JP2016078038A - Method for forming penetration hole in laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a penetration hole in a laminate which can form the penetration hole, which is small in a difference in a processing shape between a glass substrate layer and a resin composition layer and in a degree of taper, in the laminate having the glass substrate layer and the resin composition layer.SOLUTION: The method for forming a penetration hole in a laminate having at least one resin composition layer and at least one glass substrate layer performs: a step of providing a metal film having an opening part as a conformal mask on one surface of the laminate; and a step of irradiating laser light to the laminate exposed into the opening part.SELECTED DRAWING: None

Description

  The present invention relates to a method for forming a through hole in a laminate, and a method for manufacturing the laminate.

In recent years, electronic devices have been further reduced in size, weight, and functionality, and accordingly, a system in package (SiP: System in Package) in which a system composed of a plurality of LSIs (Large Scale Integration) is contained in one package. ) Development of 3D SiP technology combining technology and 3D mounting technology is underway.
In high-density mounting such as SiP, it is difficult to cope with a fine pitch with the conventional wire bonding technology, so a relay substrate called an interposer using a through electrode is required. The interposer is required to have excellent shape stability from the viewpoint of improving workability capable of forming a through-hole with high accuracy and reliability during mounting.

As an interposer, a glass epoxy resin substrate, an organic substrate such as a polyimide substrate, a ceramic substrate such as silicon, and the like have been used.
The resin substrate is advantageous in that the cost is low and a processing method (for example, Patent Document 1) is being established. However, conventionally used resin substrates are low in rigidity and inferior in dimensional stability. Therefore, deformation such as warpage may occur in the manufacturing process. The occurrence of the warp deteriorates the positioning accuracy when forming the through-hole in the interposer and may cause the reliability of the obtained semiconductor package to be deteriorated. Therefore, improvement has been desired.
On the other hand, although the ceramic substrate is excellent in shape stability, there is a problem in that it is disadvantageous in cost and inferior in versatility.
From the background as described above, studies have been made to use an insulating glass substrate as a constituent member of a laminate (see, for example, Patent Documents 2 to 3). Since the glass substrate has high rigidity and excellent dimensional stability, it can effectively suppress deformation such as warpage and is advantageous in terms of cost, and is suitable as an interposer.

JP 2008-198922 A International Publication No. 2013/042748 JP 2014-093406 A

However, glass substrates are more brittle and easier to break than resins, so they are inferior in workability, and it is difficult to form fine through-holes with high accuracy even when irradiated with laser light under the same conditions as resin substrates. It was.
Further, when the thickness of the glass substrate is increased, the difference in the diameter of the through hole between the incident side and the outgoing side of the laser light is increased, and the shape of the through hole becomes a tapered shape. Thereby, the filling property of the conductive material into the through holes may be deteriorated, and cracks due to impact, cracks, and the like may easily occur during subsequent processing.

Moreover, in order to cope with said problem, the method of laminating | stacking a resin composition layer on the surface of a glass substrate and improving the intensity | strength of a glass substrate can be considered. However, since the workability of the glass substrate and the resin composition layer is greatly different, the resin composition layer may be processed to be larger than the glass substrate layer when forming the through hole, and a step may be generated on the wall surface of the through hole. . The step causes a part of the conductive film to be peeled off when the through hole is filled with the conductive material, and the roughness of the substrate surface increases when the conductive material is completely filled. It also causes a decrease.
The present invention provides a laminate having a glass substrate layer and a resin composition layer, in which a through hole having a small difference in processing shape between the glass substrate layer and the resin composition layer and a small degree of taper can be formed. It aims at providing the formation method of the through-hole to a body.

As a result of investigations to solve the above problems, the present inventors have found that the problems can be solved by the present invention described below.
That is, the present invention provides the following [1] to [6].
[1] A method for forming a through hole in a laminate having one or more resin composition layers and one or more glass substrate layers, and having an opening as a conformal mask on one surface of the laminate A method for forming a through hole in a laminate, comprising the steps of providing a metal film and irradiating the laminate exposed in the opening with laser light.
[2] The method for forming a through hole in the laminate according to [1], wherein the glass substrate layer has a thickness of 20 to 200 μm.
[3] The method for forming a through hole in the laminate according to the above [1] or [2], wherein the metal film is copper.
[4] The method for forming a through hole in the laminate according to any one of [1] to [3], wherein the metal film has a thickness of 1 to 200 μm.
[5] The method for forming a through hole in the laminate according to any one of [1] to [4], wherein the laser is a CO ₂ laser.
[6] A method for producing a laminate having one or more resin composition layers and one or more glass substrate layers, wherein the through-holes into the laminate according to any one of the above [1] to [5] The manufacturing method of a laminated body which has the process of forming a through-hole with the formation method of these.

  According to the present invention, a through-hole having a small difference in processing shape between the glass substrate layer and the resin composition layer and a small taper can be formed in the laminate having the glass substrate layer and the resin composition layer. A method for forming a through-hole in a laminate can be provided.

It is a schematic diagram which shows the degree of a taper. It is an optical microscope photograph ((a) incident side, (b) emission side) of the through-hole formed in Example 1. It is an optical microscope photograph ((a) entrance side, (b) exit side) of the through-hole formed in Example 2. It is an optical microscope photograph ((a) entrance side, (b) exit side) of the through-hole formed in Comparative Example 1.

[Method for forming through-hole in laminate]
The method of the present invention is a method for forming a through hole in a laminate having one or more resin composition layers and one or more glass substrate layers, and is formed as a conformal mask on one surface of the laminate. And a step of irradiating the laminated body exposed in the opening with laser light.

<Laminate>
The laminate used in the method of the present invention is a laminate having one or more resin composition layers and one or more glass substrate layers.
In the present specification, the “laminate” means that when the resin composition layer constituting the laminate contains a thermosetting resin, the thermosetting resin is uncured, semi-cured or fully cured. Means everything.

(Glass substrate layer)
As a glass substrate which comprises a glass substrate layer, a 20-200-micrometer glass film is preferable from a viewpoint which balances the thinning of a laminated body, and the outstanding workability.
The thickness of the glass film can be appropriately selected depending on the application. For example, from the viewpoint of practicality such as ease of handling, the thickness is more preferably 50 to 200 μm, still more preferably 75 to 200 μm, and particularly preferably. 120-200 μm. Moreover, from a viewpoint of thickness reduction of a laminated body, More preferably, it is 20-150 micrometers, More preferably, it is 20-120 micrometers, Most preferably, it is 20-90 micrometers.
Here, the thickness of the glass substrate layer refers to the average thickness of the glass substrate layer. The average thickness of the glass substrate layer can be measured using a known thickness measuring instrument such as a micrometer or a film thickness measuring instrument. For example, in the case of a rectangular or square glass substrate layer, the thickness of the four corners and the center can be measured using a micrometer, and the average value can be obtained as the average thickness of the glass substrate layer.

As a material of the glass substrate, glass such as alkali silicate glass, non-alkali glass, and quartz glass can be used.
As the thermal expansion coefficient of the glass substrate layer is closer to the thermal expansion coefficient (approximately 3 ppm / ° C.) of the silicon chip, warpage of the laminate is suppressed. Specifically, the thermal expansion coefficient of the glass substrate layer is preferably 8 ppm / ° C. or less, more preferably 6 ppm / ° C. or less, and further preferably 4 ppm / ° C. or less.
The larger the dynamic storage elastic modulus at 40 ° C. of the glass substrate layer, the better. Specifically, the dynamic storage elastic modulus at 40 ° C. of the glass substrate layer is preferably 20 GPa or more, more preferably 25 GPa or more, and further preferably 30 GPa or more.

(Resin composition layer)
The resin composition layer used in the present invention comprises a resin composition containing one or more resins selected from thermosetting resins and thermoplastic resins (hereinafter also simply referred to as “resin composition”).
The thickness of the resin composition layer is preferably 5 to 200 μm, more preferably 5 to 150 μm, and still more preferably 5 to 100 μm. When the thickness of the resin composition layer is 5 μm or more, cracking of the laminate is suppressed, and when it is 200 μm or less, the thickness of the glass substrate layer is relatively increased. High elastic modulus can be achieved.

[Thermosetting resin]
The thermosetting resin is not particularly limited, and examples thereof include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclohexanes. Examples thereof include a pentadiene resin, a silicone resin, a triazine resin, and a melamine resin. Among these, an epoxy resin and a cyanate resin are preferable from the viewpoint of excellent moldability and electrical insulation.
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , Stilbene type epoxy resin, Triazine skeleton containing epoxy resin, Fluorene skeleton containing epoxy resin, Biphenyl type epoxy resin, Xylylene type epoxy resin, Biphenyl aralkyl type epoxy resin, Naphthalene type epoxy resin, Dicyclopentadiene type epoxy resin, Alicyclic epoxy Examples thereof include diglycidyl ether compounds of polycyclic aromatics such as resins, polyfunctional phenols and anthracene. Moreover, the phosphorus containing epoxy resin which introduce | transduced the phosphorus compound into these epoxy resins is mentioned. Among these, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferable from the viewpoint of heat resistance and flame retardancy. These epoxy resins can be used alone or in combination of two or more.

〔Thermoplastic resin〕
Although there is no restriction | limiting in particular as a thermoplastic resin, From a viewpoint of improving the heat resistance of a laminated body, a heat resistant resin is preferable. From the same viewpoint, it is more preferable to use a thermosetting resin and a heat-resistant resin in combination.

[Heat resistant resin]
Examples of the heat resistant resin include polyimide resin, polyamideimide resin, polyamide resin, polyetherimide resin, polybenzoxazole resin, polybenzimidazole resin, and a copolymer having a chemical structure of any of these resins. These may contain, for example, a siloxane skeleton, a polybutadiene skeleton, or the like, and may contain a phenolic hydroxyl group, an amide group, or the like that reacts with a thermosetting resin (for example, an epoxy group of an epoxy resin). Among these, a polyamide-imide resin having a siloxane skeleton is preferable from the viewpoint of ensuring glass adhesion. These heat resistant resins may be used alone or in combination of two or more.
The heat-resistant resin has a breaking elongation determined according to the method described in JIS (Japanese Industrial Standard) K7127 of 10% or more, an elastic modulus at 50 ° C. of 1 GPa or less, and a glass transition temperature of 160 ° C. or more. Certain resins are preferred.
Note that the glass transition temperature is higher than the decomposition temperature, and even when the glass transition temperature is not actually observed, it is included in the definition of “glass transition temperature is 160 ° C. or higher” in the present invention. It is defined as the temperature at which the mass loss measured according to the method described in JIS K7120 is 5%.

  Specific examples of the heat resistant resin include soluble polyamides “BPAM-01” and “BPAM-155” manufactured by Nippon Kayaku Co., Ltd., and soluble polyimide “Rikakot (registered trademark) SN20” manufactured by Shin Nippon Rika Co., Ltd. And “RIKACOAT (registered trademark) PN20”, soluble polyetherimide “Ultem (registered trademark)” manufactured by GE Plastics Co., Ltd., soluble polyamideimide “Viromax (registered trademark) HR11NN” manufactured by Toyobo Co., Ltd. and “Vilomax (registered trademark) HR16NN” and the like.

The content of the thermosetting resin in the resin composition is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and further preferably 25 to 80% by mass, from the viewpoint of workability and adhesion. .
The content of the heat-resistant resin in the resin composition is preferably 5 to 85% by mass, more preferably 10 to 75% by mass from the viewpoints of processability, heat resistance and adhesion.

[Other ingredients]
In addition to the above components, the resin composition contains a filler, a curing agent, a curing accelerator, an elastomer, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like. Can be added as required.

≪Filler≫
The resin composition may contain a filler. The filler is preferably used from the viewpoint of preventing scattering of the resin and adjusting the processed shape when laser processing is performed.
Fillers can be classified into inorganic fillers and organic fillers. The inorganic filler also has an effect of lowering the thermal expansion coefficient of the resin composition layer or the cured resin layer, and the organic filler also has an effect of relieving stress in the cured product.
Inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, titanate Examples include strontium, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate.
Among these, silica is preferable. Moreover, in order to improve moisture resistance, it is preferable that it is an inorganic filler surface-treated with surface treatment agents, such as a silane coupling agent.

The average primary particle size of the inorganic filler is preferably 0.1 μm or less from the viewpoint of the smoothness of the laminate. The “average primary particle size” as used herein refers to the average particle size of non-aggregated single particles, and the average primary particle size can be determined, for example, by measuring with a laser diffraction particle size distribution meter. .
As such an inorganic filler, fumed silica is preferably mentioned. Although it does not specifically limit as fumed silica, From a viewpoint of insulation reliability and heat resistance, a thing with good dispersibility in an epoxy resin is preferable, for example, in order to improve dispersibility, the surface is hydrophobized. And the like. Specifically, “AEROSIL (registered trademark) R972” manufactured by Nippon Aerosil Co., Ltd., “AEROSIL (registered trademark) R202” manufactured by the same company, and the like are preferable.
The content of fumed silica is preferably 3 to 35% by mass in the resin composition from the viewpoint of improving laser processability. When the content of fumed silica is 3% by mass or more, laser processability is improved and resin scattering can be suppressed, the through-hole shape can be kept good, and when it is 35% by mass or less, After the surface of the resin composition layer is roughened with an oxidizing agent, the adhesive strength with the conductor layer can be improved when the conductor layer is formed by plating.

Preferred examples of the organic filler include acrylic rubber particles and silicon particles. The average particle diameter of the organic filler is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less from the viewpoint of forming appropriate irregularities after the roughening treatment of the resin composition layer.
These fillers can be used alone or in combination of two or more.

≪Curing agent≫
As the curing agent, for example, when an epoxy resin is used, polyfunctional phenol compounds such as phenol novolak and cresol novolak, amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone, phthalic anhydride, pyromellitic anhydride, maleic anhydride An acid anhydride such as an acid or a maleic anhydride copolymer, a polyimide having a functional group reactive with an epoxy group, or the like can be used. These hardening | curing agents can be used individually or in combination of 2 or more types.

Examples of the curing accelerator include epoxy resin curing accelerators such as imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers.
Examples of the antioxidant include antioxidants such as hindered phenols and styrenated phenols.
Examples of the photopolymerization initiator include benzophenones, benzyl ketals, and thioxanthone photopolymerization initiators.
Examples of fluorescent brighteners include stilbene derivatives.
Examples of the adhesion improver include adhesion improvers such as urea silane and silane coupling agents.

(Layer structure of the laminate)
The laminate used in the method of the present invention is not particularly limited as long as it is a laminate having one or more resin composition layers and one or more glass substrate layers. i) Three-layer structure of resin composition layer / glass substrate layer / resin composition layer, (ii) resin composition layer / glass substrate layer, (iii) glass substrate layer / resin composition phase / glass substrate layer Is mentioned.
In the present specification, the expression “resin composition layer / glass substrate layer / resin composition layer” means that the resin composition layer, the glass substrate layer, and the resin composition layer are laminated in this order. . The same applies to the notation regarding the five-layer structure.

(Ratio of each layer in the laminate)
In the laminate of the present invention, the volume occupied by the glass substrate layer is the total volume of the glass substrate layer and the resin composition layer (hereinafter, also simply referred to as “total volume”) from the viewpoint of increasing the elastic modulus and smoothing the surface. ), Preferably 30 to 99.5% by volume, more preferably 35 to 98% by volume, and still more preferably 40 to 95% by volume.
In the laminate of the present invention, the volume occupied by the resin composition layer is preferably 0.1 to 70 in the total volume, from the viewpoint of reducing warpage during mounting and from the viewpoint of improving the adhesion between the contacting layers. Volume%, More preferably, it is 2-65 volume%, More preferably, it is 5-60 volume%.

(Laminate manufacturing method)
The laminate used in the present invention is obtained, for example, by a method of applying a resin composition to a glass substrate, or a method of laminating or pressing a film made of the resin composition (hereinafter also referred to as “resin film”) to a glass substrate. Can be manufactured. Among these, the lamination method is preferable from the viewpoint of easy production.

[Production method by coating]
The manufacturing method by application | coating is a method of apply | coating the said resin composition on the surface of a glass substrate, and forming a resin composition layer on a glass substrate. Specifically, for example, after applying the varnish obtained by dissolving the resin composition in an organic solvent to a glass substrate, the resin composition layer is formed by drying the organic solvent by heating, hot air blowing, or the like. can do. Thereafter, the resin composition layer may be further heated to cause the curing reaction to proceed.
As the coating apparatus, a coating apparatus known to those skilled in the art such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater can be used, and it is preferable to select appropriately depending on the film thickness to be produced. .

[Production method by lamination]
Examples of the production method by laminating include a method of laminating a resin film and a glass substrate by pressure lamination such as a commercially available vacuum laminate or roll laminate.
As a resin film, what has the following laminated structure is used suitably.
(I) Support film / resin composition layer (ii) Support film / resin composition layer / protective film The protective film is formed on the side opposite to the support film with respect to the resin composition layer, It is used for the purpose of preventing scratches.
As an example of producing the resin film (i), the above resin composition is dissolved in an organic solvent to prepare a varnish. Next, the resin composition layer may be formed by applying the varnish to the support film and drying the organic solvent by heating, hot air blowing, or the like.
As an example of producing the resin film of (ii) above, the above resin composition is dissolved in an organic solvent to prepare a varnish. Next, varnish is applied to one of the support film and the protective film, the other of the support film and the protective film is placed on the varnish, and the organic solvent of the varnish is dried by heating, hot air blowing, etc. Thus, a resin composition layer may be formed.
As the coating apparatus, an apparatus similar to the apparatus used in the manufacturing method by coating can be used.

Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter also referred to as “PET”) and polyethylene naphthalate; polycarbonates; polyimides; release papers; Metal foil etc. can be mentioned.
This support film serves as a support for producing an adhesive film, and is usually finally peeled or removed when producing a multilayer printed wiring board. When the copper foil is used, the copper foil can be used as a conductor layer as it is to form a circuit, and can be used as a conformal mask described later.
The support film may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
The thickness of the support film is usually 10 to 150 μm, preferably 25 to 50 μm. When it is within the above range, an adhesive film excellent in handleability and productivity can be obtained.
Next, an example of a laminating method using a resin film will be described.

When the resin film has a protective film, after removing the protective film, the resin film is pressure-bonded to the glass substrate while being pressurized and heated. Next, if necessary, the resin film and the glass substrate are preheated and then laminated.
The pressure bonding temperature (laminating temperature) at the time of laminating is preferably 60 to 140 ° C. The pressure applied during laminating is preferably 1 to 11 kgf / cm ² . Further, the pressure when using a vacuum laminator is preferably an air pressure of 20 mmHg (26.7 hPa) or less.
The laminating method may be a batch method or a continuous method using a roll. After laminating, cool to near room temperature.

[Production method by press]
The laminate used in the present invention can be produced by a pressing method.
For example, a laminated body can be manufactured by superimposing the above-described resin film main body and a glass substrate, and heating and pressing by a pressing method.
Moreover, a laminated body can also be manufactured by apply | coating and drying a resin composition to a glass substrate, drying several and making it into a B-stage state, superimposing, heating and pressurizing by a press method.

The obtained laminate may be cured by heating after peeling the support film, if necessary, so that the thermosetting resin in the resin composition layer is cured.
The conditions for heat curing may be appropriately determined according to the type of resin used and the like, but are usually 20 to 80 minutes at 150 to 220 ° C, preferably 30 to 120 minutes at 160 to 200 ° C.
The method of heat curing is not particularly limited, and may be cured using a known dryer or the like, and may be laminated and cured at the same time by heating and pressurizing by the press method.
There are no particular limitations on the pressing conditions when laminating and curing are performed simultaneously by the pressing method, but the heat curing conditions are usually 150 to 280 ° C. for 20 to 80 minutes, preferably 160 to 230 ° C. for 30 to 120 minutes. The pressing pressure is usually 1 to 5 MPa.

<Formation of through holes>
The method of the present invention includes a step of providing a metal film having an opening as a conformal mask on one surface of the laminate, and a step of irradiating the laminate exposed in the opening with laser light.
By irradiating the opening with a laser beam, the resin composition layer and the glass substrate layer exposed in the opening can be removed to form a through hole.

(Conformal mask and manufacturing method thereof)
In the method of the present invention, a metal film having an opening is used as a conformal mask.
As the metal film, for example, one or more selected from copper, nickel, aluminum, and noble metals (gold, silver, palladium, platinum, etc.) can be used. Among these, copper is preferable because it is inexpensive and has excellent resistance to laser light.
The thickness of the metal film is preferably 1 to 200 μm, more preferably 3 to 180 μm, and still more preferably 5 to 150 μm. When the thickness of the metal film is 1 μm or more, defects due to laser light can be suppressed, and when the thickness is 200 μm or less, a fine pattern can be formed.

The opening of the conformal mask may be formed by a conventionally known method. For example, it can be formed by photolithography, grinding with laser light, or the like.
The opening of the conformal mask is preferably formed by a method of irradiating the metal film with laser light after providing a metal film before forming the opening on one surface of the laminate.

As a laser for forming a conformal mask, an infrared laser such as a CO ₂ laser, a Nd: YAG (Neodymium-doped Yttrium Aluminum Garnet) laser, a Nd: YAG laser and a near-infrared region that is combined with wavelength conversion to a visible region Furthermore, known lasers such as lasers covering the ultraviolet region, KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F ₂ excimer laser (wavelength: 157 nm), etc. can be used. However, a UV-YAG laser is preferable from the viewpoint of reducing the diameter.
As the UV-YAG laser, a laser having a wavelength of 10 to 400 nm is generally used.
The number of shots can be appropriately determined according to the thickness of the metal film to be used. For example, burst shots that are continuous multiple shots are shot 5 to 20 times, and cycle shots that are single shot repeated irradiations are 3 Preferably 10 times.
The pulse width of the UV-YAG laser is not particularly limited, and can usually be selected in the range of 1 to 50 μs.

(Laser beam irradiation to the laminate)
Formation of the through hole by irradiating the laminate with laser light can be performed by a known method. For example, a processing laser light source, a scanning head for deflecting the direction of the laser light in the XY direction, a camera for reading a positioning mark of the laminate, an XY table for mounting the laminate, and processing data An opening can be formed by the following method using an input unit for inputting, a storage unit for storing machining data or a calculation result, and a device having the calculation unit.

First, a positioning mark is provided on the metal film, the position of the positioning mark is measured with a camera, and the position of the laminated body is measured to irradiate the position of the opening with laser light.
The positioning mark is preferably formed by etching or laser processing the metal film. The shape of the positioning mark is not particularly limited, and may be circular by etching into a ring shape, or may be rectangular by etching into a square shape.
Since the metal positioning mark does not transmit light, when the positioning mark is irradiated with light from below (XY table side), it can be recognized as a silhouette, and light is irradiated from above (laser light source side). In the case, it can be recognized by reflected light. That is, if the conformal mask is made of metal, it is advantageous because it can be easily read by the camera no matter which direction the light is irradiated.
Further, from the viewpoint of shortening the process, it is preferable that the positioning mark is formed by etching simultaneously with the formation of the opening after the metal film is formed.

Further, the positioning mark is read, and the driving data for the scanning head and the XY table is created so that the positional deviation of the laminated body can be corrected from the input processing data and the measured value of the laminated body position, The scanning head and the table are driven according to the driving data. For this reason, it is possible to efficiently form hundreds to thousands of through holes.
For example, by moving the stage on which the glass substrate is placed linearly and stepwise and irradiating the laser beam for each movement, it is possible to form through-holes arranged one-dimensionally, and in the linear direction In addition to this, by adding the movement of the stage in a direction perpendicular thereto, a large number of through-holes arranged in a two-dimensional array can be formed.

Examples of the laser beam for forming the through hole include the same laser as the laser for forming the conformal mask. Among these, a CO ₂ laser is preferable from the viewpoint of processability.
As the CO ₂ laser, lasers having wavelengths of 9.4 and 10.6 μm are generally used.
The number of shots can be appropriately determined depending on the depth and diameter of the through hole to be formed, but is usually selected between 3 and 20 shots.
The pulse width of the CO ₂ laser is not particularly limited, and can usually be selected in the range of 1 to 100 μs.

[Manufacturing method of laminate]
The method for producing a laminate of the present invention is a method for producing a laminate having one or more resin composition layers and one or more glass substrate layers, and the method for forming a through hole in the laminate of the present invention. And a step of forming a through hole.
The conditions for forming the laminate and the through hole are the same as the laminate and the conditions described in the method for forming a through hole in the laminate of the present invention, and the preferred embodiments are also the same.

<Desmear treatment>
After forming the through hole by the method of the present invention, a desmear treatment may be performed using a known oxidizing agent or the like, if necessary.

<Formation of conductor layer>
Next, a conductor layer may be formed on the surface of the laminate. The method for forming the conductor layer can be selected from known methods such as dry plating such as sputtering, wet plating such as electroless plating, and electroplating.

<Formation of wiring pattern>
Furthermore, you may form a wiring pattern in the conductor layer formed above. As a pattern formation method, for example, a known subtractive method, semi-additive method, or the like can be used.

  EXAMPLES Next, although an Example demonstrates this invention concretely, the scope of the present invention is not limited to these Examples.

[Preparation of resin composition varnish]
(1) Synthesis of polyamideimide resin Both ends amino group-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.) while flowing about 250 ml / min of nitrogen into a 500 ml separable flask equipped with a thermocouple, stirrer and nitrogen inlet Product name: X-22-161A) 32.0 g, (4,4′-diamino) dicyclohexylmethane (manufactured by Shin Nippon Rika Co., Ltd., product name: Wandamine (registered trademark) HM (WHM)) 0.935 g, poly 40.0 g of oxypropylene diamine (manufactured by Mitsui Chemicals Fine Co., Ltd., trade name: Jeffamine (registered trademark) D2000), 17.9 g of trimellitic anhydride (hereinafter also referred to as “TMA”) and N-methyl-2 -250 g of pyrrolidone (hereinafter also referred to as “NMP”) was added and stirred to dissolve. To this solution, 100 g of toluene was added, and after imide ring closure reaction by dehydration reflux for 6 hours at a temperature of 150 ° C. or higher, toluene was distilled off, and after cooling, 13.4 g of 4,4′-diphenylmethane diisocyanate was added, The reaction was carried out at 2 ° C. for 2 hours. Thereafter, 1.6 g of TMA was added and stirred at 80 ° C. for 1 hour to synthesize a polyamideimide resin solution.

(2) Glass Adhesive Resin Composition Varnish Composition Polyamideimide resin solution having a solid content of 70 g and 20 g of dicyclopentadiene phenol type epoxy resin (manufactured by DIC Corporation, trade name: HP7200), trisphenol methane type epoxy resin (Japan) 10 g of Kayaku Co., Ltd., trade name: EPPN-502H), 0.15 g of 1-cyanoethyl-2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2E4MZ-CN) are added, It diluted with NMP so that solid content concentration might be 30 mass%, and the resin composition varnish for glass bonding was mix | blended.

(3) Production of resin composition varnish for bonding copper foil To 10.2 g of phenolic hydroxyl group-containing polybutadiene-modified polyamide (manufactured by Nippon Kayaku Co., Ltd., trade name: BPAM-155), N, N-dimethylacetamide (hereinafter, After blending 91.4 g of “DMAc”), 40.0 g of biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000H), bisphenol A novolak (manufactured by Mitsubishi Chemical Corporation), Product name: YLH129) 12.6 g, 2-phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name: 2PZ) as a curing accelerator, fumed silica (manufactured by Nippon Aerosil Co., Ltd., product name: R972) ) After adding 3.6 g, it was diluted with a mixed solvent consisting of DMAc and methyl ethyl ketone (solid content concentration about 25% by mass). Then, the resin composition varnish for copper foil adhesion | attachment was obtained using the disperser (The product name: Nanomizer (trademark) made by Yoshida Kikai Kogyo Co., Ltd.).

[Preparation of resin film with copper foil]
Using a bar coater on the glossy surface of a 20 μm thick copper foil (Furukawa Electric Co., Ltd., trade name: NC-WS), the thickness after drying is 5 μm. It was applied so that it was dried at 140 ° C. for 10 minutes.
Next, the glass adhesive resin composition varnish was applied on the layer made of the copper foil adhesive resin composition formed above so that the thickness after drying was 5 μm, and dried at 140 ° C. for 5 minutes. The resin film with copper foil in which the resin composition layer which consists of the resin composition for copper foil adhesion | attachment and the resin composition for glass adhesion | attachment was formed on copper foil was obtained.

[Manufacture of laminates]
As the glass substrate, a glass film (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA-10G, thickness 150 μm) was used. The resin film with copper foil prepared above is arranged on both surfaces of this glass substrate so that the resin film is in contact with the glass substrate, and is hot-pressed under the conditions of 185 ° C., 3 MPa, and 1 hour by hot press, A laminate having a substrate layer and a resin composition layer was obtained.

[Formation of through holes]
Example 1
The laminate obtained above was irradiated with a UV-YAG laser under the following conditions using a UV-YAG / CO ₂ hybrid laser device (manufactured by Via Mechanics Co., Ltd., trade name: ULC-2K21 / 1C). After forming an opening in the copper foil, a CO ₂ laser was irradiated to form a through hole.
<UV-YAG laser>
・ Irradiation beam diameter: 40 μm
・ Number of burst shots: 10 times ・ Number of cycle shots: 6 times <CO ₂ laser>
・ Pulse width: 20μsec
・ Number of shots: 15 times

Example 2
In Example 1, through-holes were formed in the same manner as in Example 1 except that the irradiation beam diameter of the UV-YAG laser was changed from 40 μm to 50 μm.

Comparative Example 1
After preparing the same laminated body as the laminated body used in Example 1 and removing the copper foil of the laminated body by etching, through holes were formed in the same manner as in Example 1.

[Check the shape of the through-hole]
About the sample obtained in Comparative Example 1 and the sample in which the copper foil was removed by etching from the laminate in which through holes were formed in Examples 1 and 2, an optical microscope (trade name: Digital Microscope VHX- manufactured by Keyence Corporation) was used. 1000), the surface shapes on the incident side and the emission side after laser processing were observed, and the through-hole diameter was measured. In addition, the through-hole diameter was made into the average value of the value obtained by selecting and measuring 10 holes at random from the pattern of 10 holes x 10 holes. The optical micrographs of the through holes formed in each example and comparative example are shown in FIGS.
In addition, as shown in FIG. 1, the angle (θ) of the through-hole wall surface on the exit side is calculated from the through-hole diameter (D) on the entrance side, the through-hole diameter (d) on the exit side, and the thickness (t) of the glass substrate used. ) Was calculated by the following formula, and the value of θ was defined as the degree of taper.
Degree of taper (θ) = tan ⁻¹ [2t / (D−d)]

As is clear from Table 1, the through holes of Examples 1 and 2 formed by the method of the present invention had a smaller difference between the through hole diameters on the incident side and the output side of the through hole than the through hole of Comparative Example 1. . Further, the through holes of Examples 1 and 2 had a small degree of taper, and a value close to 90 ° without taper was obtained.
Further, as apparent from FIGS. 2 to 3, the through holes of Examples 1 and 2 had no difference in the appearance of the processing edges of the through holes on the incident side and the outgoing side.
From the above results, according to the present invention, it is possible to form a through hole having a small difference in processing shape between the glass substrate layer and the resin composition layer and a small degree of taper.

Claims (6)

  A method for forming a through hole in a laminate having one or more resin composition layers and one or more glass substrate layers, wherein a metal film having an opening as a conformal mask is formed on one surface of the laminate. A method for forming a through-hole in a laminate, comprising a step of providing and a step of irradiating the laminate exposed in the opening with laser light.   The method for forming a through hole in the laminate according to claim 1, wherein the glass substrate layer has a thickness of 20 to 200 μm.   The formation method of the through-hole to the laminated body of Claim 1 or 2 whose said metal film is copper.   The formation method of the through-hole to the laminated body of any one of Claims 1-3 whose thickness of the said metal film is 1-200 micrometers. The laser is a CO ₂ laser, a method of forming the through hole of the laminate according to any one of claims 1-4.   It is a manufacturing method of the laminated body which has one or more resin composition layers and one or more glass substrate layers, Comprising: By the formation method of the through-hole to the laminated body of any one of Claims 1-5 The manufacturing method of a laminated body which has the process of forming a through-hole.