JP2007077234A - Insulation resin, insulation film having supporting body, substrate having resin by using the same, wiring board obtained by forming conductor circuit on the substrate having the resin and method for producing the wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulation resin without reducing its flowing property, an insulation resin film having a supporting body, also a substrate material having the resin, without having a crack of its coated film, having good coated film strength and also having a low expansion rate and a small thermal deformation, a wiring board suitable for minute wiring and a method for producing the same. <P>SOLUTION: This insulation resin having the supporting body contains solution E containing a component A: silica, component B: an epoxy resin, component C: a silane-coupling agent having an epoxy group or an amino group as a functional group and component D: any of dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP), N-dimethyl acetamide (DMAC) or mixed solvent of them for a solvent in mixing the components A, B and C. The insulation resin film having the supporting body obtained by forming the layer of the insulation resin on the supporting body, the substrate material obtained by using the insulation resin film having the supporting body, the wiring board obtained by forming a conductor circuit on the substrate material having the resin and the method for producing the same are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an insulating resin, an insulating resin film with a support, a base material with a resin using the same, a wiring board in which a conductor circuit is formed on the base material with resin, and a method for manufacturing the same.

  A conventional wiring board is made by impregnating a glass cloth called prepreg with epoxy resin, stacking and integrating the semi-cured material with copper foil, and laminating and integrating with a hot press, and then using a hole called a through hole for interlayer connection And electroless plating on the inner wall of the through hole and the surface of the copper foil. If necessary, further electrolytic plating is performed to obtain the necessary thickness as a circuit conductor, and then unnecessary copper is removed to form a multilayer wiring board. It was common to manufacture.

  By the way, in recent years, electronic devices have been further reduced in size, weight and functionality, and along with this, LSIs and chip parts have been highly integrated, and their form has rapidly changed to multi-pin and miniaturization. ing. For this reason, in order to improve the mounting density of electronic components, the development of fine wiring is being advanced.

  As a method of manufacturing a wiring board that meets these requirements, there is a build-up type wiring board that uses an insulating resin that does not contain glass cloth instead of a prepreg, and forms a wiring layer while connecting only necessary portions with via holes, It is becoming mainstream as a method suitable for weight reduction, miniaturization, and miniaturization.

For example, Patent Document 1 discloses an adhesive film excellent in circuit filling property, and Patent Document 2 discloses handling property in a semi-cured state and coating reforming of an insulating resin with crosslinked NBR particles.
Japanese Patent Laid-Open No. 11-87927 JP 2000-256537 A

  These prior arts can be expected to be effective in the method of easily forming an adhesive film and the modification of the coating film. However, there is no mention of a method for reducing the coefficient of thermal expansion necessary for making fine wiring, increasing the number of signals, and increasing the solder temperature.

  In other words, the material constituting the wiring board is made of a base material even when the copper residue or resist is easy to follow during etching and even when the temperature rises to around 150 ° C. in order to achieve a light and thin electronic device. In addition, a low expansion coefficient that can reduce the difference in expansion from conductors (copper), solder, and the like is required.

In addition, the technique of forming the insulating resin in the form of a film on the inner circuit board by lamination is advantageous in terms of high productivity.
Furthermore, from the viewpoint of miniaturization, the semi-additive method has become the mainstream because the thickness of copper can be arbitrarily adjusted and the wiring accuracy of the resist easily matches the wiring accuracy of the conductor.

  In the semi-additive method described above, in order to form conductors by plating without using copper foil, it is necessary for the insulating resin to have high adhesiveness with the plated copper in addition to the characteristics of the normal insulating resin. Difficulty increases in terms of balancing the faces.

Conventional techniques have not been sufficient for such problems. That is, in order to reduce the thermal expansion of the insulating resin, a method of increasing the amount of inorganic filler in the insulating resin composition is generally used.
However, if the amount of the inorganic filler is increased, the fluidity decreases and the adhesion and filling properties of the insulating resin film to the substrate deteriorate, the insulating resin coating film becomes brittle, and cracks and strength decrease. This is because it becomes easier.

  As a result of conducting research to solve such problems, the present inventors have used nano-sized silica as an inorganic filler component, and a specific coupling agent treatment as a surface treatment for crosslinking this epoxy with an epoxy resin. Selected and found a method to treat with epoxy resin in highly polar solvent. By using a component using this method as an insulating resin component, it is possible to reduce the coefficient of thermal expansion even when the amount of silica is the same as the conventional one.

  The present invention provides an insulating resin and an insulating resin film with a support, in which fluidity does not decrease, and there is no cracking of the coating film, the coating film strength is good, and the thermal expansion is low with a low expansion coefficient. The present invention provides a substrate with resin, a wiring board suitable for fine wiring, and a manufacturing method thereof.

The present invention
Component A: silica,
B component: epoxy resin,
C component: a silane coupling agent having an epoxy group or amino group as a functional group,
D component: E containing a solvent mixed with either dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMAC) as a solvent when mixing the A component, the B component and the C component. The present invention relates to an insulating resin containing a solution.
The present invention also relates to an insulating resin in which the concentration of the resin excluding the solvent and silica is in the range of 40 to 85% by weight.
Moreover, this invention relates to the insulating resin whose silica is 0.02-5 micrometers in average particle diameter.

In the present invention, the E solution was prepared by preparing the D component, then adding the C component to the D component and stirring, further adding the A component and stirring, and finally adding the B component and stirring. The present invention relates to an insulating resin.
In the present invention, the E solution was prepared by preparing the D component, then adding the A component to the D component and stirring, further adding the C component and stirring, and finally adding the B component and stirring. The present invention relates to an insulating resin.
The present invention also relates to an insulating resin in which the amount of the silane coupling agent having an epoxy group or amino group as a functional group is 0.01 to 10% by weight based on the amount of silica.
The present invention also relates to an insulating resin in which the E solution is allowed to stand at room temperature for 5 minutes or more and then stirred at room temperature for 5 minutes or more under the condition of a rotational speed of 600 min ⁻¹ or more.

In the present invention, the epoxy resin is in a solid state or a state containing a solvent, and the solvent used when the epoxy resin containing the solvent is diluted with the above solvent, the solvent at that time is The present invention relates to an insulating resin having a removed epoxy resin concentration of 50 to 90% by weight.
The present invention also relates to an insulating resin that is added in small amounts while stirring at room temperature under the condition of a rotational speed of 600 min ⁻¹ or more to add an insulating resin varnish to the insulating resin.
In the present invention, the ratio of dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMAC) used in the E solution is 15 to 50% by weight of the total solvent used in the insulating resin. % Of the insulating resin film with a support.
The present invention also relates to an insulating resin in which the epoxy resin has an epoxy group number of 2.5 or more.
The present invention also relates to an insulating resin in which the proportion of silica in the insulating resin excluding the solvent is 30 to 65% by weight.

Moreover, this invention relates to the insulating film with a support body which apply | coats the said insulating resin to a support body and volatilizes a solvent.
Moreover, this invention relates to the board | substrate with resin formed by carrying out the thermal transfer of the said insulating film with a support body to a base material, and thermosetting.
The present invention also relates to a wiring board obtained by immersing the substrate with resin in an oxidizing aqueous solution to roughen the surface of the insulating resin and then forming a circuit conductor with plated copper.
In addition, the present invention applies the insulating resin to one or both surfaces of a substrate having an inner layer circuit, and dries it to produce an insulating film with a support, and then immerses it in an oxidizing aqueous solution to roughen the surface of the insulating resin. And then a circuit conductor is formed of plated copper.
Furthermore, this invention relates to the manufacturing method of the wiring board characterized by forming two or more said insulating resin films between circuits.

  The insulating resin and the insulating resin film with a support of the present invention have good adhesiveness and filling property to the substrate with resin without deterioration of fluidity, no cracking of the coating film, and good coating film strength. In addition, it is possible to produce a wiring board suitable for fine wiring, with the effect of low thermal expansion and low thermal deformation.

The insulating resin film with a support according to the present invention is
A component: Silica B component: Epoxy resin,
C component: a silane coupling agent having an epoxy group or amino group as a functional group,
D component: E containing dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), or dimethylacetamide (DMAC) or a mixed solvent as a solvent when mixing component A, component B and component C It is necessary to use an insulating resin containing a solution.

  As the silica of component A used in the present invention, either crushed silica having an average particle size of 0.02 to 5 μm or synthetic spherical silica can be used, but synthetic spherical silica is used from the point of uniformity of flow rate distribution. It is preferable to use it. Commercially available products include UFP-80 (trade name), UFP-30 (trade name) manufactured by Denki Kagaku Kogyo Co., Ltd., SO-G1 (trade name), SO-G2 (trade name) manufactured by Admatechs Co., Ltd. ), SO-G3 (trade name), etc. can be used.

  The reason why the average particle diameter of the silica is in the range of 0.02 to 5 μm is that when it is less than 0.02 μm, hydrophilicity increases due to increase in the surface area of the silica, and thickening increases, so that streaks and thickness unevenness are likely to occur during coating. Tend to be. On the other hand, when it exceeds 5 μm, the density of silica tends to be relatively reduced and the effect of reducing the thermal expansion coefficient tends to be reduced.

  The amount of silica is preferably in the range of 30 to 65% by weight as a proportion of the insulating resin excluding the solvent. If the amount of silica is less than 30% by weight, the thermal expansion coefficient of the entire insulating resin tends to increase because of a small amount of silica having a small coefficient of thermal expansion. On the other hand, if it exceeds 65% by weight, the ratio of the organic component in the insulating resin is reduced, so that the cured coating film becomes brittle, and there is a tendency that cracking occurs and the coating film strength decreases.

  The epoxy resin used in the present invention preferably has 2.5 or more epoxy groups. Examples of such epoxy resins include biphenyl type epoxy resins, naphthalene type epoxy resins, phosphorus-containing epoxy resins, phenol novolac type epoxy resins, and cresols. A novolac type epoxy resin or the like can be used. Among these epoxy resins, biphenyl type epoxy resins are particularly preferable from the viewpoint of high elongation and multilayer wiring board characteristics.

  Epoxy resin is used in a solid state or in a state containing a solvent, and a solvent diluted with dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMAC) is used. Is necessary.

The concentration of the epoxy resin excluding the solvent is preferably in the range of 50 to 90% by weight.
The reason for using dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), or dimethylacetamide (DMAC) as the dilution solvent for the epoxy resin is related to the dispersibility of silica. That is, silica is likely to aggregate and settle, but if the solvent having high polarity is used, the silanol group in the silica and the solvent are easily bonded to each other, and aggregation and sedimentation can be prevented.

  In addition, the reason why the concentration of the epoxy resin is preferably 50 to 90% by weight is that the amount of the solvent is increased if it is less than 50% by weight, and as a result, the solvent is less likely to volatilize during coating of the insulating resin, and it is likely to remain. There is a tendency that the working environment deteriorates due to the volatilization of the solvent in the subsequent process. Moreover, when it exceeds 90 weight%, there exists a tendency for an undissolved epoxy resin to produce easily.

In the present invention, the silane coupling agent having an epoxy group or amino group as a functional group can be represented by X-Si (OR) ₃ in the case of an epoxy group, X is an epoxy group, and OR is a methoxy group or ethoxy group. Any base can be used. For example, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane can be used. is there. The same applies to an amino group, for example, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltriethoxysilane. 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxy Silane hydrochloride can be used.

  The amount of the silane coupling agent having an epoxy group or amino group as a functional group is preferably in the range of 0.01 to 10% by weight with respect to the amount of silica. If it is less than 0.01% by weight, the effect of reducing the coefficient of thermal expansion is small, and if it exceeds 10% by weight, the coupling agent for the reaction between the coupling agent and the epoxy resin becomes excessive, and Tg and solder heat resistance tend to decrease. There is.

  Solvents for mixing the three components of component A silica, component B epoxy resin, component C epoxy group or silane coupling agent having an amino group as a functional group are dimethylformamide (DMF), N-methyl- It is necessary to use either 2-pyrrolidone (NMP) or dimethylacetamide (DMAC) or a mixed solvent. These solvents can be used because they have commonality in terms of high polarity.

That is, since the silanol group in silica has high affinity, it is advantageous from the viewpoint of dispersibility of silica and solvent to use a solvent having high polarity.
In addition, silica having a small particle size has a large surface area and thus easily aggregates. However, it is also advantageous in preventing aggregation between silicas.
A highly polar solvent includes acetonitrile, but when the boiling point is low, concentration change due to volatilization of the solvent tends to occur. Therefore, the above three types of solvents are used alone or in combination.

  Using these solvents, the concentration of a solution prepared by mixing three components of silica, epoxy resin, epoxy group or silane coupling agent having an amino group as a functional group is preferably in the range of 40 to 85% by weight. . If the concentration of the solution is less than 40% by weight, the amount of the solvent increases, so that the solvent does not easily evaporate when the insulating resin is applied, and the solvent tends to remain, and the working environment tends to deteriorate due to the solvent evaporating in the subsequent process. . On the other hand, if it exceeds 85% by weight, the flow during stirring is difficult to occur, and the dispersibility of silica and epoxy resin tends to deteriorate.

  As a procedure for preparing the solution (E), first, a solvent is prepared, and a method in which the coupling agent, silica, and epoxy resin are added in this order while stirring the solvent; Then, a method for producing a coupling agent and an epoxy resin in this order can be selected. What is important in this charging sequence is that silica is immersed in a solvent and a coupling agent, and the epoxy resin needs to be charged last. The reason for this is unknown, but it is presumed to be related to the distance between molecules.

The solution (E) prepared in the above order is allowed to stand at room temperature for 5 minutes or more and within 48 hours, and then stirred at room temperature for 5 minutes or more under the condition of a rotational speed of 600 min ⁻¹ to obtain an insulating resin. Dispersibility into the inside can be increased. That is, the solution (E) has a sharp increase in viscosity when the epoxy resin is added. This increase in viscosity occurs from around 10% by weight of the total amount of the epoxy resin to be charged.

  After adding the entire amount of epoxy resin, it becomes whip-like and lacks fluidity. The whip-like solution (E) in a non-fluid state may be used as it is, but when this solution (E) is used in small portions, a difference in concentration may occur, which is not preferable. For this reason, the solution (E) is first left to stand at room temperature for 5 minutes or more. The standing at room temperature for 5 minutes is a time for the viscosity to stabilize. In addition, if it is allowed to stand at room temperature for 5 minutes or more, it is not necessary to leave it at rest.

Next, the solution (E) which has been allowed to stand for 5 minutes or more at room temperature has its viscosity drastically lowered by stirring for 5 minutes or more under the condition of a rotational speed of 600 min ⁻¹ or more. And the viscosity of the solution (E) which was whip-like will be 0.05 Pa.s or less. By this operation, the concentration of the solution (E) is stabilized and can be used by dispensing.

A predetermined amount of the prepared solution (E) is added to the insulating resin. At this time, it is preferable to add the solution (E) while stirring little by little using a stirrer having a rotation speed of 600 min ⁻¹ or more at room temperature.
This is because the solvent in the insulating resin is a low-boiling solvent that easily volatilizes, and methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether or the like having low polarity is used alone or in combination. When the solution (E) using the above-mentioned solvent having a high polarity is added to the insulating resin containing a solvent having a low polarity, silica aggregation tends to occur unless chemical shock is taken into consideration. For this reason, it is necessary to add the prepared solution (E) while stirring little by little when adding a predetermined amount to the insulating resin.

  The ratio of dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMAC) in the prepared solution (E) is 15 to 50% by weight of the total solvent used in the insulating resin. It is preferable to set it as the range. If it is less than 15% by weight, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMAC) is deficient, and therefore, when used as an insulating resin, there is a tendency for silica aggregation and sedimentation to occur. If it exceeds 50% by weight, the solvent that is difficult to volatilize during coating increases, which is not preferable in terms of the working environment.

When the above solution (E) is produced or added to the insulating resin, an apparatus which is produced using a stirrer and has a rotation speed of 600 min ⁻¹ or more is required. There is no restriction | limiting in the shape of the rotary blade used for this stirrer, and circular shape, a cross shape, etc. can be used. The power source of the stirrer is not limited, and electricity, compressed air, etc. can be used.

  The insulating resin to which the solution (E) is added is not particularly limited, and epoxy resin, imide resin, cyanate resin, polyphenylene ether resin, phenol resin, and the like can be used. Among these, it is preferable to use an epoxy resin system from the viewpoint of chemical resistance, plating solution resistance and insulation.

  In the present invention, a liquid insulating resin is applied to a support and dried to form an insulating resin film with a support. The support is not particularly limited, and a polyester film, a polypyrene film, a methylpentene copolymer film, a polyethylene naphthalate film, a polyfluorinated ethylene fiber film, a copper foil, an aluminum foil, or the like can be used. Among these, a polyester film is preferable from the viewpoint of cost performance and ease of application of the insulating resin.

In the case of a film type, film components such as phenoxy, acrylonitrile butadiene copolymer, nanometer-sized particles of this acrylonitrile butadiene copolymer, styrene nitrile butadiene copolymer, and the like can also be used.
In addition, from the viewpoint of environmental problems, phosphorus or an N-based flame retardant can be used for making flame retardant without using bromine or antimony.

The produced insulating film with a support is thermally transferred to a substrate. The method of thermal transfer is not particularly limited as long as the uneven surface of the substrate can be filled and flattened by heating and pressurizing such as laminating and pressing.
Moreover, a well-known base material can be used for a base material. For example, glass cloth-epoxy resin, paper-phenol resin, paper-epoxy resin, glass cloth / glass paper-epoxy resin, glass cloth-polyimide film, polyimide film and the like can be used without any particular limitation. After the insulating resin is thermally transferred to these substrates, the insulating resin is heated and cured. The conditions for heat curing differ depending on the composition system of the insulating resin and the heat resistance of the substrate, but usually a heat treatment at 160 to 200 ° C. for 30 to 90 minutes is desirable.

  Next, a circuit conductor is formed on the insulating resin, and the method is performed with plated copper. When forming a circuit conductor with this plated copper, it is necessary to immerse the insulating resin in an oxidizing aqueous solution in order to ensure the adhesion between the insulating resin and the plated copper. As the oxidizing aqueous solution, a chromium / sulfuric acid roughening solution, an alkaline permanganic acid roughening solution, a sodium fluoride / chromium / sulfuric acid roughening solution, a borofluoric acid roughening solution, or the like can be used.

  In addition, in order to accelerate | stimulate melt | dissolution of the insulating resin in the immersion process of oxidizing aqueous solution, you may pass the immersion process of the solvent-alkali aqueous solution called sweller or swering before the immersion process of oxidizing aqueous solution. As the solvent-alkali aqueous solution, a mixture of diethylene glycol monobutyl ether and a strong alkali such as sodium hydroxide or potassium hydroxide can be used.

Although there is no restriction | limiting in the conditions of the immersion process of a solvent-alkali aqueous solution and the immersion process of oxidizing aqueous solution, From the surface of productivity, about 3 to 25 minutes are respectively appropriate at 50-90 degreeC.
Next, in order to neutralize the heavy metal used in the oxidizing aqueous solution, it is immersed in an aqueous solution such as stannous chloride, sulfuric acid-hydrogen peroxide solution, hydroxylammonium sulfate. Appropriate conditions are from room temperature to 45 ° C. for about 2 to 10 minutes.

Next, the process proceeds to a plated copper process. This plated copper process may be a known electroless plated copper treatment, for example, by passing through a conditioner process and a plating catalyst application treatment process, and then dipping in an electroless plating solution, thereby insulating resin. An electroless plating layer having a thickness of 0.3 to 1.5 μm is deposited thereon. If necessary, further electroplating is performed.
As the electroless plating solution used for electroless plating, a known electroless plating solution can be used, and there is no particular limitation. Also, electroplating can be performed by a known method and is not particularly limited.

  In addition, the circuit has a method such as an etching method or a semi-additive method in which copper is thickened only at a necessary portion using a plating resist, but there is no particular limitation. In addition, when setting it as a multilayer wiring board, it is necessary to carry out the adhesion process on the surface of the circuit conductor made multilayer. This bonding process may be a known method, for example, a method of forming a copper oxide needle crystal, a method of chemically dissolving copper to form an uneven surface, a method of mechanically polishing the copper surface, etc. Can be used.

Hereinafter, the present invention will be described in detail according to examples.
Example 1
(1) Preparation of solution (E) (1) -1 Weighing of materials A component: Silica (average particle size 0.04 μm, manufactured by Denki Kagaku Kogyo Co., Ltd., trade name UFP-80) ... 60 g
B component: biphenyl novolak type epoxy resin (product name NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.), diluent solvent: none 78 g
Component C: aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane, trade name KBM-903) ... 0.6 g
Component D: Solvent N-methyl-2-pyrrolidone (NMP) (reagent) ... 90 g

(1) -2 Mixing of materials Attach the cross-shaped stirring blade attached to the Shinto Kagaku Co., Ltd. made stirrer BL-1200, transfer the D component to the plastic cup, and start stirring under the condition of a rotational speed of 100 min ^-1. did.
Next, C component was dripped slowly, and after stirring whole quantity, it stirred for 2 minutes. Next, component A was added in 5 portions without stopping stirring. The number of revolutions was 600 min ⁻¹ after the second injection of the A component, and the entire amount of the A component was introduced at an introduction interval of 1 minute, and then the number of revolutions was maintained for 3 minutes. Finally, the B component was charged at the same interval as the A component, and after the entire amount was charged, the rotation speed was increased to 900 min ⁻¹ and the rotation speed was maintained for 3 minutes.

(1) -3 Standing of Solution (E) After rotating for 3 minutes under the condition of 900 min ⁻¹ , stirring was stopped, the polycup containing the solution (E) was taken out, and then allowed to stand at room temperature for 10 minutes.

(1) -4 Re-stirring of the solution (E) The solution (E) was again stirred for 10 minutes under the condition of a rotation speed of 900 min ^-1 using a stirrer BL-1200 manufactured by Shinto Kagaku Co., Ltd.
Thereafter, the concentration was measured from the weight before and after drying at 160 ° C. for 60 minutes using an aluminum shear. As a result, the concentration of the solution (E) prepared in Example 1 was 70% by weight.

(2) Production of Insulating Resin The materials shown below were weighed and stirred for 60 minutes at room temperature under the condition of a rotational speed of 600 min ⁻¹ using a stirrer BL-1200 manufactured by Shinto Kagaku Co., Ltd.
・ Solution (E): 171 g
・ Acrylonitrile butadiene rubber (manufactured by Nippon Zeon Co., Ltd., trade name Nipol-1031) ... 4g
・ Novolac phenol resin (trade name HP-850, manufactured by Hitachi Chemical Co., Ltd.) ... 17g
・ Solvent, methyl ethyl ketone ... 30g

(3) Production of insulating resin film with support The insulating resin produced in (2) was applied to a polyester film using a comma coater, dried at 90 ° C. for 10 minutes, and the insulating resin with a support having a thickness of 50 ± 3 μm. A film was prepared.

(4) Production of base material with insulating resin Glass cloth base material epoxy resin double-sided copper-clad laminate [manufactured by Hitachi Chemical Co., Ltd. having a copper foil thickness of 18 μm, a substrate thickness of t0.8 mm, and double-sided roughened foil on both sides , Product name MCL-E-67 product name]] was etched to prepare a substrate having a circuit layer (hereinafter referred to as a first circuit layer) on one side.

  Next, the insulating resin film with a support is placed on one side of the base material on the side where the insulating resin is in contact with the circuit layer, and a batch type vacuum pressure laminator (trade name MVLP-500, manufactured by Meiki Co., Ltd.) is used. The laminate was formed at 100 ° C. under a pressure of 0.5 MPa · s, a vacuum time of 30 seconds, and a pressurization time of 30 seconds. Thereafter, the polyester film was peeled off, and then the insulating resin was cured under curing conditions at 170 ° C. for 60 minutes.

(5) Fabrication of circuit conductors Via holes for interlayer connection are processed using a Hitachi Via Mechanics CO ₂ laser processing machine (LCO-1B21 type) with a beam diameter of 80 μm, a frequency of 500 Hz, a pulse width of 5 μsec, and a shot number of 7 And produced.

Next, in order to chemically roughen the insulating layer, an aqueous solution of 200 ml / L of diethylene glycol monobutyl ether and 5 g / L of NaOH was produced as a swirler, heated to 70 ° C. and immersed for 5 minutes.
Next, an aqueous solution of KMnO ₄ 60 g / L and NaOH ₄₀ g / L was prepared as a roughening solution, heated to 80 ° C. and immersed for 10 minutes. Subsequently, it was neutralized by immersing it in an aqueous solution of a neutralizing solution (SnCl ₂ 30 g / L and HCl 300 ml / L) at room temperature for 5 minutes.

After neutralization, in order to form a second circuit on the surface of the first insulating layer, first, HS-202B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a catalyst for electroless plating containing PdCl _2. Immerse in room temperature for 10 minutes, wash with water, immerse in CUST-201 plating solution (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is electroless copper plating, for 15 minutes at room temperature, and further copper sulfate electrolytic plating Went.

Thereafter, annealing was performed at 180 ° C. for 30 minutes to form a conductor layer having a thickness of 20 μm on the surface of the insulating layer.
Next, in order to remove unnecessary portions of the plated conductor by etching, the oxide film on the copper surface is removed by # 600 buffol polishing, and then an etching resist is formed and etched. Then, the etching resist is removed, and the first resist is removed. A second circuit including a via hole connected to the circuit was formed.

  Furthermore, in order to multilayer, the second circuit conductor surface was immersed in an aqueous solution of sodium chlorite 50 g / L, NaOH 20 g / L and trisodium phosphate 10 g / L at 85 ° C. for 20 minutes, washed with water, Copper oxide irregularities were formed on the surface of the second circuit conductor by drying at 80 ° C. for 20 minutes. An insulating resin film with a support was formed on the surface of the circuit conductor, thermally cured, and a circuit conductor was prepared in the same manner as described above from the formation of a via hole to prepare a three-layer multilayer wiring board.

Example 2
For the solution (E) of Example 1, the component A silica was changed to UFP-30 (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) having an average particle size of 0.12 μm without changing the blending amount. A material similar to that in Example 1 was used, and a three-layer multilayer wiring board was produced through the same steps as in Example 1.

Example 3
The solution (E) of Example 1 was carried out with the exception that the component A silica was changed to SO-E3 (trade name, manufactured by Admatechs Co., Ltd.) having an average particle diameter of 1.0 μm without changing the blending amount. Using the same material as in Example 1, a multilayer wiring board having three layers was produced through the same steps as in Example 1.

Example 4
For the solution (E) of Example 1, the C component coupling agent was used without changing the blending amount, and a coupling agent containing an epoxy group (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane, product) A material similar to that in Example 1 was used except that the name KBM-403) was changed, and a multilayer wiring board having three layers was manufactured through the same steps as in Example 1.

Example 5
For the solution (E) of Example 1, the same materials as in Example 1 were used except that the solvent of component D was changed to dimethylformamide (DMF) (reagent) without changing the blending amount. A multilayer wiring board having three layers was manufactured through the same process.

Example 6
For the solution (E) of Example 1, the same material as in Example 1 was used except that the solvent of component D was changed to dimethylacetamide (DMAC) without changing the blending amount. After that, a three-layer multilayer wiring board was produced.

Example 7
About the solution (E) of Example 1, B component biphenyl novolac type epoxy resin (Nippon Kayaku Co., Ltd., product name NC-3000-H) was converted into N-methyl What was dissolved in 2-pyrrolidone (NMP) (reagent) was used. In this case, the concentration of the epoxy resin is 80% by weight. Otherwise, the same material as in Example 1 was used, and a multilayer wiring board having three layers was produced through the same steps as in Example 1.

Example 8
In preparing the solution (E) of Example 1, the ingredients were added in the order of ingredients D, then ingredients A, then ingredients C, and finally ingredients B. Otherwise, the same material as in Example 1 was used, and a multilayer wiring board having three layers was produced through the same steps as in Example 1.

Example 9
For the solution (E) of Example 1, the B component epoxy resin was changed to biphenyl novolac type epoxy resin (Nippon Kayaku Co., Ltd., trade name NC-3000-H) and cresol novolac type epoxy resin (Sumitomo Chemical Co., Ltd.). Manufactured and trade name ESCN-190-3) is mixed with 39 g (78 g in total), and the other materials are the same as in Example 1, and a multilayer wiring board having three layers is obtained through the same steps as in Example 1. Produced.

Comparative Example 1
For the solution (E) in Example 1, the same material as in Example 1 was used, except that the solvent of D component was changed to methyl ethyl ketone without changing the blending amount, and the same process as in Example 1 was carried out to form three layers. A multilayer wiring board was prepared.

Comparative Example 2
For the solution (E) of Example 1, the same material as in Example 1 was used except that the C component aminosilane coupling agent was not used, and a three-layer multilayer wiring board was obtained through the same steps as in Example 1. Produced.

Comparative Example 3
About the solution (E) of Example 1, the compounding amount is not changed, and the C component coupling agent is an epoxy group and an amino group-free vinyl silane coupling agent (vinyl triethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) Except for changing to KBE-1003), a material similar to that in Example 1 was used, and a multilayer wiring board having three layers was manufactured through the same steps as in Example 1.

Reference example 1
The solution (E) of Example 1 was carried out with the exception that the component A silica was changed to silica having an average particle diameter of 10 μm (trade name FS-44, manufactured by Denki Kagaku Kogyo Co., Ltd.) without changing the blending amount. Using the same material as in Example 1, a multilayer wiring board having three layers was produced through the same steps as in Example 1.

Reference example 2
In preparing the solution (E) of Example 1, the B component was added next to the D component in the order of adding materials, then the C component was added, and finally the A component was added. Otherwise, the same material as in Example 1 was used, and a multilayer wiring board having three layers was produced through the same steps as in Example 1.

  About the multilayer wiring board produced above, the state observation of the solution (E), the viscosity of the solution (E), the coefficient of thermal expansion, the elongation rate of the insulating resin coating film, the adhesive strength with the outer conductor circuit, under an unsaturated atmosphere An insulation reliability acceleration test, a 288 ° C. solder heat resistance test, and an inner layer circuit embedding property after leaving the insulating film for one month at room temperature were evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Observation of state of solution (E)]
The solutions (E) prepared in each Example, Comparative Example and Reference Example were allowed to stand at room temperature for 5 hours, and the presence or absence of filler sedimentation and the occurrence of separation of the solution were observed.
[Measurement of viscosity of solution (E)]
The viscosities of the solutions (E) prepared in each Example, Comparative Example and Reference Example were measured separately before standing (immediately after preparation) and after standing for 60 minutes at room temperature. The viscosity was measured at room temperature using B-type viscosity BM-2.

[Coefficient of thermal expansion]
Insulating resin varnish obtained in the process of preparing the insulating resin of each example, comparative example and reference example was applied to copper foil, heat treatment similar to wiring board preparation was applied, and copper was etched away and cured An insulating resin coating film was obtained. This insulating resin coating film was cut into dimensions of 4 mm in width, 50 μm in insulating resin film thickness and 20 mm in length, and measured using a Du Pont 2000 type thermal analysis system 943TMA under the tensile method and a weight of 5 g. Expressed as an average coefficient of thermal expansion between 30 and 100 ° C.

[Elongation rate of coating film]
Insulating resin varnish obtained in the process of preparing the insulating resin of each example, comparative example and reference example was applied to copper foil, heat treatment similar to wiring board preparation was applied, and copper was etched away and cured An insulating resin coating film was obtained. This insulating resin coating film was cut to a width of 10 mm, an insulating resin film thickness of 50 μm, and a length of 100 mm, and the insulating resin coating film was pulled by an autograph tensile test (distance between chucks of 50 mm) to determine the elongation until it broke.

[Adhesive strength with outer layer conductor circuit]
A part with a width of 10 mm and a length of 100 mm is formed on a part of the L1 circuit layer (third circuit layer), this end is peeled off and gripped with a gripper, and the load when peeled off in a vertical direction at 50 mm at room temperature is measured. did.

[Insulation reliability acceleration test under unsaturated atmosphere]
In the multilayer wiring boards produced in each example, comparative example and reference example, the lead wire is fixed to the terminal portion by soldering so that a voltage can be applied in the interlayer direction of the insulating resin, and the insulation resistance in the interlayer direction of the insulating resin Was measured by applying a voltage of 50 V for 1 minute at room temperature. Furthermore, using this as a sample, the sample was taken out for a predetermined time while applying a DC voltage of 6 V in an unsaturated atmosphere of 130 ° C. and 85% RH, and measured by applying a voltage of 50 V for 1 minute at room temperature. the time indicating the above ⁸ Omega expressed as the time insulation reliability.

[288 ° C solder heat resistance]
The multilayer wiring boards produced in each Example, Comparative Example and Reference Example were cut into 25 mm squares, floated in a solder bath adjusted to 288 ° C. ± 2 ° C., and the time until blistering was examined.

[Embedment of inner layer circuit after insulating film is left at room temperature for one month]
The film with insulating resin produced in each example, comparative example and reference example was left at room temperature for 1 month. Then, the batch type vacuum pressurization laminator (made by Meiki Co., Ltd., trade name MVLP-500) is formed with the insulating resin film on one side of the inner circuit board in the same manner as in the example, with the insulating resin in contact with the circuit layer. Then, after peeling off the PET film, the insulating resin was cured under curing conditions at 180 ° C. for 60 minutes. At this stage, the embedding property of the insulating resin into the inner layer circuit board was evaluated. Evaluation of embedding property was performed by observing 50 holes with a 2 mm (φ) diameter hole with a metal microscope and displaying 100% OK when all the holes were embedded.

Claims (17)

Component A: silica,
B component: epoxy resin,
C component: a silane coupling agent having an epoxy group or amino group as a functional group,
D component: E containing a solvent mixed with either dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMAC) as a solvent when mixing the A component, the B component and the C component. An insulating resin containing a solution.   2. The insulating resin according to claim 1, wherein the total concentration of the resin excluding the solvent and silica is in the range of 40 to 85% by weight.   The insulating resin according to claim 1, wherein the silica has an average particle size of 0.02 to 5 μm.   The E solution is prepared by preparing the D component, then adding the C component to the D component and stirring, further adding the A component and stirring, and finally adding the B component and stirring. Insulating resin in any one of -3.   The E solution is prepared by preparing the D component, then adding the A component to the D component and stirring, further adding the C component and stirring, and finally adding the B component and stirring. Insulating resin in any one of -3.   The insulating resin according to any one of claims 1 to 5, wherein a compounding amount of the silane coupling agent having an epoxy group or an amino group as a functional group is 0.01 to 10% by weight based on the amount of silica. The insulating resin according to any one of claims 1 to 6, wherein the solution E is allowed to stand at room temperature for 5 minutes or more and then stirred at room temperature for 5 minutes or more under the condition of a rotational speed of 600 min- ¹ or more.   The epoxy resin is in a solid state or a state containing a solvent, and when the epoxy resin containing the solvent is used, the solvent is diluted with the solvent according to claim 1, and the epoxy excluding the solvent at that time The insulating resin according to claim 1, wherein the concentration of the resin is 50 to 90% by weight. The insulating resin according to any one of claims 1 to 8, wherein when the E solution is added to the insulating resin, the insulating resin varnish is added in small amounts while stirring at room temperature under the condition of a rotational speed of 600 min- ¹ or more.   The ratio of dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMAC) used in the E solution is 15 to 50% by weight of the total solvent used for the insulating resin. 10. Insulating resin in any one of 9.   The insulating resin according to claim 1, wherein the epoxy resin has an epoxy group number of 2.5 or more.   The insulating resin composition according to any one of claims 1 to 11, wherein a ratio of silica in the insulating resin excluding the solvent is 30 to 65% by weight.   The insulating resin film with a support body formed by apply | coating the insulating resin in any one of Claims 1-12 to a support body, and volatilizing a solvent.   A base material with a resin obtained by transferring the insulating resin film with a support according to claim 13 to a base material and thermosetting it.   A wiring board obtained by immersing the substrate with resin according to claim 14 in an oxidizing aqueous solution to roughen the surface of the insulating resin, and then forming a circuit conductor with plated copper.   An insulating resin according to any one of claims 1 to 12 is applied to a support on one side or both sides of a substrate having an inner layer circuit, and dried to produce an insulating resin film with a support, and then immersed in an oxidizing aqueous solution. A method of manufacturing a wiring board, characterized in that the surface of the insulating resin is roughened, and then the circuit conductor is formed of plated copper. The method for manufacturing a wiring board according to claim 16, wherein a plurality of insulating resin films with a support according to claim 13 are formed between the circuits.