JP2014120690A - Laminated plate, multilayer laminated plate, printed wiring board, multilayer printed wiring board, and method for manufacturing laminated plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated plate which can suppress warpage, hardly causes cracks, and is excellent in handleability, and to provide a printed wiring board, and a method for manufacturing the laminated plate.SOLUTION: In a laminated plate including one or more cured resin layers and one or more glass substrate layers, a shear adhesive strength between the cured resin layer and the glass substrate layer at 25°C is 20 MPa or more. A printed wiring board having a wiring circuit provided on the surface of the laminated plate, and a method for manufacturing the laminated plate are provided.

Description

  The present invention relates to a laminated board, a multilayer laminated board, a printed wiring board, a multilayer printed wiring board, and a method for producing the laminated board, which are less warped, hard to break, and easy to handle and suitable for semiconductor packages and printed wiring boards. .

In recent years, demands for thinner and lighter electronic devices have become stronger, and semiconductor packages and printed wiring boards are becoming thinner and higher in density. In order to stably mount electronic components corresponding to these reductions in thickness and density, it is important to suppress warpage that occurs during mounting.
One of the main causes of warpage occurring in the semiconductor package during mounting is a difference in thermal expansion coefficient between the laminated plate used in the semiconductor package and the silicon chip mounted on the surface of the laminated plate. For this reason, efforts are being made to bring the coefficient of thermal expansion close to the coefficient of thermal expansion of the silicon chip, that is, to lower the coefficient of thermal expansion, in the laminated sheet for semiconductor packages. Further, since the elastic modulus of the laminated plate also becomes a factor of warping, it is also effective to make the laminated plate highly elastic in order to reduce warpage. Therefore, in order to reduce warpage of the laminated plate, it is effective to reduce the expansion coefficient and increase the elasticity of the laminated plate.

  In conventional laminates, in order to reduce warpage, a low thermal expansion coefficient and a high elasticity have been achieved by adopting a resin having a high filling with an inorganic filler and a low thermal expansion coefficient (for example, Patent Documents 1 to 3). reference). However, increasing the filling amount of the inorganic filler may cause a decrease in insulation reliability, insufficient adhesion between the resin and the wiring layer formed on the surface thereof, and press molding failure during the production of the laminate. Further, the method of increasing the crosslink density of the resin and increasing the Tg to reduce the coefficient of thermal expansion has a limit because it shortens the molecular chain between the functional groups, and may cause a decrease in resin strength.

Further, as a method different from the above for reducing warpage in the laminated plate, a glass film is used as a layer having a thermal expansion coefficient substantially matching the thermal expansion coefficient of the electronic component (silicon chip), and the resin and the glass film are combined. It has been proposed to reduce heat shock stress by pressing and laminating (see, for example, Patent Document 4).
Since the substrate obtained by the manufacturing method of Patent Document 4 has a low elastic modulus and a high coefficient of thermal expansion, it is insufficient for realizing “low warpage” of the substrate. Further, the glass film has a problem that the substrate is not easily handled because the mechanical strength is low and the glass is easily broken.

JP 2004-182851 A JP 2000-243864 A JP 2000-114727 A Japanese translation of PCT publication No. 2004-512667

  The present invention has been made in view of such circumstances, and has a low thermal expansion coefficient and a high elastic modulus, so that it is possible to suppress warpage, and it is difficult to cause cracks, and a laminate that has good handleability, and a multilayer laminate. An object of the present invention is to provide a method for producing a printed wiring board, a multilayer printed wiring board, and a laminated board.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that in a laminated plate including a cured resin layer and a glass substrate layer, the adhesive force in the shear direction between the cured resin layer and the glass substrate layer is increased. By setting the pressure to 20 MPa or more, it was found that even when the cured resin layer was thinned, the mechanical strength of the laminate was increased, and a laminate that was difficult to break was obtained, and the present invention was achieved.
That is, the present invention provides the following laminated board, multilayer laminated board, printed wiring board, multilayer printed wiring board, and manufacturing method of the laminated board.

1.1 Laminated plate including one or more resin cured product layers and one or more glass substrate layers, wherein the shear adhesive force at 25 ° C. between the resin cured product layer and the glass substrate layer is 20 MPa or more. A laminated board characterized by being.
2. Said 1 laminated board which contains an inorganic filler in the said resin cured material layer.
3. The laminated board according to 1 or 2 above, wherein the glass substrate layer has a thickness of 30 to 200 μm.
4). The laminated board according to any one of the above 1 to 3, wherein the cured resin layer has a thickness of 1 to 40 µm.
5. In the resin cured product layer, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, The laminated board in any one of said 1-4 containing at least 1 sort (s) of resin chosen from a triazine resin and a melamine resin.
6). The laminated board according to any one of 2 to 5 above, wherein the inorganic filler is at least one selected from silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass.
7. The laminate according to any one of 1 to 6 above, wherein the storage elastic modulus at 40 ° C. is 10 to 70 GPa.
8). A multilayer laminate in which a plurality of laminates are laminated, and at least one laminate is any one of the laminates 1 to 7 above.
9. The printed wiring board which has a laminated board in any one of said 1-7, and the wiring circuit provided in the surface of the said laminated board.
10. 9. A multilayer printed wiring board comprising the multilayer laminated board according to 8 and a wiring circuit provided on a surface of the multilayer laminated board.

11. The manufacturing method of said 1 laminated board which forms a resin cured material layer by apply | coating the resin composition containing a thermosetting resin on a glass substrate, and drying and hardening | curing.
12 The manufacturing method of said 1 laminated board which forms a resin cured material layer by laminating | stacking the film which consists of a resin composition containing a thermosetting resin on a glass substrate using a vacuum laminator or a roll laminator, and hardening.
13. The manufacturing method of said 1 laminated board which forms the resin hardened | cured material layer by pressing and hardening after arrange | positioning the film which consists of a resin composition containing a thermosetting resin on a glass substrate.

  According to the present invention, a laminated board and a multilayer laminated board having a low thermal expansion coefficient and a high elastic modulus, capable of forming a fine circuit in which warpage is suppressed and cracks are difficult to occur and handling properties are good. Provided are a printed wiring board using the board, a multilayer printed wiring board, and a method for manufacturing a laminated board.

These are explanatory drawings of the apparatus for measuring the shearing adhesive force between a resin hardened material layer and a glass substrate layer.

Hereinafter, the present invention will be described in detail.
First, the laminate of the present invention is a laminate comprising one or more cured resin layers and one or more glass substrate layers, at 25 ° C. between the cured resin layer and the glass substrate layer. The shear adhesive strength is 20 MPa or more.
In the present invention, the laminate means that the thermosetting resin that is a constituent component is uncured or semi-cured, and the laminated board is that the thermosetting resin that is the constituent component is cured, Alternatively, it means that 90% or more of the thermosetting resin is cured. The degree of cure of this thermosetting resin can be determined from the reaction rate measured from a differential scanning calorimeter.

  In the present invention, an underfill resin post is formed so that the shear adhesive force between the cured resin layer and the glass substrate layer is perpendicular to the cured resin layer as shown in FIG. Glue the layer and the underfill resin post. A stress parallel to the surface of the cured resin layer is applied to the underfill resin post, and the measurement can be performed by a stress that isolates the cured resin layer of the portion where the underfill resin post is formed from the glass substrate.

The handleability of a printed wiring board using a laminated board or a multilayer laminated board, that is, the resistance to cracking, can be evaluated by the maximum stress of three-point bending, but such a cured resin layer and a glass substrate layer By increasing the shear adhesive strength between them, the stress to break becomes higher, and it becomes difficult to break, so the handleability is improved.
In other words, glass materials have high elasticity but are difficult to handle because they are cracked with a small force. However, in laminated boards and printed wiring boards composed of a cured resin layer and a glass substrate layer, the shear adhesive strength between these layers is increased. This makes it difficult to break and easy to handle.
Since the shear adhesive strength is temperature dependent, the shear adhesive strength at 25 ° C. (room temperature) is defined in the present invention. The laminated plate of the present invention has a shear adhesive strength of 20 MPa or more, preferably 24 MPa or more, more preferably 28 MPa or more.

The storage elastic modulus at 40 ° C. of the laminated plate is preferably 10 to 70 GPa. A glass substrate is protected as it is 10 GPa or more, and the crack of a laminated board is suppressed. When it is 70 GPa or less, stress due to the difference in coefficient of thermal expansion between the glass substrate and the cured resin layer is suppressed, and warpage and cracking of the laminate are suppressed. From this viewpoint, the storage elastic modulus of the cured resin layer is more preferably 1 to 40 GPa, and further preferably 3 to 30 GPa.
In addition, you may have metal foil, such as copper and aluminum, on the single side | surface or both surfaces of a laminated board. The metal foil is not particularly limited as long as it is used for printed wiring.

[Hardened resin layer]
In the present invention, the cured resin layer indicates that the thermosetting resin is cured or 90% or more of the thermosetting resin is cured. The degree of cure of the thermosetting resin can be measured by the reaction rate measured from a differential scanning calorimeter.
The thickness of the cured resin layer is preferably 1 to 40 μm. When the thickness is 1 μm or more, cracking of the laminate is suppressed. When the thickness is 40 μm or less, the thickness of the glass substrate is relatively increased, and the low thermal expansion coefficient and high elastic modulus of the laminate can be achieved. Moreover, it is preferable also from the point of thickness reduction and size reduction of a laminated board. From this viewpoint, the thickness of the cured resin layer is more preferably 2 to 30 μm, and further preferably 3 to 20 μm. However, the appropriate range of the thickness of the cured resin layer varies depending on the thickness and number of layers of the glass substrate layer, and the type and number of layers of the cured resin layer.

The cured resin layer preferably contains an inorganic filler. By including an inorganic filler in the cured resin layer, a laminate having a low thermal expansion coefficient and a high elastic modulus, suppressing warpage, and being difficult to crack can be obtained.
Since the laminate of the present invention has a resin cured material layer and a glass substrate layer having a low thermal expansion coefficient and a high elastic modulus as much as a silicon chip, it has a low thermal expansion coefficient and a high elastic modulus. It will be suppressed and it will be hard to produce a crack. In particular, since this laminate has a glass substrate layer with high heat resistance, low thermal expansion is remarkable in a temperature range from 100 ° C. to less than Tg of the cured resin. Further, by containing an inorganic filler in the cured resin layer, the cured resin layer has a low thermal expansion coefficient and a high elastic modulus, and the laminate including the cured resin layer has a lower expansion coefficient. And it becomes a thing with a high elasticity modulus.
Therefore, it is preferable that the cured resin layer in the laminate of the present invention contains an inorganic filler together with the thermosetting resin.

<Thermosetting resin>
The thermosetting resin contained in the cured resin of the present invention is not particularly limited. For example, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, Examples thereof include saturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. Among these, an epoxy resin is preferable because it is excellent in moldability and electrical insulation.
Further, particularly as a thermosetting resin, a resin containing an epoxy resin (A), an epoxy curing agent (B), and at least one heat resistant resin (C) selected from a polyamide resin, a polyamideimide resin and a polyimide resin is preferable. Used for.

  Examples of the epoxy resin (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac 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, triphenolphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, aralkyl novolac type epoxy resin, naphthalene type epoxy resin, Diglycidyl ethers of polycyclic aromatics such as dicyclopentadiene type epoxy resins, alicyclic epoxy resins, polyfunctional phenols and anthracene Compounds, and the like. Moreover, the phosphorus containing epoxy resin which introduce | transduced the phosphorus compound into these epoxy resins is mentioned. Among these, it is preferable to contain an aralkyl novolac type epoxy resin or an aralkyl novolac type epoxy resin from the viewpoint of heat resistance and flame retardancy. Two or more of these epoxy resins may be used in combination.

As the epoxy curing agent (B), various phenol resins, acid anhydrides, amines, hydragits and the like can be used. As the phenol resin, a novolac type phenol resin, a resol type phenol resin, or the like can be used. As the acid anhydrides, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, or the like can be used. As the amines, dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used. In order to improve reliability, a novolac type phenol resin is preferable.
As the heat resistant resin (C), a phenolic hydroxyl group-containing polybutadiene-modified polyamide resin is particularly preferably used.

<Inorganic filler>
Examples of the inorganic filler include silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. Two or more kinds of these inorganic fillers may be used in combination.

When forming fine wiring on the cured resin layer of the laminate, it is preferable that the inorganic filler has the following characteristics. That is, the inorganic filler preferably has a specific surface area of 20 m ² / g or more. Further, from the viewpoint of reducing the surface shape after the roughening treatment in the plating process, the average primary particle size is preferably 100 nm or less.
The “average primary particle size” here refers to the average particle size of aggregated particles, that is, not the secondary particle size, but the average particle size of single particles that are not aggregated. The average primary particle size can be determined by measuring with, for example, a laser diffraction particle size distribution meter. Fumed silica is preferable as the inorganic filler satisfying such conditions of specific surface area and average primary particle size.
Furthermore, the inorganic filler is preferably surface-treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance, and is preferably hydrophobized to improve dispersibility. .

  Moreover, as content of an inorganic filler, it is preferable that it is 20 mass% or less in a resin composition. When the blending amount is 20% by mass or less, a good surface shape after the roughening treatment can be maintained, and deterioration of plating characteristics and interlayer insulation reliability can be prevented. On the other hand, since the low thermal expansion and high elasticity of the resin composition can be expected by containing the inorganic filler, the content of the inorganic filler is as follows when emphasizing low thermal expansion and high elasticity as well as fine wiring formation: It is preferable to set it as 5-20 mass%.

On the other hand, when fine wiring is not formed on the cured resin layer of the laminate, silica is preferable as the inorganic filler from the viewpoint of low thermal expansion, and the coefficient of thermal expansion is as small as about 0.6 ppm / K. Spherical amorphous silica is preferred because it has little decrease in fluidity when it is highly filled. The spherical amorphous silica preferably has a cumulative 50% particle size of 0.1 to 5 μm, more preferably 0.3 to 3 μm. Here, the cumulative 50% particle diameter is the particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the powder as 100%. It can be measured with a particle size distribution measuring apparatus using
The content of the inorganic filler in the cured resin is preferably 20 to 60% by volume of the total amount of the thermosetting resin and the inorganic filler. When the content of the inorganic filler is 20 to 60% by volume of the total amount of the thermosetting resin and the inorganic filler, the effect of reducing the coefficient of thermal expansion is sufficient, and the moldability is appropriate with appropriate fluidity. Excellent. That is, when the content of the inorganic filler is 20% by volume or more, the effect of reducing the thermal expansion coefficient is sufficient, and when it is 60% by volume or less, the fluidity is increased and the moldability is improved. Moreover, since the elasticity modulus of a resin cured material layer becomes high by adding an inorganic filler, the effect which raises the elasticity modulus of a laminated board can be anticipated.

<Other ingredients>
In addition to the above components, the cured resin layer includes a curing agent, a curing accelerator, a thermoplastic resin, an elastomer, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, etc. Can be added.
As the curing agent, for example, when an epoxy resin is used, polyfunctional phenol compounds such as phenol novolac and cresol novolac; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; phthalic anhydride, pyromellitic anhydride, anhydrous Acid anhydrides such as maleic acid and maleic anhydride copolymer; polyimide and the like can be used. Several kinds of these curing agents can be used in combination.
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.
Antioxidants include hindered phenols and styrenated phenol antioxidants.
Examples of the photopolymerization initiator include photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthone.
Examples of fluorescent whitening agents include fluorescent whitening agents such as stilbene derivatives.
Examples of the adhesion improver include urea compounds such as urea silane, adhesion improvers such as silane coupling agents, and the like.

[Glass substrate layer]
As a material of the glass substrate constituting the glass substrate layer, glass such as alkali silicate glass, non-alkali glass, and quartz glass can be used, but glass having a high silicon content is preferable from the viewpoint of low thermal expansion. .
This glass substrate is preferably a thin glass film having a thickness of 30 to 200 μm from the viewpoint of thinning the laminate and from the viewpoint of workability, and the thickness is more preferably 50 to 150 μm considering practicality such as ease of handling. preferable. Furthermore, it is preferable to set it as 30 micrometers-100 micrometers from a viewpoint of thickness reduction of a laminated body.
As the thermal expansion coefficient of the glass substrate layer is closer to the thermal expansion coefficient (about 3 ppm / ° C.) of the silicon chip, warpage of the laminate or a laminate obtained from the laminate may be suppressed, but preferably 8 ppm / ° C. It is below, More preferably, it is 6 ppm / degrees C or less, More preferably, it is 4 ppm / degrees C or less.
The larger the storage elastic modulus of this glass substrate layer at 40 ° C., the better, but it is preferably 20 GPa or more, more preferably 25 GPa or more, and further preferably 30 GPa or more.

This glass substrate layer is preferably subjected to a surface treatment in order to increase the shear bond strength between the adjacent resin composition layer and the cured resin layer. Examples of the glass surface treatment include glass surface cleaning and surface treatment with a silane coupling agent or the like. As the surface cleaning of the glass, known methods such as wet cleaning with alkali, acid, organic solvent, and ultrasonic waves, and dry cleaning with UV, ozone irradiation, or the like can be used. These washings may be used alone or in combination of two or more.
The surface treatment with a silane coupling agent or the like can be performed by a known method such as wet or dry treatment such as application by a dip coating method. The type of silane coupling agent is preferably selected as appropriate depending on the resin used. For example, when using an epoxy resin, it is preferable to select an epoxy-based or amine-based silane coupling agent.
Further, the surface treatment of the glass substrate can be performed using a hydrofluoric acid roughening solution or the like.

[Manufacturing method of laminate]
The laminate of the present invention is a laminate resin composition layer comprising a thermosetting resin as described above, or a resin composition layer comprising a resin composition further containing an inorganic filler and other components, and a glass substrate layer. Can be obtained by forming a cured resin layer on the surface of the glass substrate.
There is no restriction | limiting in particular in the manufacturing method of the said laminated body, It manufactures by laminating | stacking the film which consists of a resin composition on a glass substrate <the manufacturing method of the laminated body by lamination>, and applying and drying a resin composition to a glass substrate. <Manufacturing method of laminate by coating> can be used. Among these, the method using lamination is preferable from the viewpoint of easy production.
Next, each manufacturing method will be described in detail.

<Manufacturing method of laminate by lamination>
Said laminated body can be manufactured by laminating | stacking the adhesive film using the said resin composition, and a glass substrate by pressure lamination like vacuum lamination and roll lamination. This vacuum laminating or roll laminating can be performed using a commercially available vacuum laminator or roll laminator.
In addition, as a thermosetting resin in a resin composition, what melt | dissolves below the temperature at the time of lamination is used suitably. For example, when laminating using a vacuum laminator or a roll laminator, since it is generally performed at 140 ° C. or lower, the thermosetting resin in the resin composition is preferably melted at 140 ° C. or lower.

When a laminate is produced using a vacuum laminator or a pressure laminator as described above, the above resin composition is generally prepared as an adhesive film.
As this adhesive film, there is one having the following laminated structure.
(1) A film comprising a support film / resin composition layer.
(2) A film / protective film comprising a support film / resin composition layer.
The protective film is formed on the side opposite to the support film with respect to the thermosetting resin composition of the present invention, and is used for the purpose of preventing adhesion of foreign substances and scratches.
The adhesive film having the laminated structures (1) and (2) can be produced according to a known method. In addition, what remove | excluded the support body film and the protective film from these adhesive films may be called an adhesive film main body.

As an example of producing the adhesive film of (1), the above resin composition is dissolved in an organic solvent to prepare a varnish in which an inorganic filler is dispersed, and then this varnish is applied using the support film as a support. Then, the resin composition layer can be formed by drying the organic solvent by heating or blowing hot air.
As an example of producing the adhesive film of (2), the above resin composition is dissolved in an organic solvent to prepare a varnish in which an inorganic filler is dispersed, and then this varnish is applied to one of the support films. After forming the resin composition layer by drying the organic solvent of the varnish by heating, hot air blowing, etc., a protective film is disposed on the resin composition layer on the side not in contact with the support film. Can be manufactured.

As a coating apparatus for the resin composition layer, a known coating apparatus such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater can be used, and is appropriately selected depending on the film thickness to be produced. Is preferred.
In the above adhesive film, the resin composition layer may be semi-cured.
The above support film serves as a support when producing an adhesive film, and is usually finally peeled off or removed when producing a multilayer printed wiring board.

Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter may be abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and release paper and copper. Metal foils, such as foil and aluminum foil, can be mentioned.
In addition, in the case of metal foil, the unroughened copper foil which is not roughened, the low roughened copper foil whose surface roughness (Ra) is 0.4 micrometer or less, aluminum foil, etc. are preferable. Further, these support films may be subjected to a release treatment.
When copper foil is used for the support film, the copper foil can be used as a conductor layer as it is to form a circuit. In this case, examples of the copper foil include rolled copper and electrolytic copper foil, and those having a thickness of 2 to 36 μm are generally used. When using a thin copper foil, a copper foil with a carrier may be used in order to improve workability.
The surface of the support film may be subjected to a release treatment in addition to a mat treatment or a corona treatment in order to facilitate peeling from the resin composition layer or the cured resin layer.

The thickness of the support film is usually 10 to 150 μm, preferably 25 to 50 μm. When the thickness is 10 μm or more, handleability becomes easy. On the other hand, since the support film is usually finally peeled off or removed as described above, the thickness of the support film is preferably 150 μm or less from the viewpoint of energy saving.
Note that (2) the protective film of the adhesive film is peeled off before lamination or hot pressing. As the protective film, the same material as the support film may be used, or a different material may be used. The thickness of the protective film may be the same as without support film particularly limited, and more preferably in the range of 1 to 40 [mu] m.

Next, an example of a laminating method using the above adhesive film will be described.
When it has a protective film like the adhesive film of (2), after removing a protective film, it pressure-bonds to a glass substrate, pressing and heating an adhesive film.
The lamination is preferably performed by preheating the adhesive film and the glass substrate as necessary, and laminating at a pressure bonding temperature (lamination temperature) of preferably 60 ° C. to 140 ° C. and a pressure bonding pressure of preferably 0.1 to 1.1 MPa. Moreover, when using a vacuum laminator, it is preferable to laminate under a reduced pressure with an air pressure of 20 mmHg (2.67 kPa) or less. The laminating method may be a batch method or a continuous method using a roll.
After laminating the adhesive film on the glass substrate, it is cooled to around room temperature. The support film is peeled off as necessary.

<Method for producing laminate by coating>
There is no restriction | limiting in particular in the manufacturing method of the laminated body by application | coating. For example, the above resin composition is dissolved in an organic solvent to prepare a varnish in which an inorganic filler is dispersed. The resin composition layer is formed by applying the varnish to a glass substrate and drying the organic solvent by heating or blowing hot air. This resin composition layer may be further semi-cured. Thus, a laminated body can be manufactured.

[Manufacturing method of laminate]
The laminated board of this invention can be obtained by hardening the resin composition layer of the laminated body containing the said resin composition layer and a glass substrate layer, and forming a resin cured material layer on the surface of a glass substrate.
The following method can be mentioned as a manufacturing method of a laminated board.
(I) After apply | coating the said resin composition on a glass substrate, a resin cured material layer is formed by drying and hardening (method by application | coating of a resin composition).
(II) A film (laminate) having a resin composition is laminated on the glass substrate using a vacuum laminator or a roll laminator, and dried and cured to form a cured resin layer (drying of the laminate and Method by curing).
(III) A film (laminate) made of the resin composition is placed on a glass substrate, and then pressed and cured to form a cured resin layer (method by pressing the laminate).

(I) The method by application | coating of the resin composition is a method of forming the resin composition layer on a glass substrate by the method similar to the manufacturing method of the laminated body by the said application | coating, and heat-hardening after drying.
In the method of drying and curing the laminate of (II), in the laminate obtained by the above laminate, the support film is peeled off as necessary, and then the resin composition layer is heat-cured to obtain a laminate. Can be manufactured.
The conditions for heat curing in the production of the laminate are preferably 150 to 220 ° C for 20 to 80 minutes, more preferably 160 to 200 ° C for 30 to 120 minutes. When a support film subjected to a release treatment is used, the support film may be peeled off after being cured by heating. Here, it is important to control the degree of curing of the cured resin layer of the laminate of the present invention. The degree of cure can be determined from the reaction rate measured from a differential scanning calorimeter. Specifically, it is necessary that the reaction rate of the cured resin layer is 90 to 99%. By setting it as such a reaction rate, it can prevent that the adhesive force with plated copper falls.
According to this method, since it is not necessary to pressurize at the time of manufacture of a laminated board, it is controlled that a crack arises at the time of manufacture.

In the method of pressing the laminate of (III), for example, the laminate obtained by the laminate can be cured by heating and pressurizing by a pressing method to produce a laminate.
In addition, the adhesive film using the above resin composition, the adhesive film body obtained by removing the support film and the protective film from the adhesive film, and the glass substrate are overlaid, and cured by heating and pressurizing by a pressing method. By doing so, a laminated board can also be manufactured.
Furthermore, a laminated board can also be manufactured by applying and drying a resin composition on a glass substrate and superimposing them in a B-stage state, followed by heating and pressing by a pressing method and curing.

[Multi-layer laminate and its manufacturing method]
The multilayer laminate plate of the present invention is such that at least one laminate plate of the plurality of laminate plates laminated is the laminate plate of the present invention.
There are no particular restrictions on the method for producing this multilayer laminate, and for example, a plurality of the laminates described above are laminated by interposing an adhesive film body obtained by removing a support film and a protective film from the aforementioned adhesive film. It can be produced more to be of. Moreover, a multilayer laminated board can also be manufactured by laminating | stacking the said laminated body several sheets (for example, 2-10 sheets), and carrying out lamination molding.
In the production of these multilayer laminates, a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine or the like is used, and the temperature is about 100 to 250 ° C., the pressure is about 2 to 100 MPa, and the heating time is 0.1 to 5 hours. It can be molded within a range.

[Printed wiring board and manufacturing method thereof]
The printed wiring board of the present invention includes the laminated board of the present invention and a wiring circuit provided on the surface of the laminated board. The multilayer printed wiring board of the present invention includes the multilayer laminated board and the multilayer laminated board. And a wiring circuit provided on the surface of the plate.
Next, the manufacturing method of this printed wiring board and a multilayer printed wiring board is demonstrated.

<Formation of via holes>
In the printed wiring board of the present invention, the laminated board of the present invention is drilled by a method such as drilling, laser, plasma, or a combination thereof as necessary to form via holes and through holes. As the laser, a carbon dioxide laser, a YAG laser, a UV laser, an excimer laser, or the like is generally used. After forming the via hole or the like, desmear treatment may be performed using an oxidizing agent. As the oxidizing agent, permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid are suitable, and potassium permanganate, sodium permanganate A sodium hydroxide aqueous solution (alkaline permanganic acid aqueous solution) such as the above is more preferable.

<Formation of conductor layer>
Next, a conductor layer is formed on the cured resin layer on the surface of the laminate by wet plating.
When performing wet plating, in many cases, the surface is first subjected to a roughening treatment. The surface roughness (Ra) of the cured resin layer after the roughening treatment is preferably 0.5 μm or less, more preferably 0.4 μm or less, and further preferably 0.3 μm or less. When the surface roughness (Ra) is 0.5 μm or less, it is possible to sufficiently cope with higher density of the semiconductor package.
In addition, the roughening process conditions demonstrated later can be applied to the conditions of a roughening process.

  Regarding a method for forming a circuit, in addition to the semi-additive method of forming a circuit using the plating process, a copper-clad laminate in which a copper foil is used as a carrier and the carrier copper foil and an insulating substrate are bonded together And a known method of manufacturing a wiring board, such as a subtractive method in which an unnecessary portion of a copper foil is removed by etching, or an additive method in which a circuit is formed by electroless plating at a required portion of an insulating substrate.

  Furthermore, the surface of the circuit layer is surface-treated in a state suitable for adhesiveness as necessary, but this method is not particularly limited. For example, a known production such as forming an acicular crystal of copper oxide on the surface of the circuit layer 1 with an alkaline aqueous solution of sodium hypochlorite and reducing the formed acicular crystal of copper oxide by immersion in an aqueous dimethylamine borane solution. The method can be used.

When circuit processing is carried out by plating on the cured resin layer of the laminated board or multilayer wiring board of the present invention, first, roughening treatment is performed. As the roughening liquid in this case, an oxidizing roughening liquid such as a chromium / sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride / chromium / sulfuric acid roughening liquid, or a borofluoric acid roughening liquid should be used. Can do. As the roughening treatment, for example, an aqueous solution of diethylene glycol monobutyl ether and NaOH is first heated as a swelling solution to 80 ° C., and the laminate or multilayer wiring board is immersed for 5 minutes. Next, as a roughening solution, an aqueous solution of KMnO ₄ and NaOH is heated to, for example, 80 ° C. and immersed for 10 minutes. About the concentration of these alkaline solutions, processing time, and processing temperature, it is preferable to select and use conditions appropriately so that surface roughness (Ra) may be set to 0.1-0.5 micrometer. Subsequently, it is neutralized by immersing it in a neutralizing solution, for example, an aqueous hydrochloric acid solution of stannous chloride (SnCl ₂ ) at room temperature for 5 minutes.

  After the roughening treatment, a plating catalyst application treatment for adhering palladium is performed. The plating catalyst treatment is performed by immersing in a palladium chloride plating catalyst solution. Next, an electroless plating treatment is performed by immersing in an electroless plating solution to deposit an electroless plating layer (conductor layer) having a thickness of 0.3 to 1.5 μm on the entire surface of the plating process primer layer.

  Next, after forming a plating resist, electroplating is performed to form a circuit with a desired thickness at a desired location. As the electroless plating solution used for the electroless plating treatment, a known electroless plating solution can be used, and there is no particular limitation. As the plating resist, a known plating resist can be used, and there is no particular limitation. Also, the electroplating treatment can be performed by a known method and is not particularly limited. These platings are preferably copper platings. Furthermore, an unnecessary layer of the electroless plating layer can be removed by etching to form an outer layer circuit to produce a printed wiring board. Further, a multilayer printed wiring board having a large number of layers can be produced by repeating the same process.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
In the following examples and comparative examples, (1) measurement of the thermal expansion coefficient of the laminate, (2) measurement of the storage elastic modulus, (3) shear adhesive force between the cured resin layer and the glass substrate. Measurement and (4) evaluation of the handleability of the laminate (three-point bending test) were performed by the following method.

(1) Measurement of thermal expansion coefficient of laminated plate After removing copper of the laminated plate with electroless copper plating layer obtained in each Example and Comparative Example by etching treatment, a 4 mm × 30 mm test piece was cut out and a TMA test apparatus (Tuman 2940, manufactured by DuPont) was used to measure the thermal expansion characteristics of the test piece below Tg.
In the TMA test apparatus, the temperature rising rate is 5 ° C./min, the measurement range is 20 to 200 ° C. for the 1st run, the measurement range is −10 to 280 ° C., the load is 5 g, the chuck is 10 mm, and the tensile method is used. The average coefficient of thermal expansion in the range of 30 to 100 ° C. was measured.

(2) Measurement of storage elastic modulus of laminated board After removing copper of the laminated board with the electroless copper plating layer obtained in each Example and Comparative Example by etching treatment, a test piece of 5 mm x 30 mm was cut out from the laminated board. It was.
Storage elastic modulus of the test piece at 40 ° C. using a wide-area viscoelasticity measuring device (DVE-V4, manufactured by Rheology Co., Ltd.) under the conditions of 20 mm span, 10 Hz frequency, and 1-3 μm vibration displacement (stop excitation). Was measured.

(3) Measurement of shear adhesive strength between cured resin layer and glass substrate As shown in FIG. 1, the laminates obtained in each Example and Comparative Example were perpendicular to the cured resin layer. An underfill resin post having a diameter of 3 mm was formed on and bonded to the cured resin layer. A shear force is applied at a position of 50 μm in height from the top of the cured resin layer, and shear bonding between the cured resin layer and the glass substrate at 25 ° C. is performed using a universal bond tester (manufactured by Daisy Japan, series 4000). The force was measured.

(4) Evaluation of handleability of laminated board (three-point bending test)
The maximum stress in the three-point bending test was used as a method for objectively evaluating the handleability of the laminate. First, a test piece of 20 mm × 10 mm was cut out from the laminate sample obtained in each example and comparative example.
The three-point bending test was measured using an autograph (manufactured by Shimadzu Corporation, AG-1kNX). The measurement was performed at 25 ° C. with a span interval of 3.2 mm and a sample width of 20 mm. The sample thickness was measured to be in the range of 180 μm ± 10 μm.

Example 1
(Manufacture of adhesive film A)
After blending 13.5 g of N, N-dimethylacetamide (DMAc) with 1.5 g of phenolic hydroxyl group-containing polybutadiene-modified polyamide (manufactured by Nippon Kayaku Co., Ltd., trade name: BPAM-155), biphenylaralkyl type epoxy resin (Japan) Kagaku Co., Ltd., trade name: NC-3000H) 10 g, novolac-type phenol resin (DIC, trade name: TD-2090) 3.6 g, 2-phenylimidazole (product of Shikoku Kasei Kogyo, product) (Name: 2PZ) 0.1 g of fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name: R972, specific surface area 130 m ^{2 /} g) was added and then diluted with a mixed solvent consisting of DMAc and methyl ethyl ketone (solid) Concentration of about 25% by weight). Thereafter, a uniform resin varnish A was obtained using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.).
Next, the obtained resin varnish A was applied to a release-treated surface of a release-treated polyethylene terephthalate (PET) film (PET-38X, manufactured by Lintec Co., Ltd.) so as to have a thickness of 12 μm after drying. And dried for 10 minutes to form an adhesive film A composed of a resin composition layer and a PET film.

(Surface treatment of glass substrate)
As a glass substrate, an ultrathin glass film “OA-10G” (trade name, thickness 150 μm) manufactured by Nippon Electric Glass was used. First, the glass substrate was immersed in methyl ethyl ketone, and then washed with running pure water. Next, the glass substrate was immersed in concentrated sulfuric acid (manufactured by Wako Pure Chemical Industries) for 30 minutes to clean the surface of the glass substrate.
For the surface treatment of the glass substrate, N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM573) was used as a silane coupling agent. While stirring a 1% aqueous acetic acid solution obtained by mixing 5 g of acetic acid (manufactured by Wako Pure Chemical Industries) and 490 g of pure water, 5 g of a silane coupling agent (KBM573) was added dropwise, and stirring was continued for 30 minutes. Treatment liquid A was obtained.
The cleaned glass substrate was washed with pure water and then immersed in the surface treatment solution A for 15 minutes. Thereafter, the glass substrate rinsed with pure water was dried at 105 ° C. for 30 minutes to obtain a surface-treated glass substrate A.

(Production of laminates)
Next, a laminate (resin composition layer / glass substrate layer / resin composition layer) was formed. On both surfaces of the surface-treated glass substrate A, the resin composition layer of the adhesive film A is placed in contact with the surface-treated glass substrate A, and a batch type vacuum pressure laminator “MVLP-500” (Trade name, manufactured by Co., Ltd.). The degree of vacuum at this time was 30 mmHg (40 kPa) or less, the temperature was set to 90 ° C., and the pressure was set to 0.5 MPa.
After cooling to room temperature, the PET film of the support was peeled off and cured at 180 ° C. for 60 minutes to obtain a three-layer laminate (resin cured product layer / glass substrate layer / resin cured product layer).
Table 1 shows the measurement results and evaluation results of the obtained laminate.

Example 2
In the surface cleaning of the glass substrate of Example 1, the same operation as in Example 1 was performed except that a mixed solution of concentrated hydrochloric acid and methanol (1: 1 (volume ratio)) was used instead of concentrated sulfuric acid. A laminate was obtained. Table 1 shows the measurement results and evaluation results of the obtained laminate.

Example 3
In the surface cleaning of the glass substrate of Example 1, the same operation as in Example 1 was performed except that a 10% aqueous solution of potassium hydroxide was used instead of concentrated sulfuric acid to obtain a laminate having a three-layer structure.
Table 1 shows the measurement results and evaluation results of the obtained laminate.

Example 4
In the surface treatment of the glass substrate of Example 1, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM403) was used instead of N-phenyl-3-aminopropyltrimethoxysilane. The same operation as in Example 1 was performed to obtain a laminate having a three-layer structure. Table 1 shows the measurement results and evaluation results of the obtained laminate.

Example 5
In the surface treatment of the glass substrate of Example 1, it was immersed in a 13% tetrafluoroboric acid aqueous solution for 5 minutes instead of concentrated sulfuric acid, and then washed with pure water. Further, the surface treatment with the silane coupling agent solution was not performed. Otherwise, the same operation as in Example 1 was performed to obtain a laminate having a three-layer structure. Table 1 shows the measurement results and evaluation results of the obtained laminate.

Comparative Example 1
Except not performing surface cleaning and surface treatment of the glass substrate of Example 1, the same operation as in Example 1 was performed to obtain a laminate having a three-layer structure.
Table 1 shows the measurement results and evaluation results of the obtained laminate.

Comparative Example 2
In the surface treatment of the glass substrate of Example 1, Example 1 was used except that vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM1003) was used instead of N-phenyl-3-aminopropyltrimethoxysilane. The same operation was performed to obtain a laminate having a three-layer structure.
Table 1 shows the measurement results and evaluation results of the obtained laminate.

  As is apparent from Table 1, in the laminate including the cured resin layer and the glass substrate layer, the shear adhesive force at 25 ° C. between the cured resin layer and the glass substrate layer is 20 MPa or more, so that low heat It can be seen that it is possible to produce a laminated board and a printed wiring board that have expansion and high elasticity, are hard to break and have excellent handling properties.

In the present invention, in a film obtained by laminating a resin on a glass substrate having a coefficient of thermal expansion substantially matching that of the silicon chip, the shear adhesive force at 25 ° C. between the cured resin layer and the glass substrate layer is 20 MPa or more. By doing so, it is possible to produce a laminated board and a printed wiring board which have low thermal expansion and high elasticity, are hard to break and have excellent handling properties.
Therefore, according to the present invention, a laminated board and a printed wiring board that are less warped, are less likely to break, and are easy to handle can be obtained, and can be widely used for manufacturing electronic devices and the like.

Claims (13)

  In a laminate including one or more cured resin layers and one or more glass substrate layers, a shear adhesive force at 25 ° C. between the cured resin layer and the glass substrate layer is 20 MPa or more. Laminated board.   The laminated board of Claim 1 which contains an inorganic filler in the said resin cured material layer.   The laminated board of Claim 1 or 2 whose thickness of the said glass substrate layer is 30-200 micrometers.   The laminate according to any one of claims 1 to 3, wherein the cured resin layer has a thickness of 1 to 40 µm.   In the resin cured product layer, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, The laminated board in any one of Claims 1-4 containing at least 1 sort (s) chosen from a triazine resin and a melamine resin.   The inorganic filler is at least one selected from silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. Laminated board.   The storage elastic modulus in 40 degreeC is 10-70 GPa, The laminated board in any one of Claims 1-6.   A multilayer laminate including a plurality of laminates, wherein at least one laminate is the laminate according to any one of claims 1 to 7.   A printed wiring board comprising: the laminated board according to claim 1; and a wiring provided on the surface of the laminated board.   A multilayer printed wiring board comprising the multilayer laminated board according to claim 8 and a wiring circuit provided on a surface of the multilayer laminated board.   The manufacturing method of the laminated board of Claim 1 which forms a resin cured material layer by apply | coating the resin composition containing a thermosetting resin on a glass substrate, and drying and hardening | curing.   The manufacturing method of the laminated board of Claim 1 which forms the resin hardened | cured material layer by laminating | stacking the film which consists of a resin composition containing a thermosetting resin on a glass substrate using a vacuum laminator or a roll laminator, and hardening. .   The manufacturing method of the laminated board of Claim 1 which forms a resin hardened | cured material layer by pressing and hardening after arrange | positioning the film which consists of a resin composition containing a thermosetting resin on a glass substrate.