KR102200637B1 - Cured body, method of manufacturing cured body, laminated body, printed wiring board and semiconductor device - Google Patents

Abstract

[Problem] In the manufacture of printed wiring boards, even when a thin resin composition layer is used for thinning of the layer, it is possible to realize a cured body with small undulations on the surface that provides sufficient dry film adhesion, while suppressing the occurrence of uneven roughness. Provide the skills to do.
[Solution means] In a cured product formed on a circuit board obtained by laminating a resin composition layer on a circuit board and thermally curing the resin composition layer, when the lowest melt viscosity temperature of the resin composition layer is Tv (° C.), the resin When the lamination temperature of the composition layer is Tv-35°C to Tv + 35°C, the thickness of the resin composition layer is x (㎛), and the thickness of the cured body on the circuit wiring of the circuit board is y (㎛), 0.3 <y /x ≤ 1 and y ≤ 15, the cured body.

Description

Hardened body, method of manufacturing hardened body, laminated body, printed wiring board and semiconductor device {CURED BODY, METHOD OF MANUFACTURING CURED BODY, LAMINATED BODY, PRINTED WIRING BOARD AND SEMICONDUCTOR DEVICE}

The present invention relates to a cured product, a method for producing a cured product, a laminate, a printed wiring board, and a semiconductor device.

BACKGROUND ART Printed wiring boards such as multilayer printed wiring boards and flexible printed wiring boards, which are widely used in various electronic devices, are required to be thinner in layers and fine wiring in circuits for miniaturization and high functionality of electronic devices.

As a manufacturing technique of a printed wiring board, a manufacturing method using a build-up method in which an insulating layer and a conductor layer are alternately stacked is known. In the manufacturing method by the build-up method, generally, the insulating layer is formed by thermosetting a resin composition. For example, in Patent Document 1, after laminating a resin composition layer on a circuit board using an adhesive sheet containing a resin composition layer, and thermosetting the resin composition layer to obtain a cured product, the cured product is roughened. A technique of forming an insulating layer by processing is disclosed.

Japanese Unexamined Patent Application Publication No. 2008-37957

After the formation of the insulating layer, a conductor layer (wiring layer) having a desired pattern can be formed by a technique such as a semi-positive method or a full-positive method. In general, a dry film for pattern formation is disposed on an insulating layer to develop a desired pattern and then plated to form a conductor layer having a desired pattern. At this time, from the viewpoint of fine wiring formability, it is preferable that the patterned dry film is sufficiently adhered to the insulating layer.

However, in the case of forming an insulating layer using a thin resin composition layer for thinning of the layer, the surface of the cured body formed by curing the resin composition layer is the surface undulation of the circuit board (the presence or absence of circuit wiring). The present inventors have found that there is a tendency to have undulations corresponding to ), and that the adhesion of the dry film for pattern formation may decrease due to such undulations. Although it is possible to reduce the undulations of the surface of the cured product to some extent by manipulating the lamination conditions of the resin composition layer, etc., in that case, the undulations (that is, the surface of the insulating layer on the circuit wiring of the circuit board) and concave The present inventors have found that there are cases where parts (that is, the surface of the insulating layer on the part of the circuit board where there is no circuit wiring) exhibit significantly different surface roughness after the roughening treatment (hereinafter, this phenomenon is referred to as "roughness. ) Also called non-uniformity). This may result in uneven roughness and poor local fine wiring on the surface of the insulating layer.

As described above, in the manufacture of a printed wiring board, there is room for improvement in achieving both thinning of layers and fine wiring of circuits.

In the manufacture of a printed wiring board, even when a thin resin composition layer is used for thinning of the layer, it is possible to realize a cured body with small undulations on the surface that provides sufficient dry film adhesion, while preventing the occurrence of irregularities in roughness. The challenge is to provide technology that can be suppressed.

The present inventors, as a result of earnestly examining the above problems, set the lamination temperature of the resin composition layer in the range of Tv-35°C to Tv + 35°C when the lowest melt viscosity temperature of the resin composition layer is Tv (°C). At the same time, when the thickness of the resin composition layer is x (㎛) and the thickness of the cured body on the circuit wiring of the circuit board is y (㎛), the relationship between x and y is 0.3 <y/x ≤ 1 and y ≤ 15 It was found that the above problems could be solved by making them satisfied, and the present invention was completed.

That is, the present invention includes the following contents.

[1] As a cured body formed on a circuit board obtained by laminating a resin composition layer on a circuit board and thermosetting the resin composition layer,

When the lowest melt viscosity temperature of the resin composition layer is Tv (°C), the lamination temperature of the resin composition layer is Tv-35°C to Tv + 35°C,

When the thickness of the resin composition layer is x (µm) and the thickness of the cured body on the circuit wiring of the circuit board is y (µm), 0.3 <y/x ≤ 1 and y ≤ 15.

[2] The cured product according to [1], wherein x≤25.

[3] The cured product according to [1] or [2], wherein the maximum cross-sectional height Rt of the surface of the cured product is 3.5 µm or less.

[4] The cured product according to any one of [1] to [3], which is obtained by holding the resin composition layer at a temperature less than Tv for 10 minutes or more, and then holding the resin composition layer at a temperature of Tv or more for 10 minutes or more to heat cure.

[5] A roughened cured product obtained by subjecting the cured product according to any one of [1] to [4] to a roughening treatment.

[6] In [5], the difference between the arithmetic average roughness of the surface of the roughened hardened body on the circuit wiring of the circuit board and the arithmetic average roughness of the surface of the roughened hardened body on the part of the circuit board without circuit wiring is 160 nm. The following roughened hardened body.

[7] A laminate comprising the roughened hardened body according to [5] or [6], and a conductor layer formed on the surface of the roughened hardened body.

[8] (A) Step of laminating a resin composition layer on a circuit board, and

(B) Step of forming a cured body on a circuit board by thermosetting the resin composition layer

Including,

When the lowest melt viscosity temperature of the resin composition layer is Tv (°C), the lamination temperature of the resin composition layer is Tv-35°C to Tv + 35°C,

When the thickness of the resin composition layer is x (µm) and the thickness of the cured body on the circuit wiring of the circuit board is y (µm), 0.3 <y/x ≤ 1 and y ≤ 15, wherein the method for producing a cured body.

[9] The method for producing a cured product according to [8], wherein x≤25.

[10] The method for producing a cured product according to [8] or [9], wherein the maximum cross-sectional height Rt of the surface of the cured product is 3.5 µm or less.

[11] In any one of [8] to [10], in step (B), after maintaining the resin composition layer at a temperature less than Tv for 10 minutes or more, heat curing by maintaining at a temperature of Tv or more for 10 minutes or more. , Method for producing a cured product.

[12] A printed wiring board in which an insulating layer is formed by the cured body according to any one of [1] to [4].

[13] A semiconductor device comprising the printed wiring board according to [12].

According to the present invention, in the manufacture of a printed wiring board, even when a thin resin composition layer is used for thinning of the layer, it is possible to realize a cured product with small undulations on the surface that provides sufficient dry film adhesion, and at the same time, uneven roughness occurs. Can be suppressed.

1 is a diagram schematically showing a cross section of a resin composition layer.
2 is a diagram schematically showing a cross section of a cured body provided on a circuit board in an embodiment of the present invention.

Hereinafter, the present invention will be described in detail based on its preferred embodiment.

[Hardened body]

The cured product of the present invention is obtained by laminating a resin composition layer on a circuit board and thermally curing the resin composition layer. In the cured product provided on a circuit board, when the lowest melt viscosity temperature of the resin composition layer is Tv (° C.) , When the lamination temperature of the resin composition layer is Tv-35°C to Tv + 35°C, the thickness of the resin composition layer is x (µm), and the thickness of the cured body on the circuit wiring of the circuit board is y (µm), 0.3 It is characterized in that <y/x ≤ 1 and y ≤ 15.

The "circuit board" on which the cured product of the present invention is formed refers to a board having circuit wiring patterned on one side or both sides. As a substrate used for a circuit board, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, etc. are mentioned, for example. Further, when manufacturing a printed wiring board, an inner-layer circuit board of an intermediate product on which an insulating layer and/or a conductor layer should be further formed is also included in the "circuit board" referred to in the present invention.

The thickness of the circuit wiring patterned on one or both sides of the substrate is not particularly limited, but from the viewpoint of thinning the layer, it is preferably 70 µm or less, more preferably 30 µm or less, and even more preferably 20 µm. Below. The lower limit of the thickness of the circuit wiring is not particularly limited, but is preferably 1 µm or more, more preferably 3 µm or more, and still more preferably 5 µm or more.

The line/space ratio of the circuit wiring patterned on one or both sides of the substrate is not particularly limited, but in order to suppress the undulations of the cured body surface, it is preferably 200/200 μm or less, more preferably 100/100 μm or less. , More preferably 40/40 µm or less, even more preferably 20/20 µm or less, particularly preferably 8/8 µm. The lower limit of the line/space ratio of the circuit wiring is not particularly limited, but it is preferably 0.5/0.5 µm or more, more preferably 1/1 µm or more, in order to improve the embedding of the resin between the spaces.

The cured product of the present invention is obtained by laminating a resin composition layer on such a circuit board and thermally curing the resin composition layer.

From the viewpoint of thinning the layer of the printed wiring board, it is preferable to use a thin resin composition layer. However, when a thin resin composition layer is used, the surface of the cured body to be formed tends to have large undulations corresponding to the circuit wiring pattern of the circuit board as the base. Such large undulations on the surface of the cured body lower the adhesiveness of the dry film for pattern formation, resulting in deterioration of fine wiring formability.

From the viewpoint of suppressing undulations on the surface of the cured body, the temperature at the time of laminating the resin composition layer on the circuit board (hereinafter, also referred to as ``lamination temperature'') is the lowest melt viscosity temperature of the resin composition layer as Tv (°C). When, in the range of Tv-35 ℃ to Tv + 35 ℃, preferably in the range of Tv-30 ℃ to Tv + 30 ℃, more preferably in the range of Tv-25 ℃ to Tv + 25 ℃, more preferably It is in the range of Tv-20°C to Tv + 20°C, particularly preferably in the range of Tv-15°C to Tv + 15°C.

Here, the "lowest melt viscosity temperature" of the resin composition layer refers to the temperature at which the resin composition layer exhibits the lowest melt viscosity. In addition, the "lowest melt viscosity" of a resin composition layer means the lowest viscosity exhibited by a resin composition layer when the resin of a resin composition layer melts. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the melt viscosity in the initial stage decreases with the increase in temperature, and after that, when the temperature exceeds a certain temperature, the melt viscosity increases with the temperature increase. , "Lowest melt viscosity" refers to the melt viscosity of such a minimum point. The minimum melt viscosity temperature of the resin composition layer can be measured by a dynamic viscoelastic method. Specifically, the minimum melt viscosity temperature of the resin composition layer can be obtained by performing dynamic viscoelasticity measurement under the conditions of a measurement start temperature of 60°C, a temperature increase rate of 5°C/minute, a frequency of 1 Hz, and a strain rate of 1 deg. As a dynamic viscoelasticity measuring device, "Rheosol-G3000" manufactured by UBM Co., Ltd. is mentioned, for example.

The undulations of the surface of the cured product can be evaluated by the maximum cross-sectional height Rt of the surface of the cured product. When the maximum cross-sectional height Rt of the surface of the cured product exceeds 4 μm, there is a tendency that the adhesiveness of the dry film for pattern formation is significantly lowered. From the viewpoint of realizing sufficient adhesion of the dry film for pattern formation, the cured product of the present invention preferably has a maximum cross-sectional height Rt of 3.5 µm or less, more preferably 3.3 µm or less, further preferably 3.1 µm or less, and 2.9 It is even more preferable that it is less than or equal to 2.7 μm, less than 2.5 μm, less than 2.3 μm, less than 2.1 μm, or less than 1.9 μm.

The maximum cross-sectional height Rt of the surface of the cured product can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, "WYKO NT3300" by Vico Instruments is mentioned.

By suppressing undulations on the surface of the cured body, the adhesion of the dry film for pattern formation is improved. However, in the case of forming a cured product using a thin resin composition layer, attention should be paid to the occurrence of uneven roughness. In other words, if a cured body with small undulations on the circuit board is to be formed using a thin resin composition layer, the undulations (that is, the surface of the cured body on the circuit wiring of the circuit board) and concave parts (i.e. There are cases where the surface of the cured body on top of the part without circuit wiring) exhibits significantly different surface roughness after the roughening treatment. This roughness unevenness is caused by the difference (│Ra _l -Ra ₂ │) between the arithmetic mean roughness (Ra ₁ ) of the convex portion of the undulation and the arithmetic mean roughness (Ra ₂ ) of the concave portion of the undulation on the surface of the cured body after the roughening treatment. Can be evaluated. When the value of │Ra _l -Ra ₂ │ exceeds 160 nm, it tends to result in local fine wiring defects when forming the conductor layer (circuit wiring). Such irregularity in roughness is likely to occur when a thin resin composition layer is used to install a cured product having a small surface undulation on a circuit board. Among them, i) a resin composition layer having a high inorganic filler content is used, ii. ) When forming a cured product using an adhesive sheet having a layer structure of a resin composition layer/support, the present inventors have found that it is particularly likely to occur in the case of thermosetting the resin composition layer while the support is attached.

In addition, the arithmetic mean roughness Ra of the surface of a cured product can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, "WYKO NT3300" by Vico Instruments Inc. is mentioned.

From the viewpoint of reducing the occurrence of irregularities in roughness while realizing the thinning of the layer, when the thickness of the resin composition layer is x (µm) and the thickness of the cured body on the circuit wiring of the circuit board is y (µm), x and y are It is important to perform lamination and thermal curing of the resin composition layer so as to satisfy 0.3<y/x≦1 and y≦15. In addition, the thickness x of the resin composition layer refers to the thickness of the resin composition layer before lamination on the circuit board, and the thickness y of the cured body on the circuit wiring of the circuit board refers to the thickness of the cured body immediately above the circuit wiring of the circuit board. Say.

When x and y satisfy the above relationship, even when a cured body is formed using a thin resin composition layer, occurrence of uneven roughness can be advantageously suppressed. For example, the thickness x of the resin composition layer can be less than 50 μm. Further, even when a resin composition layer having a thickness x of 40 µm or less, 35 µm or less, 30 µm or less, or 25 µm or less is used, occurrence of uneven roughness can be advantageously suppressed. The lower limit of the thickness x of the resin composition layer is not particularly limited, but is preferably 1 µm or more, more preferably 2 µm or more, and still more preferably 5 µm or more.

From the viewpoint of further suppressing the occurrence of roughness unevenness while realizing the thinning of the layer, when y ≤ 15, preferably 0.35 ≤ y/x ≤ 1, more preferably 0.4 ≤ y/x ≤ 1, more preferably 0.5≦y/x≦1, particularly preferably 0.6≦y/x≦1.

From the viewpoint of thinning of the layer, it is preferable that y≦14, more preferably y≦12, even more preferably y≦10, and y≦9, y≦8, y≦7, or y≦6. It is particularly preferred. Even when y is in such a range, when the y/x ratio is in the above range, occurrence of irregularity in illuminance can be advantageously suppressed. The lower limit of y is not particularly limited as long as the cured product of the present invention fulfills its function as an insulating layer, but is usually 0.5≦y, and preferably 1≦y. In addition, the upper limit of the y/x ratio may be less than 1.

From the viewpoint of reducing undulations on the surface of the cured body and suppressing the occurrence of uneven roughness, the resin composition layer laminated on the circuit board is maintained at a temperature less than the minimum melt viscosity temperature Tv of the resin composition layer for 10 minutes, and then Tv or more. It is preferable to heat cure by maintaining the temperature for 10 minutes. Details of the thermosetting of the resin composition layer will be described later.

As described above, the cured product of the present invention has a thickness of 15 μm or less on the circuit wiring, contributing to the thinning of the layer, and at the same time, it has a surface with small undulations so that the occurrence of irregularities in roughness can be suppressed. Also contributes to. As described above, the cured product of the present invention remarkably contributes to both the thinning of the layer and the fine wiring of the circuit in the manufacture of a printed wiring board.

In addition, Fig. 1 schematically shows a cross section of a resin composition layer used to form the cured body of the present invention. The x refers to the thickness of the resin composition layer 1 before lamination on the circuit board.

In addition, Fig. 2 schematically shows a cross section of a cured body formed on a circuit board in an embodiment of the present invention. In FIG. 2, the circuit board 3 includes the wiring circuit 4 patterned on the board 5, and the cured body 2 is provided on the circuit board 3. The y refers to the thickness of the cured body 2 on the circuit wiring 4 of the circuit board.

Hereinafter, the resin composition layer used to form the cured product of the present invention will be described.

<Resin composition layer>

The resin composition used for the resin composition layer is not particularly limited, and the cured product to be formed may be one having sufficient hardness and insulation. From the viewpoint of reducing the coefficient of thermal expansion of the obtained cured product (insulating layer) and preventing the occurrence of cracks or circuit deformation due to the difference in thermal expansion between the insulating layer and the conductor layer, the resin composition used for the resin composition layer is an inorganic filler. It is preferable to include.

As described above, the present inventors have found that when a cured product is formed using a resin composition layer having a high inorganic filler content, uneven roughness is particularly likely to occur, but according to the present invention, a resin composition having a high inorganic filler content is used. Even in the case of doing so, it is possible to advantageously suppress the occurrence of uneven illumination.

The content of the inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more, from the viewpoint of sufficiently lowering the thermal expansion coefficient of the resulting cured product.

In addition, in the present invention, the content of each component in the resin composition is a value when the total amount of nonvolatile components in the resin composition is 100% by mass.

In the present invention, it is possible to further increase the content of the inorganic filler in the resin composition while suppressing the occurrence of uneven roughness. For example, the content of the inorganic filler in the resin composition may be increased to 66% by mass or more, 68% by mass or more, or 70% by mass or more.

The upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less from the viewpoint of the mechanical strength of the cured product obtained by thermosetting the resin composition layer.

As an inorganic filler, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, Calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among these, silicas such as amorphous silica, fused silica, crystalline silica, synthetic silica and hollow silica are particularly suitable. Moreover, spherical silica is preferable as silica. The inorganic filler may be used alone or in combination of two or more. As commercially available spherical fused silica, "SOC2" and "SOC1" manufactured by Adomatex Co., Ltd. are mentioned.

The average particle diameter of the inorganic filler is preferably in the range of 0.01 µm to 2 µm, more preferably in the range of 0.05 µm to 1.5 µm, even more preferably in the range of 0.07 µm to 1 µm, and even more in the range of 0.1 µm to 0.8 µm. desirable. The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution measuring device and making the median diameter an average particle diameter. The measurement sample can be preferably used in which the inorganic filler is dispersed in water by ultrasonic waves. As a laser diffraction scattering type particle size distribution measuring device, LA-500 manufactured by Horiba Sesakusho Co., Ltd. can be used.

Inorganic fillers have one or more surfaces such as aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. to improve moisture resistance. It is preferable to be treated with a treatment agent. As a commercial product of the surface treatment agent, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mer Captopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. ``KBE903'' (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. ``KBM573'' (N-phenyl-3-aminopropyl) Trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), etc. are mentioned.

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

The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and even more preferably 0.2 mg/m 2 or more, from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the melt viscosity in the form of a sheet, 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 still more preferable.

The resin composition used for the resin composition layer contains a thermosetting resin as a resin. As the thermosetting resin, a conventionally known thermosetting resin used when forming the insulating layer of a printed wiring board can be used, and among them, an epoxy resin is preferable. The resin composition may further contain a curing agent as necessary. In one embodiment, a resin composition containing an inorganic filler, an epoxy resin, and a curing agent can be used. The resin composition used for the resin composition layer may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles.

Hereinafter, an epoxy resin, a curing agent, and an additive that can be used as a material of the resin composition will be described.

(Epoxy resin)

As an epoxy resin, for example, 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 epoxy resin, naphthol novolac epoxy resin Resin, phenol novolak type epoxy resin, tertiary-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexanedimethanol type epoxy resin, naph And a styrene ether type epoxy resin and a trimethylol type epoxy resin. Epoxy resin may be used individually by 1 type, or may use 2 or more types together.

It is preferable that the epoxy resin 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 per molecule. Among them, it has two or more epoxy groups per molecule, a liquid epoxy resin (hereinafter referred to as "liquid epoxy resin") at a temperature of 20°C, and three or more epoxy groups per molecule, and a solid phase at a temperature of 20°C. It is preferable to contain an epoxy resin (hereinafter referred to as "solid epoxy resin"). As the epoxy resin, a resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin together. In addition, the breaking strength of the cured product formed by curing the resin composition is also improved.

As the liquid epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, or a naphthalene type epoxy resin is preferable, and a bisphenol A type epoxy resin or a naphthalene type epoxy resin is more preferable. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "EXA4032SS", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation, and "jER828EL" (bisphenol A) manufactured by Mitsubishi Chemical Co., Ltd. Type epoxy resin), “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), and the like. These may be used individually by 1 type, or may use 2 or more types together.

As a solid epoxy resin, tetrafunctional naphthalene type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, biphenyl type epoxy resin, or naphthylene An ether type epoxy resin is preferable, and a tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is more preferable. Specific examples of solid epoxy resins include "HP-4700", "HP-4710" (4-functional naphthalene-type epoxy resin), "N-690" (cresol novolac-type epoxy resin), and "N" manufactured by DIC Corporation. -695" (cresol novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", " HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. (trisphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy resin), "ESN475V" (naphthol novolac-type epoxy resin) manufactured by Shinnittetsu Chemical Co., Ltd., "ESN485" (naphthol novolac-type epoxy resin), Mitsubishi Ka. "YX4000H", "YX4000HK", "YL6121" (biphenyl-type epoxy resin) manufactured by Gaku Corporation, "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., and Mitsubishi Kagaku Corporation "YL7800" (fluorene-type epoxy resin) manufactured by Shikig. Co., Ltd. is mentioned.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the amount ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:4 by mass ratio. By setting the ratio of the amount of the liquid epoxy resin to the solid epoxy resin in this range, ⅰ) suitable adhesion can be obtained when used in the form of an adhesive sheet described later, and ii) sufficient flexibility can be obtained when used in the form of an adhesive sheet. It can be used, the handling property is improved, and effects such as iii) being able to obtain a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of the above i) to iii), the ratio of the amount of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1:0.3 to 1:3.5 by mass ratio, more preferably, The range of 1:0.6 to 1:3 is more preferred, and the range of 1:0.8 to 1:2.8 is particularly preferred.

The content of the epoxy resin in the resin composition is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 45% by mass, still more preferably 5% by mass to 40% by mass, and 7% by mass to 35% by mass % Is particularly preferred.

The epoxy equivalent of the epoxy resin is preferably 50 to 3000, more preferably 80 to 2000, and still more preferably 110 to 1000. By being in this range, the crosslinking density of a cured product becomes sufficient, and an insulating layer with low surface roughness is obtained. In addition, the epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of an epoxy group.

(Hardener)

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

As the phenolic curing agent and the naphthol curing agent, from the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolac structure or a naphthol curing agent having a novolac structure is preferable. Further, from the viewpoint of adhesion (peel strength) to the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable. Among them, it is preferable to use a triazine skeleton-containing phenol novolac resin as a curing agent from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion (peel strength) with the conductor layer.

Specific examples of the phenolic curing agent and the naphthol curing agent include, for example, ``MEH-7700'', ``MEH-7810'', ``MEH-7851'' manufactured by Meiwa Kasei Co., Ltd., and manufactured by Nihon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" manufactured by Toto Kasei Co., Ltd. , "LA7052", "LA7054", and "LA3018" manufactured by DIC Corporation are mentioned.

From the viewpoint of adhesion (peel strength) with the conductor layer, an active ester curing agent is also preferable. The active ester-based curing agent is not particularly limited, but generally, an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds is 2 per molecule. Compounds having two or more are preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylate compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester 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. As a phenolic compound or a naphthol compound, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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-dihydroxy naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone , Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol compound, phenol novolac, and the like. Here, the "dicyclopentadienyldiphenol compound" refers to a diphenol compound obtained by condensation of two molecules of phenol to one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadienyldiphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, an activity containing a benzoylated phenol novolac Ester compounds are preferable, and among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadienyldiphenol structure are more preferable.

Commercially available active ester-based curing agents are active ester compounds containing dicyclopentadienyldiphenol structures, such as "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Corporation). , ``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, phenol "YLH1026" (manufactured by Mitsubishi Chemical Corporation) etc. are mentioned as an active ester compound containing a benzoylated product of novolac.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Co., Ltd., "P-d" and "F-a" manufactured by Shikoku Kasei Kogyo Corporation.

As the cyanate ester curing agent, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6 -Dimethylphenyl cyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4 -Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4- Difunctional cyanate resins such as cyanate phenyl) thioether and bis (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, and some of these cyanate resins are triazineized One prepolymer, etc. Specific examples of the cyanate ester curing agent are "PT30" and "PT60" manufactured by Longza Japan Co., Ltd. (both are phenol novolak-type polyfunctional cyanate ester resins), and "BA230". (Prepolymer in which part or all of the bisphenol A dicyanate is triazineized to become a trimer), etc. are mentioned.

The ratio of the amount of the epoxy resin and the curing agent is a ratio of [the total number of epoxy groups of the epoxy resin]: [the total number of reactors of the curing agent], and is preferably in the range of 1:0.2 to 1:2, and 1 :0.3 to 1:1.5 are more preferable, and 1:0.4 to 1:1 are more 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 curing agent. In addition, the total number of epoxy groups in the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent weight for all epoxy resins, and the total number of reactors of the curing agent refers to the solid content mass of each curing agent. The value divided by is the sum of all curing agents. By setting the ratio of the amount of the epoxy resin to the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

In one embodiment, the resin composition used to form the cured product of the present invention contains the above inorganic filler, epoxy resin, and curing agent. The resin composition includes silica as an inorganic filler, and a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin (the mass ratio of the liquid epoxy resin: the solid epoxy resin is preferably in the range of 1:0.1 to 1:4, and 1:0.3 to The range of 1:3.5 is more preferable, the range of 1:0.6 to 1:3 is more preferable, and the range of 1:0.8 to 1:2.8 is particularly preferable), as a curing agent, a phenolic curing agent, a naphthol curing agent, It is preferable to each contain at least one selected from the group consisting of an active ester curing agent and a cyanate ester curing agent. Regarding the resin composition layer including these specific components in combination, the appropriate content of the inorganic filler, the epoxy resin, and the curing agent is as described above, but among them, the content of the inorganic filler is 50% by mass to 95% by mass, and the epoxy resin It is preferable that the content is 3% by mass to 50% by mass, and the content of the inorganic filler is 50% by mass to 90% by mass, and the content of the epoxy resin is more preferably 5% by mass to 45% by mass. Regarding the content of the curing agent, the ratio of the total number of epoxy groups of the epoxy resin to the total number of the reactors of the curing agent is in the range of 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5. It is contained so as to be in the range, more preferably in the range of 1:0.4 to 1:1.

The resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles, if necessary.

(Thermoplastic resin)

Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyethersulfone resins, polyphenylene ether resins and polysulfone resins, etc. Can be mentioned. Thermoplastic resins may be used alone or in combination of two or more.

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

As a phenoxy resin, for example, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, And a phenoxy resin having at least one skeleton selected from the group consisting of a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Phenoxy resins may be used alone or in combination of two or more. Specific examples of the phenoxy resin include ``1256'' and ``4250'' (both bisphenol A skeleton-containing phenoxy resin), ``YX8100'' (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., and ``YX6954''. '' (bisphenolacetophenone skeleton-containing phenoxy resin), and in addition, ``FX280'' and ``FX293'' manufactured by Toto Chemicals Co., Ltd., ``YL7553'' and ``YL6794'' manufactured by Mitsubishi Chemicals Corporation, "YL7213", "YL7290", and "YL7482", etc. are mentioned.

Specific examples of the polyvinyl acetal resin include Denki Chemical Co., Ltd. manufactured butyral butyral 4000-2, 5000-A, 6000-C, 6000-EP, and Sekisui Chemical Co., Ltd. Elec BH series, BX series, KS series, BL series, BM series, etc. are mentioned.

As a specific example of a polyimide resin, "Lica Coat SN20" and "Lica Coat PN20" manufactured by Shin-Nippon Rica Co., Ltd. are mentioned. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (described in Japanese Unexamined Patent Application Publication No. 2006-37083), a polysiloxane skeleton. Modified polyimides, such as containing polyimides (described in JP 2002-12667 A and JP 2000-319386 A, etc.) can be mentioned.

As a specific example of a polyamide-imide resin, "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyo Boseki Co., Ltd. are mentioned. Further examples of the polyamideimide resin include modified polyamideimide such as polysiloxane skeleton-containing polyamideimide "KS9100" and "KS9300" manufactured by Hitachi Kasei Kogyo Co., Ltd.

As a specific example of a polyether sulfone resin, "PES5003P" etc. manufactured by Tsumitomo Chemical Co., Ltd. can be mentioned.

Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass. By setting the content of the thermoplastic resin in such a range, the viscosity of the resin composition becomes appropriate, and a resin composition having a uniform thickness and bulk properties can be formed. The content of the thermoplastic resin in the resin composition is more preferably 0.5% by mass to 10% by mass.

Examples of the curing accelerator include phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, and the like, and phosphorus curing accelerators, amine curing accelerators, and imidazole curing accelerators are preferred. And an amine-based curing accelerator and an imidazole-based curing accelerator are more preferable.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)tri Phenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc. are mentioned, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1, 8-diazabicyclo(5,4,0)-undecene, etc. are mentioned, and 4-dimethylamino pyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4- Methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimeritate, 1-cyanoethyl-2-phenylimida Zolium trimeritate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-one Silimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s -Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid Adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2 -a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, imidazole compounds, and epoxy resins And the adduct body of, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As a guanidine-based hardening accelerator, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-thryl)guanidine, dimethylguanidine, diphenyl Guanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0 ]Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1 ,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tril) biguanide, etc. are mentioned, and dicyandiamide , 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

Curing accelerators may be used alone or in combination of two or more. In one suitable embodiment, the curing accelerator contained in the resin composition is at least one selected from the group consisting of a phosphorus curing accelerator, an amine curing accelerator, and an imidazole curing accelerator. The content of the curing accelerator in the resin composition is preferably used in the range of 0.05% by mass to 3% by mass, when the total amount of nonvolatile components of the epoxy resin and the curing agent is 100% by mass.

Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicon flame retardant, and a metal hydroxide. Flame retardants may be used alone or in combination of two or more. The content of the flame retardant in the resin composition layer is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass, and still more preferably 1.5% by mass to 8% by mass.

As the rubber particles, for example, those that are not soluble in an organic solvent described later and are not compatible with the above-described epoxy resin, curing agent, and thermoplastic resin are used. In general, such rubber particles are prepared by increasing the molecular weight of the rubber component to a level in which it is not dissolved in an organic solvent or a resin, and forming a particle shape.

Examples of the rubber particles include core-shell rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. Core-shell type rubber particles are rubber particles having a core layer and a shell, for example, a two-layer structure in which the shell layer of the outer layer is composed of a glassy polymer, and the core layer of the inner layer is composed of a rubbery polymer, or the shell layer of the outer layer is glassy. And a three-layer structure composed of a polymer, an intermediate layer composed of a rubber-like polymer, and a core layer composed of a glass-like polymer. The glassy polymer layer is composed of, for example, a methyl methacrylate polymer or the like, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber) or the like. The rubber particles may be used alone or in combination of two or more.

The average particle diameter of the rubber particles 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 diameter of the rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic or the like, and the particle size distribution of rubber particles is prepared on a mass basis using a thick particle diameter analyzer (FPAR-1000; manufactured by Otsuka Corporation). And it can measure by making the median diameter into an average particle diameter. The content of the rubber particles 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 used to form the cured product of the present invention may contain other additives as necessary, and such other additives include, for example, organic copper compounds, organic zinc compounds, and organic cobalt compounds. And resin additives such as organic fillers, thickeners, defoaming agents, leveling agents, adhesion imparting agents, coloring agents and curable resins.

The cured body of the present invention can be used as a cured body (cured body for an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board. Among them, in the manufacture of a printed wiring board by the build-up method, it can be suitably used as a cured body for forming an insulating layer (a cured body for a build-up insulating layer of a printed wiring board), and pattern processed using a dry film for pattern formation. It can be used more suitably as a cured body for forming a conductor layer (a cured body for a build-up insulating layer of a printed wiring board forming a pattern-processed conductor layer using a pattern-forming dry film).

The resin composition layer used to form the cured product of the present invention is preferably used in the form of an adhesive sheet containing the resin composition layer from the viewpoint of being able to easily and efficiently lamination onto a circuit board.

In one embodiment, the adhesive sheet comprises a support and a resin composition layer (adhesive layer) bonded to the support.

As the support, a film made of a plastic material is suitably used. Examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as ``PET''), polyethylene naphthalate (hereinafter sometimes abbreviated as ``PEN''), polycarbonate ( Hereinafter, it may be abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Can be mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In one suitable embodiment, the support is a polyethylene terephthalate film.

The support may be subjected to a mat treatment and a corona treatment on the surface of the resin composition layer and the side to be joined. In addition, as a support, you may use a support with a release layer which has a release layer on the surface of the side to be joined with the resin composition layer.

Although the thickness of the support is not particularly limited, the range of 5 µm to 75 µm is preferable, and the range of 10 µm to 60 µm is more preferable. Further, when the support is a support with a release layer, it is preferable that the thickness of the entire support with a release layer is within the above range.

For the adhesive sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, the resin varnish is applied on a support body using a die coater, etc., and the organic solvent is further dried by heating or hot air spraying. It can be manufactured by forming a resin composition layer.

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

Although drying conditions are not specifically limited, It is dried so that content (remaining solvent amount) in a resin composition layer may become 10 mass% or less, preferably 5 mass% or less. The lower limit of the residual solvent amount is not particularly limited, but from the viewpoint of preventing an increase in the melt viscosity in the form of a sheet or handleability of the resin composition layer, it is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Although also different 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 an organic solvent, by drying at 50°C to 150°C for 3 to 10 minutes, the resin composition Layers can be formed.

In the adhesive sheet, 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 body (that is, the surface opposite to the support body). 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 adhesion of dust or the like to the surface of the resin composition layer and scratches. The adhesive sheet can be wound up and stored in a roll shape, and can be used by peeling off the protective film when producing the cured product of the present invention.

[Method of manufacturing cured body]

The method for producing a cured product of the present invention,

(A) a step of laminating a resin composition layer on a circuit board, and

(B) Step of forming a cured body on a circuit board by thermosetting the resin composition layer

Including,

When the lowest melt viscosity temperature of the resin composition layer is Tv (°C), the lamination temperature of the resin composition layer is Tv-35°C to Tv + 35°C,

When the thickness of the resin composition layer is x (µm) and the thickness of the cured body on the circuit wiring of the circuit board is y (µm), it is characterized in that 0.3 <y/x ≤ 1 and y ≤ 15.

In step (A), a resin composition layer is laminated on a circuit board. The configuration of the circuit board and the resin composition layer used in step (A) is as described above.

In the method for producing a cured product of the present invention, a resin composition layer is laminated on a circuit board at a temperature range of Tv-35°C to Tv + 35°C from the viewpoint of suppressing undulations on the surface of the cured product formed on the circuit board. From the viewpoint of suppressing undulations on the surface of the cured body formed on the circuit board, the lamination temperature of the resin composition layer in the step (A) is preferably in the range of Tv-30°C to Tv + 30°C, more preferably Tv- It is in the range of 25°C to Tv + 25°C, more preferably in the range of Tv-20°C to Tv + 20°C, particularly preferably in the range of Tv-15°C to Tv + 15°C.

The lamination of the resin composition layer onto the circuit board is preferably performed by laminating treatment such that the resin composition layer is bonded to the circuit board by roll pressing or press pressing under the above lamination temperature conditions. Among them, the vacuum lamination method of laminating under reduced pressure is more preferable.

In one suitable embodiment, the lamination of the resin composition layer onto the circuit board can be performed using the above adhesive sheet. Specifically, a lamination treatment can be performed so that the resin composition layer of the adhesive sheet is bonded to the circuit board. When the adhesive sheet has a protective film, it can be provided to the step (A) after removing the protective film. In addition, the peeling of the support may be performed between the step (A) and the step (B), or may be performed after the step (B), but from the viewpoint of suppressing the occurrence of uneven roughness, the steps (A) and (B) It is preferable to carry out between.

In the lamination treatment, considering the relationship between x and y above, the compression pressure is in the range of 1 kgf/cm 2 to 11 kgf/cm 2 (0.098 MPa to 1.078 MPa), and the compression time is in the range of 5 seconds to 180 seconds. And the air pressure is preferably carried out under reduced pressure of 20 mmHg (26.7 hPa) or less.

After the lamination treatment, the laminated adhesive sheet may be smoothed by hot pressing with a metal plate. The smoothing treatment can be performed by heating and pressing the adhesive sheet with a metal plate such as a heated SUS hard plate under normal pressure (under atmospheric pressure). Heating and pressurizing conditions can be the same as those for the lamination treatment.

The lamination treatment (and smoothing treatment) can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, a vacuum pressurized laminator manufactured by Meiki Sesakusho Co., Ltd., a vacuum applicator manufactured by Nichigo Morton Corporation, etc. are mentioned, for example.

In step (B), the resin composition layer is thermally cured to form a cured body on the circuit board.

From the viewpoint of reducing the undulations of the surface of the formed cured body and suppressing the occurrence of uneven roughness, in step (B), after maintaining the resin composition layer at a temperature T ₁ for a certain time, a temperature T ₂ higher than the temperature T ₁ is constant. It is preferable to heat cure by holding time.

The temperature T ₁ is preferably a temperature (°C) below Tv, more preferably Tv-10°C or less, still more preferably Tv-20°C or less, and particularly preferably Tv-25°C or less. The lower limit of the temperature T ₁ is preferably Tv-60°C or higher, more preferably Tv-50°C or higher, and still more preferably Tv-40°C or higher.

The time to maintain at the temperature T ₁ also depends on the value of the temperature T ₁ , but is preferably 10 minutes or longer, more preferably 10 minutes to 150 minutes, and still more preferably 15 minutes to 120 minutes.

The temperature T ₂ is preferably a temperature of Tv or higher (°C), more preferably Tv + 10°C or higher, still more preferably Tv + 20°C or higher, even more preferably Tv + 30°C, and Tv + 40°C It is particularly preferable that it is above. The upper limit of the temperature T ₂ is preferably Tv + 100°C or less, more preferably Tv + 90°C or less, more preferably Tv + 80°C or less, even more preferably Tv + 70°C or less, particularly preferably Tv + 60 ℃ or less.

Time T ₂ is maintained at a temperature that conforms to the value of temperature T _2, and preferably at least 10 minutes, more preferably from 10 minutes to 100 minutes, more preferably from 10 minutes to 80 minutes.

From the viewpoint of reducing the undulations of the surface of the formed cured body and suppressing the occurrence of uneven roughness, the thermosetting of the resin composition layer in step (B) is maintained at a temperature less than Tv for 10 minutes or more, and then at a temperature of Tv or more. It is preferable that the temperature be maintained at a temperature of Tv-60°C or higher and lower than Tv for 10 minutes or longer, and then held at a temperature of Tv or higher and Tv + 100°C or lower for 10 minutes. Tv-It is more preferable to maintain the temperature for 10 minutes or more at a temperature of not less than 60℃ and less than Tv, and then Tv + 10℃ or more and Tv + 100℃ or less for 10 minutes. Tv-50℃ or more Tv-10℃ It is more preferable to hold the temperature for 10 minutes or more at the following temperature, and then Tv + 10°C or more and Tv + 90°C or less for 10 minutes, and more preferably, Tv-40°C or more Tv-20°C or less for 10 minutes After maintaining the above, it is more preferable to carry out by holding for 10 minutes at a temperature of Tv + 20°C or higher and Tv + 80°C or lower.

Step (B) may be carried out under pressure, under normal pressure, or under reduced pressure, but from the viewpoint of reducing the undulation of the surface of the formed cured body and suppressing the occurrence of uneven roughness, preferably 0.075 mmHg to 3751 mmHg (0.1 hPa) To 5000 hPa), more preferably 1 mmHg to 1875 mmHg (1.3 hPa to 2500 hPa). Especially, it is preferable to perform process (B) under normal pressure.

The rate of temperature increase from the temperature T ₁ to the temperature T ₂ is not particularly limited, but is preferably 1.5° C./min to 30° C./min, more preferably 2° C./min to 30° C./min, and more preferably 4° C./ It is from minute to 20°C/min, even more preferably from 4°C/min to 10°C/min.

As described above, when the thickness of the resin composition layer is x (µm) and the thickness of the cured body on the circuit wiring of the circuit board is y (µm) from the viewpoint of suppressing the occurrence of uneven illumination while achieving a thin layer. It is important to perform lamination and thermal curing of the resin composition layer so that, x and y satisfy 0.3 <y/x ≤ 1 and y ≤ 15. Preferred ranges of the x, y, and y/x ratios are as described above.

[Harmonic hardened body]

The roughened hardened body of the present invention can be formed by roughening the hardened body of the present invention.

The order and conditions of the roughening treatment are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of the printed wiring board can be adopted. For example, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid can be performed in this order to roughen the surface of the cured body. Although it does not specifically limit as a swelling liquid, An alkali solution, a surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As the said alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As a commercially available swelling liquid, Swelling Dip Securiganth P (Swelling Dip Securiganth P), Swelling Dip Securiganth SBU (Swelling Dip Securiganth SBU) manufactured by Atotech Japan Co., Ltd. are mentioned, for example. . Although the swelling treatment by the swelling liquid is not particularly limited, it can be carried out, for example, by immersing the cured product in the swelling liquid at 30 to 90°C for 1 minute 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 of 40 to 80°C for 5 seconds to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the cured product in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrated Compact CP manufactured by Atotech Japan Co., Ltd. and Dosing Solution Securigans P. Moreover, an acidic aqueous solution is preferable as a neutralization liquid, As a commercial item, the reduction solution Securigans P manufactured by Atotech Japan Co., Ltd. is mentioned, for example. The treatment with the neutralizing liquid can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent solution in the neutralizing liquid at 30 to 80°C for 5 minutes to 30 minutes. From the standpoint of workability and the like, a method of immersing the object subjected to the roughening treatment with the oxidizing agent solution in a neutralization solution of 40 to 70°C for 5 to 20 minutes is preferable.

Conventionally, when a thin resin composition layer is used to form a cured body with small undulations on a circuit board, the undulations (that is, the surface of the cured body on the circuit wiring of the circuit board) and recesses (i.e., There was a case where a problem of unevenness of roughness occurred in which the surface of the cured body on the portion without circuit wiring) showed significantly different surface roughness after the roughening treatment. On the other hand, in the roughened cured product of the present invention obtained by roughening the cured product of the present invention, occurrence of uneven roughness is suppressed. That is, the roughened hardened body of the present invention has the arithmetic mean roughness (Ra _l ) of the surface of the roughened hardened body on the circuit wiring of the circuit board, and the arithmetic average roughness of the surface of the roughened hardened body on the part of the circuit board without circuit wiring ( It is characterized in that the difference of Ra ₂ ) (│Ra _l -Ra ₂ │) is small. In the roughened cured product of the present invention, the value of │Ra ₁ -Ra ₂ │ is preferably 160 nm or less, more preferably 140 nm or less, further preferably 120 nm or less, and 100 nm or less, 90 nm from the viewpoint of fine wiring formability. It is particularly preferably 80 nm or less, 70 nm or less, 60 nm or less, or 50 nm or less. The lower the value of │Ra _l -Ra ₂ │, the more preferable, and the lower limit may be 0 nm.

When using a thin resin composition layer to form a cured body with small undulations on a circuit board, the arithmetic mean roughness (Ra ₁ ) of the surface of the roughened hardened body on the circuit board of the circuit board is the part of the circuit board without circuit wiring. It tends to be higher than the arithmetic mean roughness (Ra ₂ ) of the surface of the roughened hardened body above. From the viewpoint of fine wiring formability, in the roughened cured body of the present invention, Ra ₁ is preferably 300 nm or less, more preferably 270 nm or less, further preferably 240 nm or less, 210 nm or less, 200 nm or less, 190 nm or less, 180 nm or less, It is particularly preferably 170 nm or less, or 160 nm or less. In the cured resin blend of the present invention, Ra _2, in the relationship between Ra and _1, preferably a value, the value of │Ra _l -Ra ₂ │ which the above-mentioned range. In addition, in the roughened cured product of the present invention, the lower limit of Ra ₁ and Ra ₂ is not particularly limited, but in order to stabilize the peel strength between the roughened cured product and the conductor layer formed thereon, it is 10 nm or more, 30 nm or more, etc. .

The roughened cured product of the present invention is obtained by subjecting the cured product of the present invention to a roughening treatment, and the physical property values such as the maximum cross-sectional height Rt and the thickness of the surface correspond to those of the cured product of the present invention. For example, the roughened cured product of the present invention is characterized in that the maximum cross-sectional height Rt of the surface is 3.5 µm or less, and the surface undulations are small. The roughened cured product of the present invention preferably has a maximum cross-sectional height Rt of 3.3 μm or less, more preferably 3.1 μm or less, and 2.9 μm or less, 2.7 μm or less, 2.5 μm or less, 2.3 μm or less, 2.1 μm or less, or More preferably, it is 1.9 μm or less. Further, in the roughened cured body of the present invention, the thickness of the roughened cured body on the circuit wiring of the circuit board is 15 µm or less, preferably 14 µm or less, more preferably 12 µm or less, further preferably 10 µm or less, and 9 It is even more preferable that it is less than or equal to 8 μm, less than or equal to 7 μm, or less than or equal to 6 μm. The lower limit of the thickness of the roughened cured body on the circuit wiring of the circuit board is usually 0.5 µm or more, and preferably 1 µm or more.

[Laminate]

The laminate of the present invention includes a roughened hardened body of the present invention and a conductor layer formed on the surface of the roughened hardened body.

The conductor layer is made of a metal layer, and the metal used for the conductor layer is not particularly limited, but in one suitable embodiment, the conductor layer is gold, platinum, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten. , At least one metal selected from the group consisting of iron, tin and indium. The conductor layer may be a monometallic layer or an alloy layer, and as the alloy layer, for example, an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and A layer formed from a copper-titanium alloy). Among them, from the viewpoint of versatility, cost, and ease of removal by etching, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy, An alloy layer of a copper-titanium alloy is preferable, a monometallic layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a monometallic layer of copper is still more preferable.

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

The thickness of the conductor layer is preferably 40 µm or less, more preferably 1 to 35 µm, and still more preferably 3 to 20 µm, from the viewpoint of fine wiring of the printed wiring board. Even when the metal layer has a multilayer structure, it is preferable that the thickness of the entire metal layer is within the above range.

The conductor layer can be formed into a desired wiring pattern by a known technique such as a semi-positive method and a full-positive method. In general, by disposing a dry film for pattern formation on the roughened cured body (insulation layer), developing a desired pattern, and then plating, a conductor layer having a desired pattern can be formed.

In the conventional technique, when a cured product is formed on a circuit board using a thin resin composition layer, the surface of the obtained cured product tends to have large undulations corresponding to the circuit wiring pattern of the circuit board as the base, and thus pattern formation. A problem of a decrease in the adhesion of the dry film was caused. Further, in the conventional technique, when a cured product having a small surface undulations is formed on a circuit board using a thin resin composition layer, a problem of uneven roughness may occur. On the other hand, in the technique of the present invention, as described above, since the problem of lowering the adhesion of the dry film for pattern formation or the problem of uneven roughness does not occur, a conductor layer having a fine wiring pattern on the surface of the roughened cured body is provided. It is possible to form advantageously.

In the laminate of the present invention, the line/space ratio of the conductor layer formed on the surface of the roughened cured product is preferably 20/20 μm or less, more preferably 15/15 μm or less, further preferably 10/10. It is µm or less, particularly preferably 8/8 µm or less.

[Printed wiring board]

The printed wiring board of the present invention is characterized in that an insulating layer is formed by the cured body of the present invention.

In one embodiment, the printed wiring board of this invention can be manufactured using the said adhesive sheet. In such an embodiment, the above-described "step (A)" and "step (B)" are performed so that the resin composition layer of the adhesive sheet is bonded to the circuit board, so that the cured body of the present invention can be formed on the circuit board. Moreover, when the adhesive sheet has a protective film, it can be used for manufacture after removing a protective film.

Subsequently, the hardened body formed on the circuit board is subjected to the above "harmonization treatment" to form a roughened hardened body, and then a conductor layer is formed on the surface of the roughened hardened body. Further, in the manufacture of a printed wiring board, a step of forming a via in the insulating layer, a step of removing resin residue (smear) inside the via, and the like may be further included. These steps can be carried out according to various methods known to those skilled in the art and used for manufacturing a printed wiring board.

The printed wiring board of the present invention is highly compatible with thinning of layers and fine wiring of circuits.

[Semiconductor device]

A semiconductor device can be manufactured using the above printed wiring board.

As such semiconductor devices, various semiconductor devices provided in electric appliances (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, tanks, ships and aircraft, etc.) Can be lifted.

[Example]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, in the following description, "part" and "%" mean "part by mass" and "% by mass", respectively, unless otherwise specified.

First, various measurement methods and evaluation methods will be described.

[Preparation of samples for measurement and evaluation]

(1) substrate treatment of circuit board

On both sides of a glass cloth, epoxy resin double-sided copper clad laminate (copper foil thickness of 18 µm, substrate thickness of 0.3 mm, Matsushita Denko Corporation ``R5715ES''), IPC MULTI-PURPOSE TEST BOARD NO. A circuit was formed with the pattern of IPC B-25 (line/space ratio = 175/175 µm comb pattern (remaining rate 50%)). Both surfaces of the obtained circuit board were immersed in "CZ8100" manufactured by McC. Co., Ltd., and the surface was subjected to roughening treatment.

(2) Lamination of the resin composition layer

The adhesive sheets produced in Examples and Comparative Examples were used in a batch-type vacuum pressurized laminator (MVLP-500 manufactured by Meiki Sesakusho Co., Ltd.), so that the resin composition layer was in contact with the circuit board. Laminated on both sides. Lamination of the resin composition layers was carried out by performing a lamination treatment at 120°C and a pressure of 0.74 MPa for 30 seconds after reducing the pressure for 30 seconds to reduce the pressure to 13 hPa or less for Examples 1 to 3 and Comparative Example 2. Subsequently, smoothing treatment was performed by hot pressing at 120°C and a pressure of 0.5 MPa for 60 seconds.

Regarding Comparative Example 1, a lamination treatment and a smoothing treatment were performed under the same conditions as in Examples 1 to 3 and Comparative Example 2, except that the temperature of the lamination treatment and the smoothing treatment were changed to 90°C.

(3) Thermal curing of the resin composition layer

After lamination of the resin composition layer, the PET film as a support was peeled off. Thereafter, the resin composition layer was held at 100° C. for 30 minutes, and then held at 180° C. for 30 minutes to be thermally cured to form a cured body on the circuit board.

With respect to the obtained cured product, the maximum cross-sectional height Rt of the surface of the cured product, the thickness of the cured product on the circuit wiring, and the embedding property of the resin were evaluated.

(4) formation of via holes

A via hole was formed by drilling the cured body using a CO ₂ laser processing machine "LC-2E21B/1C" manufactured by Hitachi Via Mecanicus Co., Ltd. The top diameter of the via hole on the surface of the cured body was 50 µm. In addition, the drilling conditions were: mask diameter 1.60 mm, focus offset value 0.050, pulse width 25 μs, energy 0.33 mJ/shot (output 0.66 W, frequency 2000 Hz), aperture 13, shot number 2, It was a burst mode.

(5) Harmonization treatment

After formation of the via hole, the circuit board on which the cured product was formed was subjected to roughening treatment in accordance with the following procedure to obtain a roughened cured product. That is, the circuit board on which the cured product was formed was added to a swelling liquid ("Swelling Deep Security P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60° C. for 5 minutes, followed by an oxidizing agent. Solution ("Concentrate Compact P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of approximately 6% potassium permanganate and approximately 4% sodium hydroxide) at 80°C for 15 minutes, and finally a neutralization solution (Atotech Japan Co., Ltd.) After immersing in the production "Reduction Solution Securigans P", sulfuric acid aqueous solution) at 40°C for 5 minutes, it was dried at 130°C for 15 minutes.

About the obtained roughened hardened|cured material, the roughness nonuniformity was evaluated.

(6) Formation of conductor layer

A conductor layer was formed on the surface of the roughened hardened body according to the semi-positive method.

That is, the circuit board on which the roughened hardened body was formed was immersed in an electroless copper plating liquid containing PdCl ₂ , and then heated at 150° C. for 30 minutes to perform annealing treatment. As a result, a plating seed layer was formed on the surface of the roughened hardened body.

The surface of the obtained plating seed layer was treated with a 5% sulfuric acid aqueous solution for 30 seconds, and then a dry film for pattern formation ("ALPHO 20A263", manufactured by Nichigo Morton Co., Ltd., a thickness of 20 μm) was laminated on the plating seed layer. Lamination of the dry film for pattern formation was carried out using a batch-type vacuum pressurized laminator ("MVLP-500" manufactured by Meiki Sesakusho Co., Ltd.) and reduced pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then 70°C and pressure. It was carried out by laminating treatment at 0.1 MPa for 20 seconds. Next, a glass mask formed with a comb pattern (wire length of 15 mm, 16 lines) with a 16 μm pitch of L (dry film line)/S (space) = 8/8 μm was placed on the PET film as a protective layer of the dry film. Then, UV irradiation was performed with a UV lamp at an irradiation intensity of 150 mJ/cm 2. After UV irradiation, spray treatment was performed for 30 seconds at an injection pressure of 0.15 MPa using a 1% sodium carbonate aqueous solution at 30°C. Then, it washed with water and developed (pattern formation) of a dry film. After development of the dry film, the adhesiveness of the dry film was evaluated.

The substrate having good dry film adhesion was subjected to electrolytic copper plating to form a 15 µm-thick conductor layer. Subsequently, a spray treatment was performed at an injection pressure of 0.2 MPa using a 3% sodium hydroxide solution at 50° C., and the dry film was peeled off. After that, the excess plating seed layer was removed by the SAC process manufactured by Evaradenic Acid Co., Ltd. to form a printed wiring board.

About the obtained printed wiring board, the fine wiring formability was evaluated.

<Measurement of the lowest melt viscosity temperature Tv of the resin composition layer>

The minimum melt viscosity temperature Tv of the resin composition layer in the adhesive sheet prepared in Examples and Comparative Examples was measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM). For 1 g of the sample resin composition, a parallel plate with a diameter of 18 mm was used, and the temperature was raised from the starting temperature of 60°C to 200°C at a heating rate of 5°C/min, the measurement temperature interval 2.5°C, the frequency of 1Hz, the strain rate 1deg The temperature at the lowest melt viscosity was measured under the conditions of.

<Measurement of the maximum cross-sectional height Rt of the surface of the cured body>

The maximum cross-sectional height Rt of the surface of the cured body on the circuit board is 0.82 mm × 1.1 mm using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by Vico Instruments) in a VSI contact mode and a 10x lens. It was calculated|required by the numerical value obtained by. In addition, the measurement was carried out so that the area with the circuit wiring and the portion without the circuit wiring was applied to the area where the circuit wiring of the comb pattern (remaining rate 50%) with a line/space ratio = 175/175 μm was formed. It implemented by obtaining the average value of.

In addition, in Table 1, the case where the maximum cross-sectional height Rt is 3.5 micrometers or less was set as "○", and the case where it exceeded 3.5 micrometers was set as "x".

<Measurement of the thickness of the cured body on the circuit wiring of the circuit board>

For the thickness (y) of the cured body on the circuit wiring of the circuit board, the area where the circuit wiring of the comb-tooth pattern with a line/space ratio = 175/175 μm is installed is cut into 1 cm squares, and a transparent sealing resin (Marumoto It was sealed with an unsaturated polyester resin manufactured by Ruas Co., Ltd.), the cross section was polished, and then measured by observing with a scanning electron microscope ("S4800" manufactured by Hitachi High-Technology Co., Ltd.). The measurement was performed by obtaining the average value of five points.

<Evaluation of resin landfill property>

The embedding property of the resin was evaluated by observing the surface of the cured body with a scanning electron microscope ("S4800" manufactured by Hitachi High-Technology Co., Ltd.).

In addition, in Table 1, the occurrence of voids and no bleeding out of the resin and being firmly buried were referred to as "o", and the occurrence of voids or oozing out of the resin was denoted as "x".

<Evaluation of illumination unevenness>

The roughness unevenness of the surface of the roughened hardened body is the arithmetic mean roughness of the surface of the roughened hardened body on the circuit wiring of the circuit board (Ra _l ) and the arithmetic average roughness of the surface of the roughened hardened body on the part of the circuit board without circuit wiring ( It was carried out by measuring Ra ₂ ) and determining the value of |Ra ₁ -Ra ₂ |. The arithmetic mean roughness (Ra ₁ and Ra ₂ ) of the surface of the roughened hardened body was measured using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by Vico Instruments Co., Ltd.) by a VSI contact mode and a 50x lens. It was calculated by the numerical value obtained by setting it as 123 µm, and for each of Ra ₁ and Ra ₂ , the average value of three points was calculated.

In addition, in Table 1, the case where the value of |Ra ₁ -Ra ₂ | was 160 nm or less was set to "o", and the case exceeded 160 nm was set to "×".

<Evaluation of adhesion of dry film for pattern formation>

The adhesion of the dry film for pattern formation is a scanning electron microscope (with respect to the area where the circuit wiring of the comb pattern of the line/space ratio = 175/175 µm is formed) and the adhesion state between the roughened cured body (plating seed layer) and the dry film. It evaluated by observing with "S4800" manufactured by Hitachi Hi-Technology Co., Ltd.).

In addition, in Table 1, the case where there is no peeling or swelling in the dry film was designated as "○", and the case where there was peeling and swelling was designated as "x".

<Evaluation of fine wiring formability>

The fine wiring formability was confirmed by confirming the presence or absence of peeling of the conductor layer with an optical microscope and measuring the insulation resistance of the comb pattern to determine the presence or absence of unnecessary plating seed layers.

In Table 1, when there was no peeling of the conductor layer and no residual plating seed layer, it was referred to as "○", and that there was peeling of the conductor layer and/or residual plating seed layer was indicated as "x".

[Production Example 1]

(1) Preparation of resin varnish

Liquid bisphenol A epoxy resin (epoxy equivalent 180, manufactured by Mitsubishi Chemical Co., Ltd. ``jER828EL'') 10 parts, biphenyl type epoxy resin (epoxy equivalent 269, manufactured by Nihon Kayaku Co., Ltd. ``NC3000L'') 20 parts, 4 Functional naphthalene-type epoxy resin (epoxy equivalent 163, DIC Corporation ``HP4700'') 6 parts, and phenoxy resin (Mitsubishi Chemical Corporation ``YL7553BH30'', solid content 30 mass% MEK and cyclohexanone 1: 1 solution) 10 parts were heated and dissolved in a mixed solvent of 5 parts of MEK, 5 parts of cyclohexanone and 15 parts of solvent naphtha while stirring. After cooling to room temperature, 15 parts of a triazine-containing phenol novolak-based curing agent (hydroxyl equivalent 125, DIC Corporation ``LA7054'', solid content 60 mass% MEK solution) 15 parts, naphthol-based curing agent (hydroxyl equivalent 215, Toto Kasei Co., Ltd. ``SN-485'', a solid 60% MEK solution) 15 parts, an amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), a solid 5% by mass MEK solution) 1 part, imidazole type Hardening accelerator (1-benzyl-2-phenylimidazole, Shikoku Kasei Kogyo Co., Ltd. ``1B2PZ'', solid content 5 mass% MEK solution) 0.3 parts, flame retardant (Sanko Corporation ``HCA-HQ''), 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2㎛) 5 parts, aminosilane coupling agent (Shin-Etsu Chemical 140 parts of spherical silica (average particle diameter 0.5㎛, "SOC2" manufactured by Adomatex, 0.39mg/m2 of carbon per unit area) surface-treated with Kogyo Corporation (“KBM573”), polyvinyl butyral 15 parts of a resin ("KS-1" manufactured by Sekisui Chemical Co., Ltd., a 1:1 solution of ethanol and toluene having a solid content of 15% by weight) was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

(2) Preparation of adhesive sheet 1

As a support, a PET film with a release layer (manufactured by Lintec Co., Ltd., a polyethylene terephthalate film with an alkyd release agent (AL-5)) was prepared. On the release surface of the support, the resin varnish obtained in (1) was uniformly applied with a die coater so that the thickness of the dried resin composition layer became 15 µm, and 2 to 80°C (100°C on average) The adhesive sheet 1 was formed by drying for 4 minutes. The lowest melt viscosity temperature Tv of the resin composition layer in the adhesive sheet 1 was 130°C.

[Production Example 2]

The adhesive sheet 2 was produced in the same manner as in Production Example 1 except that the resin varnish was uniformly applied with a die coater so that the thickness of the dried resin composition layer became 20 µm. The lowest melt viscosity temperature Tv of the resin composition layer in the adhesive sheet 2 was 127°C.

[Production Example 3]

The adhesive sheet 3 was produced in the same manner as in Production Example 1 except that the resin varnish was uniformly applied with a die coater so that the thickness of the dried resin composition layer became 25 µm. The lowest melt viscosity temperature Tv of the resin composition layer in the adhesive sheet 3 was 127°C.

[Production Example 4]

The adhesive sheet 4 was produced in the same manner as in Production Example 1, except that the resin varnish was uniformly applied with a die coater so that the thickness of the dried resin composition layer became 15 µm. The lowest melt viscosity temperature Tv of the resin composition layer in the adhesive sheet 4 was 130°C.

[Production Example 5]

The adhesive sheet 5 was produced in the same manner as in Production Example 1, except that the resin varnish was uniformly applied with a die coater so that the thickness of the dried resin composition layer became 10 µm. The lowest melt viscosity temperature Tv of the resin composition layer in the adhesive sheet 5 was 140°C.

<Example 1>

Using the adhesive sheet 1, a printed wiring board was manufactured in accordance with the procedure of [Preparation of a sample for measurement and evaluation]. Table 1 shows each evaluation result.

<Example 2>

Using the adhesive sheet 2, a printed wiring board was manufactured in accordance with the procedure of [Preparation of a sample for measurement and evaluation]. Table 1 shows each evaluation result.

<Example 3>

Using the adhesive sheet 3, a printed wiring board was produced in accordance with the procedure of [Preparation of a sample for measurement and evaluation].

Table 1 shows each evaluation result.

<Comparative Example 1>

Using the adhesive sheet 4, a printed wiring board was manufactured in accordance with the procedure of [Preparation of a sample for measurement and evaluation]. In addition, as shown in [Preparation of a sample for measurement and evaluation], in Comparative Example 1, the lamination temperature of the resin composition layer was 90°C. Table 1 shows each evaluation result.

<Comparative Example 2>

Using the adhesive sheet 5, a printed wiring board was manufactured in accordance with the procedure of [Preparation of a sample for measurement and evaluation]. Table 1 shows each evaluation result.

In the case of using a thin resin composition layer for thinning of the layer, if the lamination temperature of the resin composition layer is not in the range of Tv-35°C to Tv + 35°C, it results in a cured body with large undulations on the surface, and dry film adhesion This drop was confirmed (Comparative Example 1). In addition, by setting the lamination temperature of the resin composition layer in the range of Tv-35°C to Tv + 35°C, it is possible to suppress undulations on the surface of the cured body, but the relationship between x and y is 0.3 <y/x ≤ 1 and y ≤ 15 If not satisfied, it was confirmed that unevenness of illuminance occurs remarkably (Comparative Example 2).

On the other hand, in Examples 1 to 3 in which the lamination temperature of the resin composition layer is in the range of Tv-35°C to Tv + 35°C, and at the same time, x and y satisfy the relationship of 0.3 <y/x ≤ 1 and y ≤ 15 In this case, even in the case of using a thin resin composition layer for thinning of the layer, it was possible to realize a cured product with small undulations on the surface that provides sufficient dry film adhesion, and at the same time, it was possible to suppress the occurrence of uneven roughness.

1: resin composition layer
2: hardened body
3: circuit board
4: circuit wiring
5: substrate

Claims (17)

As a cured body formed on a circuit board obtained by laminating a resin composition layer on a circuit board and thermosetting the resin composition layer,
When the lowest melt viscosity temperature of the resin composition layer is Tv (°C), the lamination temperature of the resin composition layer is Tv-35°C to Tv + 35°C,
When the thickness of the resin composition layer is x (µm) and the thickness of the cured body on the circuit wiring of the circuit board is y (µm), 0.4 ≤ y/x ≤ 1 and y ≤ 15. The cured product according to claim 1, wherein x≤25. The cured product according to claim 1, wherein the maximum cross-sectional height Rt of the surface of the cured product is 3.5 μm or less. The cured product according to claim 1, obtained by holding the resin composition layer at a temperature less than Tv for 10 minutes or more, and then holding the resin composition layer at a temperature of Tv or more for 10 minutes or more to heat cure. The cured body according to claim 1, wherein 0.5 ≤ y/x ≤ 1 and y ≤ 15 when the thickness of the resin composition layer is x (µm) and the thickness of the cured body on the circuit wiring of the circuit board is y (µm). . The cured product according to claim 1, wherein the resin composition layer is formed of a resin composition comprising an epoxy resin and a curing agent selected from a phenol curing agent, a naphthol curing agent, an active ester curing agent and a benzoxazine curing agent. A roughened cured product obtained by subjecting the cured product according to claim 1 to a roughening treatment. The roughened hardened body according to claim 7, wherein the difference between the arithmetic average roughness of the surface of the roughened hardened body on the circuit wiring of the circuit board and the arithmetic average roughness of the surface of the roughened hardened body on the part of the circuit board without circuit wiring is 160 nm or less. . A laminate comprising the roughened hardened body according to claim 7 or 8 and a conductor layer formed on the surface of the roughened hardened body. (A) a step of laminating a resin composition layer on a circuit board, and
(B) Step of forming a cured body on a circuit board by thermosetting the resin composition layer
Including,
When the lowest melt viscosity temperature of the resin composition layer is Tv (°C), the lamination temperature of the resin composition layer is Tv-35°C to Tv + 35°C,
When the thickness of the resin composition layer is x (µm) and the thickness of the cured body on the circuit wiring of the circuit board is y (µm), 0.4 ≤ y/x ≤ 1 and y ≤ 15. The method for producing a cured product according to claim 10, wherein x≦25. The method for producing a cured product according to claim 10, wherein the maximum cross-sectional height Rt of the surface of the cured product is 3.5 μm or less. The method for producing a cured product according to claim 10, wherein in step (B), the resin composition layer is maintained at a temperature lower than Tv for 10 minutes or longer, and then maintained at a temperature of Tv or higher for 10 minutes or more to heat cure. The cured product according to claim 10, wherein when the thickness of the resin composition layer is x (µm) and the thickness of the cured body on the circuit wiring of the circuit board is y (µm), 0.5 ≤ y/x ≤ 1 and y ≤ 15. Manufacturing method. The resin composition according to any one of claims 10 to 14, wherein the resin composition layer comprises an epoxy resin and a curing agent selected from a phenol curing agent, a naphthol curing agent, an active ester curing agent and a benzoxazine curing agent. Formed, a method for producing a cured product. A printed wiring board in which an insulating layer is formed by the cured body according to any one of claims 1 to 6. A semiconductor device comprising the printed wiring board according to claim 16.

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