Method for manufacturing resin sheet with protective film

Abstract

The present invention addresses the problem of providing a method for manufacturing a resin sheet with a protective film, which is capable of eliminating foreign matter and improving the yield of wiring formation. The solution of the present invention is a method for producing a resin sheet with a protective film, the resin sheet with a protective film comprising, in this order, a support body provided with a release layer, a resin composition layer containing a curable resin composition, and a protective film, the manufacturing method comprises the following steps: a step of contacting a first dust removal roller with the surface of the support body on the demolding layer side; a step of forming a resin composition layer on the surface of the support body on the demolding layer side; a step of contacting a second dust removal roller with the first surface of the protective film; and a step of bonding the resin composition layer with the first surface of the protective film. The first dust removal roller has an adhesive force lower than 2.9 N / 100 mm < 2 >, and the second dust removal roller has an adhesive force lower than 2.9 N / 100 mm < 2 >.

Description

Technical Field

[0001] The present invention relates to a method for producing a resin sheet with a protective film. Background Art

[0002] Circuit substrates such as printed wiring boards and semiconductor package substrates are widely used in various electronic devices. As a manufacturing method for circuit substrates, it is known to adopt a manufacturing method of a stacking (build-up) mode of alternately overlapping insulating layers and conductor layers on an inner substrate. The insulating layer is manufactured, for example, by using a resin sheet formed with a resin composition layer on a support. Specifically, a resin composition layer is formed by laminating a resin sheet on an inner substrate, and the resin composition layer is cured to form an insulating layer (patent document 1). From the viewpoint of protecting the resin composition layer in storage and transportation, such a resin sheet is sometimes provided with a protective film covering the resin composition.

[0003] Prior art literature Patent Literature Patent document 1: Japanese Patent Application Publication No. 2020-23714. Summary of the invention

[0004] Technical problem to be solved by the invention Foreign matter may be mixed into the resin composition layer of the resin sheet. The foreign matter may become the reason for the decrease in the yield rate of the wiring forming the circuit. Therefore, in the previous manufacturing method of the resin sheet, the operation of removing the foreign matter is performed. For example, the resin varnish used to form the resin composition layer is filtered by using a filter, thereby removing the foreign matter.

[0005] In recent years, due to the demand for miniaturization of electronic devices and electronic components, the miniaturization and high density of wiring are required. If the miniaturization and high density of wiring are further developed, foreign matter smaller than before may hinder the formation of wiring. For example, foreign matter as small as tens of microns may hinder the formation of wiring. However, relying on the previous technology, it is difficult to avoid the reduction of yield due to such tiny foreign matter.

[0006] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a method for producing a resin sheet with a protective film, which can eliminate foreign matter and improve the yield of wiring formation.

[0007] Means used to solve technical problems The present inventors have conducted intensive research to solve the above-mentioned problems. As a result, the present inventors have found that the above-mentioned problems can be solved when a method for manufacturing a resin sheet with a protective film which sequentially comprises a support having a release layer, a resin composition layer comprising a curable resin composition, and a protective film comprises a step of bringing a first dust removal roller having an adhesive force in a specific range into contact with a surface on the release layer side of the support, a step of forming a resin composition layer on the surface on the release layer side of the support, a step of bringing a second dust removal roller having an adhesive force in a specific range into contact with a first surface of the protective film, and a step of bonding the resin composition layer to the first surface of the protective film, thereby completing the present invention.

[0008] That is, the present invention includes the following contents. [1] A method for producing a resin sheet with a protective film, the resin sheet with a protective film comprising, in order: a support having a release layer, a resin composition layer containing a curable resin composition, and a protective film, Wherein, the manufacturing method comprises: a step of bringing the first dust removal roller into contact with the surface of the support body on the release layer side, a step of forming a resin composition layer on the surface of the support body on the side of the mold release layer, a step of bringing the second dust removal roller into contact with the first surface of the protective film, and In the step of bonding the resin composition layer to the first surface of the protective film, the first dust removal roller has a strength lower than 2.9 N / 100 mm 2 The adhesion of the second dust removal roller is less than 2.9N / 100mm 2 Adhesion. [2] The method for producing a resin sheet with a protective film according to [1], wherein the step of forming the resin composition layer on the surface of the support on the release layer side includes the step of applying a liquid curable resin composition. [3] The method for producing a resin sheet with a protective film according to [1] or [2], further comprising a step of bringing a third dust removal roller into contact with a surface of the support body on the opposite side to the release layer. [4] The method for producing a resin sheet with a protective film according to any one of [1] to [3], wherein the method includes a step of bringing a fourth dust removal roller into contact with a second surface of the protective film opposite to the first surface. [5] The method for producing a resin sheet with a protective film according to any one of [1] to [4], wherein the curable resin composition contains a curable resin and an inorganic filler.

[0009] Effects of the Invention According to the present invention, it is possible to provide a method for producing a resin sheet with a protective film, which can eliminate foreign matter and improve the yield of wiring formation.

[0010] Brief description of the attached figure Figure 1 It is a front view schematically showing an apparatus for producing a laminated resin sheet according to a first example of the present invention. Figure 2 It is a front view schematically showing a manufacturing apparatus for a laminated resin sheet according to a second example of the present invention. DETAILED DESCRIPTION

[0011] Hereinafter, the present invention will be described with reference to the embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and any changes can be made without departing from the scope of the claims and their equivalents.

[0012] <Overview of the method for producing a resin sheet with a protective film> In a manufacturing method according to one embodiment of the present invention, a resin sheet with a protective film is manufactured, which includes a support having a release layer, a resin composition layer containing a curable resin composition, and a protective film in this order. In the following description, the "resin sheet with a protective film" may be referred to as a "laminated resin sheet".

[0013] The method for producing a laminated resin sheet according to the present embodiment includes: A step (I) of bringing a first dust removal roller having an adhesive force within a specific range into contact with the surface of the support on the release layer side, a step (II) of forming a resin composition layer on the surface of the support on the release layer side, Step (III) of bringing a second dust removal roller having an adhesive force within a specific range into contact with the first surface of the protective film, and A step (IV) of bonding the resin composition layer to the first surface of the protective film.

[0014] Furthermore, the method for producing a laminated resin sheet according to the present embodiment preferably further comprises a step (V) of bringing a third dust removal roller into contact with a surface of the support body on the side opposite to the release layer. Preferably including A step (VI) of bringing the fourth dust removing roller into contact with the second surface of the protective film opposite to the first surface.

[0015] According to the manufacturing method according to the present embodiment, it is possible to easily manufacture a laminated resin sheet (resin sheet with a protective film) that can effectively remove foreign matter and improve the yield rate of wiring formation.

[0016] <Step (I). Dust removal on the surface of the support on the release layer side> In the manufacturing method involved in the present embodiment, a support body having a release layer is used to manufacture a laminated resin sheet. The support body has: a release surface as a surface on the release layer side, and a back surface as a surface on the side opposite to the release surface. Generally speaking, for the support body, the release layer is provided as the outermost layer, so the release layer is exposed on the release surface of the support body. As such a support body, for example, a sheet having a substrate layer and a release layer formed on the substrate layer can be used.

[0017] The manufacturing method of the laminated resin sheet involved in the present embodiment includes a step (I) of contacting the first dust removal roller with the demoulding surface (i.e., the surface on the demoulding layer side) of the support. The first dust removal roller has a specific range of adhesion. Therefore, by contacting the first dust removal roller with the demoulding surface of the support, foreign matter attached to the demoulding surface can be moved to the first dust removal roller, so foreign matter can be removed from the demoulding surface. Therefore, foreign matter can be suppressed from mixing into the resin composition layer during the manufacturing process of the laminated resin sheet. Here, foreign matter "mixing into" the resin composition layer refers to the two aspects of foreign matter penetrating into the interior of the resin composition layer and foreign matter adhering to the surface of the resin composition layer.

[0018] Typically, the first dust removal roller has a circumferential surface as an adhesive surface, and the circumferential surface has an adhesive force in a specific range. The range of the adhesive force of the first dust removal roller is typically lower than 2.9 N / 100 mm. 2 , preferably 2.7N / 100mm 2 When the adhesion force is lower than the upper limit, wrinkles on the support body due to contact with the first dust removal roller can be suppressed, or part or all of the release layer can be suppressed from peeling off from the support body due to contact with the first dust removal roller. The lower limit is not particularly limited, but from the viewpoint of more effectively removing foreign matter from the release surface of the support body and significantly improving the yield of wiring formation, it is preferably 0.6N / 100mm 2 Above, preferably 1.0N / 100mm 2 above.

[0019] The adhesion force can be measured by pressing the measuring part of an adhesion force measuring instrument (for example, "A3-10N" manufactured by Ichishin Sangyo Co., Ltd., where the surface of the measuring part in contact with the adhesion surface is a flat surface formed of a metal such as stainless steel) against the adhesion surface, and taking the maximum load when the measuring part is pulled back and peeled off in a direction perpendicular to the adhesion surface. The specific measurement conditions can be the conditions described in the "Method for measuring the adhesion force of a dust removal roller" in the embodiment described later.

[0020] As the first dust removal roller, for example, a roller having an adhesive surface formed of a polymer compound (silicone rubber, non-silicone rubber, etc.) that exhibits adhesion to foreign matter can be used. The roller surface length of the first dust removal roller can be set according to the width of the support. In addition, the diameter of the first dust removal roller is not particularly limited as long as foreign matter attached to the demolding surface of the support can be removed. In addition, the first dust removal roller can be used alone or in combination of two or more.

[0021] The first dust removal roller may be a commercially available product. Examples of the first dust removal roller include polymer rubber dust removal rollers (RUS series, HSS series, LPS series, SRR series, etc.) manufactured by YanGo, dust removal rollers manufactured by TEKNEK, and dust removal rollers (CTR-S series) manufactured by CM Systems Co., Ltd.

[0022] The first dust removal roller and the support body are preferably in contact with each other at a contact pressure within an appropriate range. In one example, the contact pressure between the first dust removal roller and the support body is preferably in a range of 0.01 MPa to 0.1 MPa, and more preferably in a range of 0.02 MPa to 0.08 MPa.

[0023] There is no particular limitation on the method of bringing the first dust removal roller into contact with the demoulding surface of the support body. For example, the first dust removal roller can be brought into contact by rolling on the demoulding surface of a fixed support body. From the viewpoint of effective foreign matter removal, it is preferred that the first dust removal roller be brought into contact with the demoulding surface of the support body by transporting the support body in contact with the adhesion surface of the first dust removal roller. Usually, the first dust removal roller has an adhesion surface on its circumferential surface, so it is preferred to transport the support body in contact with the demoulding surface of the circumferential surface of the first dust removal roller. The first dust removal roller can rotate when in contact with the demoulding surface of the support body. At this time, the first dust removal roller can rotate following the transport of the support body, and can be driven to rotate by a driving force given by a driving device such as a motor. Generally speaking, the transport direction of the support body is the same as the rotation direction of the first dust removal roller.

[0024] Step (I) may include removing foreign matter attached to the first dust removal roller as required. By removing foreign matter attached to the first dust removal roller, it is possible to suppress the accumulation of foreign matter on the first dust removal roller and the decrease in the adhesion of the first dust removal roller, and it is possible to stably and effectively remove foreign matter attached to the demoulding surface of the support body for a long time.

[0025] There is no limitation on the method of removing foreign matter from the first dust removal roller. For example, the first adsorption roller used for removing foreign matter from the first dust removal roller can be brought into contact with the first dust removal roller, so that the foreign matter attached to the first dust removal roller is moved to the first adsorption roller, thereby removing the foreign matter from the first dust removal roller. To give a specific example, a first adsorption roller having an adhesive surface on its circumferential surface can be prepared, and the adhesive surface of the first adsorption roller can be brought into contact with the circumferential surface of the first dust removal roller to remove the foreign matter from the first dust removal roller. The first adsorption roller can rotate when in contact with the first dust removal roller. At this time, the first adsorption roller can rotate following the rotation of the first dust removal roller, and can be driven to rotate by a driving force given by a driving device such as a motor.

[0026] As the first adsorption roller, for example, a roller having an adhesive layer that allows dust and other foreign matter to be adsorbed on the circumferential surface can be used. From the viewpoint of effectively removing foreign matter from the first dust removal roller, it is preferred that the adhesion of the first adsorption roller is greater than that of the first dust removal roller. The first adsorption roller can be a commercially available product, for example, the dust transfer adhesive tape roller "GaplessTMULT" and "GaplessTMSRR" manufactured by YanGo, and the adhesive roller manufactured by TEKNEK. The first adsorption roller can be used alone or in combination of two or more.

[0027] The removal of foreign matter from the release surface of the support body using the first dust removal roller and the removal of foreign matter from the first dust removal roller using the first suction roller may be performed simultaneously or may not be performed simultaneously.

[0028] [Step (II). Formation of resin composition layer] The manufacturing method of the laminated resin sheet involved in the present embodiment includes a step (II) of forming a resin composition layer on the demoulding surface (i.e., the surface on the demoulding layer side) of a support. In the step (II), a resin composition layer is formed on the demoulding surface of the support from which foreign matter has been removed by contact with the first dust removal roller. Thus, the step (II) is performed after the step (I). By the step (II), a resin sheet having a support and a resin composition layer formed on the demoulding surface of the support is obtained.

[0029] The method for forming the resin composition layer is not limited. For example, by laminating a pre-prepared resin composition layer on the release surface of the support, the resin composition layer can be formed on the release surface. From the viewpoint of significantly improving the yield rate of wiring formation by reducing the chance of foreign matter adhesion, it is preferred to form the resin composition layer by a method including applying a liquid curable resin composition to the release surface of the support.

[0030] For example, when the curable resin composition is in a liquid state under the coating environment, the curable resin composition can be applied to the demoulding surface of the support. In addition, for example, the non-volatile component of the curable resin composition and the solvent can be mixed to obtain a liquid curable resin composition, and the obtained liquid curable resin composition can be applied to the demoulding surface of the support. Hereinafter, the liquid curable resin composition containing the solvent is sometimes referred to as "resin varnish". By applying the curable resin composition, a resin composition layer can be formed.

[0031] The method for applying the liquid curable resin composition is not limited, and for example, the composition can be applied using a coating device such as a die coater.

[0032] Preferably, the demoulding surface of the support is in a non-contact state that does not contact other components during the period from the removal of foreign matter by step (I) to the provision of the resin composition layer by step (II). Thus, when the laminated resin sheet is manufactured while the support is transported by a predetermined transport path, preferably, no component (e.g., a transport roller, etc.) that contacts the demoulding surface of the support is provided in the interval between the first dust removal roller and the coating device of the transport path.

[0033] Step (II) may include drying after application of the liquid curable resin composition as required. Generally, when a resin varnish containing a solvent is applied, step (II) includes drying after application. By drying, the solvent contained in the resin composition layer can be removed.

[0034] Drying can be carried out by methods such as heating and hot air blowing. The drying conditions are not particularly limited, and the drying is carried out under the conditions that the content of the solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. For example, when a resin varnish containing 30% to 60% by mass of a solvent is applied, it can be dried at 50° C. to 150° C. for 3 minutes to 10 minutes, but it also varies depending on the boiling point of the solvent.

[0035] By step (II), a resin composition layer can be formed on the demoulding surface of the support. The resin composition layer comprises a curable resin composition, preferably only a curable resin composition. The thickness of the resin composition layer is preferably set according to the thickness of the insulating layer formed using the resin composition layer. If a specific example is given, the thickness of the resin composition layer is preferably less than 200 μm, more preferably less than 70 μm, and particularly preferably less than 50 μm. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be more than 5 μm, more than 10 μm, etc.

[0036] <Step (III). Dust removal on first surface of protective film> The protective film used in the production method according to the present embodiment has a first surface and a second surface which is a surface opposite to the first surface. The first surface of the protective film corresponds to a surface to be bonded to the resin composition layer.

[0037] The manufacturing method of the laminated resin sheet involved in the present embodiment includes a step (III) of contacting the second dust removal roller with the first surface of the protective film. The second dust removal roller has a specific range of adhesion. Thus, by contacting the second dust removal roller with the first surface of the protective film, foreign matter attached to the first surface can be moved to the second dust removal roller, so foreign matter can be removed from the first surface. Therefore, foreign matter can be suppressed from mixing into the resin composition layer during the manufacturing process of the laminated resin sheet.

[0038] Typically, the second dust removal roller has a circumferential surface as an adhesive surface, and the circumferential surface has an adhesive force in a specific range. The adhesive force of the second dust removal roller is typically less than 2.9 N / 100 mm. 2 , preferably 2.7N / 100mm 2 When the adhesion force is lower than the upper limit, wrinkles of the protective film due to contact with the second dust removal roller can be suppressed. The lower limit is not particularly limited, but from the perspective of more effectively removing foreign matter from the first surface of the protective film and significantly improving the yield of wiring formation, 0.6 N / 100 mm is preferred. 2 Above, preferably 1.0N / 100mm 2 The adhesion of the second dust removal roller can be measured by the same method as the adhesion of the first dust removal roller.

[0039] As the second dust removal roller, for example, a roller similar to the first dust removal roller can be used. The roller surface length of the second dust removal roller can be set according to the width of the protective film. In addition, the diameter of the second dust removal roller is not particularly limited as long as it can remove foreign matter attached to the first surface of the protective film. In addition, the second dust removal roller can be used alone or in combination of two or more.

[0040] The second dust removal roller and the protective film are preferably in contact with a contact pressure within an appropriate range. In one example, the contact pressure range between the second dust removal roller and the protective film can be the same as the contact pressure range between the first dust removal roller and the support.

[0041] There is no particular limitation on the method of contacting the second dust removal roller with the first surface of the protective film. For example, the second dust removal roller can be made to roll on the first surface of the fixed protective film to make contact. From the viewpoint of effective foreign matter removal, it is preferred to make the second dust removal roller make contact with the first surface of the protective film by transporting the protective film in contact with the adhesive surface of the second dust removal roller. Usually, the second dust removal roller has an adhesive surface on its circumferential surface, so it is preferred to transport the protective film in contact with the first surface of the circumferential surface of the second dust removal roller. The second dust removal roller can rotate when in contact with the first surface of the protective film. At this time, the second dust removal roller can rotate following the transportation of the protective film, and can be driven to rotate by a driving force given by a driving device such as a motor. Generally speaking, the transportation direction of the protective film is the same as the rotation direction of the second dust removal roller.

[0042] Step (III) may include removing foreign matter attached to the second dust removal roller as needed. By removing foreign matter attached to the second dust removal roller, it is possible to suppress the accumulation of foreign matter on the second dust removal roller and the decrease in the adhesion of the second dust removal roller, and it is possible to stably and effectively remove foreign matter attached to the first surface of the protective film for a long time.

[0043] There is no limitation on the method of removing foreign matter from the second dust removal roller. For example, the foreign matter can be removed from the second dust removal roller by bringing the second adsorption roller used for removing foreign matter from the second dust removal roller into contact with the second dust removal roller. To give a specific example, the foreign matter can be removed from the second dust removal roller in the same manner as the removal of foreign matter from the first dust removal roller by bringing the adhesive surface of the second adsorption roller having an adhesive surface on the circumferential surface into contact with the circumferential surface of the second dust removal roller. It is preferred that the adhesion force of the second adsorption roller is greater than that of the second dust removal roller. As the second adsorption roller, for example, the same roller as the first adsorption roller can be used. The removal of foreign matter from the first surface of the self-protective film using the second dust removal roller and the removal of foreign matter from the second dust removal roller using the second adsorption roller may be performed simultaneously or at different times.

[0044] <Step (IV). Bonding of the resin composition layer and the first surface of the protective film> The manufacturing method involved in the present embodiment includes a step (IV) of bonding a resin composition layer to the first face of a protective film. Specifically, the resin sheet obtained by the step (II) is laminated with a protective film from which foreign matter has been removed in the step (III) from the first face, so that the resin composition layer is bonded to the first face of the protective film. Through this step (IV), a laminated resin sheet (resin sheet with a protective film) having a support, a resin composition layer and a protective film in sequence in the thickness direction can be obtained. In the laminated resin sheet obtained, usually, the resin composition layer is in direct contact with the protective film. Here, the "direct" contact of two components means that there is no other component between the two components in contact.

[0045] Usually, the resin sheet and the protective film are sandwiched between appropriate pressing members arranged in pairs, and at least one pressing member is pressed in the direction of the other pressing member, thereby bonding. From the viewpoint of achieving continuous lamination and improving the manufacturing efficiency of the laminated resin sheet, it is preferred to use a pressing roller arranged in a rotatable manner as the pressing member. As such a pressing roller, for example, a rubber roller, a metal roller, a composite material roller formed by a metal core material and a rubber lining, etc. can be cited.

[0046] The crimping pressure between the pressing members (the pressure applied to the resin sheet and the protective film) is not particularly limited as long as the laminated resin sheet can be manufactured. For example, it can be set in the range of 0.1MPa to 3MPa, and a range of 0.2MPa to 2.5MPa is preferred, and a range of 0.3MPa to 2MPa is more preferred.

[0047] The temperature during bonding is not particularly limited as long as the laminated resin sheet can be manufactured, and may be room temperature (about 25° C.) or heated. From the viewpoint of making the resin sheet and the protective film sufficiently close to each other, bonding is preferably performed under heated conditions, and the temperature may be, for example, in the range of 50° C. to 130° C., preferably in the range of 60° C. to 120° C.

[0048] Preferably, the first surface of the protective film is in a non-contact state that is not in contact with other components during the period from the removal of foreign matter in step (III) to the bonding with the resin composition layer in step (IV). Therefore, when the protective film is transported through a predetermined transport path while the laminated resin sheet is manufactured, it is preferred that no component (e.g., a transport roller, etc.) that contacts the first surface of the protective film is provided in the interval between the second dust removal roller and the pressing member of the transport path.

[0049] <Step (V). Dust removal on the surface of the support body opposite to the release layer> The manufacture method of the laminated resin sheet material involved in the present embodiment preferably includes the process (V) of contacting the back side (that is, the face on the side opposite to the release layer) of the 3rd dust removal roller with the support body. The 3rd dust removal roller has adhesion. Thus, by contacting the back side of the 3rd dust removal roller with the support body, foreign matter can be removed from the back side. Therefore, the foreign matter on the back side of the support body can be suppressed from being mixed into the resin composition layer in the manufacturing process (particularly the lamination process of inner layer wiring and resin sheet) of the circuit substrate using the laminated resin sheet material, so the yield rate formed by the wiring can be effectively improved.

[0050] Typically, the third dust removal roller has a peripheral surface as an adhesive surface, and the peripheral surface has adhesive force. From the viewpoint of obtaining the same effect as the first dust removal roller, the range of the adhesive force of the third dust removal roller may be the same as the range of the adhesive force of the first dust removal roller. The adhesive force of the third dust removal roller may be measured by the same method as the adhesive force of the first dust removal roller. As the third dust removal roller, for example, a roller similar to the first dust removal roller may be used. The third dust removal roller may be used alone or in combination of two or more.

[0051] The third dust removal roller and the support body are preferably in contact with a contact pressure within an appropriate range. In one example, the contact pressure range between the third dust removal roller and the support body can be the same as the contact pressure range between the first dust removal roller and the support body.

[0052] The method for bringing the third dust removing roller into contact with the back surface of the support is not particularly limited, and for example, the same method as the method for bringing the first dust removing roller into contact with the release surface of the support may be used.

[0053] Step (V) may be performed before step (I), after step (I), or simultaneously with step (I). From the viewpoint of effectively suppressing the mixing of foreign matter into the resin composition layer, step (V) is preferably performed before step (IV), more preferably before step (II).

[0054] Step (V) may include removing foreign matter attached to the third dust removal roller as needed. By removing foreign matter attached to the third dust removal roller, it is possible to suppress the accumulation of foreign matter on the third dust removal roller and the decrease in the adhesion of the third dust removal roller, and it is possible to stably and effectively remove foreign matter attached to the back side of the support body for a long time.

[0055] There is no limitation on the method of removing foreign matter from the third dust removal roller. For example, the foreign matter can be removed from the third dust removal roller by bringing the third adsorption roller used for removing foreign matter from the third dust removal roller into contact with the third dust removal roller. To give a specific example, the foreign matter can be removed from the third dust removal roller in the same manner as the removal of foreign matter from the first dust removal roller by bringing the adhesive surface of the third adsorption roller having an adhesive surface on the circumferential surface into contact with the circumferential surface of the third dust removal roller. It is preferred that the adhesion force of the third adsorption roller is greater than that of the third dust removal roller. As the third adsorption roller, for example, the same roller as the first adsorption roller can be used. The removal of foreign matter from the back side of the self-supporting body using the third dust removal roller and the removal of foreign matter from the third dust removal roller using the third adsorption roller may be performed simultaneously or at different times.

[0056] <Step (VI). Dust removal on the second surface of the protective film> The manufacture method of the laminated resin sheet material involved in the present embodiment preferably includes the operation (VI) of contacting the second side (that is, the side opposite to the first side) of the 4th dust removal roller with the protective film. The 4th dust removal roller has adhesion. Thus, by contacting the 4th dust removal roller with the second side of the protective film, foreign matter can be removed from the second side. Therefore, the foreign matter on the second side of the protective film can be suppressed from being mixed into the resin composition layer in the manufacturing process (particularly the lamination process of inner layer wiring and resin sheet) of the circuit substrate using the laminated resin sheet material, so the yield rate formed by the wiring can be effectively improved.

[0057] Typically, the fourth dust removal roller has a peripheral surface as an adhesive surface, and the peripheral surface has adhesive force. From the viewpoint of obtaining the same effect as the second dust removal roller, the range of the adhesive force of the fourth dust removal roller may be the same as the range of the adhesive force of the second dust removal roller. The adhesive force of the fourth dust removal roller may be measured by the same method as the adhesive force of the first dust removal roller. As the fourth dust removal roller, for example, a roller similar to the second dust removal roller may be used. The fourth dust removal roller may be used alone or in combination of two or more.

[0058] The fourth dust removal roller and the protective film are preferably in contact with each other at a contact pressure within an appropriate range. In one example, the contact pressure range between the fourth dust removal roller and the protective film can be the same as the contact pressure range between the second dust removal roller and the protective film.

[0059] The method for bringing the fourth dust removal roller into contact with the second surface of the protective film is not particularly limited. For example, the same method as the method for bringing the second dust removal roller into contact with the first surface of the protective film may be used.

[0060] Step (VI) may be performed before step (III), after step (III), or simultaneously with step (III). From the viewpoint of effectively suppressing incorporation of foreign matter into the resin composition layer, step (VI) is preferably performed before step (IV).

[0061] Step (VI) may include removing foreign matter attached to the fourth dust removal roller as needed. By removing foreign matter attached to the fourth dust removal roller, it is possible to suppress the accumulation of foreign matter on the fourth dust removal roller and the decrease in the adhesion of the fourth dust removal roller, and it is possible to stably and effectively remove foreign matter attached to the second surface of the protective film for a long time.

[0062] There is no limitation on the method of removing foreign matter from the fourth dust removal roller. For example, the foreign matter can be removed from the fourth dust removal roller by bringing the fourth adsorption roller used for removing foreign matter from the fourth dust removal roller into contact with the fourth dust removal roller. To give a specific example, the foreign matter can be removed from the fourth dust removal roller in the same manner as the removal of foreign matter from the first dust removal roller by bringing the adhesive surface of the fourth adsorption roller having an adhesive surface on the circumferential surface into contact with the circumferential surface of the fourth dust removal roller. It is preferred that the adhesion force of the fourth adsorption roller is greater than that of the fourth dust removal roller. As the fourth adsorption roller, for example, the same roller as the first adsorption roller can be used. The removal of foreign matter from the second surface of the self-protective film using the fourth dust removal roller and the removal of foreign matter from the fourth dust removal roller using the fourth adsorption roller may be performed simultaneously or at different times.

[0063] <Other matters related to the method for producing a laminated resin sheet> The method for producing a laminated resin sheet according to the present embodiment can be implemented using a single-sheet (leaf) support and a single-sheet protective film. When a single-sheet support and a single-sheet protective film are used, a single-sheet laminated resin sheet can be produced.

[0064] From the viewpoint of efficiently manufacturing laminated resin sheets, it is preferred to use a long-sized support and a long-sized protective film to manufacture a long-sized laminated resin sheet. A certain component is "long-sized" means that the component has a length that can be rolled into a roll, for example, it means that it has a length of more than 10 times relative to the width. The upper limit of the length is not particularly limited, for example, it can be less than 100,000 times relative to the width. By using a long-sized support and a long-sized protective film, a long-sized laminated resin sheet can be efficiently manufactured by a roll-to-roll method.

[0065] When using a long support and a protective film, the above process is usually carried out while continuously conveying the support and the protective film in the long side direction. In this case, the conveying speed of each member such as the support, the protective film, the resin sheet and the laminated resin sheet is not particularly limited, and can be, for example, in the range of 0.1 m / min to 50 m / min.

[0066] The manufacturing method of the laminated resin sheet involved in this embodiment can be combined with the above-mentioned steps to further include any steps. For example, the manufacturing method of the laminated resin sheet can include the step of winding up the laminated resin sheet obtained for recycling. The laminated resin sheet can be obtained by winding up the laminated resin sheet, and the laminated resin sheet can be stored and transported in the state of the coil.

[0067] <First specific example of the manufacturing method> Hereinafter, a first example of the method for producing a laminated resin sheet according to the present embodiment will be described with reference to the drawings. Figure 11 is a front view schematically showing a manufacturing apparatus 1 for a laminated resin sheet 50 according to a first example of the present invention. Figure 1 As shown, the manufacturing apparatus 1 is configured to form a resin composition layer 20 on a long support 10 having a base material layer 11 and a release layer 12 to obtain a long resin sheet 30 , and to laminate the resin sheet 30 and a long protective film 40 to obtain a laminated resin sheet 50 .

[0068] The manufacturing device 1 comprises: a support body dust removing section 100 arranged in a manner to remove foreign matter from a support body 10, a layer forming section 200 arranged in a manner to form a resin composition layer 20 on a demolding surface 10U of the support body 10, a protective film dust removing section 300 arranged in a manner to remove foreign matter from a protective film 40, and a laminating section 400 arranged in a manner to bond the resin composition layer 20 of a resin sheet 30 to a first surface 40D of a protective film 40.

[0069] The support dust removal section 100 includes: a first dust removal roller 110 and a third dust removal roller 120 which are arranged to rotate in the same rotation direction as the conveying direction of the support 10. The first dust removal roller 110 and the third dust removal roller 120 have adhesive surfaces with appropriate adhesive force on their peripheral surfaces 110S and 120S, respectively. In addition, in this example, the first dust removal roller 110 and the third dust removal roller 120 are arranged to face each other so that the support 10 can be conveyed between these first dust removal rollers 110 and the third dust removal rollers 120. The first dust removal roller 110 and the third dust removal roller 120 are forced in a direction of approaching each other with appropriate contact pressure in a manner that the peripheral surface 110S of the first dust removal roller 110 can contact the demolding surface 10U of the support 10, and the peripheral surface 120S of the third dust removal roller 120 can contact the back surface 10D of the support 10.

[0070] The layer forming unit 200 includes a coating device 210 and a drying device 220. The coating device 210 is provided so as to be able to apply a liquid curable resin composition 21 to the release surface 10U of the support 10. In addition, the drying device 220 is provided so as to be able to dry the resin composition layer 20 formed on the release surface 10U of the support 10 and remove the solvent. In this example, an example in which an oven is provided so as to allow the support 10 to pass is shown and described as the drying device 220.

[0071] The protective film dust removal unit 300 includes a second dust removal roller 310 and a fourth dust removal roller 320 which are arranged to rotate in the same rotation direction as the conveying direction of the protective film 40. The second dust removal roller 310 and the fourth dust removal roller 320 have adhesive surfaces having appropriate adhesive force on their peripheral surfaces 310S and 320S, respectively. In addition, in this example, the second dust removal roller 310 and the fourth dust removal roller 320 are arranged to face each other so that the protective film 40 can be conveyed between these second dust removal rollers 310 and the fourth dust removal roller 320. In addition, the second dust removal roller 310 and the fourth dust removal roller 320 are forced in a direction of approaching each other with appropriate contact pressure in a manner that the peripheral surface 310S of the second dust removal roller 310 can contact the first surface 40D of the protective film 40, and the peripheral surface 320S of the fourth dust removal roller 320 can contact the second surface 40U of the protective film 40.

[0072] The laminating unit 400 includes a pair of pressing rollers 410 and 420 that are rotatable in the same rotation direction as the conveying direction of the resin sheet 30 and the protective film 40, and a chamber 430 that accommodates these pressing rollers 410 and 420. The pressing rollers 410 and 420 are disposed facing each other so that the resin sheet 30 and the protective film 40 can be conveyed between these pressing rollers 410 and 420. In addition, a heater (not shown) is provided in the chamber 430 so that the temperature in the chamber 430 can be appropriately adjusted.

[0073] In the manufacturing method of the laminated resin sheet 50 using the manufacturing device 1, the support body 10 is transported and supplied to the support body dust removal section 100. The support body 10 supplied to the support body dust removal section 100 is transported in a manner passing between the first dust removal roller 110 and the third dust removal roller 120. When passing between the first dust removal roller 110 and the third dust removal roller 120, the peripheral surface 110S of the first dust removal roller 110 contacts the demolding surface 10U of the support body 10, and the peripheral surface 120S of the third dust removal roller 120 contacts the back side 10D of the support body 10 (steps (I) and (V)). As a result, foreign matter (not shown) on the demolding surface 10U and the back side 10D of the support body 10 is removed. Then, the support body 10 is sent to the layer forming section 200.

[0074] The support 10 sent to the layer forming unit 200 is supplied to the coating device 210. The coating device 210 applies a curable resin composition 21 to the demoulding surface 10U of the support 10 to form a resin composition layer 20 (step (II)). Then, the support 10 and the resin composition layer 20 are sent to the drying device 220, and the resin composition layer 20 is dried by the drying device 220. In this example, an example of drying the resin composition layer 20 by spending an appropriate time passing through an oven set to an appropriate temperature as the drying device 220 is shown. The solvent is removed from the resin composition layer 20 by drying, and a resin sheet 30 having the support 10 and the resin composition layer 20 is obtained. The resin sheet 30 is sent to the laminating unit 400.

[0075] In addition, in the manufacturing method of the laminated resin sheet 50 using the manufacturing device 1, the protective film 40 is separated from the support body 10 and transported to the protective film dust removal section 300. The protective film 40 supplied to the protective film dust removal section 300 is transported in a manner passing between the second dust removal roller 310 and the fourth dust removal roller 320. When passing between the second dust removal roller 310 and the fourth dust removal roller 320, the peripheral surface 310S of the second dust removal roller 310 contacts the first surface 40D of the protective film 40, and the peripheral surface 320S of the fourth dust removal roller 320 contacts the second surface 40U of the protective film 40 (process (III) and (VI)). As a result, foreign matter (not shown) on the first surface 40D and the second surface 40U of the protective film 40 is removed. Then, the protective film 40 is sent to the lamination section 400.

[0076] The resin sheet 30 and the protective film 40 sent to the laminating unit 400 enter the chamber 430 and are conveyed in a manner passing between the pressing rollers 410 and 420. When passing between the pressing rollers 410 and 420, the resin sheet 30 and the protective film 40 are pressed by the pressing rollers 410 and 420 in a state where the resin composition layer 20 of the resin sheet 30 and the first surface 40D of the protective film 40 face each other. Thus, the resin sheet 30 and the protective film 40 are laminated in a manner that the resin composition layer 20 and the first surface 40D of the protective film 40 are bonded to each other, and a long laminated resin sheet 50 having a support 10, a resin composition layer 20, and a protective film 40 is obtained in this order.

[0077] <Second specific example of the manufacturing method> Hereinafter, a second example of the method for producing the laminated resin sheet according to the present embodiment will be described with reference to the drawings. Figure 2 2 is a front view schematically showing a manufacturing apparatus 2 for a laminated resin sheet 50 according to a second example of the present invention. Figure 2As shown, the manufacturing apparatus 2 according to this example is provided with a support body dust removing unit 500 and a protective film dust removing unit 600 instead of the support body dust removing unit 100 and the protective film dust removing unit 300 , and is configured similarly to the manufacturing apparatus 1 according to the first example except for this.

[0078] The support body dust removal unit 500 includes a first dust removal roller 510 and a third dust removal roller 520. The first dust removal roller 510 and the third dust removal roller 520 in this example are arranged in the same manner as the first dust removal roller 110 and the third dust removal roller 120 involved in the first example, except that the first dust removal roller 510 and the third dust removal roller 520 are arranged at different positions in the conveying direction of the support body 10.

[0079] The first dust removal roller 510 is provided so that the support body 10 can be transported by being wound around the peripheral surface 510S of the first dust removal roller 510. Therefore, in this example, the demolding surface 10U of the transported support body 10 can contact the peripheral surface 510S of the first dust removal roller 510 at a contact pressure corresponding to the transport tension of the support body 10.

[0080] In addition, the third dust roller 520 is arranged so that the support body 10 can be wound around the peripheral surface 520S of the third dust roller 520 for transportation. Therefore, in this example, the back surface 10D of the transported support body 10 can contact the peripheral surface 520S of the third dust roller 520 according to the contact pressure corresponding to the transport tension of the support body 10.

[0081] The protective film dust removal unit 600 includes a second dust removal roller 610 and a fourth dust removal roller 620. The second dust removal roller 610 and the fourth dust removal roller 620 in this example are arranged in the same manner as the second dust removal roller 310 and the fourth dust removal roller 320 involved in the first example, except that the second dust removal roller 610 and the fourth dust removal roller 620 are arranged at different positions in the conveying direction of the protective film 40.

[0082] The second dust roller 610 is arranged so that the protective film 40 can be wound around the circumferential surface 610S of the second dust roller 610 for transportation. Therefore, in this example, the first surface 40D of the transported protective film 40 can contact the circumferential surface 610S of the second dust roller 610 at a contact pressure corresponding to the transport tension of the protective film 40.

[0083] In addition, the fourth dust roller 620 is arranged so that the protective film 40 can be wound around the peripheral surface 620S of the fourth dust roller 620 for transportation. Therefore, in this example, the second surface 40U of the transported protective film 40 can contact the peripheral surface 620S of the fourth dust roller 620 at a contact pressure corresponding to the transport tension of the protective film 40.

[0084] In the manufacturing method of the laminated resin sheet 50 using the manufacturing device 2, the support 10 is supplied to the support dust removal section 500 and transported via the first dust removal roller 510 and the third dust removal roller 520. When the support 10 supplied to the support dust removal section 500 is transported in contact with the peripheral surface 510S of the first dust removal roller 510, foreign matter (not shown) is removed from the demolding surface 10U (process (I)), and when the support 10 is transported in contact with the peripheral surface 520S of the third dust removal roller 520, foreign matter (not shown) is removed from the back surface 10D (process (V)). Then, the support 10 is sent to the layer forming section 200. Next, as in the first example, the resin composition layer 20 is formed on the demolding surface 10U of the support 10 in the layer forming section 200 to obtain the resin sheet 30 (process (II)), and the resin sheet 30 is sent to the laminating section 400.

[0085] In addition, in the manufacturing method of the laminated resin sheet 50 using the manufacturing device 2, the protective film 40 is supplied to the protective film dust removal unit 600 and transported via the second dust removal roller 610 and the fourth dust removal roller 620. When the protective film 40 supplied to the protective film dust removal unit 600 is transported in contact with the peripheral surface 610S of the second dust removal roller 610, foreign matter (not shown) is removed from the first surface 40D (process (III)), and when the protective film 40 is transported in contact with the peripheral surface 620S of the fourth dust removal roller 620, foreign matter (not shown) is removed from the second surface 40U (process (VI)). Then, the protective film 40 is sent to the laminating unit 400.

[0086] The resin sheet 30 and the protective film 40 sent to the lamination section 400 are stacked in the chamber 430 by pressing rollers 410 and 420 in a manner such that the resin composition layer 20 is bonded to the first surface 40D of the protective film 40, similarly to the first example, to obtain a long laminated resin sheet 50 having a support body 10, a resin composition layer 20 and a protective film 40 in sequence.

[0087] <Manufactured laminated resin sheet> By the above-mentioned manufacturing method, a laminated resin sheet (resin sheet with a protective film) can be manufactured. The laminated resin sheet is provided with a resin composition layer formed on the demoulding surface of the support. Foreign matter is removed from the demoulding surface by contacting with the first dust removal roller, so the foreign matter attached to the demoulding surface can be suppressed from mixing into the resin composition layer.

[0088] In addition, the resin composition layer of the laminated resin sheet is in direct contact with the first surface of the protective film. Foreign matter is removed from the first surface of the protective film by contact with the second dust removal roller. Thus, foreign matter attached to the first surface can be prevented from mixing into the resin composition layer.

[0089] In the past, there have been proposals for removing foreign matter from the demoulding surface of the support and the first surface of the protective film, but in these conventional technologies, a non-contact device using air blowing or the like is generally used to remove foreign matter. In contrast, in the present embodiment, a contact device such as a dust removal roller is used to remove foreign matter, so foreign matter can be removed effectively. In particular, the method involved in the present embodiment is excellent in that foreign matter as small as 100 μm or less (preferably about tens of μm or less) can be effectively removed.

[0090] Because foreign matter can be suppressed from mixing into the resin composition layer in this way, when the laminated resin sheet manufactured in the present embodiment is used to manufacture the circuit substrate, the yield rate of wiring formation can be improved. Specifically, foreign matter can be suppressed from penetrating into the gap between wirings rather than intentionally causing the insulation performance between wirings to decrease. In addition, the shape deformation of the wiring caused by forming a part of the wiring layer on the foreign matter, or the wiring defect caused by the part on the foreign matter, can also be suppressed. Thus, the generation of wiring that cannot function as expected can be suppressed, so the desired wiring can be formed with a high yield rate.

[0091] In addition, the dust removal roller used in this embodiment has an appropriate range of adhesion. As a result, it is possible to prevent the transportation of the support body and the protective film from being disturbed due to excessive adhesion. Therefore, it is possible to prevent wrinkles from being generated on the support body and the protective film, so that good transportation characteristics can be obtained. In addition, in particular, by having the first dust removal roller have an appropriate range of adhesion, it is possible to prevent the release layer of the support body from adhering to the first dust removal roller and being removed from the support body. As a result, the support body can be smoothly peeled off from the insulating layer during the manufacture of the circuit substrate. Therefore, the manufacture of the circuit substrate can be simplified, and the yield rate of the circuit substrate can be improved.

[0092] When the foreign matter on the back side of the support is removed by the third dust removal roller, the foreign matter on the back side can be suppressed from mixing into the resin composition layer. In addition, when the foreign matter on the second side of the protective film is removed by the fourth dust removal roller, the foreign matter on the second side can be suppressed from mixing into the resin composition layer. Thus, the foreign matter can be effectively suppressed from mixing into the resin composition layer, so the yield rate of wiring formation can be further improved.

[0093] The laminated resin sheet involved in this embodiment can be preferably used for the formation of a circuit substrate. In a circuit substrate, the laminated resin sheet is generally used for the formation of an insulating layer. Specifically, the laminated resin sheet is preferably used to solidify a resin composition layer to form an insulating layer. Since foreign matter can be suppressed from mixing into the resin composition layer, if the laminated resin sheet involved in this embodiment is used, the yield rate of the wiring formed on the insulating layer can be improved.

[0094] In particular, compared with a general technique for removing foreign matter from a sheet, the technique according to the present embodiment that can suppress the mixing of foreign matter into a resin composition layer in a laminated resin sheet for forming an insulating layer of a circuit board has the following superior significance.

[0095] When a wiring layer is formed on a sheet, generally speaking, foreign matter on the surface of the sheet may become an obstacle to the formation of wiring. Therefore, it is usually attempted to remove foreign matter on the surface of the sheet. However, the resin composition layer used for insulating layer formation needs to fill the concave-convex present on the surface of the inner substrate without gaps, so it is required to be soft to the degree of fluidity at an appropriate temperature. If such a soft resin composition layer is used to attempt to remove foreign matter using a contact device, the resin composition layer is likely to be deformed or even damaged. Therefore, if the purpose is taken into account, it is difficult to use a contact device to remove foreign matter on the surface of the resin composition layer.

[0096] In addition, when a resin composition layer is used to form an insulating layer of a circuit substrate, not only foreign matter attached to the surface of the resin composition layer, but also foreign matter inside the resin composition layer may become an obstacle to the formation of wiring. Specifically, when manufacturing a circuit substrate, the resin composition layer exposed by peeling off the protective film is usually stacked with the inner substrate, and a resin composition layer is formed on the inner substrate. Then, after the resin composition layer is cured to obtain an insulating layer, wiring is formed on the insulating layer. At this time, the resin composition layer provided on the inner substrate can be processed chemically or physically. As processing, for example: curing treatment by reacting a curable resin with heat or light; hole forming treatment using a drill, laser, etc.; decontamination treatment for removing resin residues; plating treatment for wiring formation; etc. If these processing treatments are performed, foreign matter present inside the resin composition layer may be exposed to the surface. Moreover, foreign matter exposed to the surface like this may become an obstacle to the formation of wiring.

[0097] In the past, it was believed that foreign matter inside the resin composition layer was contained in the resin composition as the raw material of the resin composition layer. However, the inventors have found that even when the resin composition is fully removed by filtration, the yield rate of wiring formation may be reduced due to foreign matter. It has also been found that foreign matter as small as that which was not considered a problem in the past may be mixed into the resin composition layer during the manufacturing process of the laminated resin sheet, and the reduction in yield caused by such small foreign matter mixed in will be manifested due to the miniaturization and high density of wiring.

[0098] In contrast, by using the laminated resin sheet manufactured by the above-mentioned manufacturing method, it is possible to effectively exclude small foreign matter that may cause a decrease in the yield rate of wiring formation while using a resin composition layer that satisfies the characteristics required for forming an insulating layer. Therefore, by using the laminated resin sheet involved in this embodiment, it is possible to improve the yield rate of wiring formation that was difficult to achieve with the conventional technology, and thus it is suitable for the insulating layer of a circuit board.

[0099] <Description of Support Body> The support used in the present embodiment is described in detail below. The support has a release layer. For the support, the release layer is provided as the outermost layer, so the release layer is exposed to the outermost surface of the support. In addition, a resin composition layer is formed on the surface of the release layer. Usually, the support has a substrate layer, and a release layer is provided on the substrate layer.

[0100] As the substrate layer, for example, thermoplastic resin film, metal foil, release paper can be mentioned, preferably thermoplastic resin film and metal foil. When a thermoplastic resin film is used as the substrate layer, as the thermoplastic resin contained in the substrate layer, for example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic polymers such as polycarbonate (PC), polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. can be mentioned. Among them, preferably polyethylene terephthalate and polyethylene naphthalate, especially preferably low-priced polyethylene terephthalate.

[0101] When a metal foil is used as the substrate layer, examples of the metal foil include copper foil and aluminum foil, preferably copper foil. The copper foil may be a foil made of a single metal of copper or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0102] The surface of the base material layer on the release layer side may be subjected to surface treatment such as matte treatment, corona discharge treatment, antistatic treatment, etc.

[0103] The thickness of the substrate layer is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm.

[0104] The release layer is a layer having the function of reducing the force (peel strength) required for peeling off the support. Specifically, due to the function of the release layer, the force required for peeling off the support in which the release layer is in contact with the resin composition layer or the insulating layer can be reduced compared to the force required for peeling off the base material layer in direct contact with the resin composition layer or the insulating layer which is a cured product thereof.

[0105] The release layer is usually formed by a release agent. As a release agent, for example, a resin can be used. In general, the resin as a release agent includes a release component as a component that can impart release properties, and can further include any component other than the release component as required. Thus, in one example, the release layer includes a release component, and can further include any component as required. In addition, in another example, the release layer can be combined by a part or all of the components contained in the release agent through reactions such as polymerization reactions and cross-linking reactions, and the release agent is solidified and formed. In this example, the release layer can include one or more components selected from the release component and any component contained in the release agent, and their reaction products (for example, polymers). As a release component, a compound that can play a role in reducing the surface free energy of the release layer or reducing the static friction coefficient of the release layer can be used.

[0106] Examples of the release component include long-chain alkyl group-containing resins, olefin resins, fluorine compounds, and wax compounds.

[0107] The resin containing a long-chain alkyl group means a resin containing a long-chain alkyl group. In addition, the long-chain alkyl group means an alkyl group having a carbon number of generally 12 or more, preferably 16 or more. Resins containing a long carbon chain in the molecule like this generally have high hydrophobicity, so they can exert high demolding properties. The upper limit of the carbon number of the long-chain alkyl group can be, for example, 25 or less. As specific examples of resins containing long-chain alkyl groups, long-chain alkyl acrylates such as tetradecyl acrylate and octadecyl acrylate, long-chain alkyl methacrylates such as tetradecyl methacrylate and octadecyl methacrylate, and (meth) acrylic resins containing long-chain alkyl groups such as polymers thereof can be cited. Unless otherwise specified, the term "(meth) acrylic resin" includes (meth) acrylic compounds and polymers thereof. In addition, unless otherwise specified, the term "(meth) acrylic compound" includes acrylic compounds containing an acryloyl group, methacrylic compounds containing a methacryloyl group, and combinations thereof. In addition, unless otherwise specified, the term "polymer" includes any one of a homopolymer and a copolymer.

[0108] Examples of the olefin resin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene.

[0109] Fluorine compounds represent compounds containing fluorine atoms in the molecule. Specific examples of fluorine compounds include compounds containing perfluoroalkyl groups, polymers of olefin compounds containing fluorine atoms, aromatic fluorine compounds such as fluorobenzene, (meth) acrylic resins containing fluorine atoms, etc. Among them, (meth) acrylic resins containing fluorine atoms are preferred. As (meth) acrylic resins containing fluorine atoms, for example, fluoroalkyl acrylates such as trifluoroethyl acrylate, fluoroaryl acrylates such as pentafluorophenyl acrylate, fluoroalkyl methacrylates such as trifluoroethyl methacrylate, fluoroaryl methacrylates such as pentafluorophenyl methacrylate, and polymers thereof, etc. can be cited.

[0110] As wax compounds, for example, natural wax, synthetic wax, and waxes obtained by combining them can be cited. Natural waxes include plant wax, animal wax, mineral wax, and petroleum wax. As plant wax, for example, candelilla wax, carnauba wax, rice wax, wood wax, and jojoba oil can be cited. As animal wax, for example, beeswax, lanolin, and spermaceti can be cited. As mineral wax, for example, montan wax, ozocerite, and ceresin can be cited. As petroleum wax, for example, paraffin wax, microcrystalline wax, and vaseline can be cited. As synthetic wax, for example, synthetic hydrocarbons, modified wax, hydrogenated wax, fatty acids, amides, amines, imides, esters, and ketones can be cited. As synthetic hydrocarbons, for example, Fischer-Tropsch wax (also known as Sasol Wax) and polyethylene wax can be cited. In addition, in the synthetic hydrocarbon, a low molecular weight (specifically, a viscosity average molecular weight of 500 or more and 20,000 or less) substance may be contained in a polymer selected from polypropylene, ethylene / acrylic acid copolymer, polyethylene glycol, polypropylene glycol, a block combination of polyethylene glycol and polypropylene glycol, and a graft combination of polyethylene glycol and polypropylene glycol. As modified wax, for example, montan wax derivatives, paraffin derivatives, and microcrystalline wax derivatives can be mentioned. The derivatives here refer to compounds obtained by any treatment of refining, oxidation, esterification, saponification, or a combination thereof. As hydrogenated wax, for example, hydrogenated castor oil and hydrogenated castor oil derivatives can be mentioned.

[0111] The mold releasing component may be used alone or in combination of two or more.

[0112] The amount of the releasing component in the releasing agent relative to 100 mass % of the non-volatile component of the releasing agent is preferably 5 mass % or more, more preferably 10 mass % or more, further preferably 15 mass % or more, preferably 90 mass % or less, more preferably 60 mass % or less, further preferably 40 mass % or less.

[0113] In addition, the amount of the release component in the release layer is preferably 5 mass % or more, more preferably 10 mass % or more, further preferably 15 mass % or more, preferably 90 mass % or less, more preferably 60 mass % or less, particularly preferably 40 mass % or less, relative to 100 mass % of the release layer.

[0114] As the arbitrary component that the release agent may contain, for example, any resin other than the release component can be cited. As the arbitrary resin, for example, epoxy resin, melamine resin, oxazoline compound, carbodiimide compound, polyester resin, polyurethane resin, (meth) acrylic resin, etc. can be cited. In addition, as the (meth) acrylic resin of any resin, for example, acrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, acrylamide, N-hydroxymethyl acrylamide, diacetone acrylamide, etc. acrylic acid compounds; methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc. methacrylic acid compounds; and their polymers, etc. Any resin may be used alone or in combination of two or more.

[0115] The amount of any resin in the release agent relative to 100 mass % of the non-volatile component of the release agent is preferably 10 mass % or more, more preferably 20 mass % or more, further preferably 40 mass % or more, preferably 90 mass % or less, more preferably 85 mass % or less, further preferably 80 mass % or less.

[0116] In addition, the amount of any resin in the release layer is preferably 10 mass % or more, more preferably 20 mass % or more, further preferably 40 mass % or more, preferably 90 mass % or less, more preferably 85 mass % or less, further preferably 80 mass % or less, relative to 100 mass % of the release layer.

[0117] As other examples of the optional components, there can be mentioned any additives such as lubricants, inorganic particles, organic particles, surfactants, antioxidants, thermal initiators, etc. The optional additives can be used alone or in combination of two or more. The amount of the optional additive is not particularly limited, for example, it can be 0.001% by mass or more and 10% by mass or less relative to 100% by mass of the total of the release component and the optional resin.

[0118] As the above-mentioned release agent, for example, alkyd release agents, polyolefin release agents, polyurethane release agents, melamine release agents, fluorine release agents, acrylic release agents and silicone release agents can be cited. Among them, from the viewpoint of manufacturing a circuit substrate with an insulating layer having good insulation, a non-silicon release agent is preferably used. In addition, from the viewpoint of particularly smoothly removing foreign matter, an acrylic release agent is more preferably used. An acrylic release agent refers to a release agent containing a (meth) acrylic resin as a release component and one or both of any resins.

[0119] The thickness of the release layer is not particularly limited, but is preferably at least 50 nm, more preferably at least 70 nm, and is preferably at most 400 nm, more preferably at most 200 nm, particularly preferably at most 130 nm.

[0120] As a support, a sheet-like member is usually used. The support may be a monolithic sheet, but from the viewpoint of realizing continuous manufacture of laminated resin sheets and improving manufacturing efficiency, a long-sized sheet is preferably used. Unless otherwise specified, a long-sized sheet refers to a sheet having a length that can be rolled into a roll, for example, a sheet having a length of more than 10 times relative to the width. The upper limit of the length is not particularly limited, for example, it may be less than 100,000 times relative to the width.

[0121] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm.

[0122] The support can be manufactured by, for example, a method comprising applying a release agent on the surface of the substrate layer. The release agent may further contain a solvent in combination with the above-mentioned release component and non-volatile components such as an optional component. When the release agent contains a solvent, the method for manufacturing the support preferably includes drying after applying the release agent.

[0123] As a solvent, from the viewpoint of suppressing rapid evaporation of the solvent to form a uniform release layer, an aqueous solvent is preferably used. As an aqueous solvent, for example, water; a mixed solvent of water and an organic solvent soluble in water such as an alcohol solvent, a ketone solvent, a glycol solvent, etc. may be mentioned. One type of solvent may be used alone, or two or more types may be used in combination. When a solvent is used, from the viewpoint of making the coating property good and forming a uniform release layer, the non-volatile component concentration of the release agent is preferably 40% by mass or less.

[0124] Examples of the method for applying the release agent include wire bar coating, reverse coating, gravure coating, die coating, knife coating, dip coating, air knife coating, curtain coating, and roll coating.

[0125] The drying temperature of the release agent is not particularly limited. In one example, the release agent may be dried in a temperature range of 80° C. to 130° C. In another example, the release agent may be dried in a temperature range of 160° C. to 240° C.

[0126] By applying a release agent to the surface of the substrate layer and drying as needed, a layer containing a non-volatile component of the release agent can be formed. This layer can be used as a release layer. In addition, the layer containing a non-volatile component of the release agent can be subjected to a curing treatment to obtain a release layer. As a curing treatment, for example, a heating treatment, an ultraviolet irradiation treatment, etc. can be cited. Usually, through the curing treatment, a part or all of the components contained in the release agent undergo a polymerization reaction and a cross-linking reaction, etc., so that the release agent can be cured, so that a release layer formed by a cured product of the release agent can be obtained.

[0127] Furthermore, the method for producing the support may include any treatment such as a stretching treatment as necessary.

[0128] <Description of protective film> Hereinafter, the protective film used in the present embodiment is described in detail. The protective film is a film laminated on the resin composition layer in order to protect the resin composition layer from physical damage or to suppress the attachment of foreign matter such as garbage. Usually, a protective film is not required during the manufacture of a circuit substrate, so a general protective film is laminated on the resin composition layer in a peelable manner.

[0129] As the protective film, for example, thermoplastic resin film and metal foil can be cited. When a thermoplastic resin is used as the protective film, the thermoplastic resin contained in the protective film can be the same as the thermoplastic resin contained in the substrate layer. In addition, the protective film can be a stretched film that has been stretched. In addition, when a metal foil is used as the protective film, the metal foil can be the same as the metal foil of the substrate layer. As commercial products of the protective film, for example, "MA430" and "MA411" (biaxially stretched polypropylene film) made by Oji F-Tex Co., Ltd. can be cited.

[0130] The surface of the protective film bonded to the resin composition layer (i.e., the first side of the protective film) may have an arithmetic mean roughness in a specific range. Specifically, the arithmetic mean roughness of the first side of the protective film is preferably 150 nm or more, more preferably 200 nm or more, further preferably 250 nm or more, preferably 2000 nm or less, more preferably 1500 nm or less, and further preferably 1200 nm or less. The arithmetic mean roughness can be measured using a non-contact surface roughness meter. As a specific example of a non-contact surface roughness meter, "WYKONT3300" made by Veeco Instruments Inc. can be cited. The arithmetic mean roughness can be measured, for example, using a non-contact surface roughness meter in VSI mode and a 50x lens, with the measurement range set to 121 μm × 92 μm.

[0131] The protective film may include a release layer. The release layer is usually formed as the outermost layer on the first surface side, so the release layer may be exposed on the first surface of the protective film. As the release layer of the protective film, the same layer as the release layer of the support may be used.

[0132] The thickness of the protective film is preferably at least 5 μm, more preferably at least 10 μm, preferably at most 75 μm, more preferably at most 50 μm, further preferably at most 40 μm. When a protective film having a release layer is used, the total thickness of the protective film including the release layer is preferably within the above range.

[0133] The protective film may be a monolithic film, but from the viewpoint of realizing continuous manufacture of laminated resin sheets and improving manufacturing efficiency, a long-sized film is preferably used. Unless otherwise specified, a long-sized film refers to a film having a length that can be rolled into a roll, for example, a film having a length of more than 10 times relative to the width. The upper limit of the length is not particularly limited, for example, it may be less than 100,000 times relative to the width.

[0134] <Description of curable resin composition> Hereinafter, the curable resin composition used in the present embodiment is described in detail. The curable resin composition is a curable resin composition, which can usually be cured by one or both of heat and light. As the curable resin composition, a composition containing (A) curable resin can be used. Hereinafter, a specific example of the composition of the curable resin composition is described, but as the curable resin composition, a composition other than the following examples can also be used.

[0135] - (A) Curable resin - The (A) curable resin that may be contained in the curable resin composition is usually selected from a thermosetting resin and a photocurable resin. As the (A) curable resin, only a thermosetting resin may be used, only a photocurable resin may be used, or a thermosetting resin and a photocurable resin may be used in combination. In addition, the (A) curable resin may be used alone or in combination of two or more.

[0136] As the thermosetting resin, a resin that can be cured when heated can be used. Examples of the thermosetting resin include epoxy resins, phenol resins, active ester resins, cyanate resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, thiol resins, and free radical polymerizable resins. The thermosetting resins can be used alone or in combination of two or more.

[0137] In one example, it is preferred to use an epoxy resin and a resin that can react with the epoxy resin to cure the curable resin composition. Hereinafter, the resin that can react with the epoxy resin to cure the curable resin composition is sometimes referred to as a "curing agent". As a curing agent, for example, phenol resins, active ester resins, cyanate resins, carbodiimide resins, anhydride resins, amine resins, benzoxazine resins, thiol resins, etc. can be cited. Among them, phenol resins, active ester resins, cyanate resins and carbodiimide resins are preferred, and phenol resins and active ester resins are more preferred. In addition, the curing agent can be used alone or in combination of two or more.

[0138] Epoxy resin is a thermosetting resin having an epoxy group. Examples of epoxy resin include bixylenol epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, and bisphenol A epoxy resin. Novolac) type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing a spiro ring, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, etc. The epoxy resin may be used alone or in combination of two or more.

[0139] From the viewpoint of obtaining a cured product having excellent heat resistance, the epoxy resin preferably includes an epoxy resin containing an aromatic structure. An aromatic structure refers to a chemical structure generally defined as an aromatic structure, and also includes polycyclic aromatics and aromatic heterocycles. Examples of epoxy resins containing an aromatic structure include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, dimethylphenol type epoxy resins, glycidylamine type epoxy resins having an aromatic structure, and epoxy resins having an aromatic structure. Glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with aromatic structure, epoxy resin with butadiene structure with aromatic structure, alicyclic epoxy resin with aromatic structure, heterocyclic epoxy resin, spiro ring-containing epoxy resin with aromatic structure, cyclohexanedimethanol type epoxy resin with aromatic structure, naphthyl ether type epoxy resin, trimethylol type epoxy resin with aromatic structure, tetraphenylethane type epoxy resin with aromatic structure, etc.

[0140] (A) The curable resin is preferably an epoxy resin having two or more epoxy groups in one molecule as an epoxy resin. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more relative to 100% by mass of the non-volatile component of the epoxy resin.

[0141] Epoxy resins include epoxy resins that are liquid at a temperature of 20° C. (hereinafter also referred to as “liquid epoxy resins”) and epoxy resins that are solid at a temperature of 20° C. (hereinafter also referred to as “solid epoxy resins”). In the curable resin composition, as the epoxy resin, only the liquid epoxy resin may be included, or only the solid epoxy resin may be included, or a combination of the liquid epoxy resin and the solid epoxy resin may be included.

[0142] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0143] As liquid epoxy resins, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure.

[0144] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation, "828US", "828EL", "jER828EL", "825", and "EPIKOTE 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation, "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation, "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "630", "630LSD", and "604" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation, "ED-523T" (glycirol-type epoxy resin) manufactured by ADEKA Corporation, and ADEKA "EP-3950L" and "EP-3980S" (glycidylamine epoxy resin) manufactured by Co., Ltd., "EP-4088S" (dicyclopentadiene epoxy resin) manufactured by ADEKA Corporation, "ZX1059" (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd., "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase ChemteX Co., Ltd., "CELLOXIDE 2021P" (alicyclic epoxy resin with an ester skeleton), "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (epoxy resins with a butadiene structure), "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resins) manufactured by Nippon Steel Chemical Materials Co., Ltd. These resins may be used alone or in combination of two or more.

[0145] The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0146] As solid epoxy resins, preferred are biphenylol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthyl ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, and phenol benzopyrrolidone type epoxy resins.

[0147] Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation, "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation, "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation, "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation, "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation, and "HP-7200HH" and "HP-7200H" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation. "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthyl ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd. "ESN475V", "ESN4100V" (naphthalene type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd., "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd., "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd., "YX4000H", "YX4000", "YX4000HK", "YL7890" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YX7700" (phenol aralkyl type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd., "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" and "YX7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These resins may be used alone or in combination of two or more.

[0148] When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio thereof (liquid epoxy resin:solid epoxy resin) is preferably from 20:1 to 1:20, more preferably from 15:1 to 1:15, particularly preferably from 10:1 to 1:10.

[0149] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5000 g / eq., more preferably 60 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., particularly preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent represents the mass of the resin per 1 equivalent of epoxy groups. The epoxy equivalent can be measured according to JIS K7236.

[0150] The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

[0151] The amount of the epoxy resin in the curable resin composition relative to 100 mass % of the non-volatile component in the curable resin composition is preferably 1 mass % or more, more preferably 5 mass % or more, further preferably 10 mass % or more, preferably 60 mass % or less, more preferably 50 mass % or less, further preferably 40 mass % or less.

[0152] Relative to 100% by mass of the resin component in the curable resin composition, the amount of the epoxy resin in the curable resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less. Unless otherwise specified, the resin component of the curable resin composition refers to the component other than the (B) inorganic filler described later in the non-volatile component of the curable resin composition.

[0153] As phenol resin, a compound having more than one, preferably more than two hydroxyl groups bonded to aromatic rings such as benzene rings and naphthalene rings in one molecule can be used. Phenolic resin can react with epoxy resin to cure curable resin composition when combined with epoxy resin, so it is sometimes called "phenol curing agent". From the viewpoint of obtaining a cured product with good heat resistance and water resistance, a phenolic resin with a phenolic structure is preferred. In addition, from the viewpoint of obtaining a cured product with good adhesion to wiring, a nitrogen-containing phenolic resin is preferred, and a phenolic resin containing a triazine skeleton is more preferred. Among them, from the viewpoint of obtaining a cured product with high heat resistance, water resistance and adhesion, a linear phenolic resin containing a triazine skeleton is preferred. Specific examples of phenol resins include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals Co., Ltd., "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel Chemicals Co., Ltd., and "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", and "TD-2090-60M" manufactured by DIC Corporation.

[0154] The amount of the phenol resin in the curable resin composition relative to 100% by mass of the non-volatile component in the curable resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less.

[0155] The amount of the phenol resin in the curable resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, relative to 100% by mass of the resin component in the curable resin composition.

[0156] As active ester resin, it is generally preferred to use compounds having ester groups with more than two highly reactive groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. Active ester resin can react with epoxy resin to cure curable resin composition when combined with epoxy resin, so it is sometimes called "active ester curing agent". The active ester resin is preferably a compound obtained by condensation reaction of carboxylic acid compound and / or thiocarboxylic acid compound with hydroxyl compound and / or thiol compound. In particular, from the viewpoint of obtaining a cured product with good heat resistance, it is preferably an active ester resin obtained from carboxylic acid compound and hydroxyl compound, and more preferably an active ester resin obtained from carboxylic acid compound and phenolic compound and / or naphthol compound. As carboxylic acid compound, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. can be cited. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, and phenolic novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0157] Specifically, as the active ester resin, preferably, a dicyclopentadiene type active ester resin, a naphthalene type active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of a novolac resin, and an active ester resin containing a benzoylated product of a phenol novolac, and more preferably, at least one selected from the group consisting of a dicyclopentadiene type active ester resin and a naphthalene type active ester resin. As the dicyclopentadiene type active ester resin, preferably, an active ester resin containing a dicyclopentadiene type diphenol structure.

[0158] Commercially available products of active ester resins include, for example, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation) as active ester resins containing a dicyclopentadiene-type diphenol structure; and "HP-B-8151-62T", "HP-C-8151-62T", "EXB-8100L-65T", "EXB-8150-60T" as active ester resins containing a naphthalene structure. , "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); as the phosphorus-containing active ester resin, "EXB9401" (manufactured by DIC Corporation) can be mentioned; as the active ester resin which is an acetylated product of a linear phenolic resin, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be mentioned; as the active ester resin which is a benzoylated product of a linear phenolic resin, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) can be mentioned, and as the active ester resin containing a styrene group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Airwater Co., Ltd.) and the like can be mentioned.

[0159] The amount of the active ester resin in the curable resin composition relative to 100 mass % of the non-volatile component in the curable resin composition is preferably 0.1 mass % or more, more preferably 1 mass % or more, further preferably 3 mass % or more, preferably 50 mass % or less, more preferably 40 mass % or less, further preferably 30 mass % or less.

[0160] The amount of the active ester resin in the curable resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, relative to 100% by mass of the resin component in the curable resin composition.

[0161] As the cyanate resin, a compound having one or more, preferably two or more, cyanate groups in one molecule can be used. When combined with an epoxy resin, the cyanate resin can react with the epoxy resin to cure the curable resin composition, so it is sometimes called a "cyanate curing agent". Examples of the cyanate resin include difunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac resins and cresol novolac resins; and prepolymers obtained by partially triazinizing these cyanate resins. Specific examples of cyanate resins include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (both are novolac-type multifunctional cyanate resins), "BA230", and "BA230S75" (prepolymers in which a part or all of bisphenol A dicyanate is triazine-treated to form a trimer).

[0162] As the carbodiimide resin, a compound having one or more, preferably two or more, carbodiimide structures in one molecule can be used. When combined with an epoxy resin, the carbodiimide resin can react with the epoxy resin to cure the curable resin composition, so it is sometimes called a "carbodiimide curing agent". Specific examples of the carbodiimide resin include aliphatic biscarbodiimides such as tetramethylene-bis(tert-butylcarbodiimide) and cyclohexanebis(methylene-tert-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly(

[0043] Polycarbodiimides include aromatic polycarbodiimides such as naphthylene carbodiimide), poly(tolylene carbodiimide), poly(methyl diisopropyl phenylene carbodiimide), poly(triethyl phenylene carbodiimide), poly(diethyl phenylene carbodiimide), poly(triisopropyl phenylene carbodiimide), poly(diisopropyl phenylene carbodiimide), poly(xylylene carbodiimide), poly(tetramethyl xylylene carbodiimide), poly(methylene diphenylene carbodiimide), and poly[methylene bis(methyl phenylene) carbodiimide]. Examples of commercially available carbodiimide resins include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-09" manufactured by Nisshinbo Chemical Co., Ltd. and "Stabaxol P", "Stabaxol P400" and "Hycasyl 510" manufactured by Rhein Chemie.

[0163] As the acid anhydride resin, a compound having one or more, preferably two or more, acid anhydride groups in one molecule can be used. When the acid anhydride resin is combined with an epoxy group, it can react with the epoxy resin to cure the curable resin composition, so it is sometimes called an "acid anhydride curing agent". Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, dihydrophthalic anhydride, and the like. Polymer-type acid anhydrides such as benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, etc. Commercially available products of the acid anhydride resin include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Rika Co., Ltd., "YH306" and "YH307" manufactured by Mitsubishi Chemical Corporation, "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd., and "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Cray Valley Company.

[0164] As the amine resin, a compound having one or more, preferably two or more, amino groups in one molecule can be used. When combined with an epoxy group, the amine resin can react with an epoxy resin to cure the curable resin composition, so it is sometimes called an "amine curing agent". As the amine resin, for example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. can be cited, among which aromatic amines are preferred. The amine resin is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine resin include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, metaphenylenediamine, metaphenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl) bis(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available products of the amine resin include, for example, "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., "EPICURE W" manufactured by Mitsubishi Chemical Corporation, and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd.

[0165] When combined with an epoxy resin, the benzoxazine resin can react with the epoxy resin to cure the curable resin composition, so it is sometimes called a "benzoxazine curing agent". Specific examples of the benzoxazine resin include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Industry Co., Ltd., "HFB2006M" manufactured by Showa High Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0166] When combined with an epoxy resin, a thiol resin can react with the epoxy resin to cure the curable resin composition, so it is sometimes called a "thiol curing agent". Examples of the thiol resin include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0167] The active group equivalent of the curing agent is preferably 50 to 3000 g / eq., more preferably 100 to 1000 g / eq., further preferably 100 to 500 g / eq., particularly preferably 100 to 300 g / eq. The active group equivalent means the mass of the curing agent per 1 equivalent of active groups.

[0168] The range of the weight average molecular weight (Mw) of the curing agent may be the same as the range of the weight average molecular weight of the epoxy resin.

[0169] When the number of epoxy groups of epoxy resin is set to 1, the number of active groups of curing agent is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.2 or more, preferably 5.0 or less, more preferably 4.0 or less, and particularly preferably 3.0 or less. "The number of epoxy groups of epoxy resin" represents the value obtained by adding up all the values ​​obtained by dividing the mass of the non-volatile components of epoxy resin present in curable resin composition by the epoxy equivalent. In addition, "the number of active groups of curing agent" represents the value obtained by adding up all the values ​​obtained by dividing the mass of the non-volatile components of curing agent present in curable resin composition by the active group equivalent.

[0170] The amount of the curing agent in the curable resin composition relative to 100 mass % of the non-volatile component in the curable resin composition is preferably 1 mass % or more, more preferably 2 mass % or more, further preferably 5 mass % or more, preferably 50 mass % or less, more preferably 40 mass % or less, further preferably 30 mass % or less.

[0171] The amount of the curing agent in the curable resin composition relative to 100% by mass of the resin component in the curable resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less.

[0172] As a free radical polymerizable resin, a compound having an ethylenically unsaturated bond can be used. Therefore, the free radical polymerizable resin may have a free radical polymerizable group containing an ethylenically unsaturated bond. As a free radical polymerizable group, for example, unsaturated hydrocarbon groups such as vinyl, allyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl, α, β-unsaturated carbonyl groups such as acryl, methacryloyl, and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl) can be cited. The number of free radical polymerizable groups contained in one molecule of the free radical polymerizable resin can be 1 or more than 2. As a free radical polymerizable resin, for example, (meth) acrylic free radical polymerizable resins, styrene free radical polymerizable resins, allyl free radical polymerizable resins, maleimide free radical polymerizable resins, etc. can be cited. The free radical polymerizable resin can be used alone or in combination of two or more.

[0173] As the photocurable resin, a resin that can be cured when exposed to light can be used. Examples of the photocurable resin include radical polymerizable resins. The photocurable resins can be used alone or in combination of two or more.

[0174] The amount of the (A) curable resin in the curable resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less, relative to 100% by mass of the non-volatile component in the curable resin composition.

[0175] The amount of the curable resin (A) in the curable resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, preferably 97% by mass or less, more preferably 96% by mass or less, particularly preferably 95% by mass or less, relative to 100% by mass of the resin component in the curable resin composition.

[0176] - (B) Inorganic fillers - The curable resin composition may contain (B) an inorganic filler as an optional component. The (B) inorganic filler is usually contained in the curable resin composition in the form of particles.

[0177] As the material of (B) inorganic filler, an inorganic compound is used. As the material of (B) inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc., can be cited. Among them, silica and alumina are preferred, and silica is particularly preferred. As silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be cited. In addition, as silica, spherical silica is preferred. (B) The inorganic filler may be used alone or in combination of two or more.

[0178] Examples of commercially available inorganic fillers (B) include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd., "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Yaduma Co., Ltd., "UFP-30", "DAW-03", and "FB-105FD" manufactured by DENKA Corporation, "SILFIL NSS-3N", "SILFIL NSS-4N", and "SILFIL NSS-5N" manufactured by Tokuyama Co., Ltd., and "CellSpheres" and "MGH-005" manufactured by Pacific Cement Co., Ltd.

[0179] (B) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, preferably 10 μm or less, more preferably 7 μm or less, and further preferably 5 μm or less. (B) The average particle size of the inorganic filler can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, a particle size distribution of an inorganic filler can be made on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median particle size can be measured as the average particle size. The sample can be measured using a sample obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. For the sample to be measured, a laser diffraction particle size distribution measuring device can be used, using a light source wavelength of blue and red, and the volume-based particle size distribution of the inorganic filler can be measured in a flow cell manner, and the average particle size can be calculated as the median particle size based on the obtained particle size distribution. Examples of the laser diffraction particle size distribution measuring apparatus include "LA-960" manufactured by Horiba, Ltd., and the like.

[0180] (B) The specific surface area of ​​the inorganic filler is preferably 1 m 2 / g or more, preferably 2m 2 / g or more, more preferably 3m 2 / g or more, preferably 60m 2 / g or less, preferably 50m 2 / g or less, more preferably 40m 2 The specific surface area can be measured by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method and calculating the specific surface area by the BET multipoint method.

[0181] From the viewpoint of improving moisture resistance and dispersibility, (B) inorganic filler material is preferably treated by a surface treatment agent. As the surface treatment agent, for example, fluorine-containing silane coupling agent, aminosilane coupling agent, epoxysilane coupling agent, mercaptosilane coupling agent, silane coupling agent, alkoxysilane, organosilazane compound, titanate coupling agent, etc. can be cited. The surface treatment agent can be used alone or in any combination of two or more.

[0182] Commercially available products of the surface treatment agent include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM-7103” (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0183] From the viewpoint that the dispersibility of (B) inorganic filler material is improved, the degree of surface treatment performed by a surface treatment agent is preferably within a specific range. Specifically, 100% by mass of inorganic filler material is preferably surface treated by a surface treatment agent of 0.2% by mass to 5% by mass, more preferably surface treated by a surface treatment agent of 0.2% by mass to 3% by mass, and further preferably surface treated by a surface treatment agent of 0.3% by mass to 2% by mass.

[0184] The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m 2 More than 0.1 mg / m 2 More preferably, 0.2 mg / m 2 On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the curable resin composition, 1.0 mg / m 2 Below, preferably 0.8mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0185] (B) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added as a solvent to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid component, a carbon analyzer can be used to measure the amount of carbon per unit surface area of ​​the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0186] The amount of the (B) inorganic filler in the curable resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, relative to 100% by mass of the non-volatile component of the curable resin composition.

[0187] - (C) Curing accelerator - The curable resin composition may contain (C) a curing accelerator as an optional component. The (C) curing accelerator has a function as a curing catalyst that accelerates the curing of the (A) curable resin.

[0188] As the (C) curing accelerator, an appropriate curing accelerator may be used according to the type of the (A) curable resin. For example, when the (A) curable resin includes an epoxy resin, as the (C) curing accelerator that can accelerate the curing of the epoxy resin, for example, phosphorus curing accelerators, urea curing accelerators, guanidine curing accelerators, imidazole curing accelerators, metal curing accelerators, amine curing accelerators, etc. may be mentioned. The (C) curing accelerator may be used alone or in combination of two or more.

[0189] Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid salt, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, para- Aromatic phosphonium salts such as tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc.; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane, etc.; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants, etc.; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di- aliphatic phosphines such as tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2 ,6-dimethylphenyl)phosphine, tri(3,5-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(2-methoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri(4-ethoxyphenyl)phosphine, tri(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether and the like.

[0190] Examples of the urea curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1, Aromatic dimethylureas such as 1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea], and the like.

[0191] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

[0192] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1') imidazole compounds and adducts of imidazole compounds and epoxy resins such as 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline. Commercially available products of imidazole curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd. and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0193] As metal curing accelerators, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be cited. Specific examples of organic metal complexes include organic cobalt complexes such as cobalt acetylacetonate (II), cobalt acetylacetonate (III), organic copper complexes such as copper acetylacetonate (II), organic zinc complexes such as zinc acetylacetonate (II), organic iron complexes such as iron acetylacetonate (III), organic nickel complexes such as nickel acetylacetonate (II), and organic manganese complexes such as manganese acetylacetonate (II). As organic metal salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

[0194] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene. Amine curing accelerators may be commercially available, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc.

[0195] The amount of the (C) curing accelerator in the curable resin composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, further preferably 0.05% by mass or more, preferably 1.0% by mass or less, more preferably 0.5% by mass or less, particularly preferably 0.2% by mass or less, relative to 100% by mass of the non-volatile component in the curable resin composition.

[0196] The amount of the (C) curing accelerator in the curable resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.10% by mass or more, and preferably 2.0% by mass or less, more preferably 1.0% by mass or less, further preferably 0.5% by mass or less, relative to 100% by mass of the resin component in the curable resin composition.

[0197] - (D) Polymer resin - The curable resin composition may contain (D) a polymer resin as an optional component. Examples of the (D) polymer resin include phenoxy resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamide-imide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketones, polyester resins, and the like. The (D) polymer resin may be used alone or in combination of two or more.

[0198] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton), "YX8100" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol S skeleton), "YX6954" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol acetophenone skeleton), "FX280" and "FX293" manufactured by Nippon Steel Chemical Materials Co., Ltd., "YL7500BH30", "YL7800BH40", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation, etc.

[0199] Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., and "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Rika Co., Ltd.

[0200] Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd., and S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0201] Examples of the polyolefin resin include low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers and other ethylene copolymer resins, polyolefin polymers such as polypropylene and ethylene-propylene block copolymers, and the like.

[0202] Examples of the polybutadiene resin include resins containing a hydrogenated polybutadiene skeleton, hydroxyl-containing polybutadiene resins, phenolic hydroxyl-containing polybutadiene resins, carboxyl-containing polybutadiene resins, acid anhydride-containing polybutadiene resins, epoxy-containing polybutadiene resins, isocyanate-containing polybutadiene resins, urethane-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins.

[0203] Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

[0204] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

[0205] Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay High Performance Polymers.

[0206] Specific examples of the polyphenylene ether resin include "NORYLSA90" manufactured by SABIC Innovative Plastics, etc. Specific examples of the polyetherimide resin include "ULTEM" manufactured by GE, etc.

[0207] Examples of polycarbonate resins include hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, anhydride-containing carbonate resins, isocyanate-containing carbonate resins, and urethane-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals Co., Ltd., and "C-1090", "C-2090", and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. Specific examples of polyetheretherketone resins include "SUMIPLOY K" manufactured by Sumitomo Chemical Co., Ltd.

[0208] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexylene dimethyl terephthalate resin.

[0209] (D) polymer resin usually has a large molecular weight. Specifically, the weight average molecular weight (Mw) of (D) polymer resin is preferably greater than 5000, more preferably 8000 or more, further preferably 10000 or more, further preferably 20000 or more, preferably 100000 or less, more preferably 70000 or less, further preferably 60000 or less, further preferably 50000 or less.

[0210] The amount of the (D) polymer resin in the curable resin composition, relative to 100 mass % of the non-volatile component in the curable resin composition, is preferably 0.01 mass % or more, more preferably 0.1 mass % or more, further preferably 1 mass % or more, preferably 20 mass % or less, more preferably 10 mass % or less, further preferably 5 mass % or less.

[0211] The amount of the (D) polymer resin in the curable resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, relative to 100% by mass of the resin component in the curable resin composition.

[0212] - (E) Optional additives - The curable resin composition may further contain (E) any additive as an optional non-volatile component in combination with the above-mentioned (A) to (D) components. (E) Optional additives include, for example, organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as Benton and montmorillonite; defoaming agents such as silicone defoamers, acrylic defoamers, fluorine defoamers, and vinyl resin defoamers; ultraviolet absorbers such as benzotriazole ultraviolet absorbers; adhesion enhancers such as urea silane; adhesion imparting agents such as triazole adhesion imparting agents, tetrazole adhesion imparting agents, and triazine adhesion imparting agents; antioxidants such as hindered phenol antioxidants; stilbene derivatives, etc. Fluorescent whitening agent; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; polymerization initiation aids such as tertiary amines; photosensitizers such as pyrazolines, anthracenes, coumarins, xanthones, and thioxanthones; organic particles. (E) Any additive may be used alone or in combination of two or more.

[0213] - (F) Solvent - The curable resin composition may be combined with the non-volatile components (A) to (E) and further contain (F) a solvent as an arbitrary volatile component. As the (F) solvent, an organic solvent is generally used. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate. Ether ester solvents such as acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (F) Solvents may be used alone or in combination of two or more.

[0214] The amount of the (F) solvent is not particularly limited, and can be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, etc., based on 100% by mass of all components in the curable resin composition, and can be 0% by mass.

[0215] - Method for producing curable resin composition - The curable resin composition can be manufactured, for example, by mixing the components that may be contained in the curable resin composition. The above components can be mixed partially or all at the same time, or can be mixed sequentially. In the process of mixing the components, the temperature can be appropriately set, so heating and / or cooling can be performed part of the time or all the time. In addition, stirring or vibration can be performed in the process of mixing the components.

[0216] - Characteristics of curable resin composition - By curing the curable resin composition, a cured product can be obtained. The cured product is preferably used to form an insulating layer of a circuit substrate. The insulating layer comprises a cured product of the curable resin composition, preferably only comprising the cured product. Usually, volatile components such as (F) solvents contained in the curable resin composition can be volatilized by the heat received during curing, so the cured product can include non-volatile components of the curable resin composition or its reaction product.

[0217] The cured product of the curable resin composition preferably has good dielectric properties. Specifically, the cured product of the curable resin composition preferably has a low relative dielectric constant. In one example, the relative dielectric constant of the cured product is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less. The lower limit is not particularly limited, and may be, for example, 1.5 or more, 2.0 or more, etc.

[0218] In addition, the cured product of the curable resin composition preferably has a low dielectric loss tangent. In one example, the dielectric loss tangent of the cured product is preferably 0.05 or less, more preferably 0.04 or less, and particularly preferably 0.03 or less. The lower limit is not particularly limited, and may be, for example, 0.001 or more, 0.002 or more, etc.

[0219] The relative dielectric constant and dielectric loss tangent of the cured product of the curable resin composition can be measured by the resonant cavity perturbation method under the conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. When the curable resin composition is thermosetting, the relative dielectric constant and dielectric loss tangent can be measured, for example, using a cured product obtained by thermally curing the curable resin composition at 180°C for 90 minutes. In addition, when the curable resin composition is photocurable, the relative dielectric constant and dielectric loss tangent can be measured by subjecting the curable resin composition to a 1 J / cm 2 The measurement was performed on a cured product obtained by heating at 180° C. for 90 minutes after irradiation with ultraviolet rays.

[0220] <Description of the method for producing a circuit board using a laminated resin sheet> As an example of the use of the laminated resin sheet involved in this embodiment, a method for manufacturing a circuit substrate is described below. The circuit substrate generally has an insulating layer obtained by curing a resin composition layer. The circuit substrate can be manufactured, for example, by a method including the following steps (i) to (iii): (i) a step of peeling off the protective film from the laminated resin sheet to obtain a resin sheet; (ii) laminating a resin sheet on the inner substrate so that the resin composition layer is bonded to the inner substrate; (iii) A step of curing the resin composition layer to form an insulating layer.

[0221] The method for manufacturing a circuit board according to this example includes a step (i) of peeling off a protective film from a laminated resin sheet to obtain a resin sheet. By peeling off the protective film, the resin composition layer is exposed, so that the resin composition layer can be bonded to an inner substrate in step (ii).

[0222] Generally, the protective film is peeled off by pulling the protective film relative to the resin sheet. For example, the resin sheet may be transported with the protective film fixed, and the protective film may be peeled off. Also, for example, the protective film may be pulled with the resin sheet fixed, and the protective film may be peeled off. Also, for example, the resin sheet may be transported while pulling the protective film, and the protective film may be peeled off.

[0223] Usually, the protective film is relatively pulled along the peeling direction at a specific angle relative to the surface of the resin composition layer to achieve the peeling of the protective film. The range of the angle presented by the peeling direction relative to the surface of the resin composition layer is not particularly limited. The peeling direction can be, for example, a parallel direction relative to the surface of the resin composition layer, or a vertical direction, or a direction other than this. In addition, the temperature conditions for peeling are not particularly limited. From the viewpoint of reducing the energy required for the manufacture of the circuit substrate, the peeling of the protective film is usually carried out at room temperature or a temperature close thereto.

[0224] The method for producing a circuit board according to this example includes, after step (i), step (ii) of laminating a resin sheet on the inner layer substrate. The lamination is performed so that the resin composition layer is bonded to the inner layer substrate.

[0225] The "inner layer substrate" used in step (ii) refers to a component that serves as a base material for a circuit substrate, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. The conductor layer may function as an inner layer wiring. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of a substrate is also referred to as an "inner layer circuit substrate". In addition, an intermediate product that requires further formation of an insulating layer and / or a conductor layer when manufacturing a circuit substrate is also included in the "inner layer substrate". In the case where the circuit substrate is a circuit board with built-in components, an inner layer substrate with built-in components can be used.

[0226] The lamination of the inner substrate and the resin sheet can be carried out, for example, by heat-pressing the resin sheet to the inner substrate from the support body side. As a component (hereinafter also referred to as "heat-pressing component") for heat-pressing the resin sheet to the inner substrate, for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) etc. can be cited. It should be noted that it is better not to press the heat-pressing component directly on the resin sheet, but to press it with an elastic material such as heat-resistant rubber so that the resin sheet fully conforms to the surface unevenness of the inner substrate.

[0227] The lamination of the inner substrate and the resin sheet can be implemented by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably implemented under reduced pressure conditions of 26.7hPa or less.

[0228] Lamination can be performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Mfg. Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and a batch vacuum pressure laminator.

[0229] After lamination, the laminated resin sheet can be smoothed by, for example, pressing the heating and pressing member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be the same as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. It should be noted that the lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0230] The method for manufacturing a circuit substrate in this example includes, after step (ii), a step (iii) of curing the resin composition layer to form an insulating layer. The curing of the resin composition layer can be carried out by a method suitable for a curable resin composition, such as heat curing or photocuring. The specific curing conditions of the resin composition layer can use the conditions commonly used when forming an insulating layer of a circuit substrate.

[0231] For example, when using a thermosetting curable resin composition such as a curable resin composition containing a thermosetting resin, the curing of the curable resin composition can be performed by thermal curing. Therefore, in this case, step (iii) may include thermally curing the resin composition layer. The thermal curing conditions of the resin composition layer will also vary depending on the type of curable resin composition. For example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and further preferably 170°C to 210°C. In addition, the curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 100 minutes.

[0232] In addition, when the resin composition layer is thermoset, the method for manufacturing the circuit substrate preferably includes preheating the resin composition layer at a temperature lower than the curing temperature before the thermoset. For example, before the resin composition layer is thermoset, the resin composition layer may be preheated at a temperature of usually 50°C to 150°C, preferably 60°C to 140°C, and more preferably 70°C to 130°C for usually more than 5 minutes, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes.

[0233] On the other hand, for example, in the case of using a photocurable curable resin composition such as a curable resin composition containing a photocurable resin, the curing of the curable resin composition can be carried out by photocuring. Therefore, in this case, step (iii) may include photocuring the resin composition layer. The photocuring conditions of the curable resin composition will also vary depending on the type of curable resin composition. For example, by exposing the resin composition layer to active light, the irradiated portion of the resin composition layer can be photocured. As active light, for example, ultraviolet rays, visible light, electron beams, X-rays, etc., are cited, and ultraviolet rays are particularly preferred. The irradiation amount of ultraviolet rays is, for example, 10mJ / cm 2 ~1000mJ / cm 2 At this time, the exposure may be performed through the support, or the exposure may be performed after the support is peeled off.

[0234] In the exposure treatment, the resin composition layer can be irradiated with active light through a mask having a pattern formed thereon. The exposure method using a mask includes a contact exposure method in which the mask is brought into contact with a workpiece and exposure is performed, and a non-contact exposure method in which parallel light is used for exposure without contact, and either method can be used.

[0235] Step (iii) may include performing a development treatment after the exposure treatment. If a development treatment is used, the portion that is not photocured (unexposed portion) can be removed to form a pattern on the insulating layer. Development is usually performed by wet development. In wet development, as a developer, a safe, stable, and easy-to-operate developer such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc. can be used. Among them, it is preferred to use a development process using an alkaline aqueous solution. As a developing method, methods such as spraying, shaking and dipping, brushing, and scraping can be used.

[0236] Furthermore, when the resin composition layer is photocured, a post-bake treatment may be performed as needed after photocuring and development. Examples of the post-bake treatment include ultraviolet irradiation treatment using a high-pressure mercury lamp and heating treatment using a clean oven. For example, ultraviolet irradiation treatment may be performed with a 0.05 J / cm2 ~10J / cm 2 The heat treatment may be performed, for example, preferably at 150°C to 250°C for 20 minutes to 180 minutes, more preferably at 160°C to 230°C for 30 minutes to 120 minutes.

[0237] The manufacturing method of the circuit board generally includes the step (iv) of removing the support. The removal of the support can be carried out before the curing of the resin composition layer, but is preferably carried out after the curing of the resin composition layer. In the case where the resin composition layer is cured under the state covered by the support, foreign matter can be suppressed from adhering to the surface of the resin composition layer in the curing process. In addition, in the case where the support is removed after the curing of the resin composition layer, the support can be particularly easily removed.

[0238] When manufacturing a circuit substrate, the process of (v) opening holes in the insulating layer, the process of (vi) roughening the insulating layer, and the process of (vii) forming a conductor layer as wiring can be further implemented. These processes (v) to (vii) can be implemented according to various methods known to those skilled in the art for the manufacture of circuit substrates. It should be noted that when the support body is removed after process (iii), the removal of the support body can be implemented between process (iii) and process (v), between process (v) and process (vi), or between process (vi) and process (vii). In addition, the formation of the insulating layer and the conductor layer of processes (i) to (vii) can be repeatedly implemented as needed to form a circuit substrate with a multilayer structure such as a multilayer printed wiring board.

[0239] Step (v) is a step of drilling holes in the insulating layer, thereby forming holes such as through holes and via holes in the insulating layer. Step (v) can be carried out using a processing method such as drilling, laser processing, plasma processing, etc., depending on the composition of the curable resin composition used to form the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the circuit board.

[0240] Step (vi) is a step of roughening the insulating layer. Usually, in step (vi), the stain (resin residue) that may be generated when the holes are formed is also removed. The steps and conditions of the roughening treatment are not particularly limited, and the known steps and conditions commonly used when forming the insulating layer of the circuit substrate can be used. For example, the insulating layer can be roughened by swelling treatment using a swelling liquid, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing liquid in sequence.

[0241] As the swelling liquid used for the roughening treatment, for example, an alkaline solution, a surfactant solution, etc. can be cited, preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As commercially available swelling liquids, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd. can be cited. The swelling treatment using the swelling liquid can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of controlling the swelling of the resin of the insulating layer to an appropriate level, it is better to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0242] As the oxidant used in the roughening treatment, an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be cited. The roughening treatment using an oxidant such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidant solution heated to 60° C. to 100° C. for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As commercially available oxidants, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited.

[0243] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment using an oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the perspective of operability, etc., it is preferred to immerse the object subjected to the roughening treatment using an oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0244] Step (vii) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer can be a single metal layer or an alloy layer. As an alloy layer, for example, a layer formed by an alloy of two or more metals selected from the above metals (for example, a nickel-chromium alloy, a copper-nickel alloy and a copper-titanium alloy) can be cited. Among them, from the viewpoints of versatility, cost, ease of pattern formation, etc., of the formation of the conductor layer, preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, more preferably a single metal layer of copper.

[0245] The conductor layer may have a single-layer structure or a multilayer structure in which two or more single metal layers or alloy layers formed of different types of metals or alloys are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of a nickel-chromium alloy.

[0246] Typically, the conductor layer is patterned to function as wiring. At this time, the range of the minimum line width / line spacing ratio of the conductor layer is preferably smaller. The range of the minimum line width / line spacing ratio of the conductor layer is preferably less than 100μm / 100μm (i.e., the pitch is less than 200μm), more preferably less than 80μm / 80μm, further preferably less than 50μm / 50μm, and further preferably less than 30μm / 30μm. The lower limit may be, for example, more than 0.5μm / 0.5μm. The spacing may be uniform or uneven throughout the conductor layer. The range of the minimum spacing of the conductor layer may be, for example, less than 200μm, less than 160μm, less than 100μm, or less than 60μm. Here, "line width" represents the wiring width of the conductor layer, and "line spacing" represents the spacing between wirings.

[0247] The thickness of the conductor layer varies depending on the desired design of the circuit board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0248] In one embodiment, the conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated by currently known techniques such as a semi-additive method and a full-additive method to form a conductor layer with a desired wiring pattern. From the perspective of simplicity of manufacturing, a semi-additive method is preferred. Below, an example of forming a conductor layer by a semi-additive method is shown.

[0249] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having a desired wiring pattern.

[0250] The manufacturing method of the circuit substrate may be combined with the above-mentioned process and further include any process. For example, the manufacturing method of the circuit substrate may include the process of setting the semiconductor chip in a manner of bonding with the conductor layer. If a specific example is given, in the case of manufacturing a circuit substrate for semiconductor chip packaging having a semiconductor chip, the manufacturing method of the circuit substrate may include the process of setting the semiconductor chip. The semiconductor chip can adopt suitable conditions that can connect the terminal electrodes of the semiconductor chip to the conductor layer formed on the insulating layer. For example, the conditions used in flip chip installation can be adopted. In addition, the semiconductor chip can be bonded with an insulating adhesive or by reflow soldering. Furthermore, the semiconductor chip set can be filled with a molded bottom filling material as needed.

[0251] Furthermore, the method for manufacturing a circuit board may include, for example, a step of forming a sealing layer, a step of forming a solder resist layer, a step of dicing the manufactured circuit board into individual pieces, and the like.

[0252] As the circuit substrate manufactured, for example, a printed wiring board and a semiconductor chip package can be cited. As the semiconductor chip package, for example, FC-CSP, MIS-BGA package, ETS-BGA package, fan-out WLP (wafer level package, Wafer Level Package), fan-in WLP, fan-out PLP (panel level package, Panel Level Package), fan-in PLP can be cited. In these semiconductor chip packages, it is better to form a rewiring formation layer by curing the above-mentioned resin composition layer. However, the circuit substrate manufactured using the laminated resin sheet involved in this embodiment is not limited to the substrate exemplified here.

[0253] The circuit substrate can be used for manufacturing semiconductor devices. The semiconductor layer has the circuit substrate. As semiconductor devices, various semiconductor devices for electrical products (such as computers, mobile phones, smart phones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and transportation vehicles (such as motorcycles, cars, trams, ships, and aircrafts) can be cited. Example

[0254] The present invention is specifically described below with reference to the following examples. However, the present invention is not limited to the following examples. In the following description, unless otherwise expressly stated, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass", respectively. In addition, the temperature conditions and pressure conditions when not specifically specified are room temperature (25°C) and atmospheric pressure (1 atm).

[0255] <Method for measuring the adhesion of dust removal rollers> The adhesion of the dust removal rollers used in the following embodiments and comparative examples is as follows. Here, the adhesion of each dust removal roller refers to the adhesion of the adhesive tape (tape) forming the surface of the dust removal roller or the circumference of the dust removal roller, and specifically refers to the adhesion measured by the following measurement method. The dust removal roller is obtained by winding the adhesive tape around a core in such a way that the adhesive layer is located outside the roll. An adhesion tester (manufactured by Ichishin Sangyo Co., Ltd., A3-10N) is set vertically relative to the circumference of the dust removal roller. The maximum load (N / 100mm) when the measuring part is pressed against the adhesive layer and pulled back is 2 The measurement was performed three times, and the average value of the three maximum loads measured was taken as the adhesion force. Adhesive tape 1: Nichiban Co., Ltd. "Karitome No. 207" (adhesive force 2.3 N / 100 mm) 2 ) ·Adhesive tape 2: "Sealing Masking Tape No. 2563" manufactured by Nichiban Co., Ltd. (adhesion force 2.7N / 100mm 2 ) Dust removal roller 3: "CLEAN DASH E" manufactured by Techno Roll Co., Ltd. (adhesion force 3.0 N / 100 mm) 2 ) Dust removal roller 4: Audio-technica "HC-730" (adhesion 0.6N / 100mm 2 ).

[0256] <Example 1> (1. Production of Support Body Having Release Layer Containing Acrylic Resin) (1-1. Production of acrylic resin (A)) Into a temperature-adjustable reactor equipped with a stirrer, a thermometer, and a condenser, 500 parts by mass of toluene, 80 parts by mass of stearyl methacrylate (the number of carbon atoms in the alkyl chain is 18), 15 parts by mass of methacrylic acid, 5 parts by mass of 2-hydroxyethyl methacrylate, and 1 part of azobisisobutyronitrile were added dropwise at a reaction temperature of 85° C. for 4 hours to carry out a polymerization reaction. Then, the reaction was completed by aging at the same temperature for 2 hours to obtain an acrylic resin (A). The acrylic resin (A) was dissolved in water containing 5% by mass of isopropyl alcohol and 5% by mass of n-butyl cellosolve to obtain a resin solution containing the acrylic resin (A) as a releasable component.

[0257] (1-2. Production of acrylic resin (B)) Methyl methacrylate (a), hydroxyethyl methacrylate (b), and aromatic urethane acrylate oligomer ("EBECRYL 220" manufactured by DAICEL-ALLNEX Co., Ltd., with 6 acryloyl groups) (c) were added to a stainless steel reaction container at a mass ratio of (a) / (b) / (c)=94 / 1 / 5. Furthermore, 2 parts by mass of sodium dodecylbenzene sulfonate as an emulsifier was added to the reaction container with respect to 100 parts by mass of the total of (a)+(b)+(c), and the mixture was stirred to prepare a mixed solution (1).

[0258] Next, a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was prepared. 60 parts by mass of the mixed solution (1), 200 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate as a polymerization initiator were added to the reaction apparatus and heated to 60° C. to prepare a mixed solution (2). The mixed solution (2) was kept heated at 60° C. for 20 minutes.

[0259] Next, a mixed solution (3) consisting of 40 parts by mass of the mixed solution (1), 50 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate was prepared, and the mixed solution (3) was added dropwise to the mixed solution (2) using a dropping funnel over 2 hours to prepare a mixed solution (4).

[0260] Then, the mixed solution (4) was kept heated to 60°C for 2 hours. The obtained mixed solution (4) was cooled to 50°C or less and then transferred to a container equipped with a stirrer and a decompression device. 60 parts by mass of 25% ammonia water and 900 parts by mass of pure water were added to the container, and the isopropyl alcohol and unreacted monomers were recovered under reduced pressure while being heated to 60°C, thereby obtaining a composition containing an acrylic resin (B) as an arbitrary resin dispersed in pure water.

[0261] (1-3. Production of release agent) A resin solution containing an acrylic resin (A) and a composition containing an acrylic resin (B) were mixed under the condition that the mass ratio (solid content mass ratio) of the acrylic resin (A) to the acrylic resin (B) was (A) / (B) = 20 / 80 to obtain an intermediate composition. Furthermore, a fluorine-based surfactant ("PLASCOAT (registered trademark) RY-2" manufactured by Huying Chemical Industry Co., Ltd.) was added to the intermediate composition under the condition of 0.1 mass parts relative to 100 mass parts of the entire intermediate composition to obtain a release agent as a liquid acrylic resin composition.

[0262] (1-4. Production of Support Body) As a substrate layer, a PET film ("T60" manufactured by Toray Industries, Ltd. (thickness 38 μm)) was prepared. A release agent was applied to one side of the substrate layer using a gravure coating machine and dried to form a release layer with a thickness of 0.1 μm. Through the above operation, a long support having a substrate layer and a release layer containing an acrylic resin was obtained.

[0263] (2. Preparation of resin composition) 8 parts of tetramethylbisphenol type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 194 g / eq.), 10 parts of biphenyl aralkyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 271 g / eq.), 2 parts of naphthalene type epoxy resin ("HP6000L" manufactured by DIC Corporation, epoxy equivalent about 213 g / eq.), 2 parts of difunctional epoxy resin ("ZX1658GS" manufactured by Nippon Steel Chemical Materials Co., Ltd., epoxy equivalent about 133 g / eq.), 4 parts of phenolic curing agent having a triazine skeleton and a cresol novolac structure ("LA-3018-50P" manufactured by DIC Corporation, phenolic hydroxyl equivalent about 151 g / eq., 2-methoxypropanol solution with a solid content of 50%), 6 parts of active ester resin ( DIC Corporation "HP-C-8151-62T", active ester equivalent of about 238 g / eq., toluene solution with a solid content of 62%), 5 parts of a phenoxy resin (Mitsubishi Chemical Corporation "YL7800BH40", MEK and cyclohexane solution with a solid content of 40%), 40 parts of an inorganic filler (average particle size 0.5 μm, surface treatment amount: 0.6 mass% aminosilane coupling agent relative to 100 mass% of the inorganic filler) surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) and 1 part of a MEK solution with a solid content of 5% of a curing accelerator (4-dimethylaminopyridine) were mixed to prepare a resin varnish as a liquid resin composition.

[0264] (3. Production of laminated resin sheet) The following operations were performed while the support and the protective film were conveyed to produce a laminated resin sheet.

[0265] (3-1. Adhesion of copper powder as foreign matter to the support) Copper powder with a mesh size of 100 μm was intentionally attached to both surfaces of the support as foreign matter.

[0266] (3-2. Dust removal of support body) A roll laminator ("VA770" manufactured by Daisei Laminator Co., Ltd.) having a pair of nip rolls rotatably disposed opposite to each other was prepared. An adhesive tape 1 ("Karitome No. 207" manufactured by Nichiban Co., Ltd., adhesive force 2.3 N / 100 mm) was fixed to the pair of nip rolls with the adhesive facing outward. 2 ), a pair of dust removal rollers are prepared. The support body is supplied to the roll laminator, and the support body is passed between the pair of dust removal rollers, so that the dust removal rollers are in contact with both surfaces of the support body to remove dust.

[0267] (3-3. Formation of Resin Composition Layer) The resin varnish was evenly applied on the release layer of the support using a die coater so that the thickness of the resin composition layer obtained after drying was 18 μm, and dried in an oven to obtain a resin sheet having a layer structure of substrate layer / release layer / resin composition layer.

[0268] (3-4. Adhesion of copper powder as foreign matter to protective film) As a protective film, a polypropylene film having a roughened surface (arithmetic mean roughness 250 nm) and a smooth surface (biaxially stretched polypropylene film manufactured by Oji F-Tex Co., Ltd., product name "MA411", thickness 15 μm) was prepared. Copper powder with a mesh size of 100 μm was intentionally attached to both surfaces of the protective film as foreign matter.

[0269] (3-5. Dust removal of protective film) A roll laminator ("VA770" manufactured by Daisei Laminator Co., Ltd.) having a pair of rotatably disposed nip rollers facing each other was prepared. An adhesive tape 1 ("Karitome No. 207" manufactured by Nichiban Co., Ltd., adhesive force 2.3 N / 100 mm) was fixed to the pair of nip rollers with the adhesive facing outward. 2 ), a pair of dust removal rollers were prepared. The protective film was supplied to the roll laminator, and the protective film was passed between the pair of dust removal rollers, so that the dust removal rollers were in contact with both sides of the protective film to remove dust.

[0270] (3-6.Lamination) The resin sheet and the protective film were supplied to a roll laminator ("VA770" manufactured by Daisei Laminator Co., Ltd.), and laminated using the roll laminator. At this time, lamination was performed by pressing at a temperature of 70° C. and a pressure of 0.3 MPa. By lamination, a laminated resin sheet having a layer structure of substrate layer / release layer / resin composition layer / protective film was obtained.

[0271] (4. Production of Evaluation Circuit Board) (4-1. Lamination of resin sheet and inner layer substrate) As the inner substrate, a copper-clad laminate ("R1515A" manufactured by Panasonic Electric Works Co., Ltd., with a copper foil thickness of 18 μm and a substrate thickness of 0.8 mm) was prepared. After peeling off the protective film from the laminated resin sheet to obtain a resin sheet having a layer structure of a substrate layer / release layer / resin composition layer, the resin sheet was laminated on both sides of the inner substrate using a batch vacuum pressurizing laminator (a two-stage stacking laminator "CVP700" manufactured by Nikko-Materials Co., Ltd.) in such a way that the resin composition layer is bonded to the inner substrate. Lamination was performed as follows: the air pressure was reduced for 30 seconds to be below 5 hPa, and the pressure was pressed at 100°C and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100°C and a pressure of 0.55 MPa for 60 seconds, and a smoothing treatment was performed.

[0272] (4-2. Curing of resin composition layer) The inner layer substrate laminated with the resin sheet was placed in an oven at 180° C. and heated for 30 minutes. The resin composition layer was thermally cured by heating to form an insulating layer.

[0273] (4-3. Formation of wiring) Next, in accordance with the following steps, wiring as a conductor layer is formed by a semi-additive process (SAP) utilizing the exposed surface profile of the insulating layer.

[0274] (1) Removal of the support: The release support has the insulating layer as the outermost layer.

[0275] (2) Electroless plating process: An electroless plating step (copper plating step using a chemical solution manufactured by Atotech Japan Ltd.) including the following steps 1 to 6 was performed on the surface of the insulating layer exposed by peeling off the support to form an electroless copper plated layer.

[0276] 1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer): The surface of the insulating layer was cleaned using Cleaning Cleaner Securiganth 902 (trade name) at 60° C. for 5 minutes.

[0277] 2. Soft etching (cleaning of the surface of the insulating layer): The surface of the insulating layer was treated with a sulfuric acid-acidified sodium persulfate aqueous solution at 30° C. for 1 minute.

[0278] 3. Pre-impregnation (for charge adjustment on the surface of the Pd insulating layer): The surface of the insulating layer was treated using Pre.Dip Neoganth B (trade name) at room temperature for 1 minute.

[0279] 4. Activator impartation (impartation of Pd to the surface of the insulating layer): The surface of the insulating layer was treated at 35° C. for 5 minutes using Activator Neoganth 834 (trade name).

[0280] 5. Reduction (reduction of Pd given to the insulating layer): The surface of the insulating layer was treated at 30° C. for 5 minutes using a mixed solution of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (trade name).

[0281] 6. Electroless copper plating process (to deposit Cu on the surface of the insulating layer (Pd surface)): The surface of the insulating layer was treated at 35°C for 20 minutes using a mixed solution of Basic Solution Printganth MSK-DK (trade name), Copper Solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) to form an electroless copper plating layer. The thickness of the formed electroless copper plating layer was 0.8 μm.

[0282] (3) Formation, exposure and development of anti-plating layer: After the electroless plating layer was formed, a plating resist layer (pattern forming dry film "RY5115" manufactured by Showa Denko K.K., thickness 15 μm) was stacked on the electroless plating layers on both sides. Next, a 15 cm square glass mask (exposure mask) on which a wiring pattern (as shown below) was formed was placed on the plating resist layer, and exposure was performed (exposure amount 210 mJ) by a stepper (projection exposure device "UX-2240" manufactured by USHIO Electric Co., Ltd.). Then, after aging at room temperature for 30 minutes, a 1 wt% sodium carbonate aqueous solution at 30°C was sprayed for 30 seconds using a spray-type developer to develop the plating resist layer (pattern formation).

[0283] Wiring pattern of glass mask: A glass mask having a comb-tooth pattern (wiring width: 25 μm, wiring distance: 25 μm, wiring length: 10 mm, 16 wirings) in which 25 wirings from the anode and the cathode face each other was used.

[0284] (4) Electrolytic plating process: Next, electrolytic copper plating was performed using a chemical solution manufactured by Atotech Japan Co., Ltd. to form an electrolytic copper plating layer having a thickness of 8 to 10 μm. By this electrolytic copper plating, a multilayer substrate having an electroless copper plating layer and an electrolytic copper plating layer on the insulating layer was obtained.

[0285] (5) Anti-plating layer peeling: The obtained multilayer substrate was immersed in a resist stripping liquid "R100S" for printed circuit boards manufactured by Mitsubishi Gas Chemical Co., Ltd. at 50° C. for 120 seconds while using ultrasonic waves to strip the plating resist layer.

[0286] (6) Flash etching: Next, the multilayer substrate was immersed in a copper seed layer etchant "Melstrip SE-300" for a semi-additive process at 25°C to remove unnecessary portions of the electroless copper plating layer, thereby obtaining an evaluation circuit substrate having comb-tooth wiring. The comb-tooth wiring is formed by a conductor layer including an electroless copper plating layer and an electrolytic copper plating layer, and has a pattern shape identical to the comb-tooth pattern of the glass mask when viewed in the thickness direction.

[0287] <Example 2> In the step (3-5), the protective film was dusted by using adhesive tape 2 ("Sealing Masking Tape No. 2563" manufactured by Nichiban Co., Ltd., adhesive force 2.7 N / 100 mm). 2 ) was used instead of the adhesive tape 1, and the same operation as in Example 1 was carried out to produce a laminated resin sheet and a circuit board for evaluation.

[0288] <Example 3> In the step (3-2), during the dust removal of the support, an adhesive tape 2 ("Sealing Masking Tape No. 2563" manufactured by Nichiban Co., Ltd., adhesive force 2.7 N / 100 mm) was used. 2 ) was used instead of the adhesive tape 1, and the same operation as in Example 1 was carried out to produce a laminated resin sheet and a circuit board for evaluation.

[0289] <Example 4> In the dust removal of the support in step (3-2) and the dust removal of the protective film in step (3-5), an adhesive tape 2 ("Sealing Masking Tape No. 2563" manufactured by Nichiban Co., Ltd., adhesive force 2.7 N / 100 mm) was used. 2 ) was used instead of the adhesive tape 1, and the same operation as in Example 1 was carried out to produce a laminated resin sheet and a circuit board for evaluation.

[0290] <Example 5> In the dust removal of the support in step (3-2) and the dust removal of the protective film in step (3-5), a dust removal roller 4 ("HC-730" manufactured by Audio-Technica, adhesive force 0.6 N / 100 mm) was used. 2 ) was used instead of the dust removal roller obtained by fixing the adhesive tape 1 to the clamping roller, and the same operation as in Example 1 was carried out to produce a laminated resin sheet and a circuit board for evaluation.

[0291] <Example 6> In the step (3-2), a dust removal roller 4 ("HC-730" manufactured by Audio-Technica, adhesive force 0.6 N / 100 mm) was used for dust removal of the support. 2 ) is used instead of the dust removal roller obtained by fixing the adhesive tape 1 to the clamping roller, and then in the dust removal of the protective film in the step (3-5), the adhesive tape 2 (Nichiban Co., Ltd. "Sealing Masking Tape No. 2563", adhesive force 2.7N / 100mm) is used. 2 ) was used instead of the adhesive tape 1, and the same operation as in Example 1 was carried out to produce a laminated resin sheet and a circuit board for evaluation.

[0292] <Comparative Example 1> In the step (3-2), the dust removal roller 3 ("CLEANDASH E" manufactured by Techno Roll Co., Ltd., with an adhesive force of 3.0 N / 100 mm) was used for dust removal of the support. 2 ) was used instead of the dust removal roller obtained by fixing the adhesive tape 1 to the clamping roller, and the same operation as in Example 1 was carried out to produce a laminated resin sheet and a circuit board for evaluation.

[0293] <Comparative Example 2> In the step (3-5), the protective film was dusted using a dust removal roller 3 ("CLEANDASH E" manufactured by Techno Roll Co., Ltd., adhesive force 3.0 N / 100 mm). 2 ) was used instead of the dust removal roller obtained by fixing the adhesive tape 1 to the clamping roller, and the same operation as in Example 1 was carried out to produce a laminated resin sheet and a circuit board for evaluation.

[0294] <Comparative Example 3> The laminated resin sheet and the evaluation circuit board were manufactured in the same manner as in Example 1 except that the support in step (3-2) and the protective film in step (3-5) were dedusted by using an air blast type dedusting device ("BF-6MB" manufactured by Shishido Electrostatics Co., Ltd.) for 10 seconds. The treatment using the air blast type dedusting device is a non-contact type dedusting treatment that dedusts static electricity by an ionizer and removes foreign matter by wind force.

[0295] <Comparative Example 4> The laminated resin sheet and the evaluation circuit board were manufactured in the same manner as in Example 1 except that the support was dusted in step (3-2) and the protective film was dusted in step (3-5) by using a non-contact ultrasonic cleaning machine ("USW-102" manufactured by Hugle Electronics Co., Ltd.) for 10 seconds. The treatment using the non-contact ultrasonic cleaning machine is a non-contact type static removal treatment that removes foreign matter by ultrasonic waves.

[0296] <Comparative Example 5> The laminated resin sheet and the circuit board for evaluation were produced in the same manner as in Example 1 except that the dust removal of the support in step (3-2) and the dust removal of the protective film in step (3-5) were carried out by using an air gun treatment. The treatment using an air gun is a non-contact type static removal treatment that removes foreign matter by air ejected from the air gun.

[0297] <Test 1. Evaluation of peelability of support body> In the step (4-3) of peeling the support, the case where the support can be peeled off smoothly from the insulating layer is evaluated as "good", and the case where part or all of the support is fixed to the insulating layer and the support cannot be peeled off smoothly is evaluated as "poor". The failure to peel off the support smoothly means that part or all of the release layer adheres to the dust removal roller and is lost in the dust removal step of the support, resulting in a decrease in the peelability of the support.

[0298] <Test 2. Evaluation of transportability of support and protective film during dust removal> When the support body is conveyed while in contact with the dust removal roller in step (3-2), observe whether wrinkles are generated on the support body. In addition, when the protective film is conveyed while in contact with the dust removal roller in step (3-5), observe whether wrinkles are generated on the protective film. The case where no wrinkles are generated is evaluated as "good", and the case where wrinkles are generated is evaluated as "bad".

[0299] <Test 3. Evaluation of wiring formation yield> The insulation resistance value of the comb-tooth wiring was measured for the evaluation circuit board using a resistance measuring instrument ("ECM-100" manufactured by J-RAS Corporation). The insulation resistance value was set to 1×10 7 The ratio of comb-tooth wiring with a value of Ω or more is 60% or more (i.e., 1×10 7 The case where the number of comb-tooth wirings with a value of Ω or greater was 15 or more) was evaluated as "good", and the case where it was less than 60% was evaluated as "bad".

[0300] <Results> The results of the above-mentioned Examples and Comparative Examples are shown in the following table.

[0301] [Table 1] [Table 1. Results of Example]

[0302] [Table 2] [Table 2. Results of Comparative Example]

[0303] <Discussion> It was confirmed from the Examples and Comparative Examples that the production method of the present invention can eliminate foreign matter and produce a laminated resin sheet (resin sheet with a protective film) that can improve the yield of wiring formation.

[0304] The above-mentioned Examples and Comparative Examples show the results of using an acrylic release agent, but the present inventors have confirmed that when using a release agent other than an acrylic agent, a laminated resin sheet that can exclude foreign matter and improve the yield of wiring formation can be produced, although the degree is different.

[0305] Explanation of symbols 1. Manufacturing device 2 Manufacturing equipment 10 Support 10U release surface (surface on the release layer side) 10D back side (the side opposite to the release layer) 11 Base material layer 12 Release layer 20 resin composition layer 21. Curable resin composition 30 resin sheet 40 protective film 40D first side 40U second side 50-layer laminated resin sheet (resin sheet with protective film) 100 Support body dust removal unit 110 first dust removal roller 110S Surface 120 Third dust removal roller 120S circumference 200 layer formation department 210 coating device 220 Drying device 300 protective film dust removal unit 310 Second dust removal roller 310S Surface 320 Fourth dust removal roller 320S Surface 400 Lamination Department 410 Pressing Roller 420 Pressing Roller Chamber 430 500 Support body dust removal unit 510 first dust removal roller 510S Surface 520 third dust removal roller 520S Surface 600 protective film dust removal unit 610 second dust removal roller 610S Surface 620 fourth dust removal roller 620S perimeter.

Claims

1. A method for producing a resin sheet with a protective film, the resin sheet with a protective film comprising, in order: a support having a release layer, a resin composition layer containing a curable resin composition, and a protective film, in, The manufacturing method comprises: a step of bringing the first dust removal roller into contact with the surface of the support body on the release layer side, a step of forming a resin composition layer on the surface of the support body on the side of the mold release layer, a step of bringing the second dust removal roller into contact with the first surface of the protective film, and a step of bonding the resin composition layer to the first surface of the protective film, The first dust removal roller has a strength lower than 2.9N / 100mm 2 The adhesion force, The second dust removal roller has a strength lower than 2.9N / 100mm 2 Adhesion.

2. The method for producing a resin sheet with a protective film according to claim 1, wherein: The step of forming the resin composition layer on the surface of the support on the release layer side includes a step of applying a liquid curable resin composition.

3. The method for producing a resin sheet with a protective film according to claim 1, wherein: The manufacturing method includes a step of bringing the third dust removing roller into contact with a surface of the support body on the opposite side to the release layer.

4. The method for producing a resin sheet with a protective film according to claim 1, wherein The manufacturing method includes a step of bringing a fourth dust removing roller into contact with a second surface of the protective film that is opposite to the first surface.

5. The method for producing a resin sheet with a protective film according to claim 1, wherein The curable resin composition contains a curable resin and an inorganic filler.

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