JP6596957B2 - Structure having conductor circuit, method for producing the same, and photosensitive resin composition - Google Patents

Description

  The present invention relates to a structure having a conductor circuit, a method for producing the structure, and a photosensitive resin composition.

  It is necessary to provide a via (opening) for electrically connecting the upper wiring layer and the lower wiring layer in the interlayer insulating material of the printed wiring board. If the number of flip chip pins mounted on the printed circuit board increases, it is necessary to provide a number of openings corresponding to the number of pins.

  As miniaturization of semiconductor elements progresses and the number of flip chip pins increases from tens of thousands to hundreds of thousands, the size of the opening formed in the interlayer insulating material of the printed wiring board also depends on the number of pins of the semiconductor element. There is a growing need for narrowing. In order to meet such a demand, development of a printed wiring board in which a thermosetting resin material is used as an interlayer insulating material and an opening is provided in the interlayer insulating material by a laser is being promoted (for example, see Patent Documents 1 to 4). .

However, the method of providing an opening in an interlayer insulating material of a printed wiring board with a laser requires introduction of a new facility such as a laser, and it is difficult to provide a relatively large opening or a minute opening of 60 μm or less. There are problems that it is necessary to use different lasers according to the aperture diameter, and it is difficult to provide a special shape.
Further, when openings are formed in the interlayer insulating material using a laser, a plurality of openings must be formed one by one. For this reason, it takes time when it is necessary to provide a large number of fine openings, and since resin residues remain around the openings, the reliability of the obtained printed wiring board is lowered unless the residues are removed. There is also a problem.

  In order to solve the problem of the method of providing an opening in a printed wiring board with such a laser, a method of providing an opening in a printed wiring board using a photosensitive resin composition has been proposed (for example, see Patent Document 5). .

JP 08-279678 A JP-A-11-054913 JP 2001-217543 A Japanese Patent Laid-Open No. 2003-017848 International Publication No. 2013/054790

However, depending on the type of thermosetting resin composition used to form the insulating layer, there is a problem that the photosensitive resin composition is not sufficiently removed when the photosensitive resin composition is removed to form the opening. It was. Such a problem also applies to a structure having a conductor circuit.
The present invention has been made in view of the above problems, and a structure having a conductor circuit, which has good removability of the photosensitive resin composition when the photosensitive resin composition is removed to form an opening, and the structure It is providing a manufacturing method and a photosensitive resin composition.

The inventors have made the following inventions.
(1) a support and a conductor circuit formed on the surface of the support;
An insulating layer laminated on the surface of the support so as to cover the conductor circuit;
An opening formed in the insulating layer such that a part of the conductor circuit is exposed;
A wiring portion formed in the insulating layer so as to be electrically connected to a part of the conductor circuit exposed in the opening;
A method of manufacturing a structure including:
A first photosensitive resin layer forming step of forming a first photosensitive resin layer on the support so that the conductor circuit is covered;
A first patterning step of subjecting the first photosensitive resin layer to an exposure process and a development process so that the first photosensitive resin layer is patterned;
A thermosetting resin layer forming step of forming a thermosetting resin layer on the support so as to cover the pattern of the first photosensitive resin layer;
A pattern exposure step of removing a part of the thermosetting resin layer to expose a predetermined portion of the pattern of the first photosensitive resin layer from the thermosetting resin layer;
An opening forming step of removing the first photosensitive resin layer exposed from the thermosetting resin layer and forming an opening in the thermosetting resin layer to expose the conductor circuit;
The first patterning step includes a heat treatment for heat-treating the pattern of the first photosensitive resin layer after the exposure process and the development process, and an ultraviolet ray applied to the pattern of the first photosensitive resin layer. The manufacturing method of a structure which performs at least one of the ultraviolet irradiation process which irradiates.

(2) Furthermore, a seed layer forming step of forming a seed layer so that at least a part of the thermosetting resin layer is covered;
A second photosensitive resin layer is formed on the seed layer so as to cover the seed layer, and an exposure process is performed on the second photosensitive resin layer so that the second photosensitive resin layer is patterned. And a second patterning step for performing development processing;
Forming a wiring portion so that at least a part of the seed layer is covered, peeling the pattern formed in the second patterning step, and forming a wiring pattern;
And a seed layer removing step of removing a seed layer in a region where the wiring part is not formed.

(3) The structure according to (2), wherein the seed layer removing process is a single multilayer printed wiring forming process from the first photosensitive resin layer forming process, and the single multilayer printed wiring forming process is repeated. Body manufacturing method.

(4) A structure manufactured by the method for manufacturing a structure according to any one of (1) to (3).

(5) A photosensitive resin composition used in the method for producing a structure according to any one of (1) to (3),
(A) a binder polymer;
(B) a photopolymerizable compound having at least one ethylenically unsaturated bond;
(C) A photopolymerization initiator, a photosensitive resin composition.

  According to the present invention, in the first patterning step, after the exposure process and the development process, the first photosensitive resin layer pattern is subjected to a heat treatment, and the first photosensitive resin layer pattern is subjected to a heat treatment. Since at least one of the ultraviolet irradiation treatment for irradiating ultraviolet rays is performed, the structure having a conductor circuit with good removability of the photosensitive resin composition when the photosensitive resin composition is removed to form the opening and its manufacture A method and a photosensitive resin composition can be provided.

It is sectional drawing which shows the manufacturing method of the structure which has a conductor circuit which concerns on one Embodiment of this invention. It is sectional drawing which shows the 1st photosensitive resin layer formation process following FIG. FIG. 3 is a cross-sectional view showing a first patterning process following FIG. 2. It is sectional drawing which shows the thermosetting resin layer formation process following FIG. FIG. 5 is a cross-sectional view showing a pattern exposure process following FIG. 4. FIG. 6 is a cross-sectional view showing an opening forming step following FIG. 5. FIG. 7 is a cross-sectional view showing a seed layer forming step following FIG. 6. FIG. 8 is a cross-sectional view showing a second patterning step following FIG. 7. FIG. 9 is a cross-sectional view showing a state in which a wiring portion is formed in the wiring portion patterning step following FIG. 8. FIG. 10 is a cross-sectional view showing a state in which the wiring portion is patterned in the wiring portion patterning step following FIG. 9. FIG. 11 is an end view schematically showing a structure having a conductor circuit having a solder resist and a nickel / gold layer on the surface on which the wiring portion is formed, following FIG. 10. It is a figure which shows an observation result.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  The method for manufacturing a structure having a conductor circuit according to the present invention is suitably used for manufacturing a multilayer printed wiring board for mounting a semiconductor element, and particularly for a printed wiring board for mounting a flip-chip type semiconductor element. In addition to manufacturing, it can also be suitably used for rewiring methods for substrateless packages such as a coreless substrate, WLP (Wafer Level Package), and eWLB (Embedded Wafer Level Ball Grid Array). Among them, the size of a semiconductor element to be mounted is large, and it is particularly suitable for a multilayer printed wiring board for electrically connecting to tens of thousands of bumps arranged in an area array on the surface of the semiconductor element.

As shown to Fig.1 (a), the copper clad laminated body 1 is prepared first. The copper clad laminate 1 has a support 1b and a metal foil 2 formed on the front and back surfaces of the support 1b. The metal foil 2 is, for example, a copper foil, but may be a gold foil, a silver foil, or the like.
Next, as shown in FIG. 1B, unnecessary metal foils in the metal foil 2 are removed by etching so that the conductor circuits 2a and 2b are formed on the front and back surfaces of the support 1b, respectively. A printed wiring board 10 is obtained.

Next, as shown in FIG. 2, the first photosensitive resin layer 3 is formed on the surface of the conductor circuit 2a and the surface of the support 1b so as to cover the conductor circuit 2a, and the conductor circuit 2b is covered. Thus, the 1st photosensitive resin layer 3 is formed in the surface of the conductor circuit 2b, and the back surface of the support body 1b (1st photosensitive resin layer formation process).
The thickness T1 of the first photosensitive resin layer 3 is preferably 2 μm to 50 μm, and more preferably 5 μm to 30 μm.
When the thickness T1 of the first photosensitive resin layer 3 is 2 μm or more, the photosensitive resin composition used for forming the first photosensitive resin layer 3 can be easily formed. A film-like photosensitive resin composition can be easily produced. When the thickness T1 of the first photosensitive resin layer 3 is 50 μm or less, it becomes easy to form a fine pattern on the first photosensitive resin layer 3.
The thickness T1 of the first photosensitive resin layer 3 refers to the thickness of portions of the first photosensitive resin layer 3 formed on the surfaces of the conductor circuit 2a and the conductor circuit 2b.

  Thereafter, an actinic ray is irradiated on a predetermined surface (a surface of a portion not removed after development processing described later) among the surfaces of the first photosensitive resin layer 3 through a mask pattern. Thereby, the part which is not removed is exposed, and the exposed part of the first photosensitive resin layer 3 is photocured (exposure processing in the first patterning step).

As a light source of actinic light, a known light source can be used. For example, a light source that effectively emits ultraviolet rays such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp is used as the light source. Can be used. Further, direct laser exposure using a direct drawing method may be used as the light source.
Exposure varies depending on the composition of the device or a photosensitive resin composition to be ^used, preferably in the ^{10mJ / cm 2 ~600mJ / cm 2} , and more preferably set to ^{20mJ / cm 2 ~400mJ / cm 2} . When the exposure amount is 10 mJ / cm ² or more, the photosensitive resin composition can be sufficiently photocured, and when the exposure amount is 600 mJ / cm ² or less, the photocuring is not excessive and the first photosensitive property after development. The pattern 3a (see FIG. 3) and the pattern 3b formed by the resin layer 3 can be stably formed.

Next, as shown in FIG. 3, a portion other than the exposed portion of the first photosensitive resin layer 3 is developed so that the pattern 3 a and the pattern 3 b are formed on the front surface and the back surface of the printed wiring board 10, respectively. To obtain a developed multilayer printed wiring board intermediate (development process in the first patterning step).
In addition, the pattern 3a and the pattern 3b of the 1st photosensitive resin layer are removed in the below-mentioned opening formation process, and become a fine opening formed in the thermosetting resin layer 4 (refer FIG. 6).

  As the developer used for the development processing in the first patterning step, for example, an alkali developer such as a solution of sodium carbonate (1 to 5% by mass aqueous solution) at 20 ° C. to 50 ° C. is used. Development is performed by a known method such as brushing or scraping. As a result, a predetermined first photosensitive resin layer pattern 3a is formed on the surface of the conductor circuit 2a, and a predetermined first photosensitive resin layer pattern 3b is formed on the surface of the conductor circuit 2b.

Next, the developed multilayer printed wiring board intermediate is subjected to heat treatment to obtain a multilayer printed wiring board intermediate 10a (heat treatment in the first patterning step). Thereby, the pattern 3a and the pattern 3b are heat-treated.
The conditions for the heat treatment are not particularly limited. For example, the printed wiring board 10 on which the pattern 3a and the pattern 3b are formed is set to 160 ° C. to 200 ° C. in a heating furnace for 30 minutes to 30 minutes to It can be processed under conditions of 1 hour.

Moreover, you may irradiate an ultraviolet-ray to the developed multilayer printed wiring board intermediate body instead of heat processing (the ultraviolet irradiation process of a 1st patterning process). Thereby, the pattern 3a and the pattern 3b are irradiated with ultraviolet rays.
Although the conditions for ultraviolet irradiation are not particularly limited, for example, the printed wiring board 10 on which the pattern 3a and the pattern 3b are formed is put into an ultraviolet irradiation apparatus, and ultraviolet rays are exposed at an exposure amount of ² J / cm ² . Can be irradiated.

Only one of the heat treatment and the ultraviolet irradiation treatment in the first patterning step may be performed, or the heat treatment and the ultraviolet irradiation treatment may be used in combination. Moreover, when using together heat processing and an ultraviolet irradiation process, whichever may be performed first.
The method for producing a structure having a conductor circuit according to the present invention includes the heat treatment and the ultraviolet irradiation treatment in the first patterning step, so that a good first photosensitive resin layer can be removed in the subsequent opening formation step. Sex is obtained.

The reason why the removability of the first photosensitive resin layer 3 is improved by going through at least one of the heat treatment and the ultraviolet irradiation treatment in the first patterning step is not necessarily clear, but the present inventors are as follows. I guess as follows.
After the exposure process and the development process in the first patterning step, thermosetting is performed on both surfaces of the printed wiring board 10 so as to cover the pattern of the first photosensitive resin layer without performing a heat treatment or an ultraviolet irradiation process. When the thermosetting resin layer forming step for forming the resin layer is performed, depending on the type of the thermosetting resin composition used, unreacted carboxylic acid contained in the pattern of the first photosensitive resin layer and thermosetting The component (for example, epoxy resin) in the conductive resin composition may react. It is considered that a reaction product is generated by such a reaction, thereby causing a problem that the pattern of the photosensitive resin layer is not sufficiently removed in the opening forming step.
Therefore, the unreacted components in the pattern of the first photosensitive resin layer are effectively reduced by performing heat treatment or ultraviolet irradiation treatment after the exposure processing and development processing of the first patterning step, and opening In the forming process, it is considered that the pattern of the first photosensitive resin layer can be sufficiently removed.

  As shown in FIG. 4, the surface of the printed circuit board 10 and the conductor circuit 2a are covered so that the pattern 3a of the first photosensitive resin layer is covered after the heat treatment or the ultraviolet irradiation treatment in the first patterning step. The thermosetting resin layer 4 is formed on the surface and the surface of the pattern 3a, and the thermosetting resin layer is formed on the back surface of the printed circuit board 10, the surface of the conductor circuit 2b, and the surface of the pattern 3b so that the pattern 3b is covered. 4 is obtained to obtain a multilayer printed wiring board intermediate 10b (thermosetting resin layer forming step). The thermosetting resin layer 4 is made of a thermosetting resin composition described later.

In the thermosetting resin layer forming step, when the thermosetting resin composition is liquid, it is applied by a known screen printing and roll coater, and when the thermosetting resin composition is a film, by vacuum lamination or the like Through the pasting step, the thermosetting resin layer 4 is formed on the front and back surfaces of the printed wiring board 10, the surfaces of the conductor circuits 2a and 2b, and the surfaces of the patterns 3a and 3b.
As the thermosetting resin composition used for forming the thermosetting resin layer, both liquid and film can be applied. In order to control the thickness of the thermosetting resin layer 4 with high accuracy, the thickness is previously set. The film-like thing which manages thickness can be used conveniently.

The thickness T2 of the thermosetting resin layer 4 is preferably 2 μm to 50 μm, more preferably 5 μm to 30 μm.
When the thickness T2 of the thermosetting resin layer 4 is 2 μm or more, it becomes easy to form a thermosetting resin composition used for forming the thermosetting resin layer 4, so that the film shape used for manufacturing the printed wiring board 10 is used. This thermosetting resin composition can be easily produced.
When the thickness T2 of the thermosetting resin layer is 50 μm or less, it becomes easy to form a fine pattern on the thermosetting resin layer 4.
The thickness T2 of the thermosetting resin layer 4 refers to the thickness of portions of the thermosetting resin layer 4 formed on the surfaces of the conductor circuit 2a and the conductor circuit 2b.

In the thermosetting resin layer forming step, the ratio (T2 / T1) of the thickness T2 of the thermosetting resin layer 4 to the thickness T1 of the first photosensitive resin layer 3 is set to 1.0 to 2.0. Is more preferable, and 1.0 to 1.5 is more preferable. Furthermore, it is more preferable that the thickness T1 of the first photosensitive resin layer 3 and the thickness T2 of the thermosetting resin layer 4 are the same thickness.
When the ratio (T2 / T1) is 1.0 or more, the pattern 3a and the pattern 3b are easily embedded with the thermosetting resin composition in the thermosetting resin layer forming step. 10) can be further improved.
On the other hand, when the ratio (T2 / T1) is 2.0 or less, an opening can be formed in the thermosetting resin layer 4 in a short time, and the multilayer printed wiring board 100 (see FIG. 10) can be more efficiently manufactured. Therefore, when the desmear process is used, deterioration of the chemical solution can be prevented.

Next, the formed thermosetting resin layer 4 is thermally cured (thermosetting step).
In the thermosetting step, it is preferable that the temperature is 150 ° C. to 250 ° C. and the heating time is 30 minutes to 300 minutes. Moreover, it is more preferable that the temperature is 160 ° C. to 200 ° C. and the heating time is 30 minutes to 120 minutes.
If the temperature is 150 ° C. or higher and the heating time is 30 minutes or longer, the thermosetting resin layer 4 can be sufficiently cured. Therefore, the thermosetting resin layer 4 is removed in the subsequent pattern exposure step and opening formation step. This makes it easier to expose the conductor circuit 2a and the conductor circuit 2b.
On the other hand, when the temperature is 250 ° C. or less and the heating time is 300 minutes or less, oxidation of the surfaces of the conductor circuit 2a and the conductor circuit 2b can be suppressed. For this reason, it can suppress that the thermosetting resin layer 4 peels in the interface of the conductor circuit 2a and the conductor circuit 2b. In the thermosetting process, a clean oven is generally used, and curing may be performed in an atmosphere of an inert gas such as nitrogen in order to suppress copper oxidation.

  Next, as shown in FIG. 5, a part of the thermosetting resin layer 4 after the thermosetting is removed so that predetermined portions of the pattern 3 a and the pattern 3 b are exposed, and the thermosetting resin layer 4 a and the thermosetting are removed. The resin layer 4b is formed to obtain the multilayer printed wiring board intermediate 10c (pattern exposure step).

A part of the thermosetting resin layer 4 after thermosetting can be removed by applying desmear treatment to the thermosetting resin layer 4 after thermosetting.
A desmear process can be implemented by immersing a to-be-processed board | substrate in liquid mixture, such as a sodium permanganate liquid, sodium hydroxide liquid, potassium permanganate liquid, chromium liquid, and a sulfuric acid, for example.
Specifically, after the substrate to be treated is swelled with hot water or a predetermined swelling liquid, residues, etc. are removed with sodium permanganate liquid, etc., and reduction (neutralization) is performed, followed by washing with water and washing with hot water. , Dry. If a sufficient opening is not formed even after a single process, the process may be performed multiple times.
The desmear process is not limited to the above. Moreover, you may perform a thermosetting process again after a desmear process. Although the effect varies depending on the thermosetting resin to be used, it is possible not only to perform thermosetting and raise the glass transition temperature, but also to achieve low thermal expansion.

Next, as shown in FIG. 6, the pattern 3 a of the first photosensitive resin layer exposed from the thermosetting resin layer 4 a is removed so that a part of the surface of the conductor circuit 2 a is exposed. The pattern 3b of the first photosensitive resin layer exposed from the thermosetting resin layer 4b is removed so that a part of the surface of 2b is exposed to obtain a multilayer printed wiring board intermediate 10d (opening forming step). .
The pattern 3a and the pattern 3b are preferably removed by applying a desmear process to the multilayer printed wiring board intermediate 10c. Thus, the opening 4h is formed in the thermosetting resin layer 4.

In the pattern exposure step, the thermosetting resin layer 4a and the thermosetting resin layer 4b may be removed using plasma treatment or polishing treatment instead of desmearing treatment. Among the desmear process, the plasma process, and the polishing process, two or more processes may be used in combination to remove the thermosetting resin layer 4a and the thermosetting resin layer 4b.
When the thickness T2 of the thermosetting resin layer 4a and the thermosetting resin layer 4b is large, the thermosetting resin layer 4a and the thermosetting resin are obtained by a polishing process such as sandblasting, mechanical polishing, and chemical mechanical polishing (CMP). It is preferable to remove the layer 4b.
Further, in the opening forming step, instead of the desmear process, the pattern 3a and the pattern 3b may be removed by using a plasma process, or the pattern 3a and the pattern 3b may be removed by using the desmear process and the plasma process in combination. Good.
The pattern exposure process and the opening formation process may be performed by individual apparatuses, or may be performed by an apparatus incorporating these processes as a series of processes.

  For the plasma treatment, for example, argon gas, nitrogen gas, helium gas, monosilane gas, oxygen gas, hydrogen gas, chlorine gas, carbon tetrafluoride gas, or the like can be used. Moreover, these can also be used together. As the plasma processing apparatus, a barrel type or parallel plate type plasma processing apparatus can be used. Note that the output, flow rate, and processing time of the plasma processing can be selected as appropriate.

  Specifically, the polishing process is performed by grinding the thermosetting resin layer 4 with abrasive cloth paper and sandpaper in which an abrasive is bonded to paper and cloth or the like, using an apparatus such as a grinder and a grinder. As the abrasive, artificial abrasives such as fused alumina and silicon carbide and natural abrasives such as garnet and emery are used, but are not limited thereto. The abrasive grain size of the abrasive is desirably ground at # 1500 or more at the end so as not to leave scratches on the surface, but is not limited thereto.

In the opening forming step, the diameter D of the opening 4h formed in the thermosetting resin layer 4a and the thermosetting resin layer 4b is preferably 60 μm or less.
Moreover, ratio (D / Dmin) of the depth D of the said opening with respect to the diameter Dmin of the minimum opening among the openings formed in the thermosetting resin layer 4a and the thermosetting resin layer 4b is 0.1-1. It is preferably 0, and more preferably 0.2 to 0.8. When the ratio (D / Dmin) is 0.1 or more, the thermosetting resin layer 4a and the thermosetting resin layer 4b do not become too thin, so the thermosetting resin layer 4a and the thermosetting resin layer 4b. Even when a fine opening is formed, the shape of the opening 4h can be kept stable.
On the other hand, when the ratio (D / Dmin) is 1.0 or less, the first photosensitive resin layer 3 is easily removed, and a fine opening having a diameter of 60 μm or less is more easily formed. The shape of the opening 4h is circular, but may be elliptical or the like. When the opening is formed in a shape other than a circle, the diameter Dmin may be a circle equivalent diameter.

Next, as shown in FIG. 7, the seed layer 5 is formed by electroless plating so that at least a part of the thermosetting resin layer 4a and the thermosetting resin layer 4b of the multilayer printed wiring board intermediate 10d is covered. A multilayer printed wiring board intermediate 10e is formed on both surfaces of the printed wiring board intermediate 10d (seed layer forming step).
In the seed layer forming step, the surface 4s of the portion of the thermosetting resin layer 4a and the thermosetting resin layer 4b where the opening 4h is not provided, and the wall surface 4w of the thermosetting resin layer 4a where the opening 4h is provided. The seed layer 5 is formed on the exposed surfaces of the conductor circuit 2a and the conductor circuit 2b.
The thickness of the seed layer 5 is not particularly limited, but is usually preferably 0.1 to 1.0 μm. The seed layer 5 can be formed by an electroless copper plating method and a sputtering method. A target in the sputtering method can be appropriately selected, but Cu is generally deposited after Ti. The thickness of Ti or Cu is not particularly limited, but is preferably about 20 to 100 nm for Ti and about 100 to 500 nm for Cu.

Next, as shown in FIG. 8, the second photosensitive resin layers on both sides of the multilayer printed wiring board intermediate 10e are patterned to obtain the multilayer printed wiring board intermediate 10f (second patterning step). In the second patterning step, first, a second photosensitive resin layer is formed on the seed layer so that the seed layer is covered. Specifically, the film-like photosensitive resin composition is adhered to both surfaces of the multilayer printed wiring board intermediate body 10e, that is, the seed layer 5 to form the second photosensitive resin layer. Thereafter, a phototool having a predetermined pattern is brought into close contact with each other, exposure processing and development processing are performed, and patterns 6a and 6b are obtained.
The pattern 6a and the pattern 6b of the second photosensitive resin layer formed on both surfaces of the multilayer printed wiring board intermediate 10e form a fine wiring pattern in a portion closer to the surface on which the semiconductor element is mounted. The pattern pitch of the pattern 6a of the second photosensitive resin layer is narrower than that of the pattern 6b of the photosensitive resin layer.

Next, as shown in FIG. 9, the wiring part 7 is formed by an electrolytic plating method such as copper electrolytic plating so that at least a part of the seed layer 5 is covered, thereby obtaining a multilayer printed wiring board intermediate 10g.
In this step, the wiring portion 7 is formed on the surface of the seed layer 5 other than the region where the pattern 6a and the pattern 6b of the second photosensitive resin layer are formed.
In the region where the opening 4h is formed, the wiring portion 7 is formed on the seed layer 5 formed on the surface of the wall surface 4w, the conductor circuit 2a, and the conductor circuit 2b.
The thickness of the wiring part 7 is preferably 1 μm to 20 μm.

Thereafter, as shown in FIG. 10, the pattern 6a and the pattern 6b are peeled off by a peeling solution to form the wiring pattern 7a and the wiring pattern 7b (wiring part patterning step).
Next, using an etchant, the seed layer 5 in a region where the wiring portion 7 is not formed is removed by etching (seed layer removing step).

  Through the above steps, a multilayer printed wiring board 100 having wiring portions (wiring patterns 7a and 7b) on the surface is obtained.

Furthermore, as shown in FIG. 11, the single layer printed wiring forming process is used as the single layer printed wiring forming process from the first photosensitive resin layer forming process described above to both the front and back surfaces of the multilayer printed wiring board 100. After repeatedly performing the multilayer printed wiring formation process, the solder resist 8 is formed on the outermost layer, and the nickel / gold layer 9 is formed by plating using a commercially available electroless nickel / gold plating solution or the like. Thus, the multilayer printed wiring board 200 can be obtained.
For example, the multilayer printed wiring board 200 has three layers of wiring portions (wiring patterns 7a and 7b) by repeating a series of steps from the first photosensitive resin layer forming step to the seed layer removing step three times. It is a thing. In the multilayer printed wiring board 200, wiring portions (wiring pattern 7a and wiring pattern 7b) formed in each thermosetting resin layer 4 are electrically connected to each other.

  In the above manufacturing method, openings having various shapes are provided by patterning the first photosensitive resin layer in the first patterning step in accordance with the shape of the opening formed in the thermosetting resin layer. Can do. In addition, in the method of manufacturing a structure having a conductor circuit, a plurality of openings can be formed at the same time, unlike the case of forming openings with a laser, and resin residues around the openings can be reduced. For this reason, even when the number of pins of the semiconductor element increases and a large number of fine openings need to be provided, a structure having excellent reliability can be manufactured sufficiently efficiently. At this time, after patterning the first photosensitive resin layer, it is possible to facilitate the removal in the step of removing the first photosensitive resin layer by heating or irradiating ultraviolet rays or using both in combination. it can.

  Therefore, the multilayer printed wiring board 100 and the multilayer printed wiring board 200 described above are suitable as printed wiring boards for mounting flip chip type semiconductor elements that are increasingly miniaturized and densified. Among them, the size of the semiconductor element to be mounted is large, and it is particularly suitable for a printed wiring board for electrically connecting to tens of thousands of bumps arranged in an area array on the surface of the semiconductor element.

  Next, although the photosensitive resin composition and thermosetting resin composition used for manufacture of the above-mentioned multilayer printed wiring board 100 and multilayer printed wiring board 200 will be described in detail, the present invention is limited to these resin compositions. It is not something.

Although the photosensitive resin composition used for manufacture of the multilayer printed wiring board 100 and the multilayer printed wiring board 200 is not specifically limited, The following are suitable. That is, the photosensitive resin composition suitable for forming the photosensitive resin layer is
(A) a binder polymer;
(B) a photopolymerizable compound having at least one ethylenically unsaturated bond;
(C) a photopolymerization initiator;
It is preferable to contain. This photosensitive resin composition can be used when forming both the first photosensitive resin layer and the second photosensitive resin layer.

  It is preferable that the photosensitive resin composition does not contain (d) an inorganic filler. In this case, the resolution after development is improved, a fine pattern can be formed, and the side surface of the opening after being peeled by the desmear process tends to be smooth. In addition, when (d) inorganic filler is included in the photosensitive resin composition, it is preferable that a maximum particle size is 5 micrometers or less and an average particle diameter is 1 micrometer or less.

  Examples of the (a) binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. An acrylic resin is preferable from the viewpoint of alkali developability. These can be used alone or in combination of two or more. (A) The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer.

  Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyltoluene, and α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, and the like. Esters of vinyl alcohol such as vinyl-n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, ( (Meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-Bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, maleic acid Examples include maleic acid monoesters such as monoethyl and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These can be used alone or in combination of two or more.

  The binder polymer (a) preferably contains a carboxyl group from the viewpoint of alkali developability, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. Can be manufactured. As the polymerizable monomer having a carboxyl group, (meth) acrylic acid is preferable, and methacrylic acid is more preferable.

  (A) The carboxyl group content of the binder polymer (the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomer used) is preferably 12 to from the viewpoint of the balance between alkali developability and alkali resistance. It is 50 mass%, More preferably, it is 12-40 mass%, More preferably, it is 15-30 mass%, Most preferably, it is 15-25 mass%. When the carboxyl group content is 12% by mass or more, alkali developability is improved, and when it is 50% by mass or less, alkali resistance can be increased.

  (A) The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, more preferably 40,000 to 150,000, even more preferably, from the viewpoint of the balance between mechanical strength and alkali developability. Is 50,000 to 120,000. When the weight average molecular weight is 20,000 or more, the developer resistance is improved, and when it is 300,000 or less, the development time can be shortened. In the present embodiment, the weight average molecular weight is a value measured by a gel permeation chromatography method and converted by a calibration curve created using standard polystyrene.

  The content of the binder polymer (a) is preferably 30 with respect to 100 parts by mass of the total amount of the component (a) the binder polymer and the component (b) the photopolymerizable compound having at least one ethylenically unsaturated bond. It is -80 mass parts, More preferably, it is 40-75 mass parts, More preferably, it is 50-70 mass parts. (A) When content of the component of a binder polymer is this range, the coating film property of the photosensitive resin composition and the intensity | strength of photocured material will become more favorable. (B) The content of the photopolymerizable compound having at least one ethylenically unsaturated bond is the content of (a) a component of the binder polymer and (b) a component of the photopolymerizable compound having at least one ethylenically unsaturated bond. Preferably it is 20-60 mass parts with respect to 100 mass parts of total amounts, More preferably, it is 30-55 mass parts, More preferably, it is 35-50 mass parts. (B) When the content of the component of the photopolymerizable compound having at least one ethylenically unsaturated bond is within this range, the photosensitivity and the coating property of the photosensitive resin composition become better.

  (B) As a photopolymerizable compound having at least one ethylenically unsaturated bond, for example, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, a bisphenol A-based (meth) acrylate compound , A compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, a urethane monomer such as a (meth) acrylate compound having a urethane bond, nonylphenoxybutaethyleneoxy (meth) acrylate, nonylphenoxyoctaethylene Oxy (meth) acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β- Hydroxypropyl-β '-(meth) acryloylo Examples thereof include xylethyl-o-phthalate and (meth) acrylic acid alkyl ester. These may be used alone or in combination of two or more.

  The content of the component (b) of the photopolymerizable compound having at least one ethylenically unsaturated bond is determined from the viewpoint of the balance between photosensitivity and resolution, and (a) the component of the binder polymer and (b) the ethylenically unsaturated group. Preferably it is 10-40 mass parts with respect to 100 mass parts of total amounts of the component of the photopolymerizable compound which has at least one saturated bond, More preferably, it is 20-30 mass parts.

  (C) As a photopolymerization initiator as a component of the photopolymerization initiator, for example, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4 '-Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholino-propanone-1, etc. aromatic ketone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-Phenylanthraquinone, 2,3-diphenylanthraki Quinones such as 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone, benzoin methyl Benzoin ether compounds such as ether, benzoin ethyl ether, and benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin, and ethyl benzoin, benzyl derivatives such as benzyldimethyl ketal, 9,10-dimethoxyanthracene, 9,10-diethoxy Substituted anthracenes such as anthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene, 2- (o-chlorophenyl) -4,5-diphenyl Midazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Methoxyphenyl) -4,5-diphenylimidazole dimer and 2,4,5-triarylimidazole dimer such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, coumarin Compounds, oxazole compounds, pyrazoline compounds, and the like. Here, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same and give the target compound, or differently give the asymmetric compound. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. In addition, 2,4,5-triarylimidazole dimer is more preferable from the viewpoint of balance between adhesion and sensitivity. These are used alone or in combination of two or more.

  The content of the (c) photopolymerization initiator is preferably based on 100 parts by mass of the total amount of (a) the binder polymer component and (b) the photopolymerizable compound component having at least one ethylenically unsaturated bond. Is 0.01-30 mass parts, More preferably, it is 0.1-20 mass parts, More preferably, it is 0.2-10 mass parts. (C) When the content of the component of the photopolymerization initiator is within this range, the photosensitivity and the internal photocurability of the photosensitive resin composition become better.

  Although it is preferable that the photosensitive resin composition is (d) filler-less without filling with an inorganic filler, it may be filled with a small amount. (D) By filling a small amount of the inorganic filler, the shrinkage amount becomes small, the rigidity becomes high, and the thickness dimensional accuracy can be improved. (D) When the filling amount of the inorganic filler is less than 5 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition, the resolution can be improved.

  (D) Examples of inorganic fillers include barium sulfate, barium titanate, powdered silicon oxide, amorphous silica, talc, clay, calcined kaolin, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. Inorganic fillers can be used. In particular, it is desirable to use a silane coupling agent in order to disperse the silica particle in the resin without agglomeration with the primary particle size. (D) The maximum particle size of the inorganic filler is preferably 2 μm or less, more preferably 1 μm or less. In addition, (d) the average particle size of the inorganic filler is preferably 300 nm or less, more preferably 100 nm or less, from the viewpoint of resolution.

  In addition, the photosensitive resin composition includes, if necessary, dyes such as malachite green, Victoria pure blue, brilliant green, and methyl violet, tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, Photochromic agents such as diethylaniline, o-chloroaniline and tertiary butyl catechol, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, adhesion-imparting agents, Leveling agent, peeling accelerator, antioxidant, fragrance, imaging agent, thermal crosslinking agent, polymerization inhibitor, etc. (a) component of binder polymer and (b) photopolymerizable compound having at least one ethylenically unsaturated bond Each containing 0.01 to 20 parts by mass with respect to 100 parts by mass in total It can be. These are used alone or in combination of two or more.

  If necessary, the photosensitive resin composition is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. And can be applied as a solution having a solid content of 30 to 60% by mass. These are used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the photosensitive resin composition, Metal surfaces, for example, iron-type alloys, such as copper, a copper-type alloy, nickel, chromium, iron, stainless steel, Preferably copper, a copper-type alloy, and an iron-type alloy It is preferable that the surface is applied as a liquid resist and dried, and then coated with a protective film, if necessary, or used in the form of a photosensitive element.

  The form of the photosensitive element includes a support and a photosensitive resin composition layer (resin layer) formed by uniformly applying and drying the solution of the photosensitive resin composition on the support. In addition, a protective film for coating the photosensitive resin composition layer may be further provided. The support can be obtained, for example, by applying and drying a photosensitive resin composition on a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester. From the viewpoint of transparency, it is preferable to use a polyethylene terephthalate film.

  Although the thermosetting resin composition used for manufacture of the multilayer printed wiring board 100 and the multilayer printed wiring board 200 is not specifically limited, The following are suitable. That is, the thermosetting resin composition suitable for the formation of the thermosetting resin layer 4 is at least one selected from the group consisting of epoxy resins, phenol resins, cyanate ester resins, polyamideimide resins, and thermosetting polyimide resins. It is preferable that the resin composition to be contained and an inorganic filler having a maximum particle size of 5 μm or less and an average particle size of 1 μm or less.

  The epoxy resin is preferably an epoxy resin having one or more glycidyl groups in the molecule. The filling amount of the inorganic filler is preferably in the range of 0 to 90% by mass, more preferably in the range of 20 to 70% by mass, and further preferably 30 to 60% by mass.

  Any epoxy resin having two or more glycidyl groups can be used as the epoxy resin, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak phenol type epoxy resin, biphenyl type epoxy are preferable. Bisphenol S type epoxy resin such as resin, bisphenol S diglycidyl ether, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bixylenol type epoxy resin such as bixylenol diglycidyl ether, hydrogenated bisphenol A glycidyl ether, etc. Bisphenol A type epoxy resins, dibasic acid-modified diglycidyl ether type epoxy resins, and the like, which can be used alone or in combination of two or more.

  Commercially available epoxy resins include naphthalene type epoxy resins such as EXA4700 (tetrafunctional naphthalene type epoxy resin) manufactured by DIC Corporation, NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd .; Nippon Kayaku Epoxidized product of a condensation product of phenols such as EPPN-502H (trisphenol epoxy resin) and an aromatic aldehyde having a phenolic hydroxyl group (trisphenol type epoxy resin); Epicron HP-7200H (dicyclo) Dicyclopentadiene aralkyl epoxy resin such as pentadiene skeleton-containing polyfunctional solid epoxy resin); biphenyl aralkyl epoxy resin such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; manufactured by DIC Corporation Novolak type epoxy resins such as Piclone N660, Epicron N690, Nippon Kayaku Co., Ltd. EOCN-104S; Tris (2,3-epoxypropyl) isocyanurate such as TEPIC made by Nissan Chemical Industries, Epicron 860 made by DIC Corporation, Epicron 900-IM, Epicron EXA-4816, Epicron EXA-4822, Araldite AER280 manufactured by Asahi Ciba Co., Ltd., Epototo YD-134 manufactured by Tohto Kasei Co., Ltd., JER834 manufactured by Mitsubishi Chemical Co., Ltd. Bisphenol A type epoxy resin such as 134; naphthalene type epoxy resin such as Epicron HP-4032 manufactured by DIC Corporation; phenol novolac type epoxy resin such as Epicron N-740 manufactured by DIC Corporation, phenol Epoxy resin of a condensate of salicylaldehyde; and Nippon Kayaku Co., Ltd. EPPN-500 series can be cited. These epoxy resins may be used alone or in combination of two or more.

  Among the above epoxy resins, biphenyl aralkyl type epoxy resins such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd. are preferable in terms of excellent adhesion and insulation with copper, It is more preferable to use EPPN-500 series manufactured by Nippon Kayaku Co., Ltd. in terms of high crosslinking density and high Tg.

  The content of the epoxy resin is preferably 30 to 90 parts by mass and more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the resin component excluding the inorganic filler component.

  As the curing agent combined with the epoxy resin, various conventionally known epoxy resin curing agents or epoxy resin curing accelerators can be blended. For example, phenol resins, imidazole compounds, acid anhydrides, aliphatic amines, alicyclic polyamines, aromatic polyamines, tertiary amines, dicyandiamide, guanidines, or epoxy adducts or microencapsulated products thereof, triphenyl Regardless of organic phosphine compounds such as phosphine, tetraphenylphosphonium, tetraphenylborate, DBU or derivatives thereof, curing agents or curing accelerators, known or commonly used ones are used alone or in combination of two or more. can do. Although it will not specifically limit if hardening of an epoxy resin can be advanced, Specifically, 4,4'- diamino diphenyl sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 2, 2-bis [4 -(4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, trimethylenebis (4-aminobenzoate), 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis [4- (4- Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9′-bis (4 Aminophenyl) fluorene, 2,2-bis can be exemplified [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like, may be used alone, or two or more.

  The cyanate ester resin is a resin that generates a cured product having a triazine ring as a repeating unit by heating, and the cured product is excellent in dielectric characteristics, and is often used particularly when high-frequency characteristics are required. Examples of cyanate ester resins include 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene, phenol novolak And cyanate esterified products of alkylphenol novolac and the like. Among these, 2,2-bis (4-cyanatophenyl) propane is preferable because it has a particularly good balance between the dielectric properties and curability of the cured product and is inexpensive. Moreover, a cyanate ester compound may be used individually by 1 type, and 2 or more types may be mixed and used for it. The cyanate ester compound used here may be partially oligomerized in advance to a trimer or a pentamer. Furthermore, a curing catalyst or a curing accelerator may be added to the cyanate resin. As the curing catalyst, metals such as manganese, iron, cobalt, nickel, copper, and zinc are used. Specifically, organic metal salts such as 2-ethylhexanoate, naphthenate, octylate, and acetylacetone are used. Used as organometallic complexes such as complexes. These may be used singly or in combination of two or more. Phenols are preferably used as the curing accelerator, and monofunctional phenols such as nonylphenol and paracumylphenol, bifunctional phenols such as bisphenol A, bisphenol F, and bisphenol S, or polyfunctional phenols such as phenol novolac and cresol novolac. Etc. can be used. These may be used singly or in combination of two or more.

  The thermosetting resin composition preferably contains a maleimide compound having at least two unsaturated N-substituted maleimide groups in the molecular structure. Specifically, for example, N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1,3 -(2-methylphenylene)] bismaleimide, N, N '-[1,3- (4-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, bis (4- Maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, Bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidosilane) Rohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) Benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4 -(3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2 -Bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimi Phenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4 -(4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) Biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2′-bi (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] Sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -α, α-dimethyl Benzyl] benzene, 1,3-bis [4- (4 -Maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimide) Phenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-Maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] Examples include benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenylmethanemaleimide and the like. These maleimide compounds may be used alone or in combination of two or more.

  Moreover, you may use a polyimide resin, a polyamideimide resin, and various carboxylic acid containing resin as another resin with which an epoxy resin is made to react. Examples of the polyamide-imide resin include “Vilomax HR11NN”, “Vilomax HR12N2”, “Vilomax HR16NN”, and the like by Toyobo Co., Ltd. Examples of the carboxylic acid-containing resin include acrylic resins, acid-modified epoxy acrylates, and acid-containing urethane resins.

  It is preferable that content of the said hardening | curing agent is 5-50 mass parts with respect to 100 mass parts of resin components except an inorganic filler component, and it is more preferable that it is 10-40 mass parts.

  As the inorganic filler, all conventionally known inorganic fillers and organic fillers can be used, and are not limited to specific ones. For example, extender pigments such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, , Copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold, platinum, and other metal powders.

  In the case of using a silica filler, it is desirable to use a silane coupling agent in order to disperse the filler in the resin without agglomeration while maintaining the primary particle size. The maximum particle size is preferably 5 μm or less, more preferably 1 μm or less. As the silane coupling agent, generally available ones can be used, for example, alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, Sulfur silane, styryl silane, alkylchlorosilane, and the like can be used.

  Specific compound names include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxy. Silane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxy Silane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyldi Tylchlorosilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane , 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Lutriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylden) -3-aminopropyltriethoxysilane, aminosilane and the like.

  The average particle size of the inorganic filler is preferably 300 nm or less, and more preferably 100 nm or less. The smaller the average particle size of the inorganic filler, the smoother the surface after desmear treatment, and the filling property of the underfill material tends to improve during subsequent flip chip mounting. The filling amount of the inorganic filler is preferably 0 to 90% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 60% by mass.

  As described above, in the method for manufacturing a printed wiring board according to the present embodiment, the first photosensitive resin layer 3 in the first patterning process according to the shape of the opening formed in the thermosetting resin layer 4. By patterning, openings 4h having various shapes can be easily formed. Further, in the method for manufacturing a printed wiring board according to the present embodiment, in addition to forming the plurality of openings 4h at the same time, unlike the case of forming the openings with a laser, the residue of the photosensitive resin around the openings 4h can be reduced. For this reason, even if the number of pins of the semiconductor element increases and it is necessary to provide a large number of fine openings 4h, a printed wiring board having excellent reliability can be manufactured sufficiently efficiently.

  Further, in the present embodiment, as a process immediately after the thermosetting resin layer forming process, a thermosetting process for thermosetting the thermosetting resin layer 4 is further provided. In the pattern exposure process and the opening forming process, plasma treatment and desmearing are performed. By performing the treatment, a part of the thermosetting resin layer 4 is removed and the first photosensitive resin layer 3 exposed from the thermosetting resin layer 4 is removed. In this case, the first photosensitive resin layer 3 can be quickly exposed by plasma treatment and desmear treatment, and residues around the opening 4h can be more reliably reduced by desmear treatment.

  Moreover, in this embodiment, as a process immediately after the thermosetting resin layer forming process, a thermosetting process for thermosetting the thermosetting resin layer 4 is further provided, and desmear treatment is performed in the pattern exposure process and the opening forming process. Thus, a part of the thermosetting resin layer 4 after thermosetting is removed, and the first photosensitive resin layer 3 exposed from the thermosetting resin layer 4 is removed. In this case, the first photosensitive resin layer 3 can be exposed promptly by the desmear process, and the residue around the opening 4h can be more reliably reduced.

  Further, in the present embodiment, as a process immediately after the thermosetting resin layer forming process, a thermosetting process for thermosetting the thermosetting resin layer is further provided, and in the pattern exposure process, by performing a polishing process, thermosetting is performed. A part of the later thermosetting resin layer 4 is removed, and the first photosensitive resin layer 3 exposed from the thermosetting resin layer 4 is removed by performing a desmear process in the opening forming step. In this case, the first photosensitive resin layer 3 can be quickly exposed by the polishing process and the desmear process, and the residue around the opening 4h can be more reliably reduced by the desmear process.

  Moreover, in this embodiment, as a process immediately after the thermosetting resin layer forming process, a thermosetting process for thermosetting the thermosetting resin layer 4 is further provided, and plasma treatment is performed in the pattern exposure process and the opening forming process. Thus, a part of the thermosetting resin layer 4 after thermosetting is removed, and the first photosensitive resin layer 3 exposed from the thermosetting resin layer 4 is removed. In this case, the first photosensitive resin layer 3 can be exposed promptly by plasma treatment, and residues around the opening 4h can be more reliably reduced.

  Further, in the present embodiment, the seed layer 5 serving as a base of the wiring pattern 7a and the wiring pattern 7b is formed by an electroless plating method so as to cover at least a part of the thermosetting resin layer 4 after the opening 4h is formed. And forming a second photosensitive resin layer so as to cover the seed layer 5, and then subjecting the second photosensitive resin layer to exposure processing and development processing to pattern the second photosensitive resin layer. After forming the wiring part 7 by the electrolytic plating method so as to cover the process and the seed layer 5, the wiring 6 is patterned by peeling the pattern 6a and the pattern 6b of the second photosensitive resin layer by peeling treatment It is preferable to further include a partial patterning step and a seed layer removing step of removing the seed layer 5 in a region where the wiring portion is not formed. By forming the seed layer 5, the wiring part 7 can be formed by electrolytic plating, and the wiring part 7 can be selectively patterned.

The printed wiring board 100 according to the present invention is a printed wiring board manufactured by the method for manufacturing a printed wiring board according to this embodiment, and the diameter of the opening 4h of the thermosetting resin layer 4 is 60 μm or less. is there. According to such a printed wiring board 100, compared with the conventional printed wiring board, the thermosetting resin layer 4 has the fine opening 4h and can have excellent reliability.
In addition, since such a printed wiring board 100 has a diameter of the opening 4h of the thermosetting resin layer 4 of 60 μm or less, it is suitable for mounting a semiconductor element having tens of thousands to hundreds of thousands of pins. It will be. Further, the printed wiring board 100 can be subjected to various kinds of processing generally performed on the printed wiring board, for example, nickel / gold plating or soldering on the surface wiring pattern.

  As mentioned above, although the suitable embodiment of the manufacturing method of the printed wiring board and resin composition concerning this invention was described, this invention is not necessarily limited to embodiment mentioned above, suitably in the range which does not deviate from the meaning Changes may be made.

  For example, in the above-described embodiment, a thermosetting process for thermosetting the thermosetting resin layer 4 is provided as a process immediately after the thermosetting resin layer forming process. However, in the pattern exposure process and the opening forming process, plasma processing is performed. When removing a part of the thermosetting resin layer 4 and removing the first photosensitive resin layer 3 exposed from the thermosetting resin layer 4, a pattern exposing step and an opening forming step are performed. A thermosetting step may be provided as a step between the steps or as a step after the opening forming step.

Example 1
<Preparation of printed wiring board having conductor circuit>
First, a copper clad laminate 1 (manufactured by Hitachi Chemical Co., Ltd., MCL-E-679FG) in which a metal foil 2 having a thickness of 12 μm was adhered to both surfaces was prepared. The thickness of the copper clad laminate 1 was 400 μm (see FIG. 1A). The metal foil 2 was etched and processed into a predetermined pattern shape (see FIG. 1B).

<Formation of first photosensitive resin layer>
Next, as shown in FIG. 2, a photosensitive resin composition having a film thickness of 10 μm to 40 μm based on a dry film resist (Phototec H-7025 manufactured by Hitachi Chemical Co., Ltd.) is prepared on both sides with a roll laminator. The photo tool which stuck and formed the pattern was stuck, and it exposed with the energy amount of 50 mJ / cm < ² > using the Oak Manufacturing Co., Ltd. EXM-1201 type exposure machine. Next, spray development was performed for 90 seconds with a 1 mass% sodium carbonate aqueous solution at 30 ° C., and the photosensitive resin composition was opened to form patterns 3a and 3b of the first photosensitive resin layer (see FIG. 3).

  Next, the copper clad laminate 1 on which the pattern of the first photosensitive resin layer was formed was put in a drying furnace heated to 180 ° C. for 60 minutes.

  The thermosetting resin layer 4 was formed on the printed wiring board using the semi-additive process-compatible insulating film (manufactured by Hitachi Chemical Co., Ltd., AS-Z3) (see FIG. 4). Specifically, first, the protective film of the insulating film is peeled off, and the insulating film is placed on both surfaces of the printed wiring board 10 (on the patterns 3a and 3b and the conductor circuits 2a and 2b) so that the support faces outward. did. An insulating film was laminated on the surface of the printed wiring board using a press-type vacuum laminator (MVLP-500 / 600, manufactured by Meiki Seisakusho Co., Ltd.). The press conditions were a press hot plate temperature of 70 ° C., a vacuuming time of 30 seconds, a laminating press time of 40 seconds, and a pressing pressure of 0.5 MPa. Next, the thermosetting resin layer 4 was formed in a clean oven at a predetermined temperature and for a predetermined time.

  Thereafter, by performing a removal process along the steps shown in Table 1, the thermosetting resin layer 4 is ground to expose the patterns 3a and 3b of the first photosensitive resin layer, and the first photosensitive resin. The layer patterns 3a and 3b were removed to obtain an evaluation substrate of Example 1 (see FIGS. 5 and 6).

(Comparative Example 1)
In Example 1, the same operation as in Example 1 was performed except that the copper clad laminate 1 on which the pattern of the first photosensitive resin layer was formed was not put into a drying furnace heated to 180 ° C. for 60 minutes, An evaluation substrate of Comparative Example 1 was obtained.
Table 2 shows the opening formation process conditions at the time of manufacturing the printed wiring board in Example 1 and Comparative Example 1.

The obtained evaluation substrate was evaluated under the following observation conditions using a field emission scanning electron microscope (manufactured by Hitachi, Ltd., S-4700). The observation results are shown in FIG.
(Observation conditions)
・ Magnification: × 150 times, × 1000 times ・ Acceleration voltage: 3 kV

  In Example 1 in which the pattern of the photosensitive resin layer was heat-treated, the residue of the pattern in the photosensitive resin layer was less than that in Comparative Example 1 in which the heat treatment was not performed. It can be seen that the removal property of the photosensitive resin composition when forming the opening by removing the resin composition is good.

1 ... Copper-clad laminate (structure)
DESCRIPTION OF SYMBOLS 1b ... Support body 2 ... Metal foil 2a, 2b ... Conductor circuit (copper foil)
DESCRIPTION OF SYMBOLS 3 ... 1st photosensitive resin layer 3a, 3b ... Pattern of 1st photosensitive resin layer 4 ... Thermosetting resin layer 4a, 4b ... Thermosetting resin layer 4h ... Opening 4s ... Surface 4w ... Wall surface 5 ... Seed Layer 6a, 6b ... Pattern of second photosensitive resin layer 7 ... Wiring portion 7a, 7b ... Wiring pattern 8 ... Solder resist 9 ... Nickel / gold layer 10 ... Printed wiring board (inner layer board)
DESCRIPTION OF SYMBOLS 100 ... Multilayer printed wiring board 200 ... Multilayer printed wiring board which has a soldering resist and a nickel / gold layer

Claims (5)

A support and a conductor circuit formed on the surface of the support;
An insulating layer laminated on the surface of the support so as to cover the conductor circuit;
An opening formed in the insulating layer such that a part of the conductor circuit is exposed;
A wiring portion formed in the insulating layer so as to be electrically connected to a part of the conductor circuit exposed in the opening;
A method of manufacturing a structure including:
A first photosensitive resin layer forming step of forming a first photosensitive resin layer on the support so that the conductor circuit is covered;
A first patterning step of subjecting the first photosensitive resin layer to an exposure process and a development process so that the first photosensitive resin layer is patterned;
A thermosetting resin layer forming step of forming a thermosetting resin layer on the support so as to cover the pattern of the first photosensitive resin layer;
A pattern exposure step of removing a part of the thermosetting resin layer to expose a predetermined portion of the pattern of the first photosensitive resin layer from the thermosetting resin layer;
An opening forming step of removing the first photosensitive resin layer exposed from the thermosetting resin layer and forming an opening in the thermosetting resin layer to expose the conductor circuit;
The first patterning step includes a heat treatment for heat-treating the pattern of the first photosensitive resin layer after the exposure process and the development process, and an ultraviolet ray applied to the pattern of the first photosensitive resin layer. The manufacturing method of a structure which performs at least one of the ultraviolet irradiation process which irradiates. Furthermore, a seed layer forming step of forming a seed layer so that at least a part of the thermosetting resin layer is covered;
A second photosensitive resin layer is formed on the seed layer so as to cover the seed layer, and an exposure process is performed on the second photosensitive resin layer so that the second photosensitive resin layer is patterned. And a second patterning step for performing development processing;
Forming a wiring portion so that at least a part of the seed layer is covered, peeling the pattern formed in the second patterning step, and forming a wiring pattern;
The method for manufacturing a structure according to claim 1, further comprising: a seed layer removing step of removing a seed layer in a region where the wiring part is not formed.   The manufacturing of the structure according to claim 2, wherein the seed layer removing step is a single multilayer printed wiring forming step from the first photosensitive resin layer forming step, and the single multilayer printed wiring forming step is repeated. Method. The said 1st patterning process is a process of heat-processing the pattern of a said 1st photosensitive resin layer after the said exposure process and the said image development process of any one of Claims 1-3. Manufacturing method of structure. The first photosensitive resin layer;
(A) a binder polymer;
(B) a photopolymerizable compound having at least one ethylenically unsaturated bond;
(C) The manufacturing method of the structure of any one of Claims 1-4 formed using the photosensitive resin composition containing a photoinitiator.