KR20240120668A - Cured body - Google Patents

Abstract

[Problem] To provide a cured body that can obtain an insulating layer with high adhesion to a conductor layer after a high-acceleration life test in a high-temperature, high-humidity environment.
[Solution] As a cured product of a resin composition containing a thermosetting resin; The hardened body has a surface with an arithmetic mean roughness Ra of less than 100 nm; When a layer of the resin composition is cured at 200°C for 90 minutes to form a cured sample layer, the contact angle of diethylene glycol-mono-n-butyl ether with respect to the surface of the cured sample layer is less than 30°, and the cured sample layer A cured body wherein the nitrogen atom concentration obtained based on the peak area of the spectrum of N1s in X-ray photoelectron spectroscopy analysis of the surface of the layer is less than 3.8 atomic%.

Description

Cured body {CURED BODY}

The present invention relates to a cured body of a resin composition containing a thermosetting resin and a method for producing the same. In addition, the present invention relates to a circuit board, a semiconductor chip package, and a semiconductor device including the cured body; and a resin sheet capable of producing the cured body.

Circuit boards and semiconductor chip packages are generally provided with an insulating layer. For example, a printed wiring board as a type of circuit board may be provided with an interlayer insulating layer as an insulating layer. Additionally, for example, a semiconductor chip package may be provided with a redistribution formation layer as an insulating layer. These insulating layers can be formed from a cured body obtained by curing a resin composition (Patent Documents 1 and 2).

[Patent Document]

[Patent Document 1] International Publication No. 2020/130100

[Patent Document 2] Japanese Patent Publication No. 2020-193365

In some cases, a conductor layer is provided on the insulating layer. This conductor layer is generally subjected to patterning processing to form wiring having an appropriate pattern shape. The conductor layer provided on the insulating layer in this way is usually required to have high adhesion to the insulating layer. Therefore, from the viewpoint of obtaining high adhesion, it has been proposed to form a conductor layer on the insulating layer after performing ultraviolet treatment and silane coupling agent treatment on the insulating layer.

However, in the conventional method, the adhesion after a highly accelerated life test (HAST test, also called accelerated environmental test) under a high temperature and high humidity environment is not satisfactory, and further improvement is required.

The present invention was created in view of the above problems, and provides a cured body capable of obtaining an insulating layer with high adhesion to a conductor layer after a highly accelerated life test (HAST test) in a high temperature and high humidity environment; Method for producing the cured body; Circuit boards, semiconductor chip packages, and semiconductor devices containing the cured body; And, the purpose is to provide a resin sheet from which the cured body can be manufactured.

The present inventor has diligently studied to solve the above problems. As a result, the present inventor set the surface roughness of the surface of the cured body on which the conductor layer is formed within a specific range, and further specified the surface properties of the cured sample layer formed by curing the resin composition as the material for the cured body under specific conditions. It was discovered that the above problems could be solved by controlling them to meet the requirements, and the present invention was completed.

That is, the present invention includes the following.

[1] As a cured product of a resin composition containing a thermosetting resin;

The hardened body has a surface with an arithmetic mean roughness Ra of less than 100 nm;

When a test was conducted to form a cured sample layer by curing a layer of the resin composition at 200°C for 90 minutes,

The contact angle of diethylene glycol-mono-n-butyl ether with respect to the surface of the cured sample layer is less than 30°,

A cured body having a nitrogen atom concentration of less than 3.8 atomic% obtained based on the peak area of the spectrum of N1s in X-ray photoelectron spectroscopy analysis of the surface of the cured sample layer.

[2] The cured body according to [1], wherein the nitrogen atom concentration obtained based on the peak area of the N1s spectrum in X-ray photoelectron spectroscopy analysis of the surface of the cured sample layer is 0.1 atomic% or more.

[3] The cured body according to [1] or [2], wherein the resin composition contains an inorganic filler.

[4] The cured body according to [3], wherein the amount of the inorganic filler in the resin composition is 40% by mass or more and 90% by mass or less with respect to 100% by mass of the non-volatile component of the resin composition.

[5] The cured body according to any one of [1] to [4], wherein the thermosetting resin contains an epoxy resin.

[6] The cured product according to any one of [1] to [5], wherein the thermosetting resin contains a phenol resin.

[7] The cured product according to any one of [1] to [6], wherein the thermosetting resin contains an active ester resin.

[8] The cured body according to any one of [1] to [7], wherein the thermosetting resin contains a maleimide resin.

[9] The cured body according to any one of [1] to [8], wherein the resin composition contains a curing accelerator.

[10] The cured body according to any one of [1] to [9], wherein the resin composition contains a resin component containing a nitrogen atom.

[11] The cured body according to any one of [1] to [10], for forming a conductor layer on the surface having an arithmetic mean roughness Ra of less than 100 nm.

[12] A circuit board comprising an insulating layer formed by the cured body according to any one of [1] to [11].

[13] A semiconductor chip package comprising the cured body according to any one of [1] to [11] and a semiconductor chip.

[14] A semiconductor device including the circuit board described in [12].

[15] A semiconductor device including the semiconductor chip package described in [13].

[16] A method for producing a cured body according to any one of [1] to [11],

A process of obtaining a cured body by curing a resin composition containing a thermosetting resin;

A process of subjecting the cured body to ultraviolet ray treatment;

A method for producing a cured body, comprising the step of subjecting the cured body to treatment with a silane coupling agent.

[17] A resin sheet comprising a support and a layer of a resin composition formed on the support;

The resin composition includes a thermosetting resin;

When the layer of the resin composition is cured to form a cured sample, and a first test is performed in which the surface of the cured sample is treated with ultraviolet rays and a silane coupling agent on the surface on the support side, the arithmetic average roughness Ra of the surface on the support side is 100 nm. is less than;

When a second test was conducted in which a layer of the resin composition was cured at 200°C for 90 minutes to form a cured sample layer,

The contact angle of diethylene glycol-mono-n-butyl ether with respect to the surface of the support side of the cured sample layer is less than 30°,

A resin sheet wherein the nitrogen atom concentration obtained based on the peak area of the N1s spectrum in X-ray photoelectron spectroscopy of the surface on the support side of the cured sample layer is less than 3.8 atomic%.

[18] In the first test, curing of the layer of the resin composition was carried out under conditions of 170°C for 30 minutes,

In the first test, ultraviolet treatment is performed by irradiating the cured sample with ultraviolet rays with a wavelength of 172 nm for 10 seconds,

In the first test, the silane coupling agent treatment involved placing the cured sample in an aqueous solution of pH 5.0 containing 5 g/liter of 3-amino-propyl trimethoxysilane and 350 g/liter of diethylene glycol-mono-n-butyl ether. , The resin sheet described in [17], which is performed by dipping at 40°C for 10 minutes.

According to the present invention, a cured body capable of obtaining an insulating layer with high adhesion to a conductor layer after a highly accelerated life test (HAST test) in a high temperature and high humidity environment; Method for producing the cured body; Circuit boards, semiconductor chip packages, and semiconductor devices containing the cured body; And, a resin sheet capable of producing the cured body can be provided.

[Figure 1] Figure 1 is a cross-sectional view schematically showing a fan-out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and may be implemented with any modification without departing from the scope of the claims and their equivalents.

<Overview of hardened body>

The cured body according to one embodiment of the present invention is a cured body of a resin composition containing a thermosetting resin. This cured body satisfies the following requirements (i) to (iii).

(i) The cured body has a surface with an arithmetic mean roughness Ra of less than 100 nm.

(ii) When a test was conducted to form a cured sample layer by curing the layer of the resin composition at 200°C for 90 minutes, the contact angle It is less than 30°.

(iii) When a test was conducted to form a cured sample layer by curing the layer of the resin composition at 200°C for 90 minutes, in XPS (X-ray Photoelectron Spectroscopy) analysis of the surface of the cured sample layer, The nitrogen atom concentration obtained based on the peak area of the spectrum of N1s is less than 3.8 atomic%.

A surface with an arithmetic mean roughness Ra of less than 100 nm of the cured body may be hereinafter referred to as a “specific smooth surface.” When a conductor layer is formed on a specific smooth surface of a cured body, high adhesion can be obtained between the conductor layer and the cured body after a highly accelerated life test (HAST test) under a high temperature and high humidity environment. Therefore, according to the cured body, an insulating layer with high adhesion to the conductor layer can be obtained after the HAST test.

Although not bound by a specific theory, the present inventors speculate the mechanism by which the above effect is obtained as follows. However, the technical scope of the present invention is not limited by the mechanism described below.

The specific smooth surface of the cured body is usually treated with ultraviolet rays and a silane coupling agent at the time the conductor layer is formed. By ultraviolet treatment, functional groups such as -COOH groups are generated on the specific smooth surface of the cured body. In addition, by treatment with a silane coupling agent, the silane coupling agent binds to and immobilizes the functional group, thereby improving the affinity of the specific smooth surface for the inorganic material. Generally, inorganic materials such as metal are used as materials for the conductor layer, so when the conductor layer is formed on a specific smooth surface, high adhesion can be obtained between the cured body and the conductor layer.

In requirement (ii), the surface properties of the cured sample layer are correlated with the properties of a specific smooth surface of the cured body before ultraviolet treatment and silane coupling agent treatment. Usually, the surface properties of the cured sample layer match the properties of the specific smooth surface of the cured body. In addition, in requirement (ii), the contact angle have a relationship Therefore, when requirement (ii) is satisfied, usually the contact angle of the treatment liquid for silane coupling agent treatment with respect to the specific smooth surface of the cured body is sufficiently small, and therefore, the specific smooth surface of the cured body is exposed to the treatment liquid for silane coupling agent treatment. Can have high affinity. Therefore, the compatibility of the treatment liquid with the specific smooth surface of the cured body can be increased, so that the bonding between the silane coupling agent and the functional group on the specific smooth surface proceeds smoothly, or the degree of the bonding can be increased to a high level within the specific smooth surface. It can be uniformized.

In addition, in requirement (iii), the nitrogen atom concentration on the surface of the cured sample layer has a correlation with the nitrogen atom concentration on the specific smooth surface of the cured body before ultraviolet treatment and silane coupling agent treatment. Usually, the nitrogen atom concentration on the surface of the cured sample layer matches the nitrogen atom concentration on the specific smooth surface of the cured body. When the nitrogen atom concentration is within the above specific range, functional groups such as -COOH group can be effectively generated by ultraviolet treatment. In addition, when requirement (iii) is satisfied, usually the specific smooth surface of the cured body can have high affinity to the treatment liquid for silane coupling agent treatment, so the specific smooth surface of the cured body is the same as described in requirement (ii). The solubility of the treatment solution to cotton can be improved.

Therefore, when the above requirements (ii) and (iii) are satisfied, a strong adhesion improvement effect is obtained by the chemical action obtained by ultraviolet treatment and silane coupling agent treatment. Therefore, after the HAST test, high adhesion can be obtained between the cured body and the conductor layer.

However, as a result of the present inventor's repeated experiments, it has been revealed that in order to effectively exert the above chemical action, a high smoothness is required for a specific smooth surface of the cured body. Considering that there has been conventional technical knowledge that higher adhesion is achieved on surfaces with lower smoothness due to the anchor effect, it is surprising that excellent adhesion is obtained after the HAST test on a specific smooth surface with high smoothness.

Depending on ultraviolet treatment and silane coupling agent treatment, generally, no change occurs in the arithmetic mean roughness Ra of the surface of the cured body. Therefore, the arithmetic mean roughness Ra of the specific smooth surface of the cured body may be measured before or after ultraviolet treatment and silane coupling agent treatment.

For example, a cured body having a specific smooth surface whose arithmetic mean roughness Ra measured before treatment with ultraviolet rays and a silane coupling agent is in a specific range that satisfies requirement (i), has the specific smooth surface treated with ultraviolet rays and a silane coupling agent. When the conductor layer is formed after performing the HAST test, high adhesion can be obtained between the cured body and the conductor layer. Therefore, the cured body according to the present embodiment includes a cured body whose specific smooth surface before ultraviolet treatment and silane coupling agent treatment has an arithmetic mean roughness Ra that satisfies requirement (i).

In addition, for example, a cured body having a specific smooth surface in a specific range where the arithmetic mean roughness Ra measured after treatment with ultraviolet rays and treatment with a silane coupling agent satisfies requirement (i), has a conductor layer formed on the specific smooth surface. In this case, high adhesion can be obtained after the HAST test between the cured body and the conductor layer. Therefore, a cured body having an arithmetic mean roughness Ra that satisfies requirement (i) on a specific smooth surface after ultraviolet treatment and silane coupling agent treatment is included in the cured body according to the present embodiment.

Usually, the cured body can achieve high adhesion between the conductor layer and the cured body not only after the HAST test but also before the HAST test. Additionally, the cured body preferably has a low dielectric loss tangent. Additionally, the cured body preferably has a high glass transition temperature.

<Requirement (i). Arithmetic average roughness Ra> of the specific smooth surface of the hardened body

The hardened body according to the present embodiment has a specific smooth surface with an arithmetic mean roughness Ra in a specific range. Specifically, the range of the arithmetic mean roughness Ra of a specific smooth surface is usually less than 100 nm, preferably less than 80 nm, more preferably less than 60 nm, preferably more than 10 nm, more preferably more than 20 nm, even more preferably is 30nm or more. When the specific smooth surface of the cured body has an arithmetic mean roughness Ra in the above range, the adhesion between the conductor layer formed on the specific smooth surface and the cured body can be improved after the HAST test, and usually, the adhesion before the HAST test is improved. It is also possible.

The arithmetic mean roughness Ra of the specific smooth surface of the hardened body can be measured based on Japanese Industrial Standards (JIS B0601-2001). Measurement can be performed using a non-contact surface roughness meter (“WYKO NT3300” manufactured by Viko Instruments). As a specific method of measuring the arithmetic mean roughness Ra, the method of <Test 4. Measurement of surface roughness Ra and Rz> in the examples described later can be adopted.

The arithmetic mean roughness Ra of the specific smooth surface of the cured body can be adjusted, for example, by the composition of the resin composition. For example, when using a resin composition containing an inorganic filler, it can be adjusted according to the particle size of the inorganic filler. In addition, for example, when obtaining a cured body by curing the resin composition layer (layer of the resin composition) provided in the resin sheet, the surface roughness of the support provided in the resin sheet can be adjusted according to the lamination conditions.

<Requirement (ii). Contact angle X of the surface of the cured sample layer>

The cured body according to the present embodiment is a cured body of a resin composition. A test was performed to form a cured sample layer by forming a layer of the resin composition (hereinafter sometimes referred to as “resin composition layer”) using the above resin composition, and curing the resin composition layer under conditions of 200°C for 90 minutes. In this case, the contact angle X of diethylene glycol-mono-n-butyl ether with respect to the surface of the cured sample layer is within a specific range.

The specific range of the contact angle It is 1° or more, more preferably 3° or more, and particularly preferably 6° or more. When the contact angle

The cured sample layer can be formed by forming a resin composition layer and curing it under curing conditions of 200°C for 90 minutes. The surface of the cured sample layer formed in this way usually has an arithmetic mean roughness Ra in the range specified in the above-mentioned requirement (i). Additionally, the contact angle X can be measured using the θ/2 method by the droplet method. Specifically, a 1.0 μL droplet of diethylene glycol-mono-n-butyl ether is attached to the surface of the cured sample layer, and the contact angle X can be measured 2000 ms after the droplet is attached. The detailed measurement method of the contact angle

The contact angle X can be adjusted, for example, by the composition of the resin component of the resin composition. Unless otherwise specified, the resin component of the resin composition refers to the component excluding the inorganic filler among the non-volatile components contained in the resin composition. For example, if there is a large amount of non-polar resin such as silicone resin, the contact angle X tends to increase. Additionally, when a polar resin is included, the contact angle X tends to become small.

Here, the cured sample layer above represents a sample to be subjected to a measurement test to specify the properties of the resin composition (and, by extension, the properties of the cured body). And requirement (ii) specifies the range of the contact angle X of diethylene glycol-mono-n-butyl ether with respect to the surface of this cured sample layer. Therefore, the specific smooth surface of the cured body may or may not have a contact angle X in a specific range.

<Requirement (iii). Nitrogen atom concentration on the surface of the cured sample layer>

As described above, the cured body according to the present embodiment is a cured body of a resin composition. When a test was performed to form a cured sample layer by curing the layer of the resin composition (resin composition layer) at 200°C for 90 minutes, the spectrum of N1s in X-ray photoelectron spectroscopy analysis of the surface of the cured sample layer The nitrogen atom concentration obtained based on the peak area is within a specific range.

The specific range of the above nitrogen atom concentration is usually less than 3.8 atomic%, preferably 3.5 atomic% or less, more preferably 3.0 atomic% or less, preferably 0.1 atomic% or more, more preferably 0.5 atomic% or more. , more preferably 1.0 atomic% or more. When the nitrogen atom concentration is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body can be improved after the HAST test, and in general, the adhesion before the HAST test can also be improved.

The cured sample layer can be formed by forming a resin composition layer as described above and curing it under curing conditions of 200°C for 90 minutes. Additionally, the nitrogen atom concentration on the surface of the cured sample layer can be measured using X-ray photoelectron spectroscopy. Specifically, the nitrogen atom concentration can be measured as the ratio of the area of the N1s peak to the area of all peaks in the spectrum measured by X-ray photoelectron spectroscopy. As a detailed measurement method of nitrogen atom concentration by X-ray photoelectron spectroscopy, the method of <Test 2.

The nitrogen atom concentration can be adjusted, for example, depending on the composition of the resin component of the resin composition. For example, by adjusting the amount of resin containing nitrogen atoms, the nitrogen atom concentration on the surface of the cured sample layer can be adjusted. However, when the resin composition layer is heated and cured, the resin in the resin composition layer may flow and a distribution may occur in the composition of the resin contained in the resin composition layer in the thickness direction. For example, even when the resin composition layer has a uniform composition in the thickness direction, the resin may flow during curing, and the resin containing nitrogen atoms may be contained so as to be distributed near the surface of the resin composition layer. The above flow may change depending on curing conditions. Therefore, it is desirable to adjust the composition of the resin composition so that the surface of the cured sample layer obtained by curing under the curing conditions of 200°C for 90 minutes, rather than under other curing conditions, has a nitrogen atom concentration in the above range.

Here, as described above, the cured sample layer represents a sample to be subjected to a measurement test for specifying the properties of the resin composition (and, by extension, the properties of the cured body). And requirement (iii) specifies the range of nitrogen atom concentration obtained based on the peak area of the spectrum of N1s in X-ray photoelectron spectroscopy analysis of the surface of this cured sample layer. Therefore, the specific smooth surface of the cured body may or may not have a nitrogen atom concentration within a specific range.

<Resin composition>

The cured body according to the present embodiment is a member obtained by curing the resin composition as described above. The resin composition contains (A) thermosetting resin as component (A). (A) As the thermosetting resin, a resin that can be cured when heat is applied can be used. (A) Thermosetting resin may be used individually or in combination of two or more types.

((A-1) epoxy resin)

(A) The thermosetting resin preferably contains (A-1) epoxy resin as the (A-1) component. (A-1) Epoxy resin is a curable resin having an epoxy group. (A-1) Examples of epoxy resins include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol. type epoxy resin, naphthol novolac type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, Glycidyl epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing Epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin. etc. can be mentioned. (A-1) One type of epoxy resin may be used individually, or two or more types may be used in combination.

(A-1) The epoxy resin preferably contains an epoxy resin containing an aromatic structure from the viewpoint of obtaining a cured body with excellent heat resistance. An aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. As an epoxy resin containing an aromatic structure, 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, and trisphenol type epoxy resin. , naphthol novolak-type epoxy resin, phenol novolac-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, bixylenol-type epoxy resin, glyphosate having an aromatic structure. Cydylamine type epoxy resin, glycidyl ester type epoxy resin having an aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, epoxy having a butadiene structure having an aromatic structure. Resin, alicyclic epoxy resin with an aromatic structure, heterocyclic epoxy resin, spiro ring-containing epoxy resin with an aromatic structure, cyclohexanedimethanol type epoxy resin with an aromatic structure, naphthylene ether type epoxy resin, trimethyl with an aromatic structure All-type epoxy resins, tetraphenylethane-type epoxy resins having an aromatic structure, etc. can be mentioned.

(A-1) The epoxy resin preferably contains an epoxy resin containing a nitrogen atom from the viewpoint of obtaining a cured body with excellent heat resistance. Examples of the epoxy resin containing a nitrogen atom include glycidylamine type epoxy resin.

(A-1) The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. (A-1) The proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile component of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, especially Preferably it is 70% by mass or more.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”) and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as “solid epoxy resins”). There is. The (A-1) epoxy resin contained in the resin composition may be only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, and phenol novolac type epoxy resin. , alicyclic epoxy resins having an ester skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER807” and “1750” (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “630”, “630LSD”, “JER630LSD”, and “604” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “ED-523T” manufactured by ADEKA (glycirol type epoxy resin); “EP-3950L” and “EP-3980S” (glycidylamine type epoxy resin) manufactured by ADEKA; “EP-4088S” manufactured by ADEKA (dicyclopentadiene type epoxy resin); “ZX-1059” manufactured by Nittetsu Chemical & Materials Co., Ltd. (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin); “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Corporation; “Celoxide 2021P” manufactured by Daicel Corporation (alicyclic epoxy resin with an ester skeleton); “PB-3600” manufactured by Daicel Corporation, “JP-100” and “JP-200” manufactured by Nippon Soda Corporation (epoxy resin with a butadiene structure); “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nittetsu Chemical & Materials. These may be used individually or in combination of two or more types.

As a solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups per molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups per molecule is more preferable.

As solid epoxy resins, xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol novolak-type epoxy resin, cresol novolak-type epoxy resin, dicyclopentadiene-type epoxy resin, and trisphenol-type epoxy resin. , naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol Phthalimidine type epoxy resin is preferred.

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

When using a combination of liquid epoxy resin and solid epoxy resin as an epoxy resin, the range of their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 20:1 to 1:10, more preferably 10. :1 to 1:5, particularly preferably 5:1 to 1:2.

(A-1) The range of the epoxy equivalent weight of the epoxy resin is preferably 50 g/eq. to 5,000 g/eq., more preferably 60 g/eq. to 3,000 g/eq., more preferably 80 g/eq. to 2,000 g/eq., particularly preferably 90 g/eq. to 1,000 g/eq. Epoxy equivalent represents the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

(A-1) The range of the weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

The amount of epoxy resin (A-1) in the resin composition can be set in a range that satisfies the above-mentioned requirements (i) to (iii). In one example, the range of the amount of the epoxy resin (A-1) is preferably 0.1% by mass or more, more preferably 1% by mass or more, with respect to 100% by mass of non-volatile components of the resin composition. It is 3% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. (A-1) When the amount of the epoxy resin is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

In addition, in one example, the range of the amount of epoxy resin (A-1) in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the resin component of the resin composition. More preferably, it is 10 mass% or more, preferably 80 mass% or less, more preferably 60 mass% or less, and even more preferably 50 mass% or less. As described above, the resin component of the resin composition refers to the component excluding the inorganic filler among the non-volatile components contained in the resin composition. (A-1) When the amount of the epoxy resin is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

((A-2) Phenolic resin)

(A) The thermosetting resin preferably contains (A-2) phenol resin as the (A-2) component. (A-2) As the phenol resin, a compound having one or more phenolic hydroxyl groups per molecule, preferably two or more, can be used. A phenolic hydroxyl group refers to a hydroxyl group bonded to an aromatic ring such as a benzene ring or a naphthalene ring. In particular, it is preferable to use the phenol resin (A-2) in combination with the epoxy resin (A-1). When the (A-1) epoxy resin and (A-2) phenol resin are used in combination, the (A-2) phenol resin is a curing agent that reacts with the (A-1) epoxy resin to form a bond to cure the resin composition. It can function as.

From the viewpoint of heat resistance and water resistance, the phenol resin (A-2) having a novolak structure is preferable. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenol resin is preferable, and a triazine skeleton-containing phenol resin is more preferable. Among them, a phenol novolak resin containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.

(A-2) Specific examples of the phenol resin include, for example, "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000" manufactured by Meiwa Kasei Corporation, and "MEH-8000" manufactured by Nippon Kayaku Corporation. “NHN”, “CBN”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485” manufactured by Nittetsu Chemical & Materials, “SN-495”, “SN-375”, “SN-395”, “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018” manufactured by DIC Corporation ”, 「LA-3018-50P」, 「LA-1356」, 「TD2090」, 「TD-2090-60M」, 「EXB-9500」, 「HPC-9500」, 「KA-1160」, 「KA-1163 ", "KA-1165", "GDP-6115L" and "GDP-6115H" manufactured by Gunei Chemical Co., Ltd., etc.

(A-2) One type of phenol resin may be used individually, or two or more types may be used in combination.

(A-2) The range of the hydroxyl equivalent weight of the phenol resin is preferably 50 g/eq. to 3000 g/eq., more preferably 100 g/eq. to 1000 g/eq., more preferably 100 g/eq. to 500 g/eq., particularly preferably 100 g/eq. to 300 g/eq. The hydroxyl equivalent weight represents the mass of the resin per 1 equivalent of the hydroxyl group.

The range of the weight average molecular weight of the (A-2) phenol resin may be the same as the range of the weight average molecular weight of the epoxy resin (A-1).

(A-1) When the epoxy group number of the epoxy resin is 1, the range of the hydroxyl group number of the (A-2) phenol resin is preferably 0.01 or more, more preferably 0.10 or more, and still more preferably 0.15 or more. , Preferably it is 5.0 or less, more preferably 2.0 or less, and especially preferably 1.0 or less. “(A-1) Epoxy group number of the epoxy resin” refers to the sum of all the values obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, “(A-2) hydroxyl group number of phenol resin” represents the sum of all the values obtained by dividing the mass of the non-volatile component of the phenol resin present in the resin composition by the hydroxyl group equivalent.

The amount of (A-2) phenol resin in the resin composition can be set in a range that satisfies the above-mentioned requirements (i) to (iii). In one example, the range of the amount of the phenol resin (A-2) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, with respect to 100% by mass of the non-volatile component of the resin composition. It is 0.5 mass% or more, preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 10 mass% or less. (A-2) When the amount of the phenol resin is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

In addition, in one example, the range of the amount of phenol resin (A-2) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, based on 100% by mass of the resin component of the resin composition. More preferably, it is 3% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. (A-2) When the amount of the phenol resin is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

((A-3) activated ester resin)

(A) The thermosetting resin preferably contains (A-3) active ester resin as the (A-3) component. (A-3) The active ester resin generally contains two highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having more than one compound are preferably used. In particular, it is preferable to use the active ester resin (A-3) in combination with the epoxy resin (A-1). When the (A-1) epoxy resin and (A-3) active ester resin are used in combination, the (A-3) active ester resin reacts with the (A-1) epoxy resin to form a bond to cure the resin composition. Shiki can function as a hardener.

(A-3) The active ester resin is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester resins obtained from carboxylic acid compounds and hydroxy compounds are preferable, and active ester resins obtained from carboxylic acid compounds, phenol compounds, and/or naphthol compounds are more preferable. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Phenol compounds or naphthol compounds include, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, (A-3) active ester resins include dicyclopentadiene type active ester resin, naphthalene type active ester resin containing a naphthalene structure, active ester resin containing acetylated product of phenol novolak, and phenol novolak. An active ester resin containing a benzoylate is preferable, and among these, at least one type selected from a dicyclopentadiene type active ester resin and a naphthalene type active ester resin is more preferable. As the dicyclopentadiene type active ester resin, an active ester resin containing a dicyclopentadiene type diphenol structure is preferable.

(A-3) Commercially available active ester resins include, for example, active ester resins containing a dicyclopentadiene type diphenol structure, such as “EXB9451”, “EXB9460”, “EXB9460S”, “EXB-8000L”, 「EXB-8000L-65M」, 「EXB-8000L-65TM」, 「HPC-8000L-65TM」, 「HPC-8000」, 「HPC-8000-65T」, 「HPC-8000H」, 「HPC-8000H-65TM 」(manufactured by DIC); As an active ester resin containing a naphthalene structure, “HP-B-8151-62T”, “EXB-8100L-65T”, “EXB-8150-60T”, “EXB-8150-62T”, and “EXB-9416-70BK” , “HPC-8150-60T”, “HPC-8150-62T”, “EXB-8” (manufactured by DIC); As a phosphorus-containing active ester resin, "EXB9401" (manufactured by DIC Corporation); As an activated ester resin which is an acetylate of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); Examples of active ester resins that are benzoylates of phenol novolak include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); Examples of the active ester resin containing a styryl group and a naphthalene structure include "PC1300-02-65MA" (manufactured by Airwater).

(A-3) One type of active ester resin may be used individually, or two or more types may be used in combination.

(A-3) The range of the equivalent weight of the active ester group of the active ester resin is preferably 50 g/eq. to 3000 g/eq., more preferably 100 g/eq. to 1000 g/eq., more preferably 100 g/eq. to 500 g/eq., particularly preferably 100 g/eq. to 300 g/eq. The active ester group equivalent represents the mass of the resin per equivalent of the active ester group.

The range of the weight average molecular weight of the (A-3) active ester resin may be the same as the range of the weight average molecular weight of the epoxy resin (A-1).

(A-1) When the epoxy group number of the epoxy resin is 1, the range of the active ester group number of the (A-3) active ester resin is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.10. or more, preferably 5.0 or less, more preferably 2.0 or less, and particularly preferably 1.0 or less. “(A-3) Number of active ester groups of active ester resin” refers to the sum of all the values obtained by dividing the mass of the non-volatile component of the active ester resin present in the resin composition by the equivalent weight of the active ester group.

The amount of active ester resin (A-3) in the resin composition can be set in a range that satisfies the above-mentioned requirements (i) to (iii). In one example, the range of the amount of the active ester resin (A-3) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on 100% by mass of the non-volatile component of the resin composition. is 0.5 mass% or more, preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 2 mass% or less. (A-3) When the amount of the active ester resin is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

In addition, in one example, the range of the amount of active ester resin (A-3) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, based on 100% by mass of the resin component of the resin composition. , more preferably 3% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. (A-3) When the amount of the active ester resin is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

((A-4) maleimide resin)

(A) The thermosetting resin preferably contains (A-4) maleimide resin as the (A-4) component. As the maleimide resin, a compound containing at least one, preferably two or more maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) per molecule can be used. You can. (A-4) In the maleimide resin, the ethylenic double bond contained in the maleimide group undergoes radical polymerization to form a bond, and the resin composition can be heat-cured. Additionally, in the presence of an appropriate catalyst such as an imidazole compound, the maleimide resin (A-4) reacts with the epoxy resin (A-1) to form a bond and can function as a curing agent that hardens the resin composition.

(A-4) As the maleimide resin, an aliphatic maleimide resin containing an aliphatic amine skeleton may be used, an aromatic maleimide resin containing an aromatic amine skeleton may be used, or a combination of these may be used. In addition, (A-4) maleimide resin may be used individually, or may be used in combination of two or more types.

(A-4) As maleimide resin, for example, (1) “BMI-3000”, “BMI-3000J”, “BMI-5000”, “BMI-1400”, “BMI-1500”, “BMI- 1700", "BMI-689" (all manufactured by Designer Molecules), and "SLK-6895-T90" (manufactured by Shin-Etsu Kagaku Kogyo), etc. (preferably an aliphatic with 36 carbon atoms derived from dimerdiamine) maleimide resin containing a skeleton); (2) A maleimide resin containing an indane skeleton described in the Invention Association Publication No. 2020-500211; (3) Nitrogen atoms of maleimide groups such as “MIR-3000-70MT” (manufactured by Nippon Kayaku Co., Ltd.), “BMI-4000” (manufactured by Yamato Kasei Co., Ltd.), and “BMI-80” (manufactured by KAI Kasei Co., Ltd.) and a maleimide resin containing a directly bonded aromatic ring skeleton.

(A-4) Maleimide resin may be used individually or in combination of two or more types.

(A-4) The range of the maleimide group equivalent of the maleimide resin is preferably 50 g/eq. to 3000 g/eq., more preferably 100 g/eq. to 1000 g/eq., and even more preferably 100 g/eq. to 500 g/eq. The maleimide group equivalent represents the mass of the resin per 1 equivalent of the maleimide group.

The range of the weight average molecular weight of the (A-4) maleimide resin may be the same as the range of the weight average molecular weight of the epoxy resin (A-1).

When the epoxy group number of the (A-1) epoxy resin is 1, the range of the maleimide group number of the (A-4) maleimide resin is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.10. or more, preferably 5.0 or less, more preferably 2.0 or less, and particularly preferably 1.0 or less. “(A-4) The maleimide group resin of the maleimide resin represents the sum of all the values obtained by dividing the mass of the non-volatile component of the maleimide resin present in the resin composition by the maleimide group equivalent.

The amount of (A-4) maleimide resin in the resin composition can be set in a range that satisfies the above-mentioned requirements (i) to (iii). In one example, the range of the amount of maleimide resin (A-4) is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.0% by mass or more, based on 100% by mass of non-volatile components of the resin composition. is 2.0 mass% or more, preferably 30 mass% or less, more preferably 20 mass% or less, and even more preferably 15 mass% or less. (A-4) When the amount of maleimide resin is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

In addition, in one example, the range of the amount of maleimide resin (A-4) in the resin composition is preferably 1% by mass or more, more preferably 4% by mass or more, based on 100% by mass of the resin component of the resin composition. , more preferably 6% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less. (A-4) When the amount of maleimide resin is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

(Any thermosetting resin)

(A) Other examples of thermosetting resins include cyanate ester resin, carbodiimide resin, acid anhydride resin, amine resin, benzoxazine resin, and thiol resin. When these resins are used in combination with the (A-1) epoxy resin, they can function as a curing agent that reacts with the (A-1) epoxy resin to form a bond and harden the resin composition. One type of hardening agent may be used individually, or two or more types may be used in combination.

(A) When the thermosetting resin contains (A-1) an epoxy resin and a curing agent in combination, (A-2) phenol resin, (A-3) active ester resin, cyanate ester resin, carbodiimide resin, acid It is desirable that the amount of curing agent such as anhydride resin, amine resin, benzoxazine resin, and thiol resin falls within a specific range. Here, in a system in which the (A-1) epoxy resin and (A-4) maleimide resin can react and combine, the (A-4) maleimide resin is also included in the curing agent. The specific range of the amount of the curing agent is preferably 0.1 mass% or more, more preferably 1 mass% or more, further preferably 3 mass% or more, based on 100 mass% of non-volatile components of the resin composition. It is 40 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less. When the amount of the curing agent is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured material after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

In addition, the range of the amount of the curing agent is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, based on 100% by mass of the resin component of the resin composition, and preferably It is 90 mass% or less, more preferably 80 mass% or less, and even more preferably 70 mass% or less. When the amount of the curing agent is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured material after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

In addition, when the epoxy group number of the (A-1) epoxy resin is 1, the range of the active group number of the curing agent is preferably 0.01 or more, more preferably 0.1 or more, further preferably 0.3 or more, and preferably It is 5.0 or less, more preferably 2.0 or less, especially preferably 1.0 or less. The “active group number of the curing agent” refers to the sum of all the values obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active group equivalent. In addition, the active group equivalent of the curing agent refers to the mass of the resin per equivalent of active groups such as phenolic hydroxyl group, active ester group, and maleimide group.

Moreover, as another example of (A) thermosetting resin, (A-4) radically polymerizable resin other than maleimide resin, etc. are mentioned. This radically polymerizable resin generally has ethylenically unsaturated bonds and can be cured by radical polymerization. Examples of the radically polymerizable resin include a styrene-based radically polymerizable resin having one or more vinyl groups directly bonded to an aromatic carbon atom, an allyl-based radically polymerizable resin having one or more allyl groups, etc. One type of radical polymerizable resin may be used individually, or two or more types may be used in combination.

The range of the weight average molecular weight of the (A) thermosetting resin may be the same as the range of the weight average molecular weight of the epoxy resin (A-1).

(Amount of thermosetting resin containing nitrogen atoms)

(A) Part or all of the thermosetting resin may contain nitrogen atoms. Examples of the thermosetting resin containing a nitrogen atom include (A-4) maleimide resin and amine resin; and resins containing a nitrogen atom such as (A-1) epoxy resin, (A-2) phenol resin, and (A-3) active ester resin. The thermosetting resin containing a nitrogen atom may be used individually or in combination of two or more types.

The amount of the thermosetting resin containing nitrogen atoms in the resin composition can be set in a range that satisfies the above-mentioned requirements (i) to (iii). In one example, the range of the amount of the thermosetting resin containing a nitrogen atom in the resin composition is (A) preferably 10% by mass or more, more preferably 20% by mass or more, based on 100% by mass of the total amount of the thermosetting resin, More preferably, it is 30 mass% or more, preferably 90 mass% or less, more preferably 80 mass% or less, and even more preferably 70 mass% or less. When the amount of the thermosetting resin containing nitrogen atoms is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

In addition, the range of the amount of the thermosetting resin containing a nitrogen atom in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 100% by mass or more of the non-volatile component of the resin composition. is 2% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. When the amount of the thermosetting resin containing nitrogen atoms is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

In addition, the range of the amount of the thermosetting resin containing a nitrogen atom in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, with respect to 100% by mass of the resin component of the resin composition. It is 10 mass% or more, preferably 90 mass% or less, more preferably 80 mass% or less, and even more preferably 70 mass% or less. When the amount of the thermosetting resin containing nitrogen atoms is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

(Amount of thermosetting resin)

The amount of (A) thermosetting resin in the resin composition can be set in a range that satisfies the above-mentioned requirements (i) to (iii). In one example, the range of the amount of thermosetting resin (A) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably, based on 100% by mass of non-volatile components of the resin composition. is 5 mass% or more, preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less. (A) When the amount of the thermosetting resin is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

In addition, the range of the amount of the thermosetting resin (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more, based on 100% by mass of the resin component of the resin composition. , Preferably it is 100% by mass or less. (A) When the amount of the thermosetting resin is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

((B) Inorganic filler)

The resin composition may further contain (B) an inorganic filler as an optional component. (B) The inorganic filler as the component (B) is usually contained in the resin composition and the cured body in the state of particles.

(B) As the material for the inorganic filler, an inorganic compound is usually used. (B) Inorganic filler materials include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and hydroxide. Aluminum, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, Examples include barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica and alumina are suitable, and silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Additionally, spherical silica is preferred as the silica. (B) Inorganic fillers may be used individually, or two or more types may be used in combination.

(B) Commercially available inorganic fillers include, for example, “SP60-05” and “SP507-05” manufactured by Nittetsu Chemical &Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Adomatex Corporation; “UFP-30”, “DAW-03”, and “FB-105FD” manufactured by Denka Corporation; “Actual writing NSS-3N”, “Actual writing NSS-4N”, and “Actual writing NSS-5N” manufactured by Tokuyama Corporation; “Cell Spears” and “MGH-005” manufactured by Taiheyo Cement Co., Ltd.; and "BA-1" manufactured by Nikki Shokubai Kasei.

(B) The range of the average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, from the viewpoint of significantly obtaining the desired effect of the present invention. Preferably it is 10㎛ or less, more preferably 7㎛ or less, even more preferably 5㎛ or less.

(B) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured as the average particle size. The measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial bottle and dispersing them by ultrasonic waves for 10 minutes. For the measurement sample, use a laser diffraction type particle size distribution measuring device, use a light source wavelength of blue and red, measure the volume-based particle size distribution of the inorganic filler using a flow cell method, and determine the median diameter from the obtained particle size distribution. The average particle diameter can be calculated as . Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba Sesakusho Co., Ltd.

(B) The range of the specific surface area of the inorganic filler is preferably 1 m2/g or more, more preferably 2 m2/g or more, particularly preferably 3 m2/g, from the viewpoint of significantly obtaining the desired effect of the present invention. g or more. There is no particular limitation on the upper limit, but it is preferably 60 m2/g or less, 50 m2/g or less, or 40 m2/g or less. The specific surface area can be measured by adsorbing nitrogen gas to the surface of the sample using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multipoint method.

(B) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Ringer, etc. can be mentioned. Surface treatment agents may be used individually, or may be used in combination of two or more types arbitrarily.

Commercially available surface treatment agents include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Kogyo Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd. silane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Kogyoso, “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Kogyoso, Shin-Etsu Chemical “SZ-31” (hexamethyldisilazane) manufactured by Kogyo Corporation, “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Kogyo Corporation, and “KBM-4803” (long chain epoxy type silane couple) manufactured by Shin-Etsu Chemical Kogyo Corporation ring agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment with the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of the (B) inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface treated with 0.2% by mass to 5% by mass of a surface treatment agent, more preferably 0.2% by mass to 3% by mass of a surface treatment agent, It is more preferable that the surface is treated with 0.3% by mass to 2% by mass of a surface treatment agent.

The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and even more preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition, 1.0 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.

(B) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, 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, etc. can be used.

The amount of (B) inorganic filler in the resin composition can be set in a range that satisfies the above-mentioned requirements (i) to (iii). In one example, the range of the amount of the inorganic filler (B) in the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably, based on 100% by mass of the non-volatile component of the resin composition. is 60 mass% or more, preferably 90 mass% or less, more preferably 86 mass% or less, and even more preferably 83 mass% or less. (B) When the amount of the inorganic filler is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

((C) Curing accelerator)

The resin composition may contain (C) a curing accelerator as an optional component. The curing accelerator (C) as component (C) does not include those corresponding to the components (A) to (B) described above. (C) The curing accelerator has a function as a curing catalyst that promotes curing of the epoxy resin (A-1).

(C) Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among them, an imidazole-based curing accelerator is preferable. (C) A hardening accelerator may be used individually, or may be used in combination of two or more types.

Examples of phosphorus-based curing accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, and bis(tetrabutylphosphonium)pyrro. Melitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium Aliphatic phosphonium salts such as tetraphenyl borate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra- p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethylphosphonium tetraphenyl borate, tris (3-methylphenyl) ethylphosphonium tetraphenyl borate, tris (2-methyl aromatic phosphonium salts such as toxyphenyl)ethylphosphonium tetraphenyl borate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; Aromatic phosphine/quinone addition reactants such as triphenylphosphine/p-benzoquinone addition reactants; Tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, 2-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, Aliphatic phosphines such as tricyclohexylphosphine; Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolyl Phosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, Tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2, 6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine , tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl- 2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2- and aromatic phosphines such as bis(diphenylphosphino)acetylene and 2,2'-bis(diphenylphosphino)diphenyl ether.

Examples of urea-based curing accelerators include 1,1-dimethylurea; Aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3- Chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4 -dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4 -nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]- 1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea ), and aromatic dimethyl ureas such as N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , 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-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, Examples include 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, and 1-(o-tolyl) biguanide.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Midazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole Sol, 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 trimellitate, 1-cyanoethyl-2-phenylimidazolium tri. Melitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Midazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-tri Azine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2- a] Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and mixtures of imidazole compounds and epoxy resins A duct body can be mentioned. Commercially available imidazole-based curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", and "2MA-OK-" manufactured by Shikoku Kasei Kogyo Co., Ltd. PW”, “2PHZ”, “2PHZ-PW”, “Cl1Z”, “Cl1Z-CN”, “Cl1Z-CNS”, “C11Z-A”; and “P200-H50” manufactured by Mitsubishi Chemical Corporation.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, and 1,8. -Diazabicyclo(5,4,0)-undecene, etc. can be mentioned. As an amine-type hardening accelerator, a commercial item may be used, for example, "MY-25" manufactured by Ajinomoto Fine Techno Co., Ltd., etc.

The amount of curing accelerator (C) in the resin composition can be set in a range that satisfies the above-mentioned requirements (i) to (iii). In one example, the range of the amount of curing accelerator (C) in the resin composition may be 0% by mass, may be greater than 0% by mass, and is preferably 0.0001% by mass or more, based on 100% by mass of non-volatile components of the resin composition. , more preferably 0.001 mass% or more, further preferably 0.002 mass% or more, preferably 2 mass% or less, more preferably 1 mass% or less, even more preferably 0.1 mass% or less.

Additionally, the range of the amount of the curing accelerator (C) may be 0% by mass or may be greater than 0% by mass, with respect to 100% by mass of the resin component of the resin composition, preferably 0.001% by mass or more, more preferably 0.01% by mass. It is mass % or more, more preferably 0.1 mass % or more, preferably 3 mass % or less, more preferably 1 mass % or less, and even more preferably 0.5 mass % or less.

((D) polymer resin)

The resin composition may further contain (D) polymer resin as an optional component. The polymer resin (D) as the component (D) does not include those corresponding to the components (A) to (C) described above. (D) One type of polymer resin may be used individually, or two or more types may be used in combination.

(D) Polymer resins include, for example, phenoxy resin, acrylic resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamidoimide resin, polyetherimide resin, polysulfone resin, and polyether. Sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. are mentioned. Among them, acrylic resin, polyimide resin, polybutadiene resin, polyphenylene ether resin, and polycarbonate resin are preferable, and acrylic resin, polyimide resin, polybutadiene resin, and polyphenylene ether resin are more preferable.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, and naphthalene. and a phenoxy resin having at least one skeleton selected from the group consisting of 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. Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both phenoxy resins containing a bisphenol A skeleton); “YX8100” manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol S skeleton); “YX6954” manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol acetophenone skeleton); “FX280” and “FX293” manufactured by Nittetsu Chemical & Materials, Inc.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL789" manufactured by Mitsubishi Chemical Corporation 1BH30” and the like.

Examples of the acrylic resin include resin containing a (meth)acrylate structure. The acrylic resin may contain a (meth)acrylate structure in the main chain or in the side chain. Here, the term “(meth)acrylate structure” includes both an acrylate structure and a methacrylate structure. Specific examples of acrylic resins include Teisan resins "SG-70L", "SG-708-6", "WS-023", "SG-700AS", "SG-280TEA", and "SG-" manufactured by Nagase Chemtex Co., Ltd. 80H”, “SG-80H-3”, “SG-P3”, “SG-600TEA”, “SG-790”; “ME-2000”, “W-116.3”, “W-197C”, “KG-25”, and “KG-3000” manufactured by Negami Kogyo Corporation; "ARUFON UH-2000" manufactured by Toa Kosei Corporation, etc. are mentioned.

Specific examples of the polyimide resin include “SLK-6100” manufactured by Shin-Etsu Chemical Co., Ltd., “Lika Coat SN20” and “Rica Coat PN20” manufactured by Nippon Rika Co., Ltd. Specific examples of polyimide resins include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides (polyimides described in Japanese Patent Application Laid-Open No. 2006-37083), and polysiloxane. Modified polyimides such as skeleton-containing polyimides (polyimides described in JP2002-12667, JP2000-319386, etc.) can be given.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include “Denka Butyral 4000-2,” “Denka Butyral 5000-A,” “Denka Butyral 6000-C,” and “Denka Butyral 6000-EP” manufactured by Denki Chemical Co., Ltd. ; Examples include S-Lec BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Sekisui Kagaku Kogyo.

Examples of polyolefin resins include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin-based polymers such as polypropylene and ethylene-propylene block copolymer.

Examples of the polybutadiene resin include hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing polybutadiene resin, phenolic hydroxyl group-containing polybutadiene resin, carboxyl group-containing polybutadiene resin, acid anhydride group-containing polybutadiene resin, and epoxy group-containing polybutadiene. Resins, polybutadiene resins containing isocyanate groups, polybutadiene resins containing urethane groups, polyphenylene ether-polybutadiene resins, etc. can be mentioned. Part or all of the polybutadiene structure of the polybutadiene resin may be hydrogenated. Specific examples of polybutadiene resins include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon 184MA6" manufactured by Kray Vale. "(polybutadiene containing acid anhydride group), "GQ-1000" manufactured by Nippon Soda Corporation (polybutadiene with hydroxyl and carboxyl groups introduced), "G-1000", "G-2000", and "G-3000" (hydroxyl groups at both terminals) polybutadiene), “GI-1000”, “GI-2000”, “GI-3000” (polybutadiene with hydrogenated hydroxyl groups at both ends), “FCA-061L” (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase Chemtex, etc. can be mentioned. Additionally, specific examples of the polybutadiene resin include polyimide resins having a polybutadiene structure, a urethane structure, and an imide structure in the molecule. The polyimide resin is a linear polyimide resin (a polyimide resin described in Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208) using hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials. It can be manufactured as mead). The content of the butadiene structure in the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the descriptions in Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208 can be taken into consideration, and this content is incorporated into this specification.

Specific examples of polyamide-imide resin include “Viromax HR11NN” and “Viromax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin include modified polyamideimides such as “KS9100” and “KS9300” (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Kasei Corporation.

Specific examples of polyetherimide resin include “Ultem” manufactured by GE Corporation.

Specific examples of polysulfone resins include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers.

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

Specific examples of polyphenylene ether resin include "NORYL SA90" manufactured by SABIC, and oligophenylene ether/styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd.

Examples of polycarbonate resins include carbonate resins containing hydroxy groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing acid anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing urethane groups, etc. there is. Specific examples of polycarbonate resin include “FPC0220” manufactured by Mitsubishi Gas Chemicals, “T6002” and “T6001” (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and “C-1090” and “C-2090” manufactured by Kuraray Corporation. ", "C-3090" (polycarbonate diol), etc. Additionally, specific examples of the polycarbonate resin include polyimide resins having an imide structure, a urethane structure, and a polycarbonate structure in the molecule. The polyimide resin can be manufactured as a linear polyimide resin using hydroxyl group-terminated polycarbonate, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials. The content of the carbonate structure in the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of International Publication No. 2016/129541 can be taken into consideration, and this content is incorporated into this specification.

Specific examples of polyetheretherketone resin include "Sumipro K" manufactured by Sumitomo Chemical Co., Ltd.

Examples of polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexanedimethyl. Terephthalate resin, etc. can be mentioned.

The polymer resin (D) may be compatible with resin components other than the polymer resin (D) and may be contained in the resin composition. The polymer resin (D) compatible in this way is usually compatible with resin components other than the polymer resin (D) and is included in the cured body. In addition, the polymer resin (D) may be incompatible with resin components other than the polymer resin (D) and may be contained in the resin composition in the form of particles. This particulate (D) polymer resin is usually incompatible with resin components other than the (D) polymer resin, and is contained in the cured body in the form of particles. Additionally, the (D) polymer resin, which is compatible with resin components other than the (D) polymer resin, and the particulate (D) polymer resin may be used in combination.

Examples of the particulate (D) polymer resin include acrylic resin particles. Specific examples of acrylic resin particles include fine particles of a resin that is chemically cross-linked to a resin showing rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber, and rendered insoluble and infusible in an organic solvent. Specific examples of commercial products include XER-91 (manufactured by Nippon Kosei Rubber Co., Ltd.); Staphylloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, manufactured by Aika Kogyo); Paralloid EXL2655, EXL2602 (above, manufactured by Ureha Chemical Kogyo), etc. can be mentioned.

(D) Polymer resin usually has a large molecular weight. Specifically, the range of the weight average molecular weight Mw of the polymer resin (D) is preferably greater than 5000, more preferably 8,000 or more, further preferably 10,000 or more, further preferably 20,000 or more, and preferably It is 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and even more preferably 50,000 or less. The weight average molecular weight Mw can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC).

The amount of polymer resin (D) in the resin composition can be set in a range that satisfies the above-mentioned requirements (i) to (iii). In one example, the range of the amount of polymer resin (D) in the resin composition may be 0% by mass, may be greater than 0% by mass, and is preferably 0.1% by mass or more, based on 100% by mass of non-volatile components of the resin composition. , more preferably 1 mass% or more, further preferably 3 mass% or more, preferably 30 mass% or less, more preferably 25 mass% or less, and even more preferably 20 mass% or less.

In addition, the range of the amount of the polymer resin (D) may be 0% by mass or may be greater than 0% by mass, preferably 1% by mass or more, more preferably 10% by mass, based on 100% by mass of the resin component of the resin composition. It is mass % or more, more preferably 20 mass % or more, preferably 80 mass % or less, more preferably 70 mass % or less, and even more preferably 65 mass % or less.

(Amount of resin component containing nitrogen atoms)

Some or all of the resin components contained in the resin composition may contain nitrogen atoms. There may be one type of resin component containing a nitrogen atom, or two or more types may be used.

The amount of the resin component containing nitrogen atoms can be set in a range that satisfies the above-mentioned requirements (i) to (iii). In one example, the range of the amount of the resin component containing a nitrogen atom in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on 100% by mass of the non-volatile component of the resin composition. Preferably it is 5 mass% or more, preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less. When the amount of the resin component containing nitrogen atoms is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

In addition, the range of the amount of the resin component containing a nitrogen atom in the resin composition is preferably 1% by mass or more, more preferably 10% by mass or more, and even more preferably 100% by mass or more of the resin component of the resin composition. It is 20 mass% or more, preferably 95 mass% or less, more preferably 90 mass% or less, and even more preferably 80 mass% or less. When the amount of the resin component containing nitrogen atoms is in the above range, the adhesion between the conductor layer formed on a specific smooth surface and the cured body after the HAST test can be particularly improved. In addition, usually, the adhesion before the HAST test can be effectively improved, or the dielectric loss tangent, storage modulus, glass transition temperature, and crosslink density of the cured body can be improved.

((E) optional additives)

The resin composition may further contain (E) optional additives as optional nonvolatile components. (E) Optional additives include, for example, organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; Leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; Thickeners such as bentone and montmorillonite; Antifoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; UV absorbers such as benzotriazole-based UV absorbers; Adhesion improvers such as urea silane; Adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; Antioxidants such as hindered phenolic antioxidants; Fluorescent whitening agents such as stilbene derivatives, surfactants such as fluorine-based surfactants and silicone-based surfactants; Flame retardants such as phosphorus-based flame retardants (e.g., phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); Dispersants such as phosphoric acid ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; Stabilizers include borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. (E) Arbitrary additives may be used individually, or may be used in combination of two or more types.

((F) Solvent)

The resin composition is usually combined with a non-volatile component such as the above-mentioned (A) to (E) components, and may also contain a solvent (F) as a volatile component. (F) As a solvent, an organic solvent is usually used. Specific examples of organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; Ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; Ether alcohol-based solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butylcarbitol); amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; Sulfoxide-based solvents such as dimethyl sulfoxide; Nitrile-based solvents such as acetonitrile and propionitrile; Aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (F) One type of solvent may be used individually, or two or more types may be used in combination.

(F) The amount of solvent is not particularly limited. In one example, the range of the amount of solvent (F) relative to 100% by mass of all components of the resin composition is 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less. It may be % by mass or less, or even 0% by mass.

(Characteristics of hardened body)

The cured body according to one embodiment of the present invention is obtained by curing the above-described resin composition. Since the resin composition contains (A) a thermosetting resin, the resin composition is generally thermoset to obtain a cured product. Usually, among the components contained in the resin composition, volatile components such as (F) solvent may be volatilized by heat during thermal curing, but non-volatile components such as components (A) to (E) may be volatilized during thermal curing. It does not volatilize by heat. Therefore, the cured body of the resin composition may contain a non-volatile component of the resin composition or a reaction product thereof.

As described above, the hardened body has a specific smooth surface. It is desirable that the specific smooth surface not only has an arithmetic mean roughness Ra in a range that satisfies requirement (i), but also has a maximum height Rz in a specific range. Specifically, the range of the maximum height Rz of a specific smooth surface is preferably 2000 nm or less, more preferably 1500 nm or less, further preferably 1000 nm or less, preferably 10 nm or more, more preferably 50 nm or more, further Preferably it is 100 nm or more. When the specific smooth surface of the cured body has a maximum height Rz in the above range, the desired effect of the present invention can be significantly achieved.

The maximum height Rz of a specific smooth surface of the hardened body can be measured based on Japanese Industrial Standards (JIS B0601-2001). Measurement can be performed using a non-contact surface roughness meter (“WYKO NT3300” manufactured by Vico Instruments). Depending on the ultraviolet treatment and the silane coupling agent treatment, generally, there is no change in the maximum height Rz of the specific smooth surface of the cured body. Therefore, the maximum height Rz of the specific smooth surface of the cured body may be measured before or after ultraviolet treatment and silane coupling agent treatment. As a specific measurement method of the maximum height Rz, the method of <Test 4. Measurement of surface roughness Ra and Rz> in the examples described later can be adopted.

A conductor layer can be formed on a specific smooth surface of the cured body. For example, if the arithmetic mean roughness Ra of a specific smooth surface measured before ultraviolet treatment and silane coupling agent treatment satisfies requirement (i), the conductor layer is can be formed. Additionally, for example, if the arithmetic mean roughness Ra of a specific smooth surface measured after treatment with ultraviolet rays and treatment with a silane coupling agent satisfies requirement (i), a conductor layer can be formed on the specific smooth surface. And, between the conductor layer thus formed and the cured body, high adhesion can be obtained after the HAST test.

In one example, when a conductor layer is formed by plating on a specific smooth surface of a cured body and a HAST test is conducted for 100 hours under high temperature and high humidity conditions of 130°C and 85%RH, after the HAST test, there is a gap between the cured body and the conductor layer. High adhesion can be achieved. The above-mentioned adhesion can be evaluated by peeling strength as the force required to peel off the conductor layer from the cured body. In the above example, the peel strength after the HAST test is preferably 0.15 kg/cm or more, more preferably 0.20 kg/cm or more, and even more preferably 0.25 kg/cm or more. The higher the upper limit, the more preferable it may be, for example, 2.00 kg/cm or less.

Since high adhesion can be obtained between the cured body and the conductor layer after the HAST test, the decrease in adhesion due to the HAST test can usually be suppressed. Therefore, the adhesion retention rate after the HAST test can be increased. The above retention rate can be expressed as a ratio of the peel strength after the HAST test to the peel strength before the HAST test. In the above example, the range of the peel strength retention rate is preferably 35% or more, more preferably 40% or more, further preferably 45% or more, and particularly preferably 50% or more. The upper limit is preferably 100% or less, but is usually 80% or less.

Usually, high adhesion can be obtained between the cured body and the conductor layer not only during the HAST test but also before the HAST test. In one example, the peel strength before the HAST test is preferably 0.30 kg/cm or more, more preferably 0.35 kg/cm or more, even more preferably 0.40 kg/cm or more, particularly preferably 0.43 kg/cm or more. . The higher the upper limit, the more preferable it may be, for example, 2.00 kg/cm or less.

The peeling strength between the insulating layer and the conductor layer can be measured based on JIS C6481. In detail, a cut is formed in the conductor layer formed on a specific smooth surface of the cured body, surrounding a rectangular portion with a width of 10 mm and a length of 100 mm. One end of this rectangular portion can be pulled in the vertical direction at a speed of 50 mm/min at room temperature, and the load (kgf/cm) when 35 mm is removed can be measured as the peeling strength. As a specific method of measuring the peel strength, the method described in <Test 3. Measurement of peel strength (adhesion strength) between the insulating layer and the conductor layer> described later can be adopted.

Taking advantage of the advantage of being able to form a conductor layer with high adhesion to a specific smooth surface as described above, the cured body is preferably used to form a conductor layer on a specific smooth surface, and to form a conductor layer on a specific smooth surface. It is more preferable to use it as an insulating layer for.

From the viewpoint of obtaining an insulating layer with low transmission loss, the cured body preferably has a low dielectric loss tangent Df. The specific range of dielectric loss tangent Df of the cured body is preferably 0.0200 or less, more preferably 0.0100 or less, further preferably 0.0080 or less, and particularly preferably 0.0060 or less. The lower the lower limit, the more preferable it may be, for example, 0.0010 or more.

The dielectric loss tangent of the cured body can be measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. As a specific method of measuring the dielectric loss tangent Df, the method described in <Test 6. Measurement of dielectric loss tangent> in the examples described later can be adopted.

The conductor layer formation method of forming a conductor layer on a specific smooth surface that has been treated with ultraviolet rays and a silane coupling agent is preferably applied to a cured body having specific physical properties. Therefore, it is desired that the insulating layer used in the application of forming a conductor layer on a specific smooth surface that has been subjected to ultraviolet ray treatment and silane coupling agent treatment as described above has specific physical properties. Therefore, from the viewpoint of being used suitably for these purposes, it is preferable that the cured body according to the present embodiment has the specific physical properties.

Specifically, it is preferable that the cured body according to the present embodiment has a storage elastic modulus in a specific range. The range of the storage elastic modulus at 25°C of the cured body is preferably 0.10 GPa or more, more preferably 0.20 GPa or more, further preferably 0.30 GPa or more, preferably 1.30 GPa or less, more preferably 1.20 GPa or less. , more preferably 1.10 GPa or less. Forming a conductor layer on a specific smooth surface that has been treated with ultraviolet rays and a silane coupling agent can be used for the purpose of using an insulating layer having a storage modulus in this range. Therefore, from the viewpoint of obtaining an insulating layer suitable for the application, it is preferable that the cured body according to the present embodiment has a storage elastic modulus in the above range.

The storage elastic modulus of the cured body can be measured by performing dynamic mechanical analysis in tensile mode under the measurement conditions of a frequency of 1 Hz and a temperature increase rate of 5°C/min. As a specific method of measuring the storage elastic modulus, the method described in <Test 7. Measurement of storage elastic modulus and glass transition temperature> described later can be adopted.

The cured body according to this embodiment preferably has a glass transition temperature Tg in a specific range. The range of the glass transition temperature Tg of the cured body is preferably 130°C or higher, more preferably 140°C or higher, further preferably 150°C or higher, preferably 190°C or lower, more preferably 180°C or lower. Preferably it is 170°C or lower. Forming a conductor layer on a specific smooth surface that has been treated with ultraviolet rays and a silane coupling agent can be used in applications that use an insulating layer with a glass transition temperature Tg in this range. Therefore, from the viewpoint of obtaining an insulating layer suitable for the application, it is preferable that the cured body according to the present embodiment has a glass transition temperature Tg in the above range.

The glass transition temperature Tg of the cured body can be measured as the glass transition temperature Tg by performing dynamic mechanical analysis in tensile mode under the measurement conditions of a frequency of 1 Hz and a temperature increase rate of 5°C/min, and the temperature at which tan δ becomes maximum. As a specific method of measuring the glass transition temperature Tg, the method described in <Test 7. Measurement of storage modulus and glass transition temperature> described later can be adopted.

The cured body according to the present embodiment preferably has a crosslinking density within a specific range. The range of crosslink density of the cured body is preferably 0.1 × 10 ^-3 mol/cm 3 or more, more preferably 1.0 × 10 ^-3 mol/cm 3 or more, and even more preferably 2.0 × 10 ^-3 mol/cm 3 or more, Preferably it is 200×10 ^-3 mol/cm3 or less, more preferably 150×10 ^-3 mol/cm3 or less, and even more preferably 100×10 ^-3 mol/cm3 or less. Forming a conductor layer on a specific smooth surface that has been treated with ultraviolet rays and a silane coupling agent can be used in applications that use an insulating layer with a crosslink density in this range. Therefore, from the viewpoint of obtaining an insulating layer suitable for the application, it is preferable that the cured body according to the present embodiment has a crosslink density in the above range.

The crosslinking density of the cured body can be measured by the following method. Thermomechanical analysis is performed on the cured body by the tensile weighting method under the measurement conditions of a load of 200 mN and a temperature increase rate of 5°C/min, and the storage modulus and loss modulus are measured. A temperature T that is 80K higher than the glass transition temperature Tg of the cured body is set, and the measured value E' (unit: GPa, that is, ×10 ⁹ Pa) of the storage elastic modulus at this temperature T is acquired. The crosslinking density n (mol/cm3) is calculated by substituting the obtained storage elastic modulus E'(Pa) into the following equation (M1). As a specific measuring method for crosslinking density, the method described in <Test 5. Measurement of crosslinking density n> described later can be adopted. The crosslinking density n can be used as an index indicating the number of crosslinked molecules present per unit volume.

n=E'/3RT 　(M1)

(In the above formula (M1), T represents a predetermined temperature T (K), E' represents the measured value (Pa) of the storage elastic modulus at a predetermined temperature T (K), and R is the gas constant. Also, as E'/3, the measured value of shear modulus G' (10 ⁹ Pa) at a given temperature T (K) may be used.

The crosslinking density can be adjusted depending on the composition of the resin composition. For example, the crosslinking density of the cured product can be adjusted by using an appropriate amount of (A) a thermosetting resin having an appropriate active group equivalent, or using an appropriate amount of an inorganic filler (B).

There are no restrictions on the shape of the hardened body. Usually, the hardened body is formed in layers. The specific smooth surface of the layered cured body is usually a plane parallel to the layer plane of the layer of the cured body. From the viewpoint of thinning, the thickness of the layered cured body is preferably 600 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less. The lower limit of the thickness is not particularly limited and may be, for example, 5 μm or more, 10 μm or more, or 20 μm or more.

<Method for manufacturing hardened body>

The cured body according to the present embodiment can be manufactured by a manufacturing method including a step of curing a resin composition containing a thermosetting resin. Usually, a method for producing a cured body includes a step of preparing a resin composition, and the resin composition prepared in the step is cured.

The resin composition may be prepared by purchasing it from the market, or it may be prepared by manufacturing it. The resin composition can be produced, for example, by mixing the above-mentioned components. Some or all of the above-mentioned components may be mixed simultaneously, or may be mixed sequentially. In the process of mixing each component, the temperature may be appropriately set, and accordingly, heating and/or cooling may be performed temporarily or over time. Additionally, in the process of mixing each component, stirring or shaking may be performed.

The prepared resin composition may be molded into an appropriate shape as needed. Usually, the resin composition is molded to obtain a cured body having a specific smooth surface. For example, when producing an insulating layer as a cured body, the resin composition layer may be obtained by molding the resin composition into a layer. For a specific example, the resin composition may be applied on a smooth surface and dried as needed to obtain a resin composition layer. Additionally, the prepared resin composition layer may be laminated on an appropriate substrate to obtain a resin composition layer on the substrate.

After preparing the resin composition, a process of curing the resin composition is performed. Usually, the resin composition is thermoset by heating. Specific curing conditions of the resin composition may vary depending on the composition of the resin composition. In one example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

The method for producing the cured body may include preheating the resin composition at a temperature lower than the curing temperature before curing the resin composition. Preheating, for example, heats the resin composition at a temperature of usually 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°C, for usually 5 minutes or more, preferably 5 minutes. It may be carried out under heating conditions with a treatment time of 15 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

By curing the resin composition as described above, a cured body having surfaces is obtained. When the surface of the cured body thus obtained has an arithmetic mean roughness Ra that satisfies requirement (i), the surface can function as a specific smooth surface, and therefore a conductor layer can be formed on the specific smooth surface. And, the cured body and the conductor layer can achieve high adhesion after the HAST test. That is, when a specific smooth surface having an arithmetic mean roughness Ra that satisfies requirement (i) is obtained before ultraviolet treatment and silane coupling agent treatment, the specific smooth surface is usually subjected to ultraviolet treatment and silane coupling agent treatment. Even after performing ring agent treatment, it can have an arithmetic mean roughness Ra that satisfies requirement (i). Therefore, by forming a conductor layer after ultraviolet treatment and silane coupling agent treatment on a specific smooth surface of the cured body, high adhesion can be achieved after the HAST test.

However, when a specific smooth surface having an arithmetic mean roughness Ra that satisfies requirement (i) is obtained after performing ultraviolet treatment and silane coupling agent treatment described later, the cured body immediately obtained by curing the resin composition must necessarily meet requirement (i) It is not necessary to have a specific smooth surface with an arithmetic mean roughness Ra that satisfies ).

The method for manufacturing a hardened body may include a step of adjusting the arithmetic mean roughness Ra of the surface of the hardened body as needed. For example, the method for producing a cured body may include a step of subjecting the cured body to a desmear treatment. For example, when a hole such as a via hole is formed in an insulating layer as a cured body, smear (resin residue) may be formed in the hole, so desmear treatment may be performed to remove the smear. . According to this desmear treatment, it is common to not only remove smears but also roughen the surface of the cured body. Therefore, according to the desmear treatment, the arithmetic mean roughness Ra of the surface of the hardened body including a specific smooth surface can be adjusted to increase. This desmear treatment is preferably performed so that a specific smooth surface having an arithmetic mean roughness Ra in a range that satisfies requirement (i) is obtained after the desmear treatment. Examples of the desmear treatment include a method of subjecting the cured body to a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

Examples of the swelling liquid used in the roughening treatment include an alkaline solution and a surfactant solution, and an alkaline solution is preferred. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Deep Securiganth P" and "Swelling Deep Securiganth SBU" manufactured by Atotech Japan. Swelling treatment with a swelling liquid can be performed, for example, by immersing the cured body in a swelling liquid of 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing swelling of the resin of the cured body to an appropriate level, it is preferable to immerse the cured body in a swelling liquid of 40°C to 80°C for 5 to 15 minutes.

Examples of the oxidizing agent used in the roughening treatment include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the cured body in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Additionally, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securiganth P” manufactured by Atotech Japan.

As a neutralizing liquid used in the roughening treatment, an acidic aqueous solution is preferable, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan. Treatment with a neutralizing liquid can be performed by immersing the treated surface that has been roughened with an oxidizing agent in a neutralizing liquid at 30°C to 80°C for 5 to 30 minutes. In terms of workability, etc., a method of immersing the object that has been roughened with an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferable.

The method for producing a cured body may further include a step of subjecting the cured body to ultraviolet ray treatment. When the method for manufacturing a hardened body includes a step of performing a desmear treatment, the ultraviolet ray treatment is usually performed after the desmear treatment. Ultraviolet treatment includes irradiating ultraviolet rays to the cured body. Specifically, ultraviolet rays are irradiated to a specific smooth surface of the cured body or to a surface on which the specific smooth surface is to be formed. By this ultraviolet treatment, functional groups can be generated on the surface of the cured body.

The wavelength of ultraviolet rays to be irradiated is preferably 160 nm or more, more preferably 172 nm or more, preferably 350 nm or less, and more preferably 300 nm or less. Moreover, the irradiation time of ultraviolet rays is preferably 1 second or longer, more preferably 2 seconds or longer, preferably 300 seconds or less, and more preferably 20 seconds or less.

The method for producing a cured body may further include a step of subjecting the cured body to treatment with a silane coupling agent. Silane coupling agent treatment is usually performed after ultraviolet ray treatment. The silane coupling agent treatment includes causing a treatment liquid containing a silane coupling agent to impinge on the cured body. Specifically, the treatment liquid is brought into contact with a specific smooth surface of the cured body or a surface on which the specific smooth surface is to be formed. By this silane coupling agent treatment, the silane coupling agent can be immobilized on the surface of the cured body.

A silane coupling agent usually contains a silicon atom, a functional group that can react and bond with an inorganic material, and a functional group that can react and bond with a resin component. The functional group that can react and bond with an inorganic material includes one that hydrolyzes the functional group to generate a group (silanol group, etc.) that can react and bond with the inorganic material. Examples of functional groups that can react and bond with inorganic materials include alkoxy groups, acetoxy groups, and chlorine atoms. In addition, examples of functional groups that can react and bind with the resin component include amino groups, glycidyl groups, and mercapto groups.

As the silane coupling agent, an amine-based silane coupling agent containing an amino group is preferable. According to the amine-based silane coupling agent, the amino group can strongly bind to the resin component, so high adhesion can be obtained. Preferred amine-based silane coupling agents include, for example, an aliphatic amine-based silane coupling agent containing an amino group (aliphatic amino group) bonded to an aliphatic hydrocarbon group; and aromatic amine-based silane coupling agents containing an amino group (aromatic amino group) bonded to an aromatic hydrocarbon group.

As an aliphatic amine-based silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N- 2-(Aminoethyl)-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-(vinylbenzyl)-2-aminoethyl -3-aminopropyltrimethoxysilane hydrochloride, 1-(3-triethoxysilylpropyl)-2-imidazoline, etc. are mentioned. Additionally, examples of the aromatic amine-based silane coupling agent include N-phenyl-3-aminopropyltrimethoxysilane.

Silane coupling agents may be used individually or in combination of two or more types.

The range of the amount of silane coupling agent in the treatment liquid is preferably 1 g/liter or more, more preferably 3 g/liter or more, further preferably 5 g/liter or more, preferably 500 g/liter or less, more preferably 500 g/liter or less. Preferably it is 300 g/liter or less, more preferably 100 g/liter or less.

The treatment liquid usually contains a solvent in combination with a silane coupling agent. As a solvent, one that can dissolve the silane coupling agent is preferable. Examples of this solvent include water and organic solvents. Among these, it is preferable that the solvent contains water. When the solvent contains water, the functional group of the silane coupling agent can be hydrolyzed to generate highly reactive groups such as silanol groups.

Preferred organic solvents include ketone-based solvents and glycol-based solvents, and among these, glycol-based solvents are more preferable. Moreover, among glycol-based solvents, glycol ether-based solvents are preferable, glycol butyl ether-based solvents are more preferable, and at least one type selected from the group consisting of ethylene-based glycol butyl ether and propylene-based glycol butyl ether is even more preferable.

As ethylene glycol butyl ether, a solvent represented by C ₄ H ₉ -(OC ₂ H ₄ ) _n1 -OH is preferable. Here, n1 represents an integer of 1 or more, and preferably represents an integer of 1 to 4. Specific examples of ethylene glycol butyl ether include ethylene glycol butyl ether (n1=1), diethylene glycol butyl ether (n1=2), triethylene glycol butyl ether (n1=3), and tetraethylene glycol butyl ether (n1=4). ) can be mentioned.

As propylene glycol butyl ether, a solvent represented by C ₄ H ₉ -(OC ₃ H ₆ ) _n2 -OH is preferable. Here, n2 represents an integer of 1 or more, and preferably represents an integer of 1 to 4. Specific examples of propylene glycol butyl ether include propylene glycol butyl ether (n2 = 1), dipropylene glycol butyl ether (n2 = 2), tripropylene glycol butyl ether (n2 = 3), and tetrapropylene glycol butyl ether (n2 = 4). ) can be mentioned.

Among the above examples, ethylene glycol butyl ether is preferable, and diethylene glycol butyl ether (for example, diethylene glycol-mono-n-butyl ether, etc.) is more preferable.

In addition, in the glycol butyl ether-based solvent described above, the butyl group may be linear or branched. Additionally, it is preferable to use a glycol butyl ether-based solvent having a butyl group at the terminal because the permeability is improved.

One type of solvent may be used individually, or two or more types may be used in combination. For example, a combination of water and an organic solvent may be used. When using a combination of water and an organic solvent such as a glycol-based solvent, the range of the amount of the organic solvent in the treatment liquid is preferably 0.1 g/liter or more, more preferably 10 g/liter or more, and even more preferably It is 50 g/liter or more, preferably 600 g/liter or less, more preferably 500 g/liter or less, and even more preferably 400 g/liter or less.

The treatment liquid may contain a pH adjuster. According to the pH adjuster, the pH of the treatment liquid can be easily adjusted to an appropriate range. Examples of the pH adjuster include amine compounds such as diethylenetriamine; Sulfuric acid; Alkaline solutions such as NaOH can be mentioned.

One type of pH adjuster may be used individually, or two or more types may be used in combination.

The amount of the pH adjuster in the treatment liquid can be set so that a treatment liquid with the desired pH is obtained. In one example, the range of the amount of the pH adjuster is preferably 3 g/liter or more, more preferably 5 g/liter or more, preferably 50 g/liter or less, and more preferably 30 g/liter or less.

The treatment liquid may contain optional additives as long as they do not significantly impair the effects of the present invention. Optional additives include, for example, a dissolution aid that promotes dissolution of the silane coupling agent; fluorine compounds; Includes surfactants, etc. Additionally, the optional additives do not need to contain a fluorine compound or surfactant. In addition, arbitrary additives may be used individually, or may be used in combination of two or more types.

The treatment liquid preferably has a pH within a specific range. The specific range of the treatment liquid is preferably 3.0 or more, more preferably 3.5 or more, even more preferably 4.5 or more, preferably 10.0 or less, more preferably 9.0 or less, even more preferably 7.0 or less, and further Preferably it is 5.5 or less.

The temperature of the treatment liquid brought into contact with the cured body is, for example, 40°C to 80°C. In addition, the contact time between the cured body and the treatment liquid is, for example, 1 minute to 20 minutes. There are no restrictions on the method of contact between the cured body and the treatment liquid. For example, the contact may be performed by immersing the cured body in the treatment liquid.

When ultraviolet treatment and silane coupling agent treatment are performed as described above, a specific smooth surface can be obtained as the surface on which the ultraviolet treatment and silane coupling agent treatment have been performed. A conductor layer can be formed on this particular smooth surface. And, the cured body and the conductor layer can achieve high adhesion after the HAST test.

The method for producing the cured body may include an additional arbitrary process in combination with the above-described processes. For example, after ultraviolet treatment and silane coupling agent treatment, a step of subjecting the cured body to heat treatment may be included. By heat treatment, the adhesion between the cured body and the conductor layer can be effectively increased. The temperature conditions for heat treatment are preferably 120°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, and preferably 180°C or lower. Additionally, the heat treatment treatment time is preferably in the range of 5 minutes to 30 minutes.

<Use of hardened body>

The cured body according to the present embodiment can be used for insulation purposes, and can be particularly suitably used as a cured body for forming an insulating layer (cured body for forming an insulating layer). For example, the cured body according to the present embodiment forms a cured body for forming an insulating layer of a semiconductor chip package (cured body for an insulating layer of a semiconductor chip package) and an insulating layer of a circuit board (including a printed wiring board). It can be suitably used as a cured body (cured body for the insulating layer of a circuit board) for the following purposes. In particular, the cured body is suitable for forming an interlayer insulating layer provided between conductor layers.

Semiconductor chip packages include, for example, FC-CSP, MIS-BGA package, ETS-BGA package, fan-out type WLP (Wafer Level Package), fan-in type WLP, and fan-out type PLP (Panel Level Package). , Fan-in type PLP.

Additionally, the cured body may be used as an underfill material, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

In addition, the above cured body can be used in a wide range of applications where materials obtained by curing a resin composition are used, such as solder resist, die bonding material, semiconductor sealing material, hole filling material, and component filling material.

<Resin sheet>

When applying the cured body to the above-mentioned use, the resin composition as a raw material for the cured body may be prepared in the form of a resin sheet. The resin sheet includes a support and a resin composition layer formed on the support. The resin composition layer contains the resin composition, and preferably contains only the resin composition.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be 5 μm or more, 10 μm or more, etc.

Examples of the support include films made of plastic materials, metal foils, and release papers, and films and metal foils made of plastic materials are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”) .), polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic, polymethyl methacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), and polyether sulfide (PES). ), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using a metal foil as a support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferable. As the copper foil, a foil made of the simple metal of copper may be used, or a foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good night.

The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface joined to the resin composition layer.

As the support, you may use a support with a mold release layer that has a mold release layer on the surface bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include at least one type of release agent selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-" manufactured by Lintec, which are PET films with a release layer containing an alkyd resin-based release agent as a main component. 7”, “Lumira T60” manufactured by Torres, “Purex” manufactured by Teijin, and “Unifill” manufactured by Unichika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using a support body with a release layer, it is preferable that the entire thickness of the support body with a release layer is within the above range.

Here, a case will be described in which the first test was conducted in which the resin composition layer of the resin sheet was cured to form a cured body, and the surface of the cured body on the support side was subjected to ultraviolet ray treatment and silane coupling agent treatment. The cured body formed in the first test is a sample for specifying the properties of the resin sheet, and may hereinafter be referred to as a “sample cured body.” When this first test is performed, the surface of the hardened sample on the support side preferably forms a specific smooth surface with an arithmetic mean roughness Ra that satisfies requirement (i). Here, the surface on the support side of the cured sample refers to the surface on the side that is joined to the support among the surfaces of the cured sample. In the first test, curing of the resin composition layer may be performed under conditions depending on the intended use of the resin sheet, for example, at 170°C for 30 minutes. Additionally, the ultraviolet irradiation treatment may be performed by irradiating the cured sample with ultraviolet rays with a wavelength of 172 nm for 10 seconds. In addition, the silane coupling agent treatment involves subjecting the cured sample to a treatment solution as an aqueous solution of pH 5.0 containing 5 g/liter of 3-amino-propyltrimethoxysilane and 350 g/liter of diethylene glycol-mono-n-butyl ether. , may be carried out by immersing at 40°C for 10 minutes. The support is peeled off before curing the resin composition layer or before treatment with ultraviolet rays.

In this way, when the first test is performed, the surface of the hardened sample on the support side preferably forms the above-mentioned specific smooth surface having an arithmetic mean roughness Ra in the specific range described in requirement (i). In addition, it is more preferable that the surface of the hardened sample on the support side has the same characteristics as the above-mentioned specific smooth surface in addition to the arithmetic mean roughness Ra. Moreover, it is more preferable that the sample cured body has the same characteristics as the cured body according to the present embodiment described above. If a resin sheet that can satisfy these requirements in the first test is used, the insulating layer as the cured body according to the above-described embodiment can be easily manufactured. From the viewpoint of obtaining such a resin sheet, it is preferable that the surface of the support in contact with the resin composition layer is smooth. For example, the surface roughness range of the surface in contact with the resin composition layer of the support may be the same as the surface roughness range of a specific smooth surface.

Additionally, a case in which a second test was conducted in which the resin composition layer of the resin sheet was cured at 200°C for 90 minutes to form a cured sample layer will be described. In this case, the surface of the cured sample layer on the support side preferably has a contact angle That is, it is preferable that the contact angle The surface on the support side above refers to the surface of the cured sample layer on the side that was bonded to the support. Using such a resin sheet, an insulating layer as a cured body according to the above-described embodiment can be easily manufactured.

In addition, when the second test is conducted in which the resin composition layer of the resin sheet is cured at 200°C for 90 minutes to form a cured sample layer, the surface of the cured sample layer on the support side preferably meets requirement (iii). It has a nitrogen atom concentration that satisfies. That is, the nitrogen atom concentration obtained based on the peak area of the N1s spectrum in the X-ray photoelectron spectroscopy analysis of the surface of the support side is preferably within the specific range described in requirement (iii). Using such a resin sheet, an insulating layer as a cured body according to the above-described embodiment can be easily manufactured.

In one embodiment, the resin sheet may further include arbitrary layers as needed. Examples of such an optional layer include a protective film similar to the support provided on the side of the resin composition layer that is not bonded to the support (that is, the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. According to the protective film, adhesion of dust and scratches to the surface of the resin composition layer can be suppressed.

The resin sheet, for example, is prepared by preparing a liquid (varnish-like) resin composition as is, or by dissolving the resin composition in a solvent, and applying this using a coating device such as a die coater. It can be manufactured by applying it on a support and further drying it to form a resin composition layer.

Examples of the solvent include the same solvent as (F) described as a component of the resin composition. One type of solvent may be used individually, or two or more types may be used in combination.

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

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it usually becomes usable by peeling the protective film.

<Circuit board>

A circuit board according to an embodiment of the present invention includes an insulating layer formed by the above-described cured body. The insulating layer contains the above-mentioned hardened body, and preferably contains only the above-mentioned hardened body. This circuit board can be manufactured, for example, by a manufacturing method including the following steps (I) and (II).

(I) Process of forming a resin composition layer on an inner layer substrate.

(II) A process of curing the resin composition layer to form an insulating layer as a cured body.

The “inner layer substrate” used in step (I) is a member that becomes the base material of the circuit board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene. Ether substrates, etc. can be mentioned. Additionally, the substrate may have a conductor layer on one or both sides, and this conductor layer may be pattern-processed. An inner layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes referred to as an “inner layer circuit board.” Additionally, when manufacturing a circuit board, an intermediate product on which an insulating layer and/or a conductor layer must be additionally formed is also included in the above-mentioned “inner layer substrate.” If the circuit board is a circuit board with embedded components, an inner layer board with embedded components may be used.

Formation of the resin composition layer on the inner layer substrate can be performed, for example, by laminating the inner layer substrate and the resin sheet. Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. As a member for heat-pressing the resin sheet to the inner layer substrate (hereinafter also referred to as “heat-pressing member”), for example, a heated metal plate (SUS head plate, etc.) or a metal roll (SUS roll, etc.) can be used. In addition, it is preferable not to press the heat-compression member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heat-compression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurization laminator manufactured by Meiki Sesakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurization laminator.

After lamination, the laminated resin sheets may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing a heat-pressing member from the support side. The press conditions for the smoothing treatment can be the same as the heat-pressing conditions for the above-mentioned lamination. Smoothing treatment can be performed using a commercially available laminator. Additionally, the lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator described above.

The support may be removed between step (I) and step (II), or may be removed after step (II).

In step (II), the resin composition layer is cured to form an insulating layer made of a cured resin composition. The surface of the insulating layer thus formed forms a specific smooth surface. This specific smooth surface is usually obtained as the surface of the insulating layer on the opposite side to the circuit board. Curing of the resin composition layer is usually performed by thermal curing. As specific curing conditions for the resin composition layer, the conditions described in the method for producing the cured body can be adopted.

The method for manufacturing a circuit board may include preheating the resin composition layer at a temperature lower than the curing temperature before thermal curing of the resin composition layer. The conditions for preheating can be those described in the method for producing a cured body.

The manufacturing method of a circuit board usually includes the following steps: (V) subjecting the insulating layer to ultraviolet treatment, (VI) subjecting the insulating layer to a silane coupling agent treatment, and (VII) forming a conductor layer. Includes additional In addition, the method for manufacturing a circuit board may further include (III) a step of perforating the insulating layer, and (IV) a step of performing a desmear treatment on the insulating layer. Steps (III) and (IV) are generally performed before steps (V) and (VI). Additionally, step (VII) is generally performed after steps (V) and (VI). When the support is removed after step (II), the support may be removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). It may be carried out in .

Process (III) is a process of perforating the insulating layer. Through step (III), holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, or plasma, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the hole may be determined appropriately according to the design of the circuit board.

Process (IV) is a process of subjecting the insulating layer to a desmear treatment. Usually, in this step (IV), the surface of the insulating layer is also roughened. Therefore, the desmear process is sometimes called “harmonization process.” Desmear treatment can be performed, for example, by the method described in the method for producing a cured body.

(V) the step of subjecting the insulating layer to ultraviolet treatment, and (VI) the step of subjecting the insulating layer to a silane coupling agent treatment include curing the resin composition layer in step (II) to form an insulating layer, and as necessary. Therefore, it is performed after performing steps (III) and (IV). Normally, the conductor layer is formed on the side of the insulating layer opposite to the circuit board, so in step (V), ultraviolet treatment is applied to the side of the insulating layer opposite to the circuit board, and in step (VI), the side of the insulating layer opposite to the circuit board is treated with ultraviolet rays. A silane coupling agent treatment is performed on the opposite side of the insulating layer. Ultraviolet treatment and silane coupling agent treatment can be performed by the method described in the method for producing a cured body. By performing these steps (V) and (VI), an insulating layer can be obtained as a cured body having a specific smooth surface that has been treated with ultraviolet rays and treated with a silane coupling agent.

The method of manufacturing a circuit board may include a step of subjecting the insulating layer to heat treatment after ultraviolet treatment and silane coupling agent treatment, but before forming the conductor layer. Heat treatment can be performed by the method described in the manufacturing method of the hardened body.

Step (VII) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium A layer formed of an alloy) may be mentioned. Among them, from the viewpoint of versatility of forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy or copper-nickel alloy , an alloy layer of a copper-titanium alloy is preferred, and a mono-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a mono-metal layer of copper This is more preferable.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating a specific smooth surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full additive method. From the viewpoint of manufacturing simplicity, the semi-additive method is preferable. Below, an example of forming a conductor layer by the semiadditive method will be shown.

First, a plating seed layer (electroless plating layer) is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After forming an electrolytic plating layer by electrolytic plating on the exposed plating layer, the mask pattern is removed. Afterwards, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer with a desired wiring pattern.

By forming the conductor layer as described above, a circuit board can be manufactured including the insulating layer as the above-mentioned hardened body and the conductor layer formed on a specific smooth surface of the insulating layer. The circuit board manufactured in this way has excellent adhesion between the insulating layer and the conductor layer, and can achieve high adhesion especially after the HAST test.

In the circuit board manufacturing method, the formation of the insulating layer and the conductor layer in steps (I) to (VII) may be repeated as necessary. By repeatedly forming the insulating layer and the conductor layer, a circuit board with a multilayer structure, such as a multilayer printed wiring board, can be manufactured.

<Semiconductor chip package>

A semiconductor chip package according to an embodiment of the present invention includes the above-described hardened body and a semiconductor chip. Usually, a semiconductor chip package includes an insulating layer formed of a hardened body. The insulating layer contains the cured body described above, and preferably contains only the cured body of the resin composition described above. Examples of this semiconductor chip package include the following.

The semiconductor chip package according to the first example includes the above-described circuit board and a semiconductor chip mounted on the circuit board. This semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit board.

The bonding conditions between the circuit board and the semiconductor chip can be any condition that allows for conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board. For example, conditions used in flip chip mounting of semiconductor chips can be adopted. Additionally, for example, the semiconductor chip and the circuit board may be bonded through an insulating adhesive.

An example of a bonding method is a method of pressing a semiconductor chip to a circuit board. As for the pressing conditions, the pressing temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the pressing time is usually in the range of 1 second to 60 seconds. range (preferably from 5 seconds to 30 seconds).

Additionally, another example of a bonding method is a method of bonding a semiconductor chip to a circuit board by reflowing it. Reflow conditions may be in the range of 120°C to 300°C.

After bonding the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material.

The semiconductor chip package according to the second example includes a semiconductor chip and an insulating layer formed of a hardened body. The semiconductor chip package according to the second example includes, for example, fan-out type WLP, fan-out type PLP, etc.

1 is a cross-sectional view schematically showing a fan-out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention. The semiconductor chip package 100 as a fan-out type WLP includes, for example, a semiconductor chip 110, as shown in FIG. 1; A sealing layer 120 formed to cover the periphery of the semiconductor chip 110; a redistribution forming layer 130 as an insulating layer provided on the surface opposite to the sealing layer 120 of the semiconductor chip 110; A rewiring layer 140 as a conductor layer; Solder resist layer 150; and a bump 160.

The manufacturing method of such a semiconductor chip package is,

(i) a process of laminating a temporarily fixed film on a substrate,

(ii) a process of temporarily fixing a semiconductor chip on a temporarily fixing film,

(iii) a process of forming a sealing layer on a semiconductor chip,

(iv) a process of peeling the substrate and temporarily fixed film from the semiconductor chip,

(v) a process of forming a redistribution formation layer on the surface from which the substrate and temporarily fixed film of the semiconductor chip are peeled,

(vi) a process of forming a redistribution layer as a conductor layer on the redistribution formation layer, and

(vii) Process of forming a solder resist layer on the redistribution layer

Includes. In addition, the method for manufacturing the above semiconductor chip package is,

(viii) Process of individualizing a plurality of semiconductor chip packages by dicing them into individual semiconductor chip packages

It may be included.

(Process (i))

Process (i) is a process of laminating a temporarily fixed film on a substrate. The laminating conditions of the base material and the temporarily fixed film may be the same as the laminating conditions of the inner layer substrate and the resin sheet in the circuit board manufacturing method.

As a base material, for example, a silicon wafer; glass wafer; glass substrate; Metal substrates such as copper, titanium, stainless steel, and cold rolled steel (SPCC); Substrates such as FR-4 substrates that have been heat-cured by impregnating glass fibers with an epoxy resin or the like; and a substrate made of bismaleimide triazine resin such as BT resin.

The temporarily fixed film can be peeled from the semiconductor chip, and any material that can temporarily fix the semiconductor chip can be used. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Co., Ltd.

(Process (ii))

Process (ii) is a process of temporarily fixing the semiconductor chip on the temporarily fixing film. Temporarily fixing a semiconductor chip can be performed using, for example, devices such as a flip chip bonder or die bonder. The layout and number of batches of semiconductor chips can be appropriately set according to the shape and size of the temporarily fixed film, the number of production semiconductor chip packages of interest, etc. For example, semiconductor chips may be aligned and temporarily fixed in a matrix of multiple rows and multiple columns.

(Process (iii))

Step (iii) is a step of forming a sealing layer on the semiconductor chip. The sealing layer can be formed, for example, from a photosensitive resin composition or a thermosetting resin composition. This sealing layer may be formed using the cured body according to the above-described embodiment. The sealing layer can usually be formed by a method including a step of forming a resin composition layer on a semiconductor chip and a step of curing this resin composition layer to form a sealing layer.

(Process (iv))

Process (iv) is a process of peeling the base material and the temporarily fixed film from the semiconductor chip. As for the peeling method, it is preferable to adopt an appropriate method depending on the material of the temporarily fixed film. Examples of the peeling method include a method of peeling the temporarily fixed film by heating, foaming, or expanding it. In addition, examples of the peeling method include irradiating ultraviolet rays to the temporarily fixed film through a base material to lower the adhesive force of the temporarily fixed film and peeling the film.

When the base material and the temporarily fixed film are peeled from the semiconductor chip as described above, the surface of the sealing layer is exposed. The method of manufacturing a semiconductor chip package may include polishing the exposed surface of the sealing layer. By polishing, the smoothness of the surface of the sealing layer can be improved.

(Process (v))

Step (v) is a step of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and temporarily fixed film have been peeled. Usually, the rewiring formation layer is formed on the semiconductor chip and the sealing layer. The rewiring formation layer can be formed with the cured body according to the above-described embodiment. The redistribution forming layer usually includes the steps of forming a resin composition layer on a semiconductor chip, curing the resin composition layer to form a redistribution forming layer, applying ultraviolet rays to the redistribution forming layer, and forming the redistribution forming layer. It can be formed by a method including the step of treating with a silane coupling agent.

The formation of the resin composition layer on the semiconductor chip is, for example, the same method as the method of forming the resin composition layer on the inner layer substrate described in the above circuit board manufacturing method, except that a semiconductor chip is used instead of the inner layer substrate. It can be done.

After forming a resin composition layer on a semiconductor chip, this resin composition layer is cured to obtain a redistribution layer as an insulating layer. The conditions for curing the resin composition layer can be those described in the method for producing the cured body. When thermally curing the resin composition layer, prior to thermal curing, the resin composition layer may be subjected to preliminary heating at a temperature lower than the curing temperature. The conditions for this preliminary heating can be those described in the method for producing a cured body.

After forming the redistribution layer, the surface of the redistribution layer is subjected to ultraviolet ray treatment and silane coupling agent treatment. Additionally, after the silane coupling agent treatment, heat treatment may be performed on the redistribution formation layer. Ultraviolet treatment, silane coupling agent treatment, and heat treatment can be performed by the method described in the method for producing a cured body. A conductor layer can be formed with high adhesion on the surface of the rewiring layer as a specific smooth surface that has been treated with ultraviolet rays and a silane coupling agent.

Additionally, after forming the redistribution forming layer, a hole may be formed in the redistribution forming layer in order to connect the semiconductor chip and the redistribution layer. The formation of holes is usually performed before ultraviolet ray treatment.

(Process (vi))

Step (vi) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method of forming the redistribution layer on the redistribution forming layer may be the same as the method of forming the conductor layer on the insulating layer in the circuit board manufacturing method. Additionally, steps (v) and (vi) may be repeatedly performed to alternately stack (build up) the redistribution layer and the redistribution formation layer.

(Process (vii))

Step (vii) is a step of forming a solder resist layer on the redistribution layer. The material of the solder resist layer can be any material that has insulating properties. Among them, from the viewpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin composition and a thermosetting resin composition are preferable. The solder resist layer may be formed from the cured body according to the above-described embodiment.

Additionally, in step (vii), bumping processing to form bumps may be performed as needed. Bumping processing can be performed using methods such as solder balls and solder plating. In addition, formation of via holes in bumping processing may be performed in the same manner as step (v).

(Process (viii))

The method for manufacturing a semiconductor chip package may include step (viii) in addition to steps (i) to (vii). Process (viii) is a process of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and dividing them into individual semiconductor chip packages. The method of dicing a semiconductor chip package into individual semiconductor chip packages is not particularly limited.

<Semiconductor device>

A semiconductor device includes the circuit board or semiconductor chip package described above. Examples of semiconductor devices include electrical appliances (e.g., computers, mobile phones, smartphones, tablet-type devices, wearable devices, digital cameras, medical devices, and televisions) and vehicles (e.g., two-wheeled vehicles). , automobiles, trains, ships, and aircraft, etc.) and various semiconductor devices.

[Example]

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples. In the following description, “part” and “%” indicating quantity mean “part by mass” and “% by mass”, respectively, unless otherwise specified. In addition, the operations described below were performed in the air at room temperature and pressure (25°C, 1 atm), unless otherwise specified.

In the following examples, glycidylamine type epoxy resin “JER630LSD”, phenolic curing agent “LA-3018-50P”, maleimide compound “SLK-6895-M90”, bismaleimide resin “BMI-3000”, The curing accelerator "1B2PZ", polymer resin A synthesized in Synthesis Example 1, and polymer resin D synthesized in Synthesis Example 2 correspond to the resin component containing a nitrogen atom.

<Synthesis Example 1. Synthesis of polymer resin A>

In a flask equipped with a stirring device, a thermometer, and a condenser, 271.7 parts by mass of propylene glycol methyl ether acetate (PGMAc), 14.1 parts by mass (0.064 mol) of isophorone diisocyanate (IPDI), and 112.2 parts by mass (0.03 mol) were added. Polybutadiene with OH groups at both ends (“G-3000” manufactured by Nippon Soda Co., Ltd., hydroxyl value: 30 mgKOH/g) was supplied to obtain a mixed solution. This mixed solution was heated to 50°C and maintained at this temperature for 1 hour. Next, it was confirmed that the amount of isocyanate groups was below the predetermined value, and 145.2 parts by mass (0.09 mol) of oligophenylene ether resin containing phenolic hydroxyl groups at both terminals (“SA90-100” manufactured by Sabic, Inc.) was added to the mixed solution. Hydroxyl equivalent: 807 g/mol) and 1 mass part (0.003 mol) of benzophenone tetracarboxylic dianhydride (BTDA) were added. After that, the mixed solution was heated to 140°C, and the reaction was continued for 4 hours. The characteristic absorption was measured using an infrared spectrum, and it was confirmed that the absorption peak at 2270 cm ^-1 , which is the characteristic absorption of the isocyanate group, completely disappeared, and the reaction was terminated at the point where the increase in viscosity stopped.

As described above, polymer resin A having a structure in which the molecular ends are sealed with a phenol resin (oligophenylene ether resin containing phenolic hydroxyl groups at both ends) was synthesized, and a solution of the polymer resin A was obtained. The weight average molecular weight of polymer resin A was 15000, and the content of non-volatile components in the solution of polymer resin A was 50 mass%.

<Synthesis Example 2. Synthesis of polymer resin D>

In a reaction vessel equipped with a stirrer, fountain, thermometer, and nitrogen gas introduction tube, aromatic tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan, 4,4'-(4,4')-isopropylidene dipene was added. A solution was obtained by injecting 65.0 g of (noxy) bisphthalic dianhydride, 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane. This solution was heated to 60°C. Next, 43.7 g of dimerdiamine (“PRIAMINE 1075” manufactured by Croda Japan) and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were added dropwise to the solution, followed by imidization at 140°C for 1 hour. reacted. As a result, a polyimide solution (30% by mass of non-volatile component) containing polymer resin D, which is a polyimide resin, was obtained. The weight average molecular weight of polymer resin D was 25000.

<Example 1>

(Manufacture of resin varnish)

3 parts of bisphenol type epoxy resin (“ZX-1059” manufactured by Nittetsu Chemical & Materials, 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent weight 169 g/eq.), naphthalene type epoxy resin (manufactured by DIC Corporation) “HP-4032D”, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent approximately 145 g/eq.) 3 parts, 2 parts inorganic filler (amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 65 parts of spherical silica surface-treated (“SO-C1” manufactured by Adomatex, average particle diameter 0.3 ㎛, specific surface area 15 m2/g), 20 parts of solution of polymer resin A (50% by mass of non-volatile components) , 3.3 parts of maleimide compound (liquid bismaleimide "SLK-6895-M90" manufactured by Shin-Etsu Chemical Co., Ltd., MEK solution with 90% mass% non-volatile components, maleimide group equivalent 345 g/eq.), phenol-based curing agent ( “LA-3018-50P” manufactured by DIC, non-volatile component 50%, phenolic hydroxyl equivalent weight 151 g/eq.) 4 parts, curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo, 1-benzyl-2-phenylimida) 0.05 parts of sol), 15 parts of cyclohexanone, and 6 parts of methyl ethyl ketone were uniformly dispersed using a mixer to obtain a resin varnish.

(Manufacture of resin sheet)

As a support, a polyethylene terephthalate film (“Lumira T6AM” manufactured by Torres, thickness 38 μm) was prepared. On this support, a resin varnish was uniformly applied so that the thickness of the dried resin composition layer was 50 μm, and dried at 80°C to 120°C (average 100°C) for 6 minutes to form a resin composition layer.

A protective film with a rough surface (polypropylene film, “Alpan MA-430” manufactured by Oji Ftex, Inc., thickness 20 μm) was prepared. The rough surface of this protective film was bonded to the resin composition layer to obtain a resin sheet having a layer structure of support/resin composition layer/protective film.

<Example 2>

Naphthalene type epoxy resin ("HP-4032D" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent weight approximately 145 g/eq.) 3 parts, naphthylene ether type epoxy resin (HP-4032D manufactured by DIC) -6000L", epoxy equivalent weight 215g/eq.) 3 parts, 3 parts inorganic filler (spherical silica surface-treated with amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C4" manufactured by Adomatex Corporation) ”, average particle diameter 1.0 ㎛, specific surface area 4.5 m2/g)) 90 parts, activated ester-based curing agent (“EXB8000L-65TM” manufactured by DIC, active group equivalent approximately 220 g/eq., toluene/MEK with 65% non-volatile component) solution) 1.54 parts, solution of polymer resin A (50 mass% of non-volatile components), 40 parts, maleimide compound (liquid bismaleimide "SLK-6895-M90" manufactured by Shin-Etsu Chemical Co., Ltd., 90 mass% of non-volatile components) MEK solution, maleimide group equivalent 345 g/eq.) 3.3 parts, phenolic hardener (“LA-3018-50P” manufactured by DIC, non-volatile component 50%) 2 parts, curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo Corporation) , 0.05 parts of 1-benzyl-2-phenylimidazole), 15 parts of cyclohexanone, and 6 parts of methyl ethyl ketone were uniformly dispersed using a mixer to obtain a resin varnish.

A resin sheet was manufactured in the same manner as in Example 1, except that the resin varnish obtained in this way was used instead of the resin varnish in Example 1.

<Example 3>

Naphthalene type epoxy resin (“HP-4032D” manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent weight approximately 145 g/eq.) 3 parts, glycidylamine type epoxy resin (manufactured by Mitsubishi Chemical Corporation) “JER630LSD”, epoxy equivalent weight 95 g/eq.) 3 parts, inorganic filler 1 (spherical silica (“UFP-30” manufactured by DENKA) surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Average particle diameter 1.0 ㎛, specific surface area 31 m2/g)) 50 parts, cresol novolak resin (“KA-1160” manufactured by DIC, hydroxyl equivalent = 117 g/eq.) 3 g, solution of polymer resin A (non-volatile component 50 mass%) 20 parts, maleimide compound (liquid bismaleimide "SLK-6895-M90" manufactured by Shin-Etsu Chemical Co., Ltd., MEK solution with 90% mass% non-volatile component, maleimide group equivalent 345 g/eq.) 6.7 Part, phenol-based curing agent (“LA-3018-50P” manufactured by DIC, non-volatile component 50%), 2 parts, curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo Corporation, 1-benzyl-2-phenylimidazole) 0.05 parts, 15 parts of cyclohexanone, and 6 parts of methyl ethyl ketone were uniformly dispersed using a mixer to obtain a resin varnish.

A resin sheet was manufactured in the same manner as in Example 1, except that the resin varnish obtained in this way was used instead of the resin varnish in Example 1.

<Example 4>

Resin varnish and A resin sheet was manufactured.

<Example 5>

The solution of polymer resin A was mixed with core-shell type polymer particles as polymer resin C (“EXL2655” from Dow; a core portion formed of a polymer of butadiene and a shell formed of a copolymer of styrene and methyl methacrylate). A resin varnish and a resin sheet were produced in the same manner as in Example 1, except that the number of core-shell particles (average particle diameter: 0.2 μm) was changed to 4 parts.

<Example 6>

A resin varnish and a resin sheet were produced in the same manner as in Example 1, except that the solution of polymer resin A was changed to 33.3 parts of a polyimide solution (non-volatile component 30% by mass) containing polymer resin D.

<Example 7>

The solution of polymer resin A was changed to 5 parts of bismaleimide resin (“BMI-3000” manufactured by Designer Molecules, molecular weight 3000, maleimide group equivalent weight 1500 g/eq.). In addition, the amount of the maleimide compound (liquid bismaleimide "SLK-6895-M90" manufactured by Shin-Etsu Chemical Co., Ltd., MEK solution with 90% mass% non-volatile components, maleimide group equivalent weight 345 g/eq.) was adjusted to 6.7 parts. Changed to part 3.3. Except for the above, the resin varnish and resin sheet were manufactured in the same manner as in Example 3.

<Comparative Example 1>

90 parts of inorganic filler 3, spherical silica particles surface-treated with inorganic filler 4 (amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Kogyo Co., Ltd.)), average particle diameter 2.0 ㎛, specific surface area 2.0 m2/g) 100 Changed to wealth. Additionally, the amount of the solution of polymer resin A (50% by mass of non-volatile components) was changed from 40 parts to 26 parts. In addition, a maleimide compound (liquid bismaleimide "SLK-6895-M90" manufactured by Shin-Etsu Chemical Co., Ltd., MEK solution containing 90% by mass of non-volatile components, maleimide group equivalent of 345 g/eq.) was not used. Except for the above, the resin varnish and resin sheet were manufactured in the same manner as in Example 2.

<Comparative Example 2>

Naphthylene ether type epoxy resin (“HP-6000L” manufactured by DIC, epoxy equivalent 215 g/eq.) 3 parts, glycidylamine type epoxy resin (“JER630LSD” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95 g/eq.) 4 parts Part, inorganic filler 3 (spherical silica (“SO-C4” manufactured by Adomatex Co., Ltd.) surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 1.0 μm, specific surface area 4.5 m2. /g)) 90 parts, activated ester curing agent (“EXB8000L-65TM” manufactured by DIC, active group equivalent of about 220 g/eq., toluene/MEK solution with 65% non-volatile components) 1.54 parts, solution of polymer resin A (non-volatile) 14 parts of phenol-based hardener ("LA-3018-50P" manufactured by DIC, 50% non-volatile component), 8 parts of curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Corporation, 1-benzyl-2) -0.05 parts of phenylimidazole, 15 parts of cyclohexanone, and 6 parts of methyl ethyl ketone were uniformly dispersed using a mixer to obtain a resin varnish.

A resin sheet was manufactured in the same manner as in Example 1, except that the resin varnish obtained in this way was used instead of the resin varnish in Example 1.

<Comparative Example 3>

3 parts of naphthalene type epoxy resin (“HP-4032D” manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent weight approximately 145 g/eq.), 3 parts of modified silicone resin containing an epoxy group (manufactured by Shinetsu Chemical Co., Ltd.) “X-22-2000”, epoxy equivalent weight 620/eq.) 3 parts, inorganic filler 3 (spherical silica surface-treated with amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Adomatex) “SO-C4”, average particle diameter 1.0㎛, specific surface area 4.5㎡/g))) 90 parts, activated ester curing agent (“EXB-8000L-65TM” manufactured by DIC, active group equivalent approximately 220g/eq., non-volatile component) 1.54 parts of 65% toluene/MEK solution), 40 parts of polymer resin A solution (50% by mass of non-volatile components), 2 parts of phenol-based curing agent (“LA-3018-50P” manufactured by DIC, 50% of non-volatile components) , 0.05 parts of curing accelerator (“1B2PZ”, 1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 15 parts of cyclohexanone, and 6 parts of methyl ethyl ketone were uniformly dispersed using a mixer, Got a resin varnish.

A resin sheet was manufactured in the same manner as in Example 1, except that the resin varnish obtained in this way was used instead of the resin varnish in Example 1.

<Test 1. Measurement of contact angle

(Basic processing of inner layer circuit board)

As an inner layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) in which the inner layer circuit was formed with copper was prepared. Both sides of this inner-layer circuit board were etched by 1 μm with a microetchant (“CZ8101” manufactured by Mech Co., Ltd.) to roughen the copper surface.

(Formation of hardened sample layer)

The protective film was peeled off from the resin sheets produced in Examples and Comparative Examples, and the resin composition layer was exposed. Using a batch vacuum pressure laminator (Nikko Materials, two-stage build-up laminator "CVP700"), it was laminated on both sides of the inner layer circuit board so that the resin composition layer was in contact with the inner layer circuit board. Lamination was performed by depressurizing for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then compressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, heat pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds. After that, the support was peeled off to expose the resin composition layer.

The resin composition layer was cured under curing conditions of 200°C for 90 minutes to form a cured sample layer on the inner layer circuit board.

The contact angle . Specifically, diethylene glycol-mono-n-butyl ether was filled into a syringe, a 1.0 μL droplet was created, and it was adhered to the surface of the cured sample layer. Diethylene glycol-mono-n-butyl ether adhered and the contact angle

<Test 2. XPS measurement>

(Basic processing of inner layer circuit board)

As an inner layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) in which the inner layer circuit was formed with copper was prepared. Both sides of this inner-layer circuit board were etched by 1 μm with a microetchant (“CZ8101” manufactured by Mech Co., Ltd.) to roughen the copper surface.

(Formation of hardened sample layer)

The protective film was peeled off from the resin sheets produced in Examples and Comparative Examples, and the resin composition layer was exposed. Using a batch type vacuum pressurized laminator (Nikko Materials, two-stage build-up laminator "CVP700"), it was laminated on both sides of the inner layer circuit board so that the resin composition layer was in contact with the inner layer circuit board. Lamination was performed by depressurizing for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then compressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, heat pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds. After that, the support was peeled off to expose the resin composition layer.

The resin composition layer was cured under curing conditions of 200°C for 90 minutes to form a cured sample layer on the inner layer circuit board.

(XPS measurement)

XPS measurement was performed on the surface of the cured sample layer using a scanning X-ray photoelectron spectroscopic analyzer (“PHI Quantera II” manufactured by Albak Phi Co., Ltd.). Based on the peak area of the measured N1s spectrum, the nitrogen atom concentration on the surface of the cured sample layer was determined. XPS measurement was performed under the following measurement conditions.

XPS measurement conditions:

X-ray beam diameter 100㎛, energy 25W, acceleration voltage 15kV

<Test 3. Measurement of peel strength (adhesion strength) between insulating layer and conductor layer>

(Preparation of samples)

(1) Base processing of inner layer circuit board:

As an inner layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) in which the inner layer circuit was formed with copper was prepared. Both sides of this inner layer circuit board were etched to 1 µm with a microetchant (“CZ8101” manufactured by Mech Co., Ltd.) to roughen the copper surface.

(2) Lamination of resin sheets:

The protective film was peeled off from the resin sheets produced in Examples and Comparative Examples. This resin sheet was laminated on both sides of the inner layer circuit board using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Makey Sesakusho) so that the resin composition layer was in contact with the inner layer circuit board. Lamination was performed by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then laminating at 100°C and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of the resin composition layer:

The laminated resin sheets were heated at 100°C for 30 minutes and then at 170°C for 30 minutes to heat-cure the resin composition layer to form an insulating layer as a cured body. Thereafter, the support was peeled off to obtain an intermediate laminate having a layer structure of insulating layer/inner layer circuit board/insulating layer.

(4) UV treatment:

The surface of the insulating layer revealed by peeling off the support was irradiated with ultraviolet rays with a wavelength of 172 nm at 25°C for 10 seconds.

(5) Silane coupling treatment:

A silane coupling agent solution (Silane The concentration of the coupling agent was 5 g/L and the concentration of the glycol solvent was 350 g/L. The pH of the solution was 5.0. The intermediate laminate was immersed in this silane coupling agent solution at 40°C for 10 minutes. After that, the intermediate laminate was dried at 60°C for 10 minutes to obtain sample substrate A.

(6) Heat treatment:

Heat treatment at 160°C for 10 minutes was applied to sample substrate A.

(7) Electroless plating process:

1. Alkaline cleaning:

The surface of sample substrate A after heat treatment was cleaned at 60°C for 5 minutes using Cleaning Cleaner Securiganth 902 (brand name).

2. Soft etching:

Subsequently, the surface of sample substrate A was treated at 30°C for 1 minute using an aqueous sulfuric acidic sodium peroxodisulfate solution.

3. Pre-dip (adjustment of charge on the surface of the insulating layer to impart Pd):

The surface of sample substrate A was then treated with Pre. Dip Neoganth B (brand name) was used and treated at room temperature for 1 minute.

4. Provision of activator (provision of Pd to the surface of the insulating layer):

Next, the surface of sample substrate A was treated at 35°C for 5 minutes using Activator Neoganth 834 (brand name).

5. Reduction (reduction of Pd given to the insulating layer):

Next, the surface of sample substrate A was treated at 30°C for 5 minutes using a mixture of Reducer Neoganth WA (brand name) and Reducer Acceralator 810 mod. (brand name).

6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface)):

Next, the surface of sample substrate A was treated with a mixture of Basic Solution Printganth MSK-DK (brand name), Copper solution Printganth MSK (brand name), Stabilizer Printganth MSK-DK (brand name), and Reducer Cu (brand name). Treated at 35°C for 20 minutes. Through the above operation, an electroless copper plating layer (0.8 μm thick) was formed on the surface of the insulating layer. After that, heat treatment was performed at 150°C for 30 minutes.

7. Electrolytic plating process:

Next, using a chemical solution manufactured by Atotech Japan, an electrolytic copper plating process was performed to form an electrolytic plating layer. A conductor layer (25 μm thick) was formed by combining the electroless copper plating layer and the electrolytic plating layer. Next, annealing was performed at 200°C for 90 minutes to obtain sample substrate B.

(Measurement of peel strength before HAST test)

The peeling strength between the insulating layer and the conductor layer was measured for sample substrate B based on JIS C6481. Specifically, the peeling strength was measured by the following method.

A cut was formed in the conductor layer of the sample substrate (B) surrounding a rectangular portion with a width of 10 mm and a length of 100 mm. One end of this rectangular part was peeled off and picked up with a kitchen utensil. The load (kgf/cm) when 35 mm of the rectangular part was peeled off in the vertical direction at a speed of 50 mm/min at room temperature was measured with a clamp, and the peel strength (peel strength before the HAST test) was determined. For the measurement, a tensile tester (“AC-50C-SL” manufactured by TSE) was used.

(Measurement of peel strength after HAST test)

Thereafter, a HAST test was performed on sample substrate B for 100 hours using a highly accelerated life test device (“PM422” manufactured by Kusumoto Kasei Co., Ltd.) under high temperature and high humidity conditions of 130°C and 85%RH. After that, an incision was made in the conductor layer of sample substrate B after the HAST test described above in the same manner as the above process (measurement of peel strength before the HAST test), and the peel strength (peel strength after the HAST test) was measured.

<Test 4. Measurement of surface roughness Ra and Rz>

For the surface of the insulating layer of sample substrate A (sample substrate A after silane coupling treatment and before heat treatment) obtained in Test 3 above, the arithmetic mean roughness Ra and maximum height Rz specified in Japanese Industrial Standards (JIS B0601-2001) was measured. The measurement was performed using a non-contact surface roughness meter (“WYKO NT3300” manufactured by Vico Instruments) in VSI mode with a 50x lens, with a measurement range of 121 µm x 92 µm.

<Test 5. Measurement of crosslink density n>

A polyimide film (“Kapton 200EN” manufactured by Torre DuPont) was prepared as a polyimide substrate. The protective film was peeled off from the resin sheets produced in Examples and Comparative Examples. This resin sheet was laminated on one side of the polyimide substrate using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Makey Sesakusho) so that the resin composition layer was in contact with the polyimide substrate. Lamination was performed by depressurizing for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then laminating at 100°C and a pressure of 0.74 MPa for 30 seconds. By the above lamination, a resin sheet with a polyimide base material was obtained.

A resin sheet with a polyimide substrate was placed on a 12-inch silicon wafer with the polyimide substrate side in contact with the silicon wafer. The four sides of the polyimide base-attached resin sheet were attached to the silicon wafer with polyimide tape. The resin composition layer was heat-cured by heating at 100°C for 30 minutes and then at 170°C for 30 minutes to form an insulating layer as a cured body. After that, the support was peeled off to obtain an intermediate laminate having a structure of insulating layer/polyimide base material/silicon wafer.

The surface of the insulating layer revealed by peeling off the support was irradiated with ultraviolet rays with a wavelength of 172 nm at 25°C for 10 seconds.

A silane coupling agent solution (Silane The concentration of the coupling agent was 5 g/L and the concentration of the glycol solvent was 350 g/L. The pH of the solution was 5.0. The intermediate laminate was immersed in this silane coupling agent solution at 40°C for 10 minutes. After that, the intermediate laminate was dried at 60°C for 10 minutes and further subjected to heat treatment at 180°C for 60 minutes to obtain sample substrate C.

The insulating layer was removed from the sample substrate C after heat treatment, and a cured body was obtained. This hardened body was cut into pieces with a width of 5 mm and a length of 15 mm to obtain test piece D. Thermomechanical analysis was performed on this test piece D by the tensile weighting method using a viscoelasticity measuring device (“DMA7100” manufactured by Hitachi High-Tech Science). Specifically, after mounting the test piece C on the thermomechanical analysis device, the storage modulus and loss modulus were measured under the measurement conditions of a load of 200 mN and a temperature increase rate of 5°C/min.

The glass transition temperature Tg (°C) was obtained from the peak top of tanδ (temperature dependence curve of the ratio of storage elastic modulus and loss modulus) obtained as a measurement result.

Next, a predetermined temperature T(K), which was 80K higher than the glass transition temperature Tg, was determined. Specifically, to convert the obtained glass transition temperature Tg (°C) into a unit K, 273 K was added, and 80 K was further added to determine the predetermined temperature T (K). In addition, in the temperature range around the predetermined temperature T(K), the value of the storage elastic modulus tends not to vary significantly, so it is within the range of -5°C to +5°C with respect to the determined predetermined temperature T(K). It is acceptable for errors to occur. Then, the measured value E' (unit: GPa, i.e., ×10 ⁹ Pa) of the storage elastic modulus at the determined predetermined temperature T (K) was obtained.

The crosslinking density n (mol/cm 3 ) was calculated by substituting the obtained storage elastic modulus E' (Pa) into the following equation (M1). Here, the crosslinking density n can be considered as an index representing the number of crosslinked molecules present per unit volume.

n=E'/3RT 　　(M1)

(In the above formula (M1), T represents a predetermined temperature T(K); E' represents the measured value (Pa) of the storage elastic modulus at a predetermined temperature T(K); R represents the gas It represents 8310000 (Pa·cm3/mol·K) as a constant. Additionally, the measured value of shear modulus G' (10 ⁹ Pa) at a given temperature T (K) may be used as E'/3.

<Test 6. Measurement of dielectric loss tangent>

The insulating layer was removed from the sample substrate C obtained in Test 5 above, and a cured body was obtained. For this cured body, the dielectric loss tangent Df was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Measurements were made on three test pieces, and the average value was calculated.

<Test 7. Measurement of storage modulus and glass transition temperature>

The insulating layer was removed from the sample substrate C obtained in Test 5 above, and a cured body was obtained. This cured body was cut to obtain a test piece with a width of 7 mm and a length of 40 mm. For this test piece, dynamic mechanical analysis was performed in tensile mode using a dynamic mechanical analysis device (“DMS-6100” manufactured by Seiko Instruments). Specifically, the test piece was mounted on the above device and measured under measurement conditions of a frequency of 1 Hz and a temperature increase rate of 5°C/min. The storage modulus (E') at 25°C in these measurements was read. Additionally, the temperature at which tan δ reached its maximum was read as the glass transition temperature Tg.

<Result>

The results of the above-mentioned examples and comparative examples are shown in the table below. In the table below, the amount of each component represents the mass part of the non-volatile component. In addition, the meaning of the abbreviated name is as follows.

Ra: Arithmetic mean roughness.

Rz: Maximum height.

Tg: Glass transition temperature.

Peel strength before HAST: Peel strength between the insulating layer and the conductor layer before the HAST test.

Peel strength after HAST: Peel strength between the insulating layer and the conductor layer after the HAST test.

<Review>

In Comparative Example 1, the surface roughness of the surface of the cured body was large, and therefore high adhesion could not be obtained. In addition, Comparative Example 2 was able to obtain high adhesion before the HAST test, but swelling occurred in the conductor layer during the HAST test, and the peeling strength itself could not be measured after the HAST test. In Comparative Example 2, the nitrogen atom concentration on the surface of the cured sample layer was large, and the nitrogen atom concentration on the surface of the insulating layer was also large, so it is assumed that absorption increased and swelling occurred. Additionally, in Comparative Example 3, high adhesion could not be obtained before the HAST test. In Comparative Example 3, the contact angle

In contrast, in all examples, high adhesion was obtained after the HAST test. From the results of this example, it can be confirmed that high adhesion after the HAST test can be achieved by the present invention.

100 semiconductor chip packages
110 semiconductor chip
120 sealing layer
130 Rewiring cambium
140 rewiring layer
150 solder resist layer
160 bump

Claims (18)

As a cured body of a resin composition containing a thermosetting resin;
The hardened body has a surface with an arithmetic mean roughness Ra of less than 100 nm;
When a test was conducted to form a cured sample layer by curing a layer of the resin composition at 200°C for 90 minutes,
The contact angle of diethylene glycol-mono-n-butyl ether with respect to the surface of the cured sample layer is less than 30°,
A cured body having a nitrogen atom concentration of less than 3.8 atomic% obtained based on the peak area of the spectrum of N1s in X-ray photoelectron spectroscopy analysis of the surface of the cured sample layer. The cured body according to claim 1, wherein the nitrogen atom concentration obtained based on the peak area of the spectrum of N1s in X-ray photoelectron spectroscopy analysis of the surface of the cured sample layer is 0.1 atomic% or more. The cured body according to claim 1, wherein the resin composition contains an inorganic filler. The cured body according to claim 3, wherein the amount of the inorganic filler in the resin composition is 40% by mass or more and 90% by mass or less with respect to 100% by mass of the non-volatile component of the resin composition. The cured body according to claim 1, wherein the thermosetting resin contains an epoxy resin. The cured body according to claim 1, wherein the thermosetting resin contains a phenolic resin. The cured body according to claim 1, wherein the thermosetting resin comprises an activated ester resin. The cured body according to claim 1, wherein the thermosetting resin contains a maleimide resin. The cured body according to claim 1, wherein the resin composition contains a curing accelerator. The cured body according to claim 1, wherein the resin composition contains a resin component containing a nitrogen atom. The cured body according to claim 1, for forming a conductor layer on the surface having an arithmetic mean roughness Ra of less than 100 nm. A circuit board comprising an insulating layer formed by the cured body according to any one of claims 1 to 11. A semiconductor chip package comprising the cured body according to any one of claims 1 to 11 and a semiconductor chip. A semiconductor device comprising the circuit board according to claim 12. A semiconductor device comprising the semiconductor chip package according to claim 13. A method for producing a cured body according to any one of claims 1 to 11, comprising:
A process of obtaining a cured body by curing a resin composition containing a thermosetting resin;
A process of subjecting the cured body to ultraviolet ray treatment;
A method for producing a cured body, comprising the step of subjecting the cured body to treatment with a silane coupling agent. A resin sheet comprising a support and a layer of a resin composition formed on the support;
The resin composition includes a thermosetting resin;
When the layer of the resin composition is cured to form a cured sample, and a first test is performed in which the surface of the cured sample is treated with ultraviolet rays and a silane coupling agent on the surface on the support side, the arithmetic average roughness Ra of the surface on the support side is 100 nm. is less than;
When a second test was conducted in which a layer of the resin composition was cured at 200°C for 90 minutes to form a cured sample layer,
The contact angle of diethylene glycol-mono-n-butyl ether with respect to the surface of the support side of the cured sample layer is less than 30°,
A resin sheet wherein the nitrogen atom concentration obtained based on the peak area of the N1s spectrum in X-ray photoelectron spectroscopy analysis of the surface on the support side of the cured sample layer is less than 3.8 atomic%. The method of claim 17, wherein in the first test, curing of the layer of the resin composition is performed under conditions of 170°C for 30 minutes,
In the first test, ultraviolet treatment is performed by irradiating the cured sample with ultraviolet rays with a wavelength of 172 nm for 10 seconds,
In the first test, the silane coupling agent treatment was performed by placing the cured sample in an aqueous solution of pH 5.0 containing 5 g/liter of 3-amino-propyltrimethoxysilane and 350 g/liter of diethylene glycol-mono-n-butyl ether. , a resin sheet made by dipping at 40°C for 10 minutes.