Foil Powder Co., Ltd. A mixture of spherical silver powder (50% by weight) having a volume average particle diameter of 4 μm and flaky silver powder (50% by weight) having a volume average particle diameter of 3 μm Barium sulfate: Sakai Chemical Industry Co., Ltd. B-32 (volume average particle size 0.3 granular barium sulfate powder)
Epicoat 807: Bisphenol F-type epoxide {Epicoat 807 manufactured by Japan Epoxy Resin Co., Ltd.}
Curing agent: Imidazole 2MZ-A (2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine) manufactured by Shikoku Kasei Co., Ltd.
DPE-6: Dipentaerystol hexaacrylate {Kyoeisha Co., Ltd. DPE-6A}
Photoradical generator: Irgacure 184, manufactured by Ciba Specialty Chemicals
Antifoaming agent: KF6003 (Carbinol-modified silicone) manufactured by Shin-Etsu Chemical Co., Ltd.
Thixotropic agent: Disparon 3900 (Polyamide) manufactured by Enomoto Kasei Co., Ltd.

<Board>
Using a FR-4 double-sided copper-clad laminate (compliant with JIS C 6480-1994 “General Rules for Copper-clad Laminates for Printed Wiring Boards”), a core substrate having openings shown in Table 2 is disclosed in Japanese Patent Application Laid-Open No. 2002-141661. Prepared according to the official gazette.

<Example 1>
A release film (5) {polyester film of the same size as the substrate: re-peeling film ST thickness 50 μm made by Panac Co., Ltd.} is placed on the substrate fixing base (4), and the substrate K1 (6) is fixed to the fixing base (4). Was fixed by fitting into the recesses (the same depth as the total thickness of the substrate and the release film (5)). Next, after placing the resin paste J1 on the edge of the substrate (FIG. 2), the inside of the vacuum chamber (3) is depressurized to 150 Pa, the moving speed is 10.0 mm / second, the rotational peripheral speed is 120.0 mm / second, non-contact Filling was performed at an interval of 0.5 mm between the roll and the substrate, a pressing pressure of 3 MPa of the doctor (7), and an angle of 15 degrees between the doctor and the substrate surface (filling step a: FIGS. 3 to 4). After filling, the pressure in the vacuum chamber (3) is returned to atmospheric pressure, then the angle between the doctor and the substrate surface is changed to 15 degrees, and filling is performed again at the same moving speed and peripheral speed. A substrate was obtained (filling step b: FIGS. 2 to 4).

  The filled substrate was heated and cured (curing step d) at 130 ° C. for 30 minutes in a circulating air oven to obtain a cured substrate. Next, the surface is flattened by flattening using a uniaxial non-woven cloth buffing device (trade name “IDB-600” manufactured by Ishii Notation Co., Ltd., roughness 320 buff twice, roughness 600 buff twice) (flatness) The resin-filled substrate 1 was obtained by the following step g). Next, 100 filling points were randomly selected from the filling places having openings, and the number of defective fillings was evaluated as follows.

<Number of filling defects>
Using a tabletop hand cutter (trade name “Hand Cutter PC-300” manufactured by Sanhayato Co., Ltd.), the substrate is cut perpendicularly to the substrate surface, and a polishing / polishing machine (trade name “Struers Planopol-3”, Marumoto Kogyo Co., Ltd.). The cut surface was polished using a product manufactured by Co., Ltd., and the filled cross section having the opening was leveled. Then, this filling section was observed with a microscope (magnification 200 times), the number of dents and voids generated without being completely filled in the opening was counted, and this number (number of defective occurrences) is shown in Table 3. A recess having a step of 10 μm or more between the surface of the filled resin and the substrate surface around the opening was defined as a recess, and a cavity (bubble) having a diameter of 10 μm or more was defined as a void.

<Examples 2 to 40>
Resin-filled substrate 2 in the same manner as in Example 1 except that the substrate, the resin paste, the pressure in the vacuum chamber, the moving speed, the peripheral speed, and the distance between the non-contact roll and the substrate were changed to the contents described in Table 3. ~ 40 was obtained. The number of defective fillings evaluated in the same manner as in Example 1 is shown in Table 3.
When temporary curing (preliminary curing step c) was performed between the filling step (a) and the filling step (b), “Yes” is written in the column of the temporary curing step in Table 3, and Thus, when the temporary curing step c was not performed, “none” was described. The temporary curing (temporary curing step) was performed by subjecting the filled substrate to a heat treatment at 130 ° C. for 30 minutes in a circulating air heating oven.

<Examples 41 to 52>
The substrate, the resin paste, the pressure in the vacuum chamber, the moving speed, the peripheral speed, and the distance between the non-contact roll and the substrate are changed to the contents shown in Table 4, and the conditions of the temporary curing step c are 1 J / cm ² UV. Resin-filled substrates 41 to 52 were obtained in the same manner as in Example 1 except that the irradiation was changed. The number of defective fillings evaluated in the same manner as in Example 1 is shown in Table 4.
In addition, when temporary hardening (preliminary hardening process c) was implemented between the filling process (a) and the filling process (b), “Yes” is described in the column of the temporary hardening process in Table 4, and Thus, when the temporary curing step c was not performed, “none” was described. The temporary curing (preliminary curing step c) was performed by irradiating with 1 J / cm ² of ultraviolet rays.

<Examples 53 to 64>
The substrate, the resin paste, the pressure in the vacuum chamber, the moving speed, the peripheral speed, and the distance between the non-contact roll and the substrate are changed to the contents shown in Table 5, and as shown in FIG. 13) Resin-filled substrates 53 to 64 as shown in FIG. 6 were obtained in the same manner as in Example 1 except that (stainless steel metal mask) was used. The number of defective fillings evaluated in the same manner as in Example 1 is shown in Table 5. When temporary curing (preliminary curing step c) was performed between the filling step (a) and the filling step (b), “Yes” is written in the column of the temporary curing step in Table 5, and Thus, when the temporary curing was not carried out, “none” was described. Temporary curing (preliminary curing step c) is performed by irradiating ultraviolet rays of 1 J / cm ^{2 in} Examples 59 to 64, and the others are heat-treated at 130 ° C. for 30 minutes in a circulating heating oven. It was done by doing.

<Example 65>
The resin paste J1 was passed through a 250-mesh stainless steel mesh plate with an emulsion thickness of 20 μm using a screen printing hole filling and filling device {screen printing device “SSA-PC660” manufactured by Tokai Seiki Co., Ltd. ”, a printing speed of 20 mm / second, and a printing pressure of 0. After screen printing on the substrate surface of the substrate K7 at 5 MPa and a squeegee angle of 15 degrees under atmospheric pressure and filling the opening with a resin paste, the substrate was heated in a circulating air oven at 130 ° C. for 30 minutes. A temporarily cured substrate as shown in FIG. At this time, all the openings were filled with the resin paste from the substrate surface to 1 mm (the depth of the remaining openings was 3.0 mm).
Next, the temporarily cured substrate was turned over, and the back surface of the substrate K7 (the surface on the back side of the screen printed surface) was the same as in Example 1 (but no release film was used) as shown in FIG. A resin-filled substrate 65 was obtained.

<Examples 66 to 72>
FIG. 10 shows the same as in Example 65 except that the substrate, resin paste, pressure in the vacuum chamber, moving speed, peripheral speed, and distance between the non-contact roll and the substrate are changed to the contents shown in Table 6. Such resin-filled substrates 66 to 72 were obtained.
In addition, when temporary curing (preliminary curing step c) was performed between the filling step (a) and the filling step (b), “Yes” is written in the column of the temporary curing step in Table 6, and Thus, when the temporary curing was not carried out, “none” was described. The temporary curing (preliminary curing step c) was performed by subjecting the filled substrate to a heat treatment at 130 ° C. for 30 minutes in a circulating air heating oven. Table 6 shows the number of filling defects evaluated in the same manner as in Example 1.

<Examples 73 to 80>
Except for changing the substrate, resin paste, pressure in the vacuum chamber, moving speed, peripheral speed, distance between the non-contact roll and the substrate to the contents described in Table 7, and not using a release film In the same manner as in Example 1, resin-filled substrates 76 ′ to 83 ′ were obtained.
In addition, when temporary hardening was implemented between the filling process (a) and the filling process (b), “Yes” is described in the column of the temporary hardening process in Table 7, and the temporary hardening process c as in Example 1 was performed. When not implemented, it was described as “none”. The temporary curing step c was performed by subjecting the filled substrate to a heat treatment at 130 ° C. for 30 minutes in a circulating heating oven.
Next, the back surfaces of the resin-filled substrates 76 ′ to 83 ′ were filled under the same conditions as described above to obtain resin-filled substrates 76 to 83.
The number of defective fillings evaluated in the same manner as in Example 1 is shown in Table 7.

<Comparative Examples 1-28>
Substrate, resin paste, pressure in vacuum chamber, moving speed, peripheral speed, spacing between non-contact roll and substrate are the same as in Example 1 except that the content described in Table 8 is changed. The process b, the temporary curing process d, and the planarization process g were performed to obtain comparative resin-filled substrates 1 to 17.
In Comparative Examples 1 to 17, when temporary curing was performed between the filling step (a) and the filling step (b), “Yes” is written in the column of the temporary curing step in Table 8, and Example 1 When the temporary curing step c was not performed as described above, it was described as “none”. The temporary curing (preliminary curing step c) was performed by subjecting the filled substrate to a heat treatment at 130 ° C. for 30 minutes in a circulating air heating oven.
Further, in Comparative Examples 18 to 28, a screen printing hole filling and filling apparatus {screen printing apparatus “SSA-PC660” manufactured by Tokai Seiki Co., Ltd.}, and a metal mask with a thickness of 100 μm having a through hole diameter 1.2 times the opening diameter of the substrate After filling the resin paste by screen printing at a printing speed of 20 mm / second, a printing pressure of 0.5 MPa, and a squeegee angle of 15 degrees, it was heated in a circulating air oven at 130 ° C. for 30 minutes to fill the comparative resin Substrates 18 to 28 were obtained.
Note that the comparative resin-filled substrates 18 to 28 of Comparative Examples 18 to 28 could not be flattened (surface polished) under the same flattening conditions as in Example 1, and convex resin remained on the substrate surface.
The number of defective fillings evaluated in the same manner as in Example 1 is shown in Table 8.

  According to the manufacturing method shown in the comparative example, filling defects such as dents and voids frequently occur, whereas in the manufacturing method of the present invention, the resin-filled substrate does not cause filling defects such as dents and voids in the opening. Could be manufactured easily. Moreover, in the manufacturing method of this invention, even if the opening part from which an opening area and depth differ exists, these were able to be filled simultaneously.

  In the manufacturing method of the present invention, a resin paste is filled in openings (concave portions and / or through holes) in the manufacturing process of printed wiring boards (build-up printed wiring boards, multilayer laminated printed wiring boards, double-sided printed wiring boards, etc.). It can be used for the production of resin-filled substrates. In addition, it can be used in a method of filling and polishing an opening formed in a plate-like material made of metal, stone, glass, concrete and / or plastic to smooth a flat surface.

It is sectional drawing which showed typically the component part of an upper cone type disk and a lower plane disk among the viscoelasticity measuring apparatuses for measuring the loss elastic modulus (G ") in this invention. In an Example, it is the vertical sectional view which showed typically the state at the time of the start of a filling process among the aspects which apply the manufacturing method of this invention. In an Example, it is the vertical sectional view which showed typically the state in the filling process of the filling process among the aspects which apply the manufacturing method of this invention. In an Example, it is the vertical sectional view which showed typically the state at the time of completion | finish of filling of a filling process among the aspects which apply the manufacturing method of this invention. In Examples 53-64, it is the vertical sectional view which showed typically the state which performed the filling process and formation of the resin film simultaneously among the signs that the manufacturing method of the present invention is applied. It is sectional drawing which showed typically the resin filling board | substrate manufactured in Examples 53-64. It is sectional drawing which showed typically an example of the front-end | tip shape of the front-end | tip of a doctor. It is sectional drawing which showed typically an example of the front-end | tip shape of the front-end | tip of a doctor. It is sectional drawing which showed typically the pre-hardening board | substrate manufactured in Examples 65-72. It is sectional drawing which showed typically the resin filling board | substrate manufactured in Examples 65-72. It is the perspective view which showed the guard (14) typically. It is a perspective view which shows notionally the positional relationship of a doctor (7), a non-contact roll (8), and a guard (14).

Explanation of symbols

1. Upper cone disk 1. Lower flat disk 2. Vacuum chamber 4. Substrate fixing base 5. Release film 6. Substrate 7. Doctor 8 Non-contact roll (R)
9. Resin paste (J)
10. 10. Rotating shaft of non-contact roll (R) Bottomed hole (via hole)
12 Through hole (through hole)
13. Spacer 14. guard

Claims (10)

(R) rotation while the non-contact roll (R) is linearly moved at a moving speed (i) (mm / sec) in a direction horizontal to the substrate surface and in a direction perpendicular to the rotation axis of (R). By rotating (R) at a peripheral speed (v) (mm / sec) so that the rotation direction of the portion on the substrate side from the axis is opposite to the moving direction, a loss elastic modulus (G ″) of 50 to 100,000 Pa is obtained. A filling step of filling a resin paste (J) having an opening provided in the substrate;
A method for producing a resin-filled substrate, wherein the moving speed (i) and the peripheral speed (v) are in a relationship of v> 10 × i. The method for producing a resin-filled substrate according to claim 1, wherein the shortest distance between the substrate and the non-contact roll (R) is 0.1 to 5 mm. The method for producing a resin-filled substrate according to claim 1, wherein the filling step is a step of simultaneously filling openings having different opening areas and / or depths. The method for producing a resin-filled substrate according to claim 1 or 2, wherein the filling step is a step of simultaneously filling openings having different opening areas and / or depths and forming a resin layer on the substrate surface. 5. The method according to claim 1, wherein the filling step includes a step (a) of filling under a pressure of 10 to 10,000 Pa, and a step (b) that is performed after the step (a) and is filled under an atmospheric pressure. The manufacturing method of the resin-filled board | substrate of description. Step (e) and Step (e) including at least a through hole as an opening, and filling the resin paste (J) under atmospheric pressure with respect to the substrate surface opposite to Step (a) before Step (a) The manufacturing method of the resin-filled board | substrate of Claim 5 including the temporary hardening process (f) of the resin paste (J) after e). Resin paste (J) comprises filler (F) and curable resin and / or thermoplastic resin, and the content of (F) is based on the total weight of (F), curable resin and thermoplastic resin. The method for producing a resin-filled substrate according to claim 1, wherein the content is 30 to 95% by weight. A resin-filled substrate produced by the production method according to claim 1. A build-up multilayer printed wiring board configured by laminating an insulating layer and / or a wiring layer on the resin-filled substrate according to claim 8. An electronic device incorporating the build-up multilayer printed wiring board according to claim 9.