JP6690692B2 - Method for producing roughened cured body - Google Patents

Description

  The present invention relates to a roughened cured body. Furthermore, the present invention relates to a laminated body, a printed wiring board and a semiconductor device using the roughened cured body.

  As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers (circuits) are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing the resin composition. Then, the cured body of the resin composition is subjected to a roughening treatment to form a roughened cured body, and a conductor layer can be formed on the surface of the roughened cured body.

  Due to the recent tendency toward lightness, thinness, shortness, and miniaturization, circuit miniaturization has been promoted in printed wiring boards. Patent Document 1 discloses a technique of adjusting the surface roughness of a roughened cured body by using a special support in order to contribute to miniaturization of a circuit.

JP, 2014-36051, A

  As an index showing the surface roughness of the roughened cured body, the arithmetic mean roughness (Ra) which is a parameter relating to the height of the surface unevenness is well known. It is said that it is necessary to reduce the surface roughness of the roughened cured body in order to miniaturize the circuit, and various efforts have been made to reduce Ra on the surface of the roughened cured body.

  In the process of studying the miniaturization of circuits, the present inventors have found that the Ra value and the fine circuit forming ability do not necessarily correlate when the surface roughness of the roughened cured body is low to some extent. It was That is, it has been found that it is difficult to further miniaturize the circuit by reducing Ra on the surface of the roughened cured body.

  An object of the present invention is to provide a roughened cured body that enables further miniaturization of a circuit.

  As a result of diligent studies on the above problems, the present inventors have found that the shapes and intervals of the irregularities on the surface of the roughened cured body correlate with the fine circuit forming ability. Based on such knowledge, the present inventors have found that further miniaturization of a circuit can be realized by introducing a specific uneven shape or a specific uneven space to the surface of the roughened cured body, and complete the present invention. Came to.

That is, the present invention includes the following contents.
[1] A roughened cured body obtained by roughening a cured body of a resin composition,
The surface of the roughened cured body has an arithmetic average roughness (Ra) of 500 nm or less,
When electroless plating is performed on the surface of the roughened hardened body to form a roughened hardened body with plating, in a cross section of the roughened hardened body with plating in a direction perpendicular to the surface of the roughened hardened body with plating, plating is performed. The length X of the plating region on the straight line L1 obtained by linearizing the interface of the roughened hardened body by the least-squares method and 0 parallel to the straight line L1 and from the straight line L1 in the depth direction of the roughened hardened body. A roughened cured body in which the length Y of the plating region on the straight line L2 separated by 2 μm satisfies the condition of Y / X ≦ 1.
[2] When the length of the plating region on the straight line L3 which is parallel to the straight line L1 and is Z (μm) away from the straight line L1 in the depth direction of the roughening cured body is Y ′, Y ′ / X The roughened cured product according to [1], wherein the minimum value of Z satisfying ≦ 0.05 is 3 or less.
[3] A roughened cured product obtained by roughening a cured product of a resin composition,
A roughened hardened body having an average spacing (Sm) of irregularities on the surface of the roughened hardened body of 2000 nm or less.
[4] The roughened cured body according to any one of [1] to [3], wherein the surface of the roughened cured body has an arithmetic average roughness (Ra) of 200 nm or less.
[5] The cured product of the resin composition is
A first thermosetting treatment for thermosetting the resin composition at a temperature T ₁ ,
[1] to [4] obtained by a thermosetting treatment including a second thermosetting treatment in which the resin composition after the first thermosetting treatment is thermoset at a temperature T ₂ higher than the temperature T ₁ . The roughened cured body according to any one of the above.
[6] The roughened cured product according to [5], wherein the resin composition after the first thermosetting treatment has a minimum melt viscosity of 11,000 poise to 300,000 poise.
[7] The roughened cured product according to any one of [1] to [6], wherein the resin composition contains an inorganic filler having an average particle diameter of 0.01 μm to 0.3 μm.
[8] The roughened cured product according to any one of [1] to [7], wherein the resin composition contains one or more selected from the group consisting of a naphthol-based curing agent and an active ester-based curing agent.
[9] A laminate including the roughened cured body according to any one of [1] to [8] and a conductor layer formed on the surface of the roughened cured body.
[10] The laminated body according to [9], wherein the conductor layer includes a circuit having a wiring pitch of 16 μm or less.
[11] A printed wiring board including an insulating layer formed of the roughened cured body according to any one of [1] to [8].
[12] A semiconductor device including the printed wiring board according to [11].

  According to the present invention, it is possible to provide a roughened cured body that enables further miniaturization of a circuit.

FIG. 1 is a schematic cross-sectional view of a roughened hardened body with plating formed by electroless plating on a roughened hardened body having a recess having a smaller opening diameter than the internal maximum diameter on its surface. FIG. 2 is a schematic cross-sectional view of a roughened hardened body with plating formed by electroless plating on a roughened hardened body having on its surface a concave portion having an opening diameter larger than the maximum internal diameter. FIG. 3 is a schematic sectional view (1) showing a method for measuring the length of the plating region on the straight line L2. FIG. 4 is a schematic sectional view (2) showing a method for measuring the length of the plating region on the straight line L2.

  Hereinafter, the present invention will be described in detail with reference to its preferred embodiments.

[Roughened hardened material]
The roughened cured material of the present invention is characterized by having fine recesses on the surface, the opening diameter of which is equal to or larger than the internal maximum diameter. Here, the internal maximum diameter refers to the maximum diameter inside the recess.

  In the process of studying circuit miniaturization, the inventors of the present invention, when the surface roughness of the roughening cured body is low to some extent (for example, Ra is 500 nm or less), the value of Ra and the fine circuit forming ability. It was found that it does not necessarily correlate with. As a result of studying the uneven shape of the surface of the roughened hardened body, when the surface roughness of the roughened hardened body is low to a certain extent, a recess having an opening diameter smaller than the maximum internal diameter tends to be formed on the surface. Found. In the roughened hardened body having the jar-shaped concave portion whose inside is thus bulged, the conductor in the concave portion is removed when the unnecessary portion (non-circuit forming portion) of the conductor layer is removed by etching during circuit formation. It is difficult to do so, and it is presumed that when etching is performed under the condition that the conductor in the concave portion can be sufficiently removed, the dissolution of the wiring pattern becomes remarkable, which hinders miniaturization of the circuit.

  On the other hand, the roughening-cured product of the present invention has a somewhat low surface roughness (for example, Ra is 500 nm or less), and has a concave portion having an opening diameter equal to or larger than the internal maximum diameter on the surface. . As a result, unnecessary portions of the conductor layer can be easily removed during circuit formation, and further miniaturization of the circuit can be achieved.

  In the present invention, the uneven shape of the surface of the roughened cured body (specifically, the shape of the concave portion) is the plating when the surface of the roughened cured body is electroless plated to form a roughened cured body with plating. The distribution of the plating area in the vicinity of the interface between the roughened and hardened body can be expressed as an index.

  Specifically, on a straight line L1 obtained by linearizing the interface between the plating and the roughened cured body by the least-squares method in the cross section of the roughened cured body with the plated in a direction perpendicular to the surface of the roughened cured body with the plating. The ratio of the length X of the plating region on the straight line L1 to the length Y of the plating region on the straight line L2 which is parallel to the straight line L1 and is 0.2 μm away from the straight line L1 in the depth direction of the roughened cured body ( Y / X), and the obtained value of the ratio Y / X can be used as an index.

  FIG. 1 is a schematic cross-sectional view of a roughened cured body with plating formed by electroless plating on a roughened cured body having a recess having a smaller opening diameter than the internal maximum diameter on its surface. The roughened hardened body with plating shown in FIG. 1 is formed by roughening hardened body 1 having a concave portion whose opening diameter is smaller than the maximum internal diameter on the surface and electroless plating on the surface of the roughened hardened body. And plating 20 included. The length X of the plating region on the straight line L1 obtained by linearizing the interface between the plating and the roughened cured body by the least squares method is, for example, as shown in FIG. 1 in which three roughened portions are formed on the surface of the roughened cured body. The roughened cured product with plating can be obtained by adding the lengths x1, x2 and x3 of the plating regions derived from the three recesses. Actually, a large number of recesses are formed on the surface of the roughened hardened body, and the length X is obtained by adding the lengths of the plating regions derived from these recesses. The same applies to the length Y of the plating region on the straight line L2. In the roughened hardened body with plating shown in FIG. 1, all the recesses have an opening diameter smaller than the maximum internal diameter, and the lengths x1, x2, and x3 of the plating region on the straight line L1 are: It is shorter than the lengths y1, y2 and y3 of the plating regions on the straight line L2. Not limited to such an aspect, when the ratio (Y / X) of the length X and the length Y obtained by the above procedure exceeds 1, even if it is equal to or larger than the internal maximum diameter. Even if a concave portion having an opening diameter is formed in part, it is still unsuitable in terms of fine circuit forming ability. When the ratio Y / X exceeds 1, a concave portion having an opening diameter smaller than the internal maximum diameter is formed at least in part, which results in a local defect of fine circuit forming ability. is there.

  FIG. 2 shows a schematic cross-sectional view of a roughened hardened body with plating formed by electroless plating on a roughened hardened body having on its surface a concave portion having an opening diameter larger than the maximum internal diameter. The roughened hardened body with plating described in FIG. 2 is formed by roughening hardened body 10 having a concave portion having an opening diameter larger than the maximum internal diameter on the surface and electroless plating on the surface of the roughened hardened body. And plating 20 included. The procedure for obtaining the length X of the plating area on the straight line L1 and the length Y of the plating area on the straight line L2 is the same as above. In the roughened hardened body with plating shown in FIG. 2, all the recesses have an opening diameter larger than the internal maximum diameter, and the lengths x1, x2 and x3 of the plated regions on the straight line L1 are It is longer than the lengths y1, y2 and y3 of the plating regions on the straight line L2, respectively. Such an aspect is ideal for realizing excellent fine circuit forming ability, but the present inventors obtain good fine circuit forming ability when the ratio Y / X is 1 or less. I have confirmed that.

  Therefore, in one embodiment, the present invention is a roughened cured product obtained by roughening a cured product of a resin composition, wherein the surface of the roughened cured product has an arithmetic average roughness (Ra) of 500 nm or less. And when a roughened hardened body with plating is formed by electroless plating on the surface of the roughened hardened body, in a cross section of the roughened hardened body with plating in a direction perpendicular to the surface of the roughened hardened body with plating. , The length X of the plating region on the straight line L1 obtained by linearizing the interface between the plating and the roughened hardened body by the least squares method, and the depth of the roughened hardened body which is parallel to the straight line L1 and from the straight line L1 The length Y of the plating region on the straight line L2 that is 0.2 μm apart in the direction satisfies the condition of Y / X ≦ 1.

  From the viewpoint of achieving further miniaturization of the circuit, the ratio Y / X is 1 or less, preferably 0.98 or less, more preferably 0.96 or less, still more preferably 0.94 or less, and even more preferably 0. 0.92 or less, particularly preferably 0.9 or less, 0.88 or less, 0.86 or less, 0.84 or less, 0.82 or less, 0.8 or less, 0.78 or less, 0.76 or less, or 0. It is 74 or less. The lower limit of the ratio Y / X is not particularly limited and is preferably low, but it can usually be 0.2 or more, 0.3 or more.

  The cross section of the roughened cured product with plating can be suitably observed using a FIB-SEM composite device. Examples of the FIB-SEM composite device include "SMI3050SE" manufactured by SII Nano Technology Co., Ltd. FIB (Focused Ion Beam) is used to cut out a cross section of the roughened cured body with plating in a direction perpendicular to the surface of the roughened cured body with plating, and then the cross section is observed by an SEM (scanning electron microscope) to perform plating. It is possible to acquire a cross-sectional SEM image near the interface between the roughened cured body and The observation width and the observation magnification by SEM are not particularly limited as long as the uneven shape of the surface of the roughened cured body can be appropriately grasped, and may be determined according to the specifications of the apparatus used.

  When a straight line L1 is obtained by linearizing the interface between the plating and the roughened hardened body by the least-squares method, the interface between the plated and the roughened hardened body is defined in the acquired cross-sectional SEM image with reference to the convex portion of the roughened hardened body. It may be linearized by the least squares method. Thereby, the approximate straight line L1 can be provided on the opening surface of the recess. Hereinafter, a method of calculating the ratio Y / X will be described with the plated side in the cross-sectional SEM image as the upper side and the roughened cured body side as the lower side.

  The acquired cross-sectional SEM image is equally divided into sections having a predetermined width, and the position of the roughened hardened body existing on the uppermost side of each section is adopted as a reference point. For example, a cross-sectional SEM image of the observation width W (μm) can be divided into n equal parts into sections of a predetermined width W / n (μm), and n reference points can be obtained. W and n may be set as described in <Evaluation of Concavo-convex shape of roughened cured body surface> described later. Although the details will be described later, the roughened cured body is obtained by roughening a cured body of a resin composition containing an inorganic filler and a resin component. Therefore, “the position of the roughened cured body existing on the uppermost side” means the position of the resin component when the resin component exists on the uppermost side, and the inorganic filler when the inorganic filler exists on the uppermost side. The position of the material. The obtained n reference points are subjected to coordinate conversion, and an approximate straight line based on the n reference points, that is, the straight line L1 is obtained by the least square method.

  The straight line L2 can be obtained by drawing a straight line parallel to the straight line L1 0.2 μm below the straight line L1.

  The procedure for obtaining the lengths X and Y of the plated area is as described above. By obtaining a sufficient number of cross-sectional SEM images, it is possible to obtain overall characteristics regarding the uneven shape of the roughened cured body surface. When a plurality of cross-section SEM images are acquired, the length X can be obtained by summing the lengths of the plating regions on the straight line L1 for all cross-section SEM images. The same applies to the length Y and Y'described later.

  In the present invention, when the inorganic filler is present on the straight line L1, the inorganic filler region is treated as follows in calculating the length X. When at least a part of the inorganic filler is in contact with the resin component, the inorganic filler region is treated as a roughened cured body region. On the other hand, when the inorganic filler is not in contact with the resin component and is covered with the electroless plating, the inorganic filler area is treated as a plating area. The same applies when the inorganic filler is present on the straight line L2. For example, in the roughened hardened body with plating whose schematic cross-sectional view is shown in FIG. 3, the inorganic filler 12 having a portion in contact with the resin component 11 exists on the straight line L2. In this case, the inorganic filler region is treated as a roughened hardened body region, and the length of the inorganic filler region is not included in the length y of the plating region. On the other hand, in the roughened cured body with plating whose schematic cross-sectional view is shown in FIG. 4, the inorganic filler 12 not in contact with the resin component 11 but covered with the electroless plating is present on the straight line L2. In this case, the inorganic filler region is treated as a plating region, and the length of the inorganic filler region is included in the length y of the plating region. This is because when the inorganic filler is covered with the electroless plating, it is highly likely that the inorganic filler is removed together with the electroless plating when the unnecessary conductor layer is removed when the circuit is formed.

  From the viewpoint of achieving further miniaturization of the circuit, it is preferable that the depth of the recesses formed on the surface of the roughened cured body is not more than a predetermined value. In one embodiment, when the length of the plating region on the straight line L3 that is parallel to the straight line L1 and is separated from the straight line L1 by Z (μm) in the depth direction of the roughening cured body is Y ′, Y ′ The minimum value of Z satisfying /X≦0.05 is preferably 3 or less, more preferably 2.8 or less, further preferably 2.6 or less, and 2.4 or less. Even more preferably, it is 2.2 or less, 2 or less, 1.8 or less, 1.6 or less, 1.4 or less, 1.2 or less, or particularly preferably 1 or less. Although the lower limit of the minimum value of Z is not particularly limited, it can usually be more than 0.2, 0.3 or more, 0.4 or more, 0.6 or more.

  From the viewpoint of achieving further miniaturization of the circuit, the length of the plating region on the straight line L3 that is parallel to the straight line L1 and is separated from the straight line L1 in the depth direction of the roughening cured body by Z (μm) is Y ′. In this case, the minimum value of Z at which Y ′ is 0 is preferably 3 or less, more preferably 2.8 or less, further preferably 2.6 or less, and 2.4 or less. Is even more preferable, and 2.2 or less, 2 or less, 1.8 or less, 1.6 or less, 1.4 or less, 1.2 or less, or 1 or less is particularly preferable. Although the lower limit of the minimum value of Z is not particularly limited, it can usually be more than 0.2, 0.3 or more, 0.4 or more, 0.6 or more.

  As long as the ratio Y / X is 1 or less, the arithmetic average roughness (Ra) of the surface of the roughened cured body is preferably lower from the viewpoint of further miniaturization of the circuit. Ra of the surface of the roughened cured body is preferably 400 nm or less, more preferably 350 nm or less, further preferably 300 nm or less, still more preferably 250 nm or less, particularly preferably 240 nm or less, 220 nm or less, 200 nm or less, 180 nm or less, 160 nm or less. Or 150 nm or less. The lower limit of Ra is not particularly limited, but may be usually 10 nm or more, 20 nm or more, 30 nm or more. The arithmetic mean roughness (Ra) of the surface of the roughened cured body can be measured using a non-contact surface roughness meter. As the non-contact type surface roughness meter, for example, "WYKO NT3300" manufactured by Beecoin Instruments is listed.

  The present inventors have also found that the uneven shape of the surface of the roughened cured body (specifically, the shape of the recess) correlates well with the average interval (Sm) of the unevenness of the surface of the roughened cured body. Specifically, for a roughened hardened body having a concave portion with an opening diameter smaller than the internal maximum diameter as shown in FIG. 1, the value of Sm is large and the opening diameter is larger than the internal maximum diameter as shown in FIG. It was found that the value of Sm was small for the roughened cured body having large concave portions on the surface. The present inventors have confirmed that the roughened cured material having the ratio Y / X of 1 or less tends to have an Sm value of 2000 nm or less.

  Therefore, in one embodiment, the present invention is a roughened cured product obtained by subjecting a cured body of a resin composition to a roughening treatment, wherein the average interval (Sm) of the irregularities on the surface of the roughened cured product is 2000 nm or less. There is a roughened cured body.

  From the viewpoint of achieving further miniaturization of the circuit, the average spacing (Sm) of the irregularities on the surface of the roughened cured body is 2000 nm or less, preferably 1950 nm or less, more preferably 1900 nm or less, still more preferably 1850 nm or less, and even more It is preferably 1800 nm or less, particularly preferably 1750 nm or less, or 1700 nm or less. Although the lower limit of Sm is not particularly limited, it can be usually 500 nm or more, 700 nm or more. The average spacing (Sm) of the irregularities on the surface of the roughened cured body can be measured by using a non-contact surface roughness meter, as in Ra. The average spacing (Sm) of surface irregularities means the average spacing between profile peaks of the surface uneven profile. By profile peak is meant the highest peak between the points across and above the average line of the relief profile. Sm is a standard parameter defined by ISO 4287 and JIS B 0601.

  In such an embodiment as well, the preferable range of the arithmetic average roughness (Ra) of the surface of the roughened cured body is as described above.

  The thickness of the roughened cured product of the present invention is preferably 3 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, 15 μm or more, or 20 μm or more from the viewpoint of obtaining good insulation. Further, the thickness of the roughened cured body of the present invention is preferably 100 μm or less, more preferably 90 μm or less, still more preferably 80 μm or less, 70 μm or less, or 60 μm or less from the viewpoint of thinning a printed wiring board.

  The roughened cured body of the present invention may have a multi-layer structure composed of two or more layers. In the case of a roughened cured product having a multilayer structure, the total thickness is preferably within the above range.

  Hereinafter, the resin composition used for forming the roughened cured body of the present invention will be described.

<Resin composition>
The resin composition used for forming the roughened cured body of the present invention has a cured body having sufficient hardness and insulating properties, and the roughened body obtained by roughening the cured body is There is no particular limitation as long as the desired uneven shape and uneven spacing are satisfied. For example, the resin composition includes a resin composition containing a thermosetting resin and a curing agent. As the thermosetting resin, a conventionally known thermosetting resin used when forming an insulating layer of a printed wiring board can be used, and an epoxy resin is preferable. Therefore, in one embodiment, the resin composition includes an epoxy resin and a curing agent. The resin composition may further contain additives such as an inorganic filler, a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler, if necessary. In addition, in this invention, "resin component" means the component other than an inorganic filler among the components which comprise a resin composition.

-Epoxy resin-
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, Phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing ether Carboxymethyl resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. The epoxy resins may be used alone or in combination of two or more.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, the resin composition is a solid epoxy resin at a temperature of 20 ° C. (also referred to as “solid epoxy resin”) alone, or a solid epoxy resin and a liquid epoxy resin at a temperature of 20 ° C. (hereinafter, “ Liquid epoxy resin ”). As the solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule is more preferable. As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

  The liquid epoxy resin has a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, and a butadiene structure. Epoxy resins are preferable, and bisphenol A type epoxy resins, bisphenol F type epoxy resins, and naphthalene type epoxy resins are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032H”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “jER828US”, “jER828EL” manufactured by Mitsubishi Chemical Corporation. "(Bisphenol A type epoxy resin)," jER807 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac type epoxy resin)," ZX1059 "(bisphenol A type epoxy resin and bisphenol manufactured by Nippon Steel & Sumitomo Metal Corporation) Mixture of F type epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., "Ceroxide 2021P" (trade name) manufactured by Daicel Corporation (alicyclic epoxy resin having ester skeleton) ), "PB-3600" Epoxy resin) having an butadiene structure. These may be used alone or in combination of two or more.

  As the solid epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, And bisphenol AF type epoxy resin are more preferable. Specific examples of the solid epoxy resin include "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690", and "N-695" (cresol novolac) manufactured by DIC Corporation. Type epoxy resin), "HP7200", "HP7200H", "HP7200HH" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000". (Naphthylene ether type epoxy resin), "EPPN-502H" (Trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", " NC3000L "," NC3100 "(Bifeni Type epoxy resin), “ESN475V” (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolac type epoxy resin), “YX4000H” and “YL6121” (biphenyl) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., Mitsubishi Chemical Corporation ) "YL7800" (fluorene type epoxy resin), Mitsubishi Chemical Corporation "jER1010" (solid bisphenol A type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "jER1031S" (tetraphenyl) Ethane type epoxy resin) and the like.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their amount ratio (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 8 by mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin and the solid epoxy resin in such a range, i) suitable adhesiveness is brought when used in the form of an adhesive film described later, ii) used in the form of an adhesive film In this case, sufficient flexibility can be obtained, handleability can be improved, and iii) a cured product having sufficient breaking strength can be obtained. The mass ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 0.3 to 1: 7, and 1: 0.6 to 1: The range of 6 is more preferable, and the range of 1: 0.8 to 1: 5 is particularly preferable.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, and still more preferably 110 to 1000. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing one equivalent of epoxy group.

  The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

  3 mass% -40 mass% are preferable, as for content of the epoxy resin in a resin composition, 5 mass% -35 mass% are more preferable, 10 mass% -30 mass% are still more preferable.

  In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

-Curing agent-
The curing agent is not particularly limited as long as it has a function of curing an epoxy resin, and examples thereof include a phenol curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and Examples include carbodiimide-based curing agents. The curing agents may be used alone or in combination of two or more.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion strength (peel strength) with the conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenolic curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. . A triazine skeleton-containing phenol novolac-based curing agent and a triazine skeleton-containing naphthol novolac-based curing agent are preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with a conductor layer. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD2090" manufactured by DIC Corporation. And the like.

  From the viewpoint of obtaining a roughened cured material having excellent heat resistance, an active ester curing agent is also preferable. The active ester-based curing agent is not particularly limited, but in general, an ester group having a high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, and ester of heterocyclic hydroxy compound is contained in one molecule. Compounds having two or more of them are preferably used. The active ester type curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, phloroglucin, Examples thereof include benzenetriol, dicyclopentadiene type diphenol compound, and phenol novolac. Here, the “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

  Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable, Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene type diphenol structure. ), “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, and benzoyl phenol novolac. Examples of the active ester compound containing a compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Highpolymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Chemicals Co., Ltd.

  Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenyl propane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether. Phenol novolac and Polyfunctional cyanate resin derived from resol novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd., and "BA230" (a part or all of bisphenol A dicyanate). A tripolymer of which is a triazine) and the like.

  Specific examples of the carbodiimide-based curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Inc.

  Among these, the naphthol-based curing agent and the active ester-based curing agent provide a cured product having high resistance to a roughening treatment and a roughened cured product having a low surface roughness. On the other hand, the naphthol-based curing agent and the active ester-based curing agent are roughened hardened bodies having concave portions whose opening diameter is smaller than the internal maximum diameter on the surface, that is, the above-mentioned roughened hardened bodies having a ratio Y / X of more than 1. The present inventors have found that it is easy to reduce It is possible to reduce the value of the ratio Y / X to some extent by suppressing the use amount of the naphthol-based curing agent and the active ester-based curing agent to a low level. There is a limit to adjustment, and there is concern that Ra will rise. Although the details will be described later, in the present invention, the value of the ratio Y / X is desired by operating the curing conditions of the resin composition and the like to adjust the phase separation size and the degree of cross-linking density of the cured product. The range can be adjusted to. The naphthol-based curing agent and the active ester-based curing agent have inherently excellent curing characteristics such as providing a roughened cured body with low surface roughness. Therefore, in one embodiment in which the effect of the present invention can be more enjoyed, the resin composition contains one or more selected from the group consisting of a naphthol-based curing agent and an active ester-based curing agent.

  The total content of the naphthol-based curing agent and the active ester-based curing agent in the curing agent is preferably 20% by mass or more, more preferably 30% by mass or more, when the nonvolatile component in the curing agent is 100% by mass. It is preferably 40% by mass or more. The upper limit of the total content is preferably less than 80% by mass, more preferably 75% by mass or less, or 70% by mass or less.

  The amount ratio of the epoxy resin and the curing agent is preferably [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the curing agent] in the range of 1: 0.2 to 1: 2, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1.2 is further preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Further, the total number of epoxy groups of the epoxy resin is a value obtained by summing the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is It is a value obtained by summing the values obtained by dividing the solid content mass of each curing agent by the reactive group equivalent for all curing agents.

-Inorganic filler-
The resin composition may include an inorganic filler. By including the inorganic filler, the coefficient of thermal expansion of the obtained roughened cured body can be suppressed to be low.

  The material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, and the like, with silica being particularly preferred. That. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Spherical silica is preferable as the silica. The inorganic fillers may be used alone or in combination of two or more. Examples of commercially available spherical fused silica include "SO-C2" and "SO-C1" manufactured by Admatechs Co., Ltd.

  The average particle size of the inorganic filler is preferably 3 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less, and even more preferably 0 from the viewpoint of obtaining a roughened cured body having the above-mentioned desired uneven shape and unevenness interval. 0.7 μm or less, particularly preferably 0.5 μm or less, 0.4 μm or less, or 0.3 μm or less. On the other hand, the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm or more, from the viewpoint of obtaining a resin varnish having an appropriate viscosity and good handleability when forming the resin varnish. , And more preferably 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more. When an inorganic filler having a small average particle size is used, the phase separation size of the obtained cured product can be suppressed to be small, which is advantageous in achieving a roughened cured product having the above-mentioned desired uneven shape and uneven spacing. The present inventors have confirmed that. In a particularly preferred embodiment, the resin composition contains an inorganic filler having an average particle size of 0.01 μm to 0.3 μm. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis with a laser diffraction particle size distribution measuring device, and the median diameter can be used as the average particle diameter for measurement. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring device, "LA-500", "LA-750", "LA-950" manufactured by Horiba Ltd. can be used.

  The inorganic filler is an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, a titanate coupling agent, from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents such as Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical Co., Ltd. “KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Co., Ltd. and the like can be mentioned.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is from the viewpoint of improving the dispersibility of the inorganic filler, and by suppressing the phase separation size of the obtained cured product to be small, the roughened cured product having the desired uneven shape and uneven spacing. from the viewpoint of obtaining, preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} or more is more preferable. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish and the melt viscosity in the film form from being excessively increased, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less Is more preferable.

  The amount of carbon per unit surface area of the inorganic filler can be measured after cleaning the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. can be used.

  From the viewpoint of obtaining a roughened cured product having a low coefficient of thermal expansion, the content of the inorganic filler in the resin composition is preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, It is 55 mass% or more, 60 mass% or more, 65 mass% or more, or 70 mass% or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, from the viewpoint of the mechanical strength of the obtained roughened cured body. Is.

-Thermoplastic resin-
Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins. The thermoplastic resins may be used alone or in combination of two or more.

  The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-manufactured by Showa Denko KK as a column. 804L / K-804L can be calculated by using chloroform or the like as a mobile phase at a column temperature of 40 ° C. and using a calibration curve of standard polystyrene.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene. Examples include phenoxy resins having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both are bisphenol A skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation, "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" ( Bisphenol acetophenone skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX7553", "YL6794", "YL7213" manufactured by Mitsubishi Chemical Corporation, Examples thereof include "YL7290" and "YL7482".

  Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, Denki Kagaku Kogyo Co., Ltd., "Electrical butyral 4000-2", "Electrical butyral 5000-A", "Electrical butyral 6000-C", "Electrical butyral 6000-EP". The S-REC BH series, BX series, KS series, BL series, and BM series manufactured by Sekisui Chemical Co., Ltd. may be mentioned.

  Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin also include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (described in JP-A 2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

  Specific examples of the polyamide-imide resin include “Vylomax HR11NN” and “Vylomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. .

-Curing accelerator-
The resin composition layer may include a curing accelerator.

  Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Of these, amine curing accelerators and imidazole curing accelerators are preferable. The curing accelerator may be used alone or in combination of two or more. The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 0.005% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass.

-Flame retardant-
Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides, and the like. The flame retardants may be used alone or in combination of two or more. The content of the flame retardant in the resin composition is not particularly limited, but it is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass.

-Organic filler-
As the organic filler, any organic filler that can be used in the production of printed wiring boards may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.

  The rubber particles are not particularly limited as long as they are fine particles of a resin that is chemically insoluble in an organic solvent and infusible by subjecting a resin exhibiting rubber elasticity to a chemical cross-linking treatment.For example, acrylonitrile-butadiene rubber particles, butadiene rubber particles, Examples thereof include acrylic rubber particles. Specific examples of the rubber particles include XER-91 (manufactured by Japan Synthetic Rubber Co., Ltd.), Staphyroid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, Aika Kogyo KK), Paraloid. EXL2655, EXL2602 (above, Kureha Chemical Industry Co., Ltd. product) etc. are mentioned.

  The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in an appropriate organic solvent by ultrasonic waves, and the particle size distribution of the organic filler is measured by mass using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). It can be measured by making it as a standard and setting the median diameter as the average particle diameter. The content of the organic filler in the resin composition is preferably 1% by mass to 10% by mass, more preferably 2% by mass to 5% by mass.

  The resin composition may further contain other components, if necessary. Such other components include, for example, organocopper compounds, organometallic compounds such as organozinc compounds and organocobalt compounds, and thickeners, defoamers, leveling agents, adhesion promoters, and resins such as colorants. Examples include additives.

  The roughened cured body of the present invention can be used as a roughened cured body for forming an insulating layer of a printed wiring board (roughened cured body for insulating layer of printed wiring board). Among them, in the production of a printed wiring board by a build-up method, it can be suitably used as a roughened hardened body for forming an insulating layer (a roughened hardened body for a buildup insulating layer of a printed wiring board). It can be more suitably used as a roughened cured body for forming a conductor layer (a roughened cured body for a buildup insulating layer of a printed wiring board on which a conductor layer is formed by plating).

  When using the roughened cured body of the present invention in a printed wiring board, the resin composition used to form the roughened cured body of the present invention, from the viewpoint of easily and efficiently laminating the inner layer substrate, It is preferably used in the form of an adhesive film including a layer made of the resin composition.

  In one embodiment, the adhesive film includes a support and a layer made of a resin composition bonded to the support (hereinafter, also simply referred to as “resin composition layer”).

  A resin composition layer having a multilayer structure may be used to form a roughened cured body having a multilayer structure.

  Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material is preferably used. Examples of the plastic material include polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic such as polycarbonate (PC) and polymethylmethacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether. Examples include sulfide (PES), polyether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In a preferred embodiment, the support is a polyethylene terephthalate film.

  Examples of commercially available supports include "Lumirror T6AM", "Lumirror R56", "Lumirror R80" (PET film) manufactured by Toray Industries, Inc., and "G2LA" (PET film) manufactured by Teijin DuPont Films Ltd. , "Teonex Q83" (PEN film) and the like.

  The support may have a matte treatment or a corona treatment applied to the surface on the side to be joined to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be joined to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Co., Ltd., which are alkyd resin release agents.

  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. When the support is a support with a release layer, the total thickness of the support with a release layer is preferably within the above range.

  The adhesive film, for example, a resin varnish prepared by dissolving the resin composition in a solvent is prepared, and the resin varnish is applied onto a support using a die coater or the like, and further dried to form a resin composition layer. Can be manufactured by.

  Examples of the solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, acetic acid esters such as propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The solvent may be used alone or in combination of two or more.

  Drying may be performed by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C to 150 ° C for 3 minutes to 10 minutes. An object layer can be formed.

The minimum melt viscosity V ₀ of the resin composition layer is preferably 300 poises to 12000 poises, from the viewpoint of suppressing resin bleeding during production of a printed wiring board and achieving good stackability (circuit embedding property). It is preferably 500 poises to 10,000 poises, or 700 poises to 8000 poises. Therefore, in one embodiment, the roughened cured product of the present invention is obtained by roughening the cured product of the resin composition using a resin composition having a minimum melt viscosity of 300 poises to 12000 poises. The “minimum melt viscosity” of the resin composition layer refers to the minimum viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant heating rate to melt the resin, the melt viscosity decreases with an increase in temperature in the initial stage, and thereafter, when the temperature exceeds a certain temperature, the melt viscosity increases with a temperature increase. To rise. The "minimum melt viscosity" refers to the melt viscosity at such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method, and can be measured, for example, according to the method described in <Measurement of minimum melt viscosity> described later.

  In the adhesive film, a protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and prevent scratches. The adhesive film can be wound into a roll and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

The roughened cured body of the present invention is obtained by subjecting the cured body of the above resin composition to a roughening treatment. For example, the roughened cured product of the present invention is produced by a method including the following steps (A) and (B).
(A) A step of thermally curing the resin composition to form a cured body. (B) A step of roughening the cured body to form a roughened cured body.

As described above, the resin composition is preferably used in the form of an adhesive film including a layer made of the resin composition. Therefore, in a preferred embodiment, step (A) comprises
(A1) providing a resin composition layer using an adhesive film including a support and a layer made of a resin composition bonded to the support; and (A2) thermally curing the resin composition layer. To obtain a cured product. The target (that is, the inner layer substrate) on which the resin composition layer is provided in (A1) will be described later.

  The constitution of the resin composition used in the step (A) is as described above. From the viewpoint of being able to advantageously realize a roughened cured body having the desired uneven shape and uneven spacing, it is preferable to use a resin composition containing an epoxy resin, a curing agent, and an inorganic filler (preferably silica). It is more preferable to use a resin composition containing a resin, a curing agent, an inorganic filler (preferably silica), and a thermoplastic resin, and an epoxy resin, a curing agent, an inorganic filler (preferably silica), a thermoplastic resin, and It is more preferable to use a resin composition containing a curing accelerator. In addition to having a low surface roughness, the curing agent selected from the group consisting of a naphthol-based curing agent and an active ester-based curing agent can be advantageously realized from a roughened cured body having the above-mentioned desired uneven shape and uneven spacing. At least one selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin as the thermoplastic resin, and a curing accelerator from the group consisting of an amine-based curing accelerator and an imidazole-based curing accelerator. It is preferable to use at least one selected from the above.

The thermosetting of the resin composition in the step (A) heat-cures the resin composition at a temperature T ₁ from the viewpoint that a roughened cured body having the above-described desired uneven shape and uneven spacing can be more easily realized. A heat curing treatment including a heat curing treatment of No. 1 and a second heat curing treatment of thermally curing the resin composition after the first heat curing treatment at a temperature T ₂ higher than the temperature T ₁ (hereinafter, “step It is also preferable to carry out the heat treatment. Thus, in one embodiment, the cured product of the resin composition, a first heat curing treatment for thermally curing the resin composition at temperatures T _1, from the temperature T ₁ of the resin composition after the first heat-curing treatment Is obtained by a heat curing treatment including a second heat curing treatment in which the heat curing is performed at a high temperature T ₂ . In the embodiment using the adhesive film, the “resin composition” may be read as “resin composition layer” and applied. The same applies to the following description.

When the resin composition is heat-cured by the step heat-curing treatment, it is not limited to the two-step heating (T ₁ → T ₂ ), and may be the three-step (T ₁ → T ₂ → T ₃ ) or more multi-step heating. Good.

From the viewpoint of being able to advantageously realize a roughened cured body having the above-mentioned desired uneven shape and uneven spacing, the first heat-curing treatment preferably has a minimum melt viscosity V ₁ of the resin composition after the first heat-curing treatment. Is preferably carried out in the range of 11,000 poise to 300,000 poise. The lower limit of the minimum melt viscosity V ₁ is more preferably 12000 poises or more, 13000 poises or more, or 14000 poises or more. The upper limit of the minimum melt viscosity V ₁ is more preferably 290000 poises or less, 280000 poises or less, 270000 poises or less, or 260000 poises or less. When the first thermosetting treatment is carried out so that the minimum melt viscosity V ₁ falls within such a range, it is possible to proceed with thermosetting in a state where the respective components constituting the resin composition have high compatibility. It is possible to suppress excessive movement of each component constituting the resin composition during the heat curing treatment at a higher temperature such as the second heat curing treatment. This makes it possible to proceed with thermosetting in a state where the phase separation size and the degree of cross-linking density are relatively small, and is advantageous in achieving a roughened cured body having the above-mentioned desired uneven shape and uneven spacing. The inventors have confirmed.

In a preferred embodiment using an adhesive film, the support may be peeled between (A1) and (A2), or may be peeled after (A2). The support is preferably peeled off after (A2) from the viewpoint of being able to advantageously realize the roughened cured material having the desired uneven shape and uneven spacing. That is, it is preferable to heat cure the resin composition layer with the support attached. In such a case, the temperature T ₁ of the _first thermosetting treatment is preferably [softening point of support −50] (° C.) or higher, more preferably [softening point of support −30] (° C.) or higher, further It is preferably [softening point of support −10] (° C.) or higher, or [softening point of support] (° C.) or higher. The upper limit of the temperature T ₁ is preferably [support softening point +30] (° C) or lower, more preferably [support softening point +25] (° C) or lower, or [support softening point +20] (° C). It is the following. When these conditions are satisfied, it is possible to obtain a cured product having a smooth surface and a phase separation size in an appropriate range, and it is advantageous in achieving the desired uneven shape and uneven spacing after the roughening treatment. The inventors have confirmed.

  The time for performing the first thermosetting treatment is not particularly limited as long as the effects of the present invention are exhibited, and may be determined according to the composition of the resin composition and the like. The time for performing the first thermosetting treatment may be, for example, 5 minutes to 180 minutes, 10 minutes to 150 minutes, or 15 minutes to 120 minutes.

The temperature T ₂ of the _second thermosetting treatment is higher than the temperature T ₁ . The temperature T ₂ is not particularly limited as long as a cured product having sufficient hardness can be obtained, and may be determined according to the composition of the resin composition and the like. The temperature T ₂ is preferably (T ₁ +10) ° C. or higher, more preferably (T ₁ +20) ° C. or higher, (T ₁ +30) ° C. or higher, (T ₁ +40) ° C. or higher, or (T ₁ +50) ° C. or higher. Is. The upper limit of the temperature T ₂ is preferably (T ₁ +150) ° C. or lower, more preferably (T ₁ +140) ° C. or lower, (T ₁ +130) ° C. or lower, (T ₁ +120) ° C. or lower, (T ₁ +110) ° C. Or below, or (T ₁ +100) ° C. or below. The lower limit of the temperature T ₂ is usually 150 ° C. or higher, 160 ° C. or higher, and the upper limit of the temperature T ₂ is usually 240 ° C. or lower, 230 ° C. or lower, 220 ° C. or lower.

  The time for performing the second thermosetting treatment is not particularly limited as long as the effects of the present invention are exhibited, and may be determined according to the composition of the resin composition and the like. The time for performing the second heat curing treatment may be, for example, 5 minutes to 120 minutes, 10 minutes to 90 minutes, or 15 minutes to 60 minutes.

From the viewpoint of being able to advantageously realize the roughened cured body having the above-described desired uneven shape and uneven spacing, after the second heat curing treatment, the cured body is returned from the temperature T ₂ to room temperature with a predetermined temperature decreasing profile. Is preferred. Curing at a temperature decrease rate of preferably 10 ° C./min or less, more preferably 8 ° C./min or less, further preferably 6 ° C./min or less, 5 ° C./min or less, 4 ° C./min or less, or 3 ° C./min or less. It is preferable to bring the body back from room temperature T ₂ to room temperature. Although the lower limit of the temperature lowering rate is not particularly limited, it can be usually 0.5 ° C./min or more, 1 ° C./min or more. When such a condition is satisfied, a cured product having a smooth surface and a phase separation size in an appropriate range can be obtained, and it is advantageous in achieving the desired uneven shape and uneven spacing after the roughening treatment. The inventors have confirmed.

  The pressure of the atmosphere at the time of heat curing is not particularly limited, and it may be performed under normal pressure, reduced pressure, or increased pressure.

  The procedure and conditions of the roughening treatment in the step (B) are not particularly limited, and known procedures and conditions usually used when forming an insulating layer of a printed wiring board can be adopted.

  For example, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid can be performed in this order to roughen the cured product. The swelling liquid is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and the alkaline solution is preferable. As the alkaline solution, sodium hydroxide solution and potassium hydroxide solution are preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid can be performed, for example, by immersing the cured product in the swelling liquid at 30 to 90 ° C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the cured product to an appropriate level, it is preferable to immerse the cured product in a swelling liquid at 40 to 80 ° C. for 5 to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the cured product in the oxidizing agent solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30 ° C to 80 ° C for 5 minutes to 30 minutes.

  The thus obtained roughened cured product of the present invention has a low surface roughness and also has a concave portion having an opening diameter equal to or larger than the internal maximum diameter on the surface. This makes it possible to easily remove unnecessary portions of the conductor layer when forming a circuit, and to achieve further miniaturization of the circuit when manufacturing a printed wiring board.

[Laminate]
The laminate of the present invention includes the roughened cured body of the present invention and a conductor layer formed on the surface of the roughened cured body.

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Including metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more kinds of metals selected from the above group (for example, nickel-chromium alloy, copper. Layers formed from nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, easiness of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper. A nickel alloy or an alloy layer of copper / titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. Metal layers are more preferred.

  The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the roughening cured body is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

  The thickness of the conductor layer depends on the desired design of the printed wiring board, but is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

  The conductor layer may be formed by plating. For example, a conductor layer (circuit) having a desired wiring pattern can be formed by plating the surface of the roughened and hardened body by a conventionally known technique such as a semi-additive method. An example of forming a circuit by the semi-additive method will be shown below.

  First, a plating seed layer is formed on the surface of the roughened cured body by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After forming a conductor layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a circuit having a desired wiring pattern.

  As described above, the roughened cured body of the present invention has a low surface roughness and also has a concave portion having an opening diameter equal to or larger than the internal maximum diameter on the surface. As a result, unnecessary portions of the conductor layer can be easily removed during circuit formation, and further miniaturization of the circuit can be achieved. For example, the ratio (L / S) of the circuit width (line; L) to the width (space; S) between circuits is 10 μm / 10 μm or less (that is, wiring pitch is 20 μm or less), L / S = 9 μm / 9 μm or less (wiring A circuit having a pitch of 18 μm or less) can be formed with high yield. Furthermore, L / S = 8 μm / 8 μm or less (wiring pitch 16 μm or less), L / S = 7 μm / 7 μm or less (wiring pitch 14 μm or less), L / S = 6 μm / 6 μm or less (wiring pitch 12 μm or less), L / S A fine circuit with S = 5 μm / 5 μm or less (wiring pitch 10 μm or less) and L / S = 4 μm / 4 μm or less (wiring pitch 8 μm or less) can be formed with high yield. Therefore, in a preferred embodiment, the conductor layer includes a circuit having a wiring pitch of 16 μm or less.

[Printed wiring board]
The printed wiring board of the present invention is characterized by including an insulating layer formed of the roughened cured body of the present invention.

  In one embodiment, the printed wiring board of the present invention can be manufactured using the above adhesive film. In such an embodiment, after the adhesive film is laminated on the inner layer substrate so that the resin composition layer is bonded to the inner layer substrate, the above-mentioned “step (A)” and “step (B)” are performed. The roughened cured body of the present invention can be formed on an inner layer substrate.

  The "inner layer substrate" is mainly a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or a conductor layer patterned on one or both sides of the substrate. A circuit board on which a (circuit) is formed. In addition, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is to be formed when manufacturing a printed wiring board is also included in the "inner layer board" in the present invention.

  The lamination of the inner layer substrate and the adhesive film can be performed, for example, by thermocompression bonding the adhesive film to the inner layer substrate from the support side. Examples of the member that heat-bonds the adhesive film to the inner layer substrate (hereinafter, also referred to as “thermo-compression bonding member”) include a heated metal plate (SUS end plate or the like), metal roll (SUS roll), or the like. It is preferable that the thermocompression-bonding member is not directly pressed onto the adhesive film, but is pressed via an elastic material such as heat resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner layer substrate.

  The lamination of the inner layer substrate and the adhesive film may be carried out by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed by a commercially available vacuum laminator. The commercially available vacuum laminator is as described above.

  After laminating, the smoothing treatment of the laminated adhesive film may be performed under normal pressure (under atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The press conditions for the smoothing treatment can be the same as the above-mentioned thermocompression bonding conditions for the lamination. The smoothing treatment can be performed with a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

  Next, a conductor layer is formed on the surface of the roughened cured body (insulating layer) formed on the inner layer substrate. The method of forming the conductor layer is as described above. When manufacturing a printed wiring board, a step of making holes in the insulating layer may be further performed. These steps may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards.

[Semiconductor device]
A semiconductor device can be manufactured using the printed wiring board of the present invention. Examples of the semiconductor device include various semiconductor devices provided for electric products (for example, computers, mobile phones, digital cameras and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of the printed wiring board of the present invention. The "conducting portion" is a "location for transmitting an electric signal in the printed wiring board", and the location may be a surface or an embedded portion. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bumpless method are used. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using a bump-free build-up layer (BBUL)" is a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and wiring on the printed wiring board". Is.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Measurement and evaluation method>
First, the measurement / evaluation method in the physical property evaluation in this specification will be described.

[Preparation of measurement / evaluation substrate]
(1) Substrate treatment of circuit board Both sides of glass cloth base material epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) on which a circuit is formed Was etched by 1 μm with a microetching agent (“CZ8100” manufactured by MEC Co., Ltd.) to roughen the copper surface.

(2) Lamination of Adhesive Film The protective film was peeled off from the adhesive films prepared in Examples and Comparative Examples. Using the batch type vacuum pressure laminator (Nichigo Morton Co., Ltd. 2-stage build-up laminator "CVP700"), the resin composition layer is bonded to the circuit board by using the exposed adhesive film of the resin composition layer. , Laminated on both sides of the circuit board. The lamination was performed by reducing the pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then performing pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa. Next, the laminated adhesive film was subjected to hot pressing at 100 ° C. and a pressure of 0.5 MPa under atmospheric pressure for 60 seconds to be smoothed.

(3) Curing of resin composition layer After laminating the adhesive film, the resin composition layer was thermally cured to form a cured product on both surfaces of the circuit board. At that time, regarding Examples 1, 2, 4 and Comparative Example 1, the resin composition layer was thermally cured in a state where the PET film as the support was attached. Regarding Example 3 and Comparative Example 2, the resin composition layer was thermoset after the PET film as the support was peeled off.

The thermosetting of the resin composition layer includes a _first thermosetting process of thermosetting at a temperature T ₁ and a second thermosetting process of thermosetting at a temperature T ₂ higher than the temperature T _1. It was carried out by treatment. Specifically, the following Condition 1 (Example 1), Condition 2 (Example 2), Condition 3 (Example 3 and Comparative Example 2), Condition 4 (Example 4), or Condition 5 (Comparative Example 1) is used. It was carried out.
Condition 1: Heat-cured at 150 ° C. (after being placed in an oven at 150 ° C.) for 30 minutes, and at 170 ° C. (after being transferred to an oven at 170 ° C.) for 30 minutes. Then, the substrate was taken out in a room temperature atmosphere.
Condition 2: Heat-cured at 80 ° C. (after being placed in an oven at 80 ° C.) for 30 minutes, and then at 175 ° C. (after being transferred to an oven at 175 ° C.) for 30 minutes. Then, the substrate was taken out in a room temperature atmosphere.
Condition 3: Heat-cured at 100 ° C. (after being placed in an oven at 100 ° C.) for 30 minutes, and then at 175 ° C. (after being transferred to an oven at 175 ° C.) for 30 minutes. Then, the substrate was taken out in a room temperature atmosphere.
Condition 4: Heat-cured at 150 ° C. (after being placed in an oven at 150 ° C.) for 30 minutes, and at 170 ° C. (after being transferred to an oven at 170 ° C.) for 30 minutes. Then, the substrate was returned to room temperature (25 ° C.) with a temperature decrease profile of 2.5 ° C./min.
Condition 5: Heat-cured at 100 ° C. (after being placed in an oven at 100 ° C.) for 30 minutes, and then at 175 ° C. (after being transferred to an oven at 175 ° C.) for 30 minutes. Then, the substrate was taken out in a room temperature atmosphere.

(4) Roughening treatment When heat-cured with the support, the support was peeled off. The substrate with the cured body exposed was immersed in a swelling solution ("Aering Tech Japan Co., Ltd.""Swelling dip securigant P", an aqueous solution containing diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 5 minutes (Example 3 and Comparative Example). example 2) or 10 minutes (examples 1, 2, 4 and Comparative example 1), oxidizing agent (Atotech Japan Co., Ltd., "concentrate compact _{CP", KMnO 4: 60g / L,} NaOH: a 40 g / L Aqueous solution) at 80 ° C. for 20 minutes, and finally, a neutralization solution (“Reduction Solution Seculigant P” manufactured by Atotech Japan KK, sulfuric acid aqueous solution) is immersed at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes. Then, the roughened cured material was formed on both surfaces of the circuit board. The obtained substrate is referred to as "evaluation substrate A".

(5) Formation of Circuit A circuit was formed on the surface of the roughened cured body according to the semi-additive method.

(5-1) Electroless plating The surface of the roughened cured body was electroless plated. The electroless plating was performed using Atotech Japan Co., Ltd. pharmaceutical solution in the following procedure. A plating having a thickness of 1 μm was formed. The obtained substrate is referred to as "evaluation substrate B". The evaluation board B is a board having a roughened cured body with plating formed on both surfaces of a circuit board.

1. Alkaline cleaning (cleaning the surface of the roughened hardened body and adjusting the charge)
The surface of the roughened cured body was washed at 60 ° C. for 5 minutes using “Cleaning Cleaner Security 902”.
2. Soft etching (cleaning)
The substrate after alkali cleaning was treated at 30 ° C. for 1 minute with an aqueous solution of sulfuric acid-acidic sodium peroxodisulfate.
3. Predip (Adjustment of charge on surface of roughened hardened body to impart Pd)
The substrate was then treated with "Pre. Dip Neoganth B" for 1 minute at room temperature.
4. Activator (Applying Pd to the surface of roughened hardened body)
After pre-dip, the substrate was treated with "Activator Neoganth 834" at 35 ° C for 5 minutes.
5. Reduction (reduction of Pd applied to the roughened cured body)
The substrate was then treated with a mixture of "Reducer Neoganth WA" and "Reducer Accelerator 810 mod." At 30 ° C for 5 minutes.
6. Electroless copper plating (Cu deposition on the surface of the roughened hardened body (Pd surface))
After the reduction, the substrate was treated with a mixed solution of “Basic Solution Printganth MSK-DK”, “Copper solution Printganth MSK”, “Stabilizer Printganth MSK-DK” and “Reducer Cu” at 35 ° C. for 20 minutes. The obtained substrate was heat-treated at 150 ° C. for 30 minutes.

(5-2) Formation of Wiring Pattern After electroless plating, the substrate surface was treated with a 5% sulfuric acid aqueous solution for 30 seconds. Then, a dry film for pattern formation (“Photec RY-3600” manufactured by Hitachi Chemical Co., Ltd., thickness 19 μm) was used with a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). , Laminated on both sides of the substrate. The lamination was performed by reducing the pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then applying pressure at 70 ° C. and a pressure of 0.1 MPa for 20 seconds.

  After that, a glass mask (photomask) on which a wiring pattern (details are shown below) is formed is placed on a dry film, and light is irradiated by a projection exposure machine (“UX-2240” manufactured by USHIO INC.). did. Then, a 1% sodium carbonate aqueous solution at 30 ° C. was sprayed for 30 seconds at an injection pressure of 0.15 MPa. Then, it was washed with water and the dry film was developed (pattern formation).

Glass mask wiring pattern:
A glass mask having ten comb tooth patterns i) to vii) below was used.
i) L / S = 4 μm / 4 μm, that is, a comb tooth pattern with a wiring pitch of 8 μm (wiring length 15 mm, 16 lines)
ii) L / S = 5 μm / 5 μm, that is, a comb tooth pattern with a wiring pitch of 10 μm (wiring length 15 mm, 16 lines)
iii) L / S = 6 μm / 6 μm, that is, a comb tooth pattern with a wiring pitch of 12 μm (wiring length 15 mm, 16 lines)
iv) L / S = 7 μm / 7 μm, that is, a comb tooth pattern with a wiring pitch of 14 μm (wiring length 15 mm, 16 lines)
v) L / S = 8 μm / 8 μm, that is, a comb tooth pattern with a wiring pitch of 16 μm (wiring length 15 mm, 16 lines)
vi) L / S = 9 μm / 9 μm, that is, a comb tooth pattern with a wiring pitch of 18 μm (wiring length 15 mm, 16 lines)
vii) L / S = 10 μm / 10 μm, that is, a comb tooth pattern with a wiring pitch of 20 μm (wiring length 15 mm, 16 lines)

  After development of the dry film, electrolytic copper plating was performed to form an electrolytic copper plating layer (conductor layer) having a thickness of 10 μm (total thickness with the electroless copper plating layer was about 11 μm).

  Next, a 3% sodium hydroxide solution at 50 ° C. was spray-treated at an injection pressure of 0.2 MPa to peel the dry film from both sides of the substrate. After heating at 190 ° C. for 60 minutes to perform annealing, an unnecessary conductor layer (copper layer) is removed using a flash etching etchant (SAC process etchant manufactured by Ebara Densan Co., Ltd.). This formed a circuit. The obtained substrate is referred to as “evaluation substrate C”.

<Measurement of minimum melt viscosity>
The melt viscosity of the resin composition layer of the adhesive film prepared in Preparation Example was measured using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM). About 1 g of the sample resin composition, using a parallel plate having a diameter of 18 mm, the temperature was raised from a starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min, a measurement temperature interval of 2.5 ° C., a frequency of 1 Hz, The dynamic viscoelastic modulus was measured under the measurement condition of strain 1 deg, and the minimum melt viscosity (poise) was measured. Minimum melt viscosity V ₀ for the resin composition layer immediately after production (initial stage) and minimum melt viscosity V for the resin composition layer after the first thermosetting treatment in (3) of [Preparation of substrate for measurement / evaluation] I asked for ₁ .

<Measurement of Arithmetic Average Roughness (Ra) and Average Spacing of Concavo-convex>
For the evaluation board A, using a non-contact surface roughness meter ("WYKO NT3300" manufactured by Becoin Instruments Co., Ltd.), the Ra and Sm values were determined by VSI contact mode and a numerical value obtained by setting the measurement range to 121 μm × 92 μm with a 50 × lens. I asked. The values were determined by calculating the average value of 10 points randomly selected. The Sm value was the average value of Sm (x) and Sm (y).

<Evaluation of uneven shape on surface of roughened cured body>
The evaluation substrate B was subjected to cross-section observation using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nano Technology Co., Ltd.). Specifically, a cross section in a direction perpendicular to the surface of the evaluation substrate B was carved out by FIB (focused ion beam), and a SEM image of a cross section near the interface between the plating and the roughening cured body (observation width 7.5 μm, observation magnification x36000). Got For each sample, 10 randomly selected cross-section SEM images were acquired. Hereinafter, the evaluation procedure will be described with the plated side in the cross-sectional SEM image as the upper side and the roughened cured body side as the lower side.

-Lines L1 and L2-
The straight line L1 was obtained by linearizing the interface between the plating and the roughened cured body with the least squares method, with the convex portion of the roughened cured body as a reference. Specifically, the obtained cross-sectional SEM image was divided into 5 sections each having a width of 1.5 μm, and the position of the roughened cured body existing on the uppermost side of each section was adopted as a reference point. Incidentally, "the position of the roughened cured body existing on the uppermost side" means the position of the resin component when the resin component exists on the uppermost side, and the inorganic filling state when the inorganic filler exists on the uppermost side. The position of the material. The obtained five reference points were subjected to coordinate transformation, and an approximate straight line based on these five reference points, that is, a straight line L1 was obtained by the least squares method. A straight line parallel to the straight line L1 was drawn 0.2 μm below the straight line L1 to obtain a straight line L2. Straight lines L1 and L2 were obtained for the acquired cross-sectional SEM images at 10 locations.

-Length X and Y-
With respect to the acquired SEM images of the cross-sections at 10 locations, the lengths of the plating regions on the straight line L1 were summed to obtain the length X. Similarly, the lengths Y of the obtained cross-section SEM images of 10 locations were obtained by summing the lengths of the plating regions on the straight line L2. When the inorganic filler is present on the straight line L1, the inorganic filler region was treated as follows in calculating the length X. When at least a part of the inorganic filler was in contact with the resin component, the inorganic filler region was treated as a roughened cured body region. On the other hand, when the inorganic filler was not in contact with the resin component and covered with electroless plating, the inorganic filler region was treated as a plating region. When the inorganic filler is present on the straight line L2, the same treatment was performed. The Y / X ratio was calculated using the obtained X and Y. The obtained Y / X ratio is an index of the uneven shape of the surface of the roughened cured body, and when the Y / X ratio is 1 or less, a concave portion having an opening diameter equal to or larger than the internal maximum diameter is formed on the surface. When the Y / X ratio is larger than 1, it means that a recess having an opening diameter smaller than the internal maximum diameter is formed on the surface.

-Depth Z-
The length of the plating region on the straight line L3 that is parallel to the straight line L1 and is Z (μm) away from the straight line L1 in the depth direction (downward direction) of the roughening-cured body with respect to the acquired cross-sectional SEM images of 10 locations. When the sum of Y'is Y ', the minimum value of Z at which Y'is 0 was determined.

<Evaluation of fine circuit forming ability>
With respect to the comb tooth patterns of the above i) to vii) of the evaluation substrate C, the presence or absence of peeling of the circuit is confirmed with an optical microscope, and the insulation resistance of the comb tooth pattern is measured for the presence of residues of unnecessary electroless copper plating layer. I confirmed by doing. Then, when there was no problem in 9 or more out of 10 comb-shaped patterns, it was determined as pass. The fine circuit forming ability was evaluated by the minimum L / S ratio and the wiring pitch which were judged to be acceptable. In the evaluation, the smaller the minimum L / S ratio and the wiring pitch which are determined to be acceptable, the more excellent the fine circuit forming ability is.

<Preparation Example 1> (Preparation of Resin Varnish 1)
6 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1: 1 mixture of bisphenol A type and bisphenol F type), bixylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation) "YX4000HK", epoxy equivalent of about 185) 10 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent 269) 5 parts, dicyclopentadiene type epoxy resin (DIC Corporation "HP-" 7200HH ”, epoxy equivalent 280) 5 parts, and phenoxy resin (“ YX7553BH30 ”manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30 mass%) 12 parts, solvent naphtha 30 parts It was heated and dissolved with stirring. After cooling to room temperature, 10 parts of a triazine skeleton-containing cresol novolac curing agent (hydroxyl group equivalent 151, "LA-3018-50P" manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), Active ester type curing agent (“HPC8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, toluene solution of 65% by weight of non-volatile component) 10 parts, amine type curing accelerator (4-dimethylaminopyridine (DMAP), 1.6 parts of solid content 5 mass% MEK solution, 1 part of imidazole curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), solid content of 5 mass% MEK solution), flame retardant (Sanko ) Manufactured by "HCA-HQ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene- 0-oxide, average particle size 2 μm) 2 parts, spherical silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Admatex Co., Ltd., average) After mixing 130 parts of a particle size of 0.5 μm and a carbon amount per unit surface area of 0.38 mg / m ² ) and uniformly dispersing with a high speed rotating mixer, the resin was filtered with a cartridge filter (“SHP050” manufactured by ROKITECNO). Varnish 1 was prepared.

<Preparation Example 2> (Preparation of Resin Varnish 2)
10 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), 10 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), biphenyl type Epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent 269) 10 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", solid content 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) 1: 10 parts of 1 solution) was dissolved in 25 parts of solvent naphtha with heating while stirring. After cooling to room temperature, 5 parts of a triazine skeleton-containing phenol novolac-based curing agent (hydroxyl group equivalent 125, "LA-7054" manufactured by DIC Corporation, MEK solution having a solid content of 60%), an active ester curing agent (DIC Corporation "HPC8000-65T", active group equivalent of about 223, toluene solution of 65 mass% of non-volatile components) 15 parts, amine curing accelerator (DMAP, MEK solution of solid content 5 mass%) 2 parts, Spherical silica (“SO-C1” manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size of 0.25 μm, and carbon amount per unit surface area 0.36 mg / m ² ) 100 parts were mixed and uniformly dispersed with a high-speed rotary mixer, and then a cartridge filter (“SHP made by ROKITECNO” 030 ") to prepare Resin Varnish 2.

<Preparation Example 3> (Preparation of Resin Varnish 3)
Bisphenol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059", 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169) 4 parts, naphthalene type epoxy resin (DIC "HP4032SS") , Epoxy equivalent about 144) 5 parts, bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 185) 10 parts, biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., epoxy) Equivalent 269) 10 parts and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) 10 parts while stirring in 15 parts of solvent naphtha. It was heated and dissolved. After cooling to room temperature, 10 parts of a triazine skeleton-containing phenol novolac-based curing agent (hydroxyl group equivalent 125, “LA-7054” manufactured by DIC Corporation, MEK solution having a solid content of 60%), a naphthol-based curing agent ( Nippon Steel & Sumikin Chemical Co., Ltd. "SN-485", hydroxyl equivalent 215, solid content 60% MEK solution 10 parts, polyvinyl butyral resin (glass transition temperature 105 ° C, Sekisui Chemical Co., Ltd. "KS-1" 10% of a mixed solution of ethanol and toluene having a solid content of 15% of 1: 1, an amine curing accelerator (DMAP, a MEK solution having a solid content of 5% by mass) 1 part, a flame retardant (“HCA” manufactured by Sanko Co., Ltd.). -HQ ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts, amino Spherical silica surface-treated with an orchid coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm, carbon amount per unit surface area) 90 parts of 0.38 mg / m ² ) was mixed and uniformly dispersed with a high speed rotation mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECNO) to prepare a resin varnish 3.

<Preparation Example 4> (Preparation of Resin Varnish 4)
A point where the compounding amount of the triazine skeleton-containing phenol novolac type curing agent (hydroxyl group equivalent 125, "LA-7054" manufactured by DIC Corporation, MEK solution with a solid content of 60%) was changed to 5 parts, the naphthol type curing agent (Nippon Steel & Sumitomo Metal Corporation Chemical compound "SN-485", hydroxyl group equivalent 215 MEK solution of 60% solid content) was changed to 20 parts, imidazole curing accelerator (1B2PZ, MEK solution of solid content 5% by mass). ) A resin varnish 4 was prepared in the same manner as in Preparation Example 3 except that 1 part was added.

<Preparation Example 1> Preparation of Adhesive Film 1 As a support, a PET film (“Lumirror T6AM” manufactured by Toray Industries, Inc.) release-treated with an alkyd resin release agent (“AL-5” manufactured by Lintec Co., Ltd.), A thickness of 38 μm and a softening point of 130 ° C.) were prepared. The resin varnish 1 was applied to the release surface of the support with a die coater and dried at 80 ° C. to 110 ° C. (average 100 ° C.) for 3 minutes to form a resin composition layer. The thickness of the resin composition layer was 20 μm. Then, on the surface of the resin composition layer that is not bonded to the support, a polypropylene film ("Alphan MA-411" manufactured by Oji Special Paper Co., Ltd., thickness 15 µm) is used as a protective film on the rough surface of the protective film. Was laminated so as to be bonded to the resin composition layer to obtain an adhesive film 1.

<Production Example 2> Production of adhesive film 2 An adhesive film 2 was produced in the same manner as in Production Example 1 except that the resin varnish 2 was used instead of the resin varnish 1.

<Production Example 3> Production of adhesive film 3 An adhesive film 3 was produced in the same manner as in Production Example 1 except that the resin varnish 3 was used instead of the resin varnish 1.

<Production Example 4> Production of Adhesive Film 4 An adhesive film 4 was produced in the same manner as in Production Example 1 except that the resin varnish 4 was used instead of the resin varnish 1.

<Example 1>
Using the adhesive film 1, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

<Example 2>
Using the adhesive film 2, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

<Example 3>
Using the adhesive film 3, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

<Example 4>
Using the adhesive film 1, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

<Comparative Example 1>
Using the adhesive film 1, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

<Comparative example 2>
Using the adhesive film 4, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

The evaluation results are shown in Table 2.

1 roughening hardened body having a concave portion having an opening diameter smaller than the inner maximum diameter on the surface 10 roughening cured body having a concave portion having an opening diameter larger than the inner maximum diameter on the surface 11 resin component 12 inorganic filler 20 plating L1 plating and A straight line L2 obtained by linearizing the interface of the roughened cured product by the least squares method. A line parallel to the straight line L1 and separated from the straight line L1 by 0.2 μm in the depth direction of the roughened cured product.

Claims (16)

The Engineering as (1) support and the resin composition layer are bonded and subjected to a first heat curing treatment for thermally cured at a temperature T _1, the first temperature of the resin composition layer after the heat curing treatment A step of obtaining a cured product by subjecting it to a second heat curing treatment in which it is heat cured at a temperature T ₂ higher than T ₁ .
Step (2) A step of returning the cured product obtained by the second thermosetting treatment to room temperature from the temperature T ₂ at a temperature lowering rate of 10 ° C./min or less,
Step (3) A step of peeling the support bonded to the cured body from the cured body after returning to room temperature, and a step (4) After the support is peeled, the cured body is roughened to be roughened and cured. The process of forming the body,
A method for producing a roughened cured body, comprising :
A method for producing a roughened cured body, wherein the first heat-curing treatment is performed so that the minimum melt viscosity V ₁ of the resin composition layer after the first heat-curing treatment is in the range of 11,000 poise to 300,000 poise. When the surface of the roughened hardened body obtained in step (4) is electroless plated to form a roughened hardened body with plating, the roughened hardened body with plating in a direction perpendicular to the surface of the roughened hardened body with plating In the cross-section of the body, the length X of the plating region on the straight line L1 obtained by linearizing the interface between the plating and the roughening-hardened body by the least-squares method, and the roughening hardening from the straight line L1 that is parallel to the straight line L1 The method for manufacturing a roughened cured body according to claim 1, wherein the length Y of the plating region on the straight line L2 that is 0.2 μm apart in the depth direction of the body satisfies the condition of Y / X ≦ 1. The roughening-cured body according to claim 1 or 2 , wherein the time for performing the first heat curing treatment is 5 minutes to 180 minutes, and the time for performing the second heat curing treatment is 5 minutes to 120 minutes. Production method. T ₁ is, [the softening point of the support -50] (° C.) or more and less [the softening point of the support +30] (° C.), the roughened cured body according to any one of claims 1 to 3 Production method. T _{2 is,} (T 1 +10) at ℃ above, in the method of manufacturing a roughened cured body according to any one of claims 1-4. T ₂ is at 0.99 ° C. or higher, the production method of the roughened cured product according to any one of claims 1-5.   Further, a step (0) of preparing a resin varnish in which the resin composition is dissolved in a solvent, coating the resin varnish on a support, and drying the resin varnish to obtain a resin composition layer bonded to the support. The manufacturing method of the roughening hardening body of any one of Claims 1-6 containing.   The method for producing a roughened cured body according to any one of claims 1 to 7, wherein the support is a film made of a plastic material.   The method for producing a roughened cured body according to any one of claims 1 to 8, wherein the support has a release layer on the surface on the side to be joined with the resin composition layer.   The method for producing a roughened cured body according to any one of claims 1 to 9, wherein the resin composition layer contains an epoxy resin and a curing agent.   The method for producing a roughened cured body according to any one of claims 1 to 10, wherein the resin composition layer contains one or more selected from the group consisting of a naphthol-based curing agent and an active ester-based curing agent.   The method for producing a roughened cured body according to any one of claims 1 to 11, wherein the resin composition layer contains an inorganic filler.   The method for producing a roughened cured body according to claim 12, wherein the inorganic filler has an average particle diameter of 0.01 µm to 0.3 µm. The method for producing a roughened cured body according to any one of claims 1 to 13, wherein the temperature decrease rate in step (2) is 3 ° C / minute or less. The minimum melt viscosity V of the resin composition layer before the first thermosetting treatment ₀ Is 500 poises to 10000 poises, The method for producing a roughened cured body according to any one of claims 1 to 14. The method for producing a roughened cured body according to claim 1, wherein the roughened cured body has a thickness of 100 μm or less.

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