KR20240043114A - Resin composition - Google Patents

Abstract

[Problem] To provide a resin composition capable of forming an insulating layer with excellent impact properties.
[Solution] A resin composition containing (A) a curable resin and (B) an inorganic filler, wherein the specific gravity of the cured product obtained by curing the resin composition is 1.6 g/cm3 or less, and the thermal expansion coefficient of the cured product obtained by curing the resin composition is 1.6 g/cm3 or less. A resin composition having a temperature of 40 ppm/°C or less.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to resin compositions.

As a manufacturing technology for printed wiring boards, a manufacturing method using a build-up method is known in which insulating layers and conductor layers are stacked alternately. In a manufacturing method using a build-up method, generally, the insulating layer is formed by a cured product obtained by curing a resin composition (Patent Document 1).

Japanese Patent Publication No. 2020-23714

Semiconductor devices provided with printed wiring boards include portable devices such as smartphones. These portable devices are often subject to shock. For example, portable devices may accidentally fall when in use, and therefore may receive shock from falling. When subjected to impact, the insulating layer and the conductive layer in the printed wiring board may peel off, or cracks may form in the insulating layer. Therefore, there is a demand for the development of a resin composition capable of forming an insulating layer with excellent impact resistance.

The present invention was created in view of the above problems, and includes a resin composition capable of forming an insulating layer with excellent impact resistance; A cured product of the resin composition; A sheet-like laminated material containing the above resin composition; a resin sheet having a resin composition layer formed of the resin composition; a printed wiring board including an insulating layer containing a cured product of the resin composition; and a semiconductor device including the printed wiring board.

The present inventor has diligently studied to solve the above problems. As a result, the present inventor discovered that the above problems could be solved by appropriately adjusting the composition of the resin composition containing (A) the curable resin and (B) the inorganic filler, and completed the present invention.

That is, the present invention includes the following.

[1] A resin composition containing (A) a curable resin and (B) an inorganic filler,

The specific gravity of the cured product obtained by curing the resin composition is 1.6 g/cm3 or less,

A resin composition wherein the cured product obtained by curing the resin composition has a thermal expansion coefficient of 40 ppm/°C or less.

[2] (B) The resin composition according to [1], wherein the inorganic filler has an average particle diameter of 0.01 μm or more and 5 μm or less.

[3] (B) The resin composition according to [1] or [2], wherein the BET specific surface area of the inorganic filler is 1 m 2 /g or more and 100 m 2 /g or less.

[4] The resin composition according to any one of [1] to [3], in which the (B) inorganic filler contains a hollow inorganic filler (B-1) having voids therein.

[5] (B-1) The resin composition according to [4], wherein the hollow inorganic filler has a porosity of 10% by volume or more.

[6] (C) The resin composition according to any one of [1] to [5], further comprising organic particles.

[7] The resin composition according to [6], wherein the amount of (C) organic particles is 2% by mass or more based on 100% by mass of non-volatile components of the resin composition.

[8] (C) The organic particles have a shell portion and an interior portion formed within the shell portion,

The resin composition according to [6] or [7], wherein the interior portion contains a rubber component or is hollow.

[9] (A) The resin composition according to any one of [1] to [8], wherein the curable resin is selected from the group consisting of thermosetting resin and photocurable resin.

[10] The resin composition according to [9], wherein the thermosetting resin includes at least one type selected from the group consisting of epoxy resin, phenol resin, activated ester resin, cyanate resin, and radical polymerizable resin.

[11] The resin composition according to [9] or [10], wherein the photocurable resin contains a radically polymerizable resin.

[12] A resin composition comprising (A) a curable resin, (B) an inorganic filler, and (C) an organic particle,

(B) the inorganic filler includes a hollow inorganic filler (B-1) having voids therein,

(B-1) The hollow inorganic filler has a porosity of 10% by volume or more,

With respect to 100 volume% of non-volatile components of the resin composition, (B) the amount of inorganic filler is 40 volume% or more,

A resin composition in which the amount of (B-1) hollow inorganic filler is 10 volume% or more based on 100 volume% of non-volatile components of the resin composition.

[13] The resin composition according to any one of [1] to [12], which is used for forming an insulating layer.

[14] A cured product of the resin composition according to any one of [1] to [13].

[15] A sheet-like laminated material containing the resin composition according to any one of [1] to [13].

[16] A resin sheet having a support and a resin composition layer formed on the support from the resin composition according to any one of [1] to [13].

[17] A printed wiring board provided with an insulating layer containing a cured product of the resin composition according to any one of [1] to [13].

[18] A semiconductor device comprising the printed wiring board according to [17].

According to the present invention, a resin composition capable of forming an insulating layer with excellent impact resistance; A cured product of the resin composition; A sheet-like laminated material containing the above resin composition; a resin sheet having a resin composition layer formed of the resin composition; a printed wiring board including an insulating layer containing a cured product of the resin composition; And a semiconductor device including the printed wiring board can be provided.

[Figure 1] Figure 1 is a front view schematically showing a drop test performed to evaluate impact resistance.

Hereinafter, the present invention will be described by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be implemented with arbitrary changes without departing from the scope of the claims and equivalents thereof.

In the following description, the term “(meth)acrylic” includes acrylic, methacryl, and combinations thereof. Additionally, the term “(meth)acrylate” includes acrylates, methacrylates, and combinations thereof. Additionally, the term “(meth)acrylonitrile” includes acrylonitrile, methacrylonitrile, and combinations thereof.

[One. Overview of the resin composition according to the first embodiment]

The resin composition according to the first embodiment of the present invention contains (A) a curable resin and (B) an inorganic filler in combination. Additionally, the cured product obtained by curing this resin composition has a specific gravity within a specific range. Additionally, the cured product obtained by curing this resin composition has a coefficient of thermal expansion within a specific range. According to a resin composition that satisfies these requirements, an insulating layer with excellent impact resistance can be formed. Therefore, when the insulating layer containing the cured product of the resin composition according to the first embodiment of the present invention receives an impact, peeling between the insulating layer and the conductive layer can be suppressed, and cracks are formed in the insulating layer. can be prevented from happening. In the following description, the property that can suppress peeling between the insulating layer and the conductive layer when subjected to impact is sometimes referred to as "impact peeling resistance," and the property that can suppress cracking when subjected to impact is sometimes referred to as "impact peeling resistance." Sometimes it is referred to as “impact crack resistance.”

The resin composition according to the first embodiment of the present invention preferably contains (C) organic particles in combination with (A) a curable resin and (B) an inorganic filler. In addition, the resin composition according to the first embodiment of the present invention may further contain arbitrary components.

The present inventor speculates the mechanism by which the above excellent impact resistance is obtained by the resin composition according to the first embodiment of the present invention as follows. However, the technical scope of the present invention is not limited by the mechanism described below.

Generally, (A) the curable resin has a large thermal expansion coefficient, and (B) the inorganic filler has a small thermal expansion coefficient. Therefore, in order to obtain a cured product having a coefficient of thermal expansion in a specific small range, the resin composition is required to contain a large amount of the (B) inorganic filler. Therefore, the fact that the cured product of the resin composition has a coefficient of thermal expansion in a specific small range indicates that the amount of the (B) inorganic filler contained in the resin composition is large. In this way, when the amount of the inorganic filler (B) is large, the inorganic filler (B) functions as an aggregate in the cured product, and the rigidity of the cured product can be increased. In addition, as the rigidity of the cured product is high, the resistance to impact of the cured product can be increased.

Additionally, since the specific gravity of the inorganic material is generally greater than that of the resin, when the amount of the inorganic filler is increased, the specific gravity of the cured product tends to increase. Therefore, in the resin composition according to the first embodiment of the present invention, the type and amount of the (B) inorganic filler are controlled in order to keep the specific gravity of the cured product within a specific small range while using a large amount of the (B) inorganic filler. For example, by using an appropriate amount of hollow inorganic filler (B-1) having voids inside, the cured product can have a specific gravity within a specific small range. In general, the cured product of a conventional resin composition containing a curable resin and an inorganic filler tended to have increased brittleness when the amount of the inorganic filler was large. On the other hand, if the specific gravity of the cured product is set to a specific small range by studying the (B) inorganic filler, the brittleness of the cured product can be significantly suppressed and resistance to impact can be increased. According to the present inventor's examination, especially when the (B) inorganic filler contains the (B-1) hollow inorganic filler, the energy of impact is alleviated by the voids in the (B-1) hollow inorganic filler, and the impact resistance is improved. I think it is improving. Additionally, when the resin composition contains organic particles (C), it is believed that the energy of impact is synergistically alleviated by the action of the organic particles (C), thereby achieving effective improvement in impact resistance.

[2. (A) Curable resin]

The resin composition according to the first embodiment of the present invention contains (A) curable resin as the (A) component. (A) The curable resin may be selected from the group consisting of thermosetting resin and photocurable resin. Therefore, as the curable resin (A), only a thermosetting resin may be used, only a photocurable resin may be used, or a combination of a thermosetting resin and a photocurable resin may be used. In addition, curable resin may be used individually or in combination of two or more types.

As the thermosetting resin, a resin that can be cured when heat is applied can be used. Examples of thermosetting resins include epoxy resins, phenol resins, activated ester resins, cyanate resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, thiol resins, and radically polymerizable resins. Thermosetting resins may be used individually or in combination of two or more types. Among these, the thermosetting resin preferably contains at least one type selected from the group consisting of epoxy resin, phenol resin, active ester resin, cyanate resin, and radical polymerizable resin.

In particular, from the viewpoint of significantly obtaining the effects of the present invention, it is preferable to use a combination of an epoxy resin and a resin that can cure the resin composition by reacting with the epoxy resin. A resin that can react with an epoxy resin and harden the resin composition may hereinafter be referred to as a “curing agent.” Examples of the curing agent include phenol resin, activated ester resin, cyanate resin, carbodiimide resin, acid anhydride resin, amine resin, benzoxazine resin, and thiol resin. Among them, phenol resin, active ester resin, cyanate resin, and carbodiimide resin are preferable, and phenol resin, active ester resin, and cyanate resin are more preferable. In addition, one type of hardening agent may be used individually, and two or more types may be used in combination.

Epoxy resin is a curable resin having an epoxy group. As epoxy resins, for example, 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, trisphenol type epoxy resin. Resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl Diester type epoxy resin, cresol novolak 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, spirocyclic 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. Resins, etc. can be mentioned. Epoxy resins may be used individually or in combination of two or more types.

The epoxy resin preferably contains an epoxy resin containing an aromatic structure from the viewpoint of obtaining a cured product with excellent heat resistance. An aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. Examples of the epoxy resin containing an aromatic structure include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, dicyclopentadiene-type epoxy resin, 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, glyphosaccharide having an aromatic structure. Cydylamine type epoxy resin, glycidyl ester type epoxy resin with an aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with an aromatic structure, epoxy with a butadiene structure with 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) The curable resin is an epoxy resin and preferably contains an epoxy resin having two or more epoxy groups in one molecule. The ratio of the epoxy resin having two or more epoxy groups per 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, and particularly preferably 70% by mass. It is more than %.

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 resin composition may contain only a liquid epoxy resin as an epoxy resin, may contain only a solid epoxy resin, or may contain 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 novolak-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 preferred.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F type) manufactured by Mitsubishi Chemical Corporation epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “630”, “630LSD”, 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); “ZX1059” manufactured by Nittetsu Chemical & Materials Chemicals 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 the 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 novolac-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, Phenolphthalimidine 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", and "HP6000" (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.; "YX7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER1031S” (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. are mentioned. These may be used individually or in combination of two or more types.

When using a combination of liquid epoxy resin and solid epoxy resin as an epoxy resin, their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1. to 1:10, particularly preferably 7:1 to 1:7.

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 110 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.

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 in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 5% by mass or more, when the non-volatile component in the resin composition is 100% by mass. Preferably it is 50 mass% or less, more preferably 40 mass% or less, and particularly preferably 35 mass% or less. When the amount of the epoxy resin is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The amount of epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, especially preferably 20% by mass or more, when the resin component in the resin composition is 100% by mass. is 80 mass% or less, more preferably 70 mass% or less, particularly preferably 65 mass% or less. Unless otherwise specified, the resin component of the resin composition refers to the component excluding the (B) inorganic filler among the non-volatile components of the resin composition. When the amount of the epoxy resin is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

As the phenol resin, a compound having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or naphthalene ring per molecule can be used. When a phenol resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so it is sometimes referred to as a “phenol-based curing agent.” From the viewpoint of heat resistance and water resistance, a phenol resin having a novolac 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. Specific examples of phenol resins include, for example, “MEH-7700”, “MEH-7810”, and “MEH-7851” manufactured by Meiwa Kasei Corporation, and “NHN”, “CBN”, and “GPH” manufactured by Nippon Kayaku Corporation. , “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495”, “SN-375” manufactured by Nittetsu Chemical & Materials Co., Ltd. , “SN-395”, “LA-7052”, “LA-7054”, “LA-3018”, “LA-3018-50P”, “LA-1356”, “TD2090”, “TD-” manufactured by DIC Corporation. 2090-60M”, etc.

As the active ester resin, compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. It is used widely. When combined with an epoxy resin, the active ester resin can react with the epoxy resin and harden the resin composition, so it is sometimes referred to as an “active ester-based curing agent.” The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. 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. As phenol compounds or naphthol compounds, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, 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, the active ester resin includes a dicyclopentadiene-type active ester resin, a naphthalene-type active ester resin containing a naphthalene structure, an active ester resin containing an acetylate of phenol novolac, and a benzoylate of phenol novolac. The following active ester resins are preferable, and among them, at least one type selected from dicyclopentadiene-type active ester resins and naphthalene-type active ester resins is more preferable. As the dicyclopentadiene type active ester resin, an active ester resin containing a dicyclopentadiene type diphenol structure is preferable.

Commercially available active ester resins include, for example, active ester resins containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", and "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 acetylated product 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).

As the cyanate resin, a compound having one or more, preferably two or more, cyanate groups in one molecule can be used. When cyanate resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so it is sometimes referred to as a “cyanate-based curing agent.” As cyanate resin, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis (2,6-dimethyl) phenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate) Natephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins such as phenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolac, etc., prepolymers in which these cyanate resins are partially triazinated, etc. can be mentioned. Specific examples of cyanate resin include "PT30" and "PT60" (both phenol novolak-type polyfunctional cyanate resins), "BA230", and "BA230S75" (all or part of bisphenol A dicyanate) manufactured by Lonza Japan. and prepolymers that have been triazinated into trimers).

As the carbodiimide resin, a compound having one or more, preferably two or more, carbodiimide structures in one molecule can be used. When combined with an epoxy resin, carbodiimide resin can react with the epoxy resin and harden the resin composition, so it is sometimes referred to as a “carbodiimide-based curing agent.” Specific examples of carbodiimide resin include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); Biscabodiimides such as aromatic biscabodiimides such as phenylene-bis(xylylcarbodiimide); Aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide). ; Poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(di Ethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly (methylenediphenylenecarbodiimide), and aromatic polycarbodiimide such as poly[methylenebis(methylphenylene)carbodiimide]. Commercially available products of carbodiimide resin include, for example, “Carbodylight V-02B,” “Carbodylight V-03,” “Carbodylight V-04K,” and “Carbodylight V” manufactured by Nisshinbo Chemical Co., Ltd. -07” and “Carbody Light V-09”; “Stabakusol P”, “Stabakusol P400”, and “Hycadyl 510” manufactured by Line Chemistry, etc. can be mentioned.

As the acid anhydride resin, a compound having one or more, preferably two or more, acid anhydride groups in one molecule can be used. When acid anhydride resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so it is sometimes referred to as an “acid anhydride-based curing agent.” Specific examples of acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, Dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride , Benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3,3a ,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis( and polymeric acid anhydrides such as anhydrotrimellitate) and styrene-maleic acid resin, which is a copolymerization of styrene and maleic acid. Commercially available acid anhydride resins include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Nippon Rika Corporation; “YH-306” and “YH-307” manufactured by Mitsubishi Chemical Corporation; “HN-2200” and “HN-5500” manufactured by Hitachi Kasei Corporation; “EF-30,” “EF-40,” “EF-60,” and “EF-80” manufactured by Cray Vale Co., Ltd. can be mentioned.

As the amine resin, a compound having one or more, preferably two or more amino groups in one molecule can be used. When an amine resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so it is sometimes referred to as an “amine-based curing agent.” Examples of amine resins include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among these, aromatic amines are preferable. The amine resin is preferably a primary amine or a secondary amine, and is more preferably a primary amine. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylmethane. minodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl , 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3- Dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4) -aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, and bis(4-(3-aminophenoxy)phenyl)sulfone. Examples of commercially available amine resins include “SEIKACURE-S” manufactured by Seika Corporation; "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard A-B", and "Kayahard A-S" manufactured by Nippon Kayaku Corporation; “Epicure W” manufactured by Mitsubishi Chemical Corporation; "DTDA" manufactured by Sumitomo Seika Co., Ltd., etc. are mentioned.

When benzoxazine resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so it is sometimes referred to as a “benzoxazine-based curing agent.” Specific examples of benzoxazine resin include “JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemicals; “HFB2006M” manufactured by Showa Kobunshi Corporation; “P-d” and “F-a” manufactured by Shikoku Kaseiko Kogyo Co., Ltd. can be mentioned.

When a thiol resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so it is sometimes referred to as a “thiol-based curing agent.” Examples of thiol resins include trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate. there is.

The active group equivalent of the curing agent is preferably 50 g/eq. to 3,000 g/eq., more preferably 100 g/eq. to 1,000 g/eq., more preferably 100 g/eq. to 500 g/eq., particularly preferably 100 g/eq. to 300 g/eq. The active group equivalent is the mass of the curing agent per equivalent of the active group.

When the number of epoxy groups in the epoxy resin is 1, the number of active groups in the curing agent is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.5 or more, preferably 5.0 or less, more preferably 4.0 or less. , especially preferably 3.0 or less. “Number of epoxy groups in an 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, the “number of active groups of the curing agent” refers to the total value obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active group equivalent.

The amount of the curing agent in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 5% by mass or more, when the non-volatile component in the resin composition is 100% by mass. is 50 mass% or less, more preferably 40 mass% or less, particularly preferably 30 mass% or less. When the amount of the curing agent is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer containing the cured resin composition can be effectively improved.

The amount of the curing agent in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 20% by mass or more, when the resin component in the resin composition is 100% by mass. It is 80 mass% or less, more preferably 70 mass% or less, and especially preferably 60 mass% or less. When the amount of the curing agent is within the above range, the impact peeling resistance and impact cracking resistance of the insulating layer containing the cured resin composition can be effectively improved.

As the radical polymerizable resin, a compound having an ethylenically unsaturated bond can be used. Therefore, the radically polymerizable resin may have a radically polymerizable group containing an ethylenically unsaturated bond. Examples of the radically polymerizable group include unsaturated hydrocarbon groups such as vinyl group, allyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, 2-vinylphenyl group, 3-vinylphenyl group, and 4-vinylphenyl group; and α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, and maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group). The number of radically polymerizable groups contained in one molecule of the radically polymerizable resin may be one, but is preferably two or more. One type of radical polymerizable resin may be used individually, or two or more types may be used in combination.

Preferred radically polymerizable resins include, for example, styrene-based radically polymerizable resins. The styrene-based radically polymerizable resin may be a compound having at least one vinyl group directly bonded to an aromatic carbon atom, preferably at least two vinyl groups. Examples of the styrene-based radically polymerizable resin include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, Low molecular weight (molecular weight less than 1,000) styrene-based compounds such as 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; and high molecular weight (molecular weight 1,000 or more) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resin and styrene-divinylbenzene copolymer.

As the styrene-based radically polymerizable resin, a modified polyphenylene ether resin having a vinylphenyl group is preferable. The vinylphenyl group may include a 2-vinylphenyl group, a 3-vinylphenyl group, a 4-vinylphenyl group, or a group in which the aromatic carbon atom thereof is further substituted with one or more alkyl groups. Among them, as the styrene-based radically polymerizable resin, a resin represented by the following formula (A-1) is particularly preferable.

[Formula A-1]

(In Formula A-1,

R ¹¹ and R ¹² each independently represent an alkyl group;

R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group;

R ³¹ and R ³² each independently represent a vinylphenyl group;

Y ¹ represents a single bond, -C(R ^y ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ -;

R ^y each independently represents a hydrogen atom or an alkyl group;

Y ² represents a single bond or an alkylene group;

p represents 0 or 1;

q and r each independently represent an integer of 1 or more)

The q unit and r unit may be the same or different for each unit.

In Formula A-1, R ¹¹ and R ¹² each independently represent an alkyl group, and are preferably a methyl group.

In the formula A-1, R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group, and are preferably a hydrogen atom.

In the formula A-1, R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

In Formula A-1, R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group, and are preferably a hydrogen atom or a methyl group.

In Formula A-1, R ³¹ and R ³² each independently represent a vinylphenyl group.

In Formula A-1, Y ² represents a single bond or an alkylene group. Alkylene group means a straight-chain, branched-chain and/or cyclic divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group with 1 to 14 carbon atoms, more preferably an alkylene group with 1 to 10 carbon atoms, and particularly preferably an alkylene group with 1 to 6 carbon atoms. Examples of alkylene groups include -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )- , -CH(CH ₃ )-CH ₂ -, -C(CH ₃ ) ₂ -, and the like. Preferably, Y ² is an alkylene group (especially preferably -CH ₂ -).

In Formula A-1, Y ¹ represents a single bond, -C(R ^y ) ₂ -, -O-, -CO-, -S-, -SO-, or -SO ₂ -, and is preferably a single bond. , -C(R ^y ) ₂ - or -O-, and particularly preferably a single bond. R ^y each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

In Formula A-1, p represents 0 or 1, and is preferably 1.

In the formula A-1, q and r each independently represent an integer of 1 or more, preferably an integer of 1 to 200, and more preferably an integer of 1 to 100.

Specific examples of the resin represented by the formula A-1 include, for example, a resin represented by the following formula A-1-1. Examples of the resin represented by the formula A-1-1 include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

[Formula A-1-1]

Other preferred radically polymerizable resins include, for example, maleimide-based radically polymerizable resins. The maleimide-based radically polymerizable resin may be a compound having one or more maleimide groups, preferably two or more maleimide groups. The maleimide-based radically polymerizable resin may be an aliphatic maleimide compound containing an aliphatic amine skeleton, or may be an aromatic maleimide compound containing an aromatic amine skeleton. Among them, as the maleimide-based radically polymerizable resin, a resin represented by the following formula (A-2) is particularly preferable.

[Formula A-2]

(In Formula A-2,

R ^a each independently represents a hydrogen atom or an alkyl group;

Ring E, Ring F, and Ring G each independently represent an aromatic ring that may have a substituent;

Z each independently represents a single bond, -C(R ^z ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-;

R ^z each independently represents a hydrogen atom or an alkyl group;

s represents an integer of 1 or more;

t each independently represents 0 or 1;

u each independently represents 0, 1, 2 or 3)

The s unit, t unit, and u unit may be the same or different for each unit.

In the formula A-2, R ^a each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In the formula A-2, ring E, ring F and ring G each independently represent an aromatic ring which may have a substituent, preferably a benzene ring which may have a substituent, and more preferably an alkyl group and It is a benzene ring that may be substituted with a group selected from aryl groups, and is particularly preferably an unsubstituted benzene ring.

In Formula A-2, Z is each independently a single bond, -C(R ^z ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or - It represents NHCO-, and is preferably a single bond, -C(R ^z ) ₂ - or -O-, more preferably a single bond or -C(R ^z ) ₂ -, and especially preferably a single bond. . R ^z each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

In the formula A-2, s represents an integer of 1 or more, and is preferably an integer of 1 to 10.

In Formula A-2, t each independently represents 0 or 1, and is preferably 1.

In the formula A-2, u each independently represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and especially preferably 1. .

Specific examples of the resin represented by the formula A-2 include, for example, a resin represented by the following formula A-2-1. Examples of the resin represented by the formula A-2-1 include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.

[Formula A-2-1]

Another preferred radically polymerizable resin includes, for example, a (meth)acrylic radically polymerizable resin. The (meth)acrylic radically polymerizable resin may be a compound having one or more, preferably two or more, acryloyl groups and/or methacryloyl groups. (meth)acrylic radically polymerizable resins include, for example, cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, and tricyclodecanedi. Methanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di. (meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylol ethane tri(meth)acrylate low molecular weight (molecular weight less than 1,000) aliphatic (meth)acrylic acid ester compounds such as glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate; Dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-dioldi(meth) Acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di low molecular weight (molecular weight less than 1,000) ether-containing (meth)acrylic acid ester compounds such as (meth)acrylate and propoxylated bisphenol A di(meth)acrylate; Tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate low molecular weight (molecular weight less than 1,000) isocyanurate-containing (meth)acrylic acid ester compounds; and high molecular weight (molecular weight 1,000 or more) acrylic acid ester compounds such as (meth)acrylic modified polyphenylene ether resin. Commercially available products of (meth)acrylic radical polymerizable resin include, for example, “A-DOG” (dioxane glycol diacrylate) manufactured by Shinnakamura Chemical Co., Ltd. and “DCP-A” manufactured by Kyoeisha Chemical Co., Ltd. (Tricyclodecane dimethanol diacrylate), “DCP” (Tricyclodecane dimethanol dimethacrylate), Nippon Kayaku Co., Ltd.’s “KAYARAD R-684” (Tricyclodecane dimethanol diacrylate), “KAYARAD R-604” (dioxane glycol diacrylate), “SA9000” manufactured by SABIC Innovative Plastics, and “SA9000-111” (methacryl-modified polyphenylene ether).

Another preferred radically polymerizable resin includes, for example, an allyl-based radically polymerizable resin. The allyl-based radically polymerizable resin may be a compound having one or more allyl groups, preferably two or more allyl groups. Examples of the allyl-based radically polymerizable resin include diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylic acid, and 2,3-naphthalene dicarboxylic acid. Aromatic carboxylic acid allyl ester compounds such as diallyl naphthalenecarboxylic acid; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; Allylsilane compounds such as diallyldiphenylsilane, etc. can be mentioned. Commercially available allyl-based radically polymerizable resins include, for example, “TAIC” (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd., and “DAD” (Diphen) manufactured by Nisshoku Technofine Chemicals Co., Ltd. diallyl acid), "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., brand name "DAND" (diallyl 2,3-naphthalenecarboxylic acid) manufactured by Nippon Joryukyo Chemical Co., Ltd., Shikoku Kasei Kogyoso Co., Ltd. “ALP-d” (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Nippon Kayaku Co., Ltd., “RE- 810NM” (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane), “DA-MGIC” (1,3-diallyl-5-glycidyl) manufactured by Shikoku Kasei Co., Ltd. isocyanurate) and the like.

Additionally, as the radical polymerizable resin, those described in the section on photocurable resin may be used.

The ethylenically unsaturated bond equivalent weight of the radically polymerizable resin is preferably 20 g/eq. to 3,000 g/eq., more preferably 50 g/eq. to 2,500 g/eq., more preferably 70 g/eq. to 2,000 g/eq., particularly preferably 90 g/eq. to 1,500 g/eq. The ethylenically unsaturated bond equivalent represents the mass of the radical polymerizable resin per equivalent of the ethylenically unsaturated bond.

The weight average molecular weight (Mw) of the radically polymerizable resin is preferably 40,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, but may be, for example, 150 or more.

The amount of radically polymerizable resin in the resin composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, especially preferably 1.0 mass% or more, when the non-volatile component in the resin composition is 100 mass%. , Preferably it is 10 mass% or less, More preferably, it is 5.0 mass% or less, Especially preferably, it is 3.0 mass% or less. When the amount of the radically polymerizable resin is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The amount of radically polymerizable resin in the resin composition is preferably 0.1 mass% or more, more preferably 1.0 mass% or more, especially preferably 2.0 mass% or more, when the resin component in the resin composition is 100 mass%, Preferably it is 15 mass% or less, more preferably 10 mass% or less, and especially preferably 8.0 mass% or less. When the amount of the radically polymerizable resin is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

As the photocurable resin, a resin that can be cured when exposed to light can be used. Examples of photocurable resins include radically polymerizable resins. One type of photocurable resin may be used individually, or two or more types may be used in combination.

As the radically polymerizable resin used as the photocurable resin, those described in the section on thermosetting resin may be used. Moreover, from the viewpoint of enabling development with an alkaline developer, a resin having an ethylenically unsaturated bond and a carboxyl group is preferable as a radically polymerizable resin as a photocurable resin.

The resin having an ethylenically unsaturated bond and a carboxyl group may have a radical polymerizable group containing an ethylenically unsaturated bond and a carboxyl group in combination. Examples of radically polymerizable groups include those mentioned above. Among them, (meth)acryloyl group is preferable. The term “(meth)acryloyl group” includes acryloyl group, methacryloyl group, and combinations thereof. The number of radically polymerizable groups per resin molecule may be one or two or more. When the resin contains two or more radically polymerizable groups per molecule, these radically polymerizable groups may be the same or different. Additionally, the number of carboxyls per resin molecule may be one or two or more.

The resin having an ethylenically unsaturated bond and a carboxyl group preferably contains a naphthalene skeleton. The resin having an ethylenically unsaturated bond and a carboxyl group may contain one naphthalene skeleton or two or more naphthalene skeletons in one molecule. In addition, the resin having an ethylenically unsaturated bond and a carboxyl group preferably has two or less radically polymerizable groups per naphthalene skeleton. Additionally, it is preferable that the radically polymerizable group is included in a substituent of the naphthalene skeleton. In addition, the resin having an ethylenically unsaturated bond and a carboxyl group preferably has two or less carboxyl groups per naphthalene skeleton. Moreover, it is preferable that the carboxyl group is included in the substituent of the naphthalene skeleton.

Preferred resins having an ethylenically unsaturated bond and a carboxyl group include resins containing a structure represented by the following formula (A-3). The resin having an ethylenically unsaturated bond and a carboxyl group may have only one or more structures represented by the following general formula (A-3). The number of structures represented by the formula (A-3) per molecule of the resin having an ethylenically unsaturated bond and a carboxyl group is preferably 1 to 10, more preferably 1 to 6. In the formula A-3, R ¹ may be bonded to any carbon atom that can be bonded among the carbon atoms contained in the naphthalene skeleton. Therefore, R ¹ may be bonded to a carbon atom of the same benzene ring or to a carbon atom of a different benzene ring with respect to the terminal bond. The terminal binding hand represents a binding hand other than the binding hand binding to R ¹ and the binding hand binding to OR ⁰ among the binding hands binding to the naphthalene ring, and specifically, the binding hand drawn at the left end of Formula A-3 indicates. For example, the combination of positions of the terminal bond in the naphthalene skeleton and the bond bonded to R ¹ is positions 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, Positions 1 and 7, positions 1 and 8, positions 2 and 3, positions 2 and 6, and positions 2 and 7 are also acceptable.

[Formula A-3]

In the formula A-3, R ¹ and R ² each independently represent an alkylene group which may have a substituent. The number of carbon atoms of R ¹ and R ² is usually 1 to 20, preferably 1 to 10, and more preferably 1 to 6. In addition, the alkylene group may be linear or branched. Examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, and preferably methylene group. Substituents that R ¹ and R ² may have include, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, and a nitro group. group, hydroxy group, mercapto group, oxo group, etc.

In the formula A-3, X represents an arylene group which may have a substituent. The number of carbon atoms of X is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 10. Examples of the arylene group include phenylene group, anthracenylene group, phenanthrenylene group, and biphenylene group, and are preferably phenylene groups. Examples of the substituent that X may have include the same substituents that R ¹ and R ² may have.

In the formula A-3, a represents 0 or 1, and is preferably 1. Here, a is the number of groups X.

In Formula A-3, b represents 0 or 1. Additionally, in Formula A-3, c represents 0 or 1. Here, b and c are the numbers of groups R ¹ and groups R ² , respectively. However, for b and c, b+c does not become 0. It is preferred that both b and c are 1.

In Formula A-3, OR ⁰ represents a substituent on the naphthalene skeleton. R ⁰ each independently represents an organic group containing a radically polymerizable group and a carboxyl group. Preferably, R ⁰ represents a group represented by the following formula A-4.

[Formula A-4]

In Formula A-4, R ³ represents a trivalent group. R ³ preferably represents a trivalent hydrocarbon group which may have a substituent (however, a hetero atom may be present between carbon-carbon bonds (CC bonds)). Among them, R ³ is preferably a trivalent aliphatic hydrocarbon group which may have a substituent. Examples of the substituents that R ³ may have include the same substituents that R ¹ and R ² may have.

In the formula A-4, R ⁴ represents an organic group containing a radically polymerizable group. A preferable example of an organic group containing a radically polymerizable group includes a (meth)acryloyloxy group. “(Meth)acryloyloxy group” includes acryloyloxy group, methacryloyloxy group, and combinations thereof.

In Formula A-4, R ⁵ represents an organic group containing a carboxyl group. Examples of organic groups containing a carboxyl group include -OCO-R ⁶ -COOH. Here, R ⁶ represents a divalent group. As R ⁶ , a divalent hydrocarbon group that may have a substituent is preferable. The number of carbon atoms of R ⁶ is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 6. Examples of the divalent hydrocarbon group include linear or branched acyclic alkylene groups such as methylene group, ethylene group, propylene group, and butylene group; A saturated or unsaturated divalent alicyclic hydrocarbon group; Arylene groups such as phenylene group and naphthylene group can be mentioned. Among them, a divalent alicyclic hydrocarbon group and an arylene group are preferable, and a 4-cyclohexenylene group and a phenylene group are particularly preferable. In addition, examples of the substituents that R ⁶ may have include the same substituents that R ¹ and R ² may have. -CO-R ⁶ -COOH in -OCO-R ⁶ -COOH may be a residue of carboxylic acid anhydride. Examples of carboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. .

In the formula A-3, d usually represents an integer of 1 to 6, preferably 1 to 3, and more preferably 1 to 2. Here, d represents the number of groups OR ⁰ .

The weight average molecular weight of the resin having an ethylenically unsaturated bond and a carboxyl group is preferably 500 or more, more preferably 1,000 or more, still more preferably 1,500 or more, and still more preferably 2,000 or more from the viewpoint of film forming properties. The upper limit is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,500 or less from the viewpoint of developability.

The acid value of the resin having an ethylenically unsaturated bond and a carboxyl group is preferably 0.1 mg KOH/g or more, more preferably 0.5 mg KOH/g or more, especially preferably, from the viewpoint of keeping the solubility in an alkaline developer within an appropriate range. Preferably it is 1 mg KOH/g or more, preferably 150 mg KOH/g or less, more preferably 120 mg KOH/g or less, and particularly preferably 100 mg KOH/g or less.

The acid value can be measured by the following method. First, after weighing about 1 g of the resin solution, 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein, an indicator, is added to the solution, and titration is performed using a 0.1N ethanolic KOH solution. Then, the acid value is calculated using the following equation X1.

[Equation X1]

A = Vf×5.611/(Wp×I)

Meanwhile, in the above equation It represents the ratio [mass %] of non-volatile components.

The amount of radically polymerizable resin as the photocurable resin is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, when the non-volatile component in the resin composition is 100% by mass. and is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less. When the amount of the radically polymerizable resin is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The amount of radically polymerizable resin as the photocurable resin is preferably 20% by mass or more, more preferably 30% by mass or more, especially preferably 40% by mass or more, when the resin component in the resin composition is 100% by mass. , Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less, Especially preferably, it is 65 mass% or less. When the amount of the radically polymerizable resin is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The amount of curable resin (A) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, especially preferably 30% by mass or more, when the non-volatile component in the resin composition is 100% by mass. and is preferably 70 mass% or less, more preferably 60 mass% or less, and particularly preferably 50 mass% or less. (A) When the amount of the curable resin is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition can be effectively improved.

The amount of curable resin (A) in the resin composition is preferably 60% by mass or more, more preferably 70% by mass or more, especially preferably 80% by mass or more, when the resin component in the resin composition is 100% by mass. , Preferably it is 97 mass% or less, more preferably 95 mass% or less, and especially preferably 90 mass% or less. (A) When the amount of the curable resin is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition can be effectively improved.

[3. (B) Inorganic filler]

The resin composition according to the first embodiment of the present invention contains (B) an inorganic filler as the (B) component. (B) The inorganic filler is usually contained in the resin composition in particle form.

(B) As a material for the inorganic filler, an inorganic compound can be 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.

Additionally, as a material for the (B) inorganic filler, an inorganic composite oxide may be used. Inorganic composite oxide refers to an oxide containing two or more types of atoms selected from the group consisting of metal atoms and semimetal atoms. As such an inorganic composite oxide, an oxide containing a combination of silicon and one or more types of atoms selected from the group consisting of metal atoms other than silicon and metalloid atoms is preferable. Metal atoms combining with silicon include aluminum, lead, nickel, cobalt, copper, zinc, zirconium, iron, lithium, magnesium, barium, potassium, calcium, titanium, boron, sodium, etc. Among them, aluminum is Particularly desirable. Therefore, as the inorganic composite oxide, oxides containing silicon and aluminum are preferable, and aluminosilicates are particularly preferable.

Among these (B) inorganic filler materials, silica, alumina and aluminosilicate are suitable, and silica is particularly suitable. (B) Inorganic fillers may be used individually or in combination of two or more types.

(B) Inorganic fillers can be classified into (B-1) hollow inorganic fillers that have voids inside, and (B-2) solid inorganic fillers that do not have voids inside. (B) The inorganic filler preferably contains (B-1) a hollow inorganic filler. Since the (B-1) hollow inorganic filler has voids inside the particles of the (B-1) hollow inorganic filler, it may generally have a smaller specific gravity than the (B-2) solid inorganic filler. Therefore, when the inorganic filler (B) contains the hollow inorganic filler (B-1), the specific gravity of the cured product of the resin composition can be reduced. Additionally, when using a hollow inorganic filler (B-1), the relative dielectric constant of the cured product of the resin composition can usually be lowered.

(B-1) The hollow inorganic filler may be a single hollow particle having only one void inside the particle, may be a multi-hollow particle having two or more voids inside the particle, or may be a combination of single hollow particles and multi-hollow particles. .

(B-1) Since the hollow inorganic filler has voids, it usually has a porosity greater than 0 volume%. From the viewpoint of effectively improving the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition, the porosity of the hollow inorganic filler (B-1) is preferably 10% by volume or more, more preferably 15% by volume. It is volume % or more, especially preferably 20 volume % or more. In addition, from the viewpoint of the mechanical strength of the cured product of the resin composition, the porosity of the hollow inorganic filler (B-1) is preferably 95 volume% or less, more preferably 90 volume% or less, particularly preferably 85 volume% or less. am.

The porosity P (volume %) of a particle is the volume-based ratio of the total volume of one or two or more pores inside the particle to the entire volume of the particle based on the outer surface of the particle (total volume of pores/particle) is defined as the volume of). The _porosity p is calculated by _the following equation You can.

[Equation

(B) Hollow inorganic particles generally have voids formed within the particles and an outer shell formed of an inorganic material surrounding the voids. Usually, the voids are separated from the outside of the particle by an outer shell portion. At this time, it is preferable that the voids do not communicate with the outside of the particle. Therefore, it is preferable that the outer shell is an inorganic pore shell that does not have a hole that communicates the void with the outside of the particle. That the outer shell is an inorganic hole can be confirmed by observation with a transmission electron microscope (TEM).

(B-1) The average particle diameter of the hollow inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, preferably 5 μm or less, more preferably 4 μm or more. ㎛ or less, particularly preferably 3 ㎛ or less. (B-1) When the average particle diameter of the hollow inorganic filler is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The average particle diameter of particles can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by using a laser diffraction scattering type particle size distribution measuring device to create the particle size distribution of particles on a volume basis and making the median diameter the average particle size. The measurement sample of the inorganic filler can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone in 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-1) The BET specific surface area of the hollow inorganic filler is preferably 1 m2/g or more, more preferably 2 m2/g or more, particularly preferably 5 m2/g or more, and preferably 100 m2/g. g or less, more preferably 50 m2/g or less, particularly preferably 30 m2/g or less. (B-1) When the BET specific surface area of the hollow inorganic filler is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved. The BET specific surface area of the particle can be measured by adsorbing nitrogen gas on 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 multi-point method. You can.

(B-1) Commercially available hollow inorganic fillers may be used. Commercially available (B-1) hollow inorganic fillers include “Cell Spears” and “MGH-005” manufactured by Taiheiyo Cement Co., Ltd.; Examples include “Esperique” and “BA-1” manufactured by Nikki Shokubai Kasei. Additionally, (B-1) the hollow inorganic filler may be manufactured by a conventional method. For example, (B-1) hollow silica particles as an example of a hollow inorganic filler include a step of preparing an aqueous solution containing a substance capable of forming voids and a basic compound; A process of mixing and stirring the aqueous solution and an alkoxysilane to precipitate silica particles; It may be manufactured by a method including a step of removing a material that can form voids from silica particles to obtain a hollow silica precursor, and a step of calcining the hollow silica precursor.

(B-1) The hollow 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. One type of surface treatment agent may be used individually, and two or more types may be used in arbitrary combination.

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

The degree of surface treatment with a surface treatment agent is preferably within a specific range from the viewpoint of improving dispersibility. Specifically, 100% by mass of the inorganic filler is preferably surface treated with 0.2% by mass to 8% by mass of a surface treatment agent, more preferably 0.2% by mass to 5% by mass of a surface treatment agent, It is more preferable that the surface is treated with 0.3% by mass to 3% 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 preventing 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.

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 (mass %) of the hollow inorganic filler (B-1) in the resin composition is preferably 5 mass % or more, more preferably 10 mass % or more, when the non-volatile component in the resin composition is 100 mass %, Particularly preferably, it is 15 mass% or more, preferably 80 mass% or less, more preferably 70 mass% or less, and particularly preferably 60 mass% or less. (B-1) When the amount of the hollow inorganic filler is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition can be effectively improved.

The amount (volume %) of the hollow inorganic filler (B-1) in the resin composition is preferably 5 volume % or more, more preferably 10 volume % or more, assuming that the non-volatile component in the resin composition is 100 volume %. Particularly preferably, it is 15 volume% or more, preferably 80 volume% or less, more preferably 70 volume% or less, and particularly preferably 60 volume% or less. (B-1) When the amount of the hollow inorganic filler is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition can be effectively improved.

(B) The inorganic filler may contain (B-2) a solid inorganic filler. (B-2) Commercially available solid 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.

(B-2) The average particle diameter of the solid inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, preferably 10 μm or less, more preferably 5 μm or more. ㎛ or less, particularly preferably 3 ㎛ or less.

(B-2) The BET specific surface area of the solid inorganic filler is preferably 0.1 m2/g or more, more preferably 0.5 m2/g or more, particularly preferably 1 m2/g or more, and preferably 100 m2/g. g or less, more preferably 70 m2/g or less, particularly preferably 40 m2/g or less.

The solid inorganic filler (B-2) is preferably treated with a surface treatment agent like the hollow inorganic filler (B-1).

The amount (mass %) of the solid inorganic filler (B-2) in the resin composition may be 0 mass % or may be greater than 0 mass % when the non-volatile component in the resin composition is 100 mass %, and is preferably 10 mass %. It is more than 50 mass%, more preferably 45 mass% or less, especially preferably 40 mass% or less.

The amount (volume %) of the solid inorganic filler (B-2) in the resin composition may be 0 volume %, or may be greater than 0 volume %, when the non-volatile component in the resin composition is 100 volume %, and is preferably 5 volume %. It is more than 50 volume%, more preferably 10 volume% or more, especially 20 volume% or more, preferably 50 volume% or less, more preferably 40 volume% or less, especially preferably 30 volume% or less.

The proportion of voids contained in the entire inorganic filler (B), including both the (B-1) hollow inorganic filler and (B-2) solid inorganic filler, is calculated as the porosity (volume %) of the (B) inorganic filler. (B) The porosity (volume %) of the inorganic filler is a representative value representing the ratio of pores to the volume of the (B) inorganic filler on a volume basis, and is expressed as “total volume of pores/(B) total volume of inorganic filler”. displayed. (B) The specific range of the porosity of the inorganic filler is preferably 10 volume% or more, more preferably 15 volume% or more, particularly preferably 20 volume% or more, preferably 80 volume% or less, more preferably is 70 volume% or less, particularly preferably 60 volume% or less.

The average particle diameter of the entire inorganic filler (B), including both the (B-1) hollow inorganic filler and (B-2) solid inorganic filler, is preferably 0.01 μm or more, more preferably 0.1 μm or more, especially preferably is 0.3 μm or more, preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less. (B) When the average particle diameter of the inorganic filler is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The BET specific surface area of the entire inorganic filler (B), including both the (B-1) hollow inorganic filler and (B-2) solid inorganic filler, is preferably 1 m2/g or more, more preferably 2 m2/g or more. , particularly preferably 5 m2/g or more, preferably 100 m2/g or less, more preferably 50 m2/g or less, particularly preferably 30 m2/g or less. (B) When the BET specific surface area of the inorganic filler is in the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The amount (mass %) of the inorganic filler (B) in the resin composition is preferably 20 mass % or more, more preferably 30 mass % or more, especially preferably, when the non-volatile component in the resin composition is 100 mass %. is 40 mass% or more, preferably 80 mass% or less, more preferably 70 mass% or less, and particularly preferably 60 mass% or less. (B) When the amount of the inorganic filler is in the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition can be effectively improved.

The amount (volume %) of the inorganic filler (B) in the resin composition is preferably 20 volume % or more, more preferably 30 volume % or more, especially preferably, when the non-volatile component in the resin composition is 100 volume %. is 40 volume% or more, preferably 80 volume% or less, more preferably 75 volume% or less, particularly preferably 70 volume% or less. (B) When the amount of the inorganic filler is in the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition can be effectively improved.

[4. (C) organic particles]

The resin composition according to the first embodiment of the present invention preferably contains (C) organic particles as component (C) in combination with (A) curable resin and (B) inorganic filler. (C) Organic particles exist in particulate form in the resin composition, and are usually contained in the cured product while maintaining their particulate form.

Since the organic particles (C) contain an organic material, they usually have a larger coefficient of thermal expansion than the inorganic filler (B) and a smaller specific gravity than the inorganic filler (B). Therefore, by using (C) organic particles, the thermal expansion coefficient and specific gravity of the cured product of the resin composition can be adjusted. Additionally, since (C) organic particles generally tend to have higher flexibility than (B) inorganic fillers, the (C) organic particles can increase the resistance to stress of the cured resin composition.

(C) As organic particles, particles having a uniform composition as a whole may be used, or particles having a non-uniform composition may be used. For example, a multilayer particle having a shell portion and an internal portion formed within the shell portion is preferred. In addition, the multilayer particle may include parts other than the shell part and the interior part. For example, the multilayer particle may further include an arbitrary part within the internal portion. Additionally, for example, the multilayer particle may include an arbitrary layer between the shell portion and the interior portion. Usually, since the interior portion is covered with a shell portion, the multilayer particles can be highly dispersed in the resin composition regardless of the composition of the interior portion, and thus the degree of freedom in composition of the interior portion can be increased. Therefore, since the interior part having a composition suitable for the insulating layer can be adopted, the characteristics of the insulating layer can be improved. The double-layered particle referred to here does not necessarily refer to only those in which the shell portion and the interior portion are clearly distinguishable, but also include those in which the boundary between the shell portion and the interior portion is unclear, and the interior portion may not be completely covered with the shell portion.

The shell portion of the multi-layer particle is usually formed of polymer. The polymer forming the shell portion may be a homopolymer as a polymer of one type of monomer, or may be a copolymer as a copolymer of two or more types of monomers. As for the type of polymer and monomer thereof forming the shell portion, it is preferable to select one that suppresses agglomeration of (C) organic particles and can be well dispersed in the resin composition. The specific type may depend on the composition of the curable resin (A), but preferred examples of monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acrylate. (meth)acrylic acid esters such as octyl acrylate and glycidyl (meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; Aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; (meth)acrylonitrile, etc. can be mentioned. These monomers may be used individually or in combination of two or more types.

The interior portion of the multi-layer particle preferably contains an organic material different from that contained in the shell portion. In this way, multi-layered particles having an interior portion containing an organic material may have a core portion corresponding to the interior portion and a shell portion covering the core portion, and are therefore sometimes called “core-shell particles.” Among these, it is preferable that the interior portion contains a rubber component. When the organic particles (C) contain multilayer particles containing a rubber component in the internal portion, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition can be effectively improved. As the rubber component, for example, a resin that exhibits an elastic modulus of 1 GPa or less can be used when a tensile test is performed at a temperature of 25°C and a humidity of 40%RH in accordance with Japanese Industrial Standards (JIS K7161). In addition, as the rubber component, for example, a resin having a glass transition temperature of preferably 0°C or lower, more preferably -10°C or lower, further preferably -20°C or lower, particularly preferably -30°C or lower. can be used. The glass transition temperature can be measured by DSC (differential scanning calorimetry) at a temperature increase rate of 10°C/min. These rubber components include, for example, polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure and polycarbonate structure in the molecule. It can be prepared as a resin having one or more structures selected from the following structures.

Specific examples of the rubber component include silicone-based elastomers such as polydimethylsiloxane; Polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene Olefin-based thermoplastic elastomers such as copolymers, isobutylene-butadiene copolymers, ethylene-propylene-diene terpolymers, and ethylene-propylene-butene terpolymers; Thermoplastic elastomers such as acrylic thermoplastic elastomers such as propyl poly(meth)acrylate, butyl poly(meth)acrylate, cyclohexyl poly(meth)acrylate, and octyl poly(meth)acrylate. Additionally, silicone-based rubber such as polyorganosiloxane rubber may be mixed with the rubber component.

In the multilayer particle containing a rubber component, the amount of the rubber component is preferably 40 mass% or more, more preferably 50 mass% or more, and particularly preferably 60 mass% or more. There is no particular limitation on the upper limit, but from the viewpoint of sufficiently covering the internal portion with the shell portion, it may be, for example, 95% by mass or less, 90% by mass, etc.

Multilayer particles having an internal portion containing a rubber component include, for example, a step of preparing a core particle containing a rubber component and forming a shell portion by graft copolymerizing a monomer component copolymerizable with the rubber component contained in the core particle. It can be manufactured by a manufacturing method including the following process. Additionally, commercially available products may be used as the multilayer particles having an internal portion containing a rubber component. Commercially available products include, for example, “CHT” manufactured by Chamil Industries; “B602” manufactured by UMGABS; “Paraloid EXL-2602”, “Paraloid EXL-2603”, “Paraloid EXL-2655”, “Paraloid EXL-2311”, “Paraloid EXL-2313”, “Paraloid” manufactured by Dow Chemical Nippon Corporation. EXL-2315”, “Paraloid KM-330”, “Paraloid KM-336P”, “Paraloid KCZ-201”; “Metablene C-223A”, “Metablen E-901”, “Metablene S-2001”, “Metablen W-450A” and “Metablene SRK-200” manufactured by Mitsubishi Rayon Corporation; “Kaneace M-511”, “Kaneace M-600”, “Kaneace M-400”, “Kaneace M-580”, and “Kaneace MR-01” manufactured by Kaneka Corporation; Staphylloids “AC3832” and “AC3816N” manufactured by Aika Kogyo Co., Ltd. are included.

It is preferable that the internal portion of the multi-layered particle is a hollow portion. That is, it is preferable that the multi-layered particles have a hollow portion as a void surrounded by a shell portion. In this way, multilayer particles having hollow parts as internal parts are sometimes called “hollow organic particles.” When the organic particles (C) contain multi-layer particles including hollow portions as internal portions, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

Multilayer particles containing hollow parts usually have a porosity greater than 0 volume%. From the viewpoint of effectively improving the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition, the porosity of the multilayer particles is preferably 10 volume% or more, more preferably 15 volume% or more, and particularly preferably It is more than 20 volume%. Additionally, from the viewpoint of mechanical strength of the cured product of the resin composition, the porosity of the multilayer particles is preferably 90 volume% or less, more preferably 90 volume% or less, and particularly preferably 80 volume% or less.

Multilayer particles containing hollow parts include, for example, Japanese Patent Application Laid-Open No. 2006-265394, Japanese Patent Application Laid-Open No. 2007-238792, International Publication No. 2011/040376, Japanese Patent Application Laid-Open No. 2016-190980, It can be manufactured by the method described in documents such as International Publication No. 2018/051794 and Japanese Patent Application Laid-Open No. 2020-189978. Additionally, commercially available products may be used as the multi-layered particles containing hollow portions. Examples of commercially available products include "XX-5598Z" manufactured by Sekisui Kaseihin Kogyo Co., Ltd.

(C) Organic particles may be used individually or in combination of two or more types.

(C) The organic particles may be treated with a surface treatment agent. (C) Examples of surface treatment agents for organic particles include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; Carboxylic acids such as acetic acid, propionic acid, butyric acid, and acrylic acid, sulfonic acids such as p-toluenesulfonic acid, ethylsulfonic acid, and dodecylbenzenesulfonic acid, phosphoric acids such as polyoxyethylene alkyl ether phosphoric acid, and organic acids such as phosphonic acid and phosphinic acid; Silane coupling agents such as tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, and 8-(meth)acryloxyoctyltrimethoxysilane; Isocyanate-based compounds such as ethyl isocyanate, etc. can be mentioned.

(C) The average particle diameter of the organic particles is preferably smaller than the average particle diameter of the hollow inorganic filler (B-1). (C) The specific average particle diameter of the organic particles is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.10 μm or more, preferably 5 μm or less, more preferably 2 μm or less. , more preferably 1㎛ or less. (C) The average particle diameter of the organic particles can be measured using a zeta potential particle size distribution measuring device.

The amount (mass %) of the (C) organic particles in the resin composition is preferably 0.5 mass % or more, more preferably 1.5 mass % or more, especially preferably, when the non-volatile component in the resin composition is 100 mass %. is 2% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, especially preferably 10% by mass or less. (C) When the amount of the organic filler is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The amount (volume %) of the (C) organic particles in the resin composition is preferably 0.5 volume % or more, more preferably 1.5 volume % or more, especially preferably, when the non-volatile component in the resin composition is 100 volume %. is 2.0 volume% or more, preferably 20 volume% or less, more preferably 15 volume% or less, particularly preferably 10 volume% or less. (C) When the amount of the organic filler is in the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The amount (mass %) of the (C) organic particles in the resin composition is preferably 1.0 mass % or more, more preferably 1.5 mass % or more, especially preferably, when the resin component in the resin composition is 100 mass %. It is 2.0 mass% or more, preferably 30 mass% or less, more preferably 20 mass% or less, and especially preferably 15 mass% or less. (C) When the amount of the organic filler is in the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The mass ratio of the (C) organic particles and the (B-1) hollow inorganic filler ((C) organic particles/(B-1) hollow inorganic filler) in the resin composition is preferably 0.01 or more, more preferably 0.02 or more. , especially preferably 0.03 or more, preferably 0.50 or less, more preferably 0.40 or less, particularly preferably 0.30 or less. When the mass ratio ((C) organic particles/(B-1) hollow inorganic filler) is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The volume ratio of the (C) organic particles and the (B-1) hollow inorganic filler ((C) organic particles/(B-1) hollow inorganic filler) in the resin composition is preferably 0.01 or more, more preferably 0.03 or more, Particularly preferably, it is 0.05 or more, preferably 0.50 or less, more preferably 0.30 or less, and particularly preferably 0.20 or less. When the volume ratio ((C) organic particles/(B-1) hollow inorganic filler) is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The total mass of the (C) organic particles and (B-1) hollow inorganic filler in the resin composition is preferably 5 mass% or more, more preferably 10 mass%, when the non-volatile component in the resin composition is 100 mass%. % or more, particularly preferably 15 mass % or more, preferably 80 mass % or less, more preferably 75 mass % or less, particularly preferably 70 mass % or less. When the total mass of the organic particles (C) and the hollow inorganic filler (B-1) is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured resin composition can be effectively improved.

The total volume of the (C) organic particles and (B-1) hollow inorganic filler in the resin composition is preferably 10 volume% or more, more preferably 15 volume%, assuming that the non-volatile component in the resin composition is 100 volume%. % or more, particularly preferably 20 volume% or more, preferably 85 volume% or less, more preferably 80 volume% or less, particularly preferably 75 volume% or less. When the total volume of the organic particles (C) and the hollow inorganic filler (B-1) is within the above range, the impact peeling resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition can be effectively improved.

[5.(D) Curing accelerator]

The resin composition according to the first embodiment of the present invention may further contain a curing accelerator (D) as an optional component in combination with the components (A) to (C). The curing accelerator (D) as the component (D) does not include those corresponding to the components (A) to (C). (D) The curing accelerator has a function as a curing catalyst that promotes curing of the curable resin (A).

(D) As the curing accelerator, an appropriate one can be used depending on the type of curable resin (A). For example, when the (A) curable resin contains an epoxy resin, (D) curing accelerators that can accelerate curing of the epoxy resin include, for example, phosphorus-based curing accelerators, urea-based curing accelerators, and guanidine-based curing accelerators. Accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators can be mentioned. (D) 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. Mellitate, 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, di-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 ), aromatic dimethyl ureas such as N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea], and the like.

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. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 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 Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid addition Water, 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 imidazole compounds and epoxy resins Adduct type may 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 Kaseikogyo Co., Ltd. PW”, “2PHZ”, “2PHZ-PW”, “Cl1Z”, “Cl1Z-CN”, “Cl1Z-CNS”, “C11Z-A”; "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. are mentioned.

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 the amine-based curing accelerator, a commercial product may be used, for example, “MY-25” manufactured by Ajinomoto Fine Techno Co., Ltd., etc.

The amount of curing accelerator (D) in the resin composition may be 0% by mass or may be greater than 0% by mass when the non-volatile component in the resin composition is 100% by mass, and is preferably 0.01% by mass or more, more preferably It is 0.02 mass% or more, especially preferably 0.05 mass% or more, preferably 1.0 mass% or less, more preferably 0.5 mass% or less, especially preferably 0.2 mass% or less.

The amount of curing accelerator (D) in the resin composition may be 0% by mass or may be greater than 0% by mass when the resin component in the resin composition is 100% by mass, and is preferably 0.01% by mass or more, more preferably 0.05% by mass. It is % by mass or more, particularly preferably 0.10 mass % or more, preferably 2.0 mass % or less, more preferably 1.0 mass % or less, and particularly preferably 0.5 mass % or less.

[6.(E) Polymerization initiator]

The resin composition according to the first embodiment of the present invention may further include (E) a polymerization initiator as an optional component in combination with the components (A) to (D). The polymerization initiator (E) as the component (E) does not include those corresponding to the components (A) to (D). (E) The polymerization initiator may be used individually, or may be used in combination of two or more types.

(E) The type of polymerization initiator can be selected depending on the type of (A) curable resin. For example, when the curable resin (A) contains a radically polymerizable resin as the photocurable resin, it is preferable to use a photopolymerization initiator as the polymerization initiator (E).

(E) As a polymerization initiator, for example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl) ) methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, etc. α-aminoalkylphenone-based polymerization initiator; Oxime ester polymerization initiators such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, and 1-(O-acetyloxime); Benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine Oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy -1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2 , 4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. In addition, a sulfonium salt-based photopolymerization initiator can also be used.

(E) Examples of commercially available polymerization initiators include "Omnirad907", "Omnirad369", "Omnirad379", "Omnirad819", and "OmniradTPO" manufactured by IGM, and "IrgacureTPO", "IrgacureOXE-01", and "IrgacureOXE" manufactured by BASF. -02”, “N-1919” manufactured by ADEKA, etc.

The amount of (E) polymerization initiator in the resin composition may be 0% by mass or may be greater than 0% by mass when the non-volatile component in the resin composition is 100% by mass, and is preferably 0.01% by mass or more, more preferably It is 0.1 mass% or more, especially preferably 1 mass% or more, preferably 10 mass% or less, more preferably 7 mass% or less, and particularly preferably 5 mass% or less.

The amount of (E) polymerization initiator in the resin composition may be 0 mass% or may be greater than 0 mass% when the resin component in the resin composition is 100 mass%, and is preferably 0.01 mass% or more, more preferably 0.1 mass%. It is % by mass or more, particularly preferably 1 mass % or more, preferably 20 mass % or less, more preferably 15 mass % or less, and particularly preferably 10 mass % or less.

[7.(F) Thermoplastic resin]

The resin composition according to the first embodiment of the present invention may further include (F) a thermoplastic resin as an optional component in combination with the components (A) to (E). The thermoplastic resin (F) as the component (F) does not include those corresponding to the components (A) to (E).

(F) Thermoplastic resins include, for example, phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamidoimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, Polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. can be mentioned. (F) Thermoplastic resins may be used individually, or may be used in combination of two or more types.

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 type of 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 a 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 are bisphenol A skeleton-containing phenoxy resins); “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 Shinnittetsu Sumikin Kagaku Corporation; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891" manufactured by Mitsubishi Chemical Corporation. BH30” and the like.

Specific examples of the polyimide resin include “SLK-6100” manufactured by Shin-Etsu Chemical Co., Ltd., “Licca Coat SN20” and “Licca Coat PN20” manufactured by Nippon Rika Co., Ltd.

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. ; Sekisui Kagakukogyo Co., Ltd.'s S-Lec BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series can be mentioned.

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 poly. Examples include butadiene resin, isocyanate group-containing polybutadiene resin, urethane group-containing polybutadiene resin, and polyphenylene ether-polybutadiene resin.

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

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

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

Specific examples of polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of polyetherimide resin include “Ultem” manufactured by GE Corporation.

Examples of the polycarbonate resin include carbonate resin containing a hydroxy group, carbonate resin containing a phenolic hydroxyl group, carbonate resin containing a carboxy group, carbonate resin containing an acid anhydride group, carbonate resin containing an isocyanate group, carbonate resin containing a urethane group, etc. You can. 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. 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.

(F) The weight average molecular weight (Mw) of the thermoplastic resin is preferably greater than 5,000, more preferably 8,000 or more, further preferably 10,000 or more, particularly preferably 20,000 or more, and preferably 100,000 or less. Preferably it is 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

The amount of the (F) thermoplastic resin in the resin composition may be 0 mass% or may be greater than 0 mass% when the non-volatile component in the resin composition is 100 mass%, and is preferably 0.01 mass% or more, more preferably It is 0.1 mass% or more, especially preferably 1 mass% or more, preferably 20 mass% or less, more preferably 10 mass% or less, and particularly preferably 5 mass% or less.

The amount of the (F) thermoplastic resin in the resin composition may be 0% by mass or may be greater than 0% by mass when the resin component in the resin composition is 100% by mass, and is preferably 0.1% by mass or more, more preferably 1% by mass. It is more than 2% by mass, especially preferably 2% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, especially preferably 10% by mass or less.

[8. (G) optional additives]

The resin composition according to the first embodiment of the present invention may be combined with the above components (A) to (F) and may further contain (G) an optional additive as an optional non-volatile component. (G) Optional additives include, for example, organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; Leveling agents such as silicone-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 phenol antioxidants; Fluorescent whitening agents such as stilbene derivatives; Surfactants such as fluorine-based surfactants and silicone-based surfactants; 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, inorganic flame retardants (e.g., antimony trioxide), etc. flame retardants; Dispersants such as phosphoric acid ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; Stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers; Photopolymerization initiation aids such as tertiary amines; Photosensitizers such as pyrarizones, anthracenes, coumarins, xanthone types, and thioxanthone types can be mentioned. (G) Arbitrary additives may be used individually, or may be used in combination of two or more types.

[9. (I) Solvent]

The resin composition according to the first embodiment of the present invention may further contain a solvent (I) as an optional volatile component in combination with non-volatile components such as the components (A) to (G). (I) As a solvent, an organic solvent is usually used. 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 solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); 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. (I) One type of solvent may be used individually, or two or more types may be used in combination.

(I) The amount of solvent is not particularly limited, but when all components in the resin composition are 100% by mass, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, It may be 15 mass% or less, 10 mass% or less, etc., and may be 0 mass%.

[10. Specific gravity of the cured product of the resin composition]

The cured product obtained by curing the resin composition according to the first embodiment of the present invention has a specific gravity within a specific range. The specific range of the specific gravity of the cured product is usually 1.6 g/cm 3 or less, preferably 1.58 g/cm 3 or less, and more preferably 1.56 g/cm 3 or less. The lower limit of the specific gravity of the cured product is preferably 1.0 g/cm 3 or more, more preferably 1.02 g/cm 3 or more, and particularly preferably 1.05 g/cm 3 or more. The resin composition from which a cured product having a specific gravity in the above range is obtained can improve the impact peeling resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition.

When the resin composition is a thermosetting resin composition that can be cured by heating, the cured product whose specific gravity is evaluated can be obtained by curing the resin composition at 180°C for 90 minutes. In addition, when the resin composition is a photocurable resin composition that can be cured by exposure to light, the cured product whose specific gravity is evaluated is irradiated with actinic light at 1 J/cm2 to the resin composition, and then heated at 180°C for 90 minutes. obtained. As a specific method for obtaining the cured product, the method described in the Examples described later can be adopted. Additionally, the method described in the Examples described later can be adopted as a method for measuring the specific gravity of the cured product.

The specific gravity of the cured product of the resin composition can be adjusted depending on the composition of the resin composition. For example, according to the method (B) of increasing the amount of the inorganic filler, the specific gravity can be increased. Additionally, the specific gravity of the cured product can be reduced by, for example, using (B-1) a hollow inorganic filler having a large porosity or increasing the amount of the (B-1) hollow inorganic filler. Additionally, (A) the specific gravity of the cured product may be adjusted by adjusting the type and amount of the curable resin.

[11. Thermal expansion coefficient of the cured product of the resin composition]

The cured product obtained by curing the resin composition according to the first embodiment of the present invention has a coefficient of thermal expansion within a specific range. The specific range of the thermal expansion coefficient of the cured product is usually 40 ppm/°C or less, preferably 30 ppm/°C or less, and more preferably 25 ppm/°C or less. The lower limit of the thermal expansion coefficient of the cured product is preferably 5 ppm/°C or higher, more preferably 10 ppm/°C or higher, and particularly preferably 15 ppm/°C or higher. The resin composition from which a cured product having a coefficient of thermal expansion in the above range is obtained can improve the impact peeling resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition.

When the resin composition is a thermosetting resin composition that can be cured by heating, the cured product for which the thermal expansion coefficient is evaluated can be obtained by curing the resin composition at 180°C for 90 minutes. In addition, when the resin composition is a photocurable resin composition that can be cured by exposure to light, the cured product for which the thermal expansion coefficient is evaluated is obtained by irradiating the resin composition with actinic light at 1 J/cm2 and then heating it at 180°C for 90 minutes. You can. As a specific method for obtaining the cured product, the method described in the Examples described later can be adopted. In addition, the thermal expansion coefficient of the cured product is the average coefficient of linear thermal expansion in the temperature range from 25℃ to 150℃, and can be measured by thermomechanical analysis using the tensile weighting method under the measurement conditions of a load of 1g and a temperature increase rate of 5℃/min. there is. As a specific method of measuring the thermal expansion coefficient of the cured product, the method described in the Examples described later can be adopted.

The thermal expansion coefficient of the cured product of the resin composition can be adjusted depending on the composition of the resin composition. For example, according to the method (B) of increasing the amount of the inorganic filler, the thermal expansion coefficient can be reduced. Additionally, by increasing the resin component, the thermal expansion coefficient can be increased. Additionally, the thermal expansion coefficient may be changed by adjusting the types of inorganic fillers and resin components.

[12. Resin composition according to the second embodiment]

The resin composition according to the second embodiment of the present invention is (i) the resin composition contains (C) organic particles; (ii) (B) the inorganic filler comprises (B-1) a hollow inorganic filler; (iii) (B-1) the hollow inorganic filler has a porosity in a specific range; (iv) the amount of (B) inorganic filler relative to 100% by volume of non-volatile components of the resin composition is within a specific range; (v) the amount of the (B-1) hollow inorganic filler relative to 100% by volume of the non-volatile component of the resin composition is within a specific range; (vi) It is the same as the resin composition according to the first embodiment of the present invention, except that the specific gravity and coefficient of thermal expansion of the cured product obtained by curing the resin composition do not need to be within a specific range.

The range of the porosity of the (B-1) hollow inorganic filler of the resin composition according to the second embodiment of the present invention is usually 10 volume% or more, and the (B-1) hollow inorganic filler of the resin composition according to the first embodiment of the present invention has a range of porosity of 10% by volume or more. It is desirable to be in the same range as the porosity of.

In addition, the amount of the inorganic filler (B) in the resin composition according to the second embodiment of the present invention is usually 40 volume% or more with respect to 100 volume% of non-volatile components of the resin composition, (B) It is preferable that it is in the same range as the amount of the inorganic filler.

In addition, the amount of hollow inorganic filler (B-1) in the resin composition according to the second embodiment of the present invention is usually 10 volume% or more with respect to 100 volume% of non-volatile components of the resin composition, and It is preferable that it is in the same range as the amount of the hollow inorganic filler (B-1) in the resin composition.

In addition, the specific gravity and thermal expansion coefficient of the cured product obtained by curing the resin composition according to the second embodiment of the present invention may be in a different range from the specific gravity and thermal expansion coefficient of the cured product of the resin composition according to the first embodiment, but may be in the same range. It is desirable to have The specific gravity and thermal expansion coefficient of the cured resin composition according to the second embodiment can be measured and adjusted by the same method as the specific gravity and thermal expansion coefficient of the cured resin composition according to the first embodiment.

According to the resin composition according to the second embodiment of the present invention, the same advantages as the resin composition according to the first embodiment can be obtained.

[13. [Method for producing resin composition]

In the following description, unless otherwise specified, the term “resin composition” refers to both the resin composition according to the first embodiment and the resin composition according to the second embodiment. The resin composition can be produced, for example, by mixing components that may be included in the resin composition. Some or all of the above 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, stirring or shaking may be performed in the process of mixing each component.

[14. Physical properties of resin composition]

The cured product of the resin composition according to the first embodiment and the resin composition according to the second embodiment has excellent impact resistance. Therefore, an insulating layer excellent in impact resistance can be formed with a cured product of these resin compositions. In detail, the insulating layer formed from the cured product of the resin composition may have excellent impact peel resistance and impact crack resistance.

Specifically, when an insulating layer is formed on the conductor layer with a cured resin composition, the insulating layer can suppress peeling from the conductor layer due to impact. At this time, copper foil can be used as the conductor layer, for example. Additionally, the insulating layer can be formed by providing a resin composition layer containing a resin composition on a conductor layer and curing the resin composition. When the resin composition is thermosetting, curing of the resin composition can be performed by heating at 180°C for 90 minutes. In addition, when the resin composition is photocurable, curing of the resin composition can be performed by irradiating ultraviolet rays at 1 J/cm2 and then heating at 180°C for 90 minutes.

In one example, a sample including a conductor layer and an insulating layer formed of a cured resin composition on the conductor layer exhibits peeling of the insulating layer from the conductor layer when an impact is applied in a drop test described later. It can be suppressed. Specifically, when a drop test is performed on five samples, the number of samples in which peeling of the insulating layer from the conductor layer occurs is preferably 1 or less, and more preferably 0. .

Additionally, when an insulating layer is formed from a cured resin composition, the insulating layer can suppress the formation of cracks and partial cracks due to impact. At this time, the insulating layer can be formed by preparing a resin composition layer containing a resin composition and curing the resin composition. When the resin composition is thermosetting, curing of the resin composition can be performed by heating at 180°C for 90 minutes. In addition, when the resin composition is photocurable, curing of the resin composition can be performed by irradiating ultraviolet rays at 1 J/cm2 and then heating at 180°C for 90 minutes.

In one example, a sample provided with an insulating layer formed from a cured product of a resin composition can suppress cracking and partial breakage of the insulating layer when an impact is applied in a drop test described later. Specifically, when a drop test is performed on five samples, the number of samples in which cracks or partial breaks in the insulating layer occur can preferably be 1 or less, and more preferably 0.

The drop test can be performed by the following method. Fig. 1 is a front view schematically showing a drop test performed to evaluate impact resistance. As shown in FIG. 1, the sample 11 is fixed to the bottom of a cylindrical weight 12 weighing 200 g using an adhesive tape (not shown) to prepare a test body 13. The test body 13 is freely dropped three times with the sample 11 downward from a height H of 1.5 m on a steel disk 14 made of SS400 with a thickness of 20 mm and a diameter of 200 mm. When the dropped test specimen 13 collides with the steel disc 14, an impact is applied to the sample 11 from the weight 12. Therefore, the drop test can be used to evaluate the impact resistance of the insulating layer included in the sample 11.

For the specific operation of the impact resistance evaluation method, the method described in the Examples described later can be adopted.

The cured product of the resin composition according to the first embodiment and the resin composition according to the second embodiment may have a low relative dielectric constant. Therefore, an insulating layer with a low relative dielectric constant can be formed with a cured product of these resin compositions. In one example, the relative dielectric constant of the cured product is preferably 3.1 or less, more preferably 3.0 or less, and particularly preferably 2.9 or less. The lower limit is not particularly limited and may be, for example, 1.5 or more, 2.0 or more, etc.

The cured product of the resin composition according to the first embodiment and the resin composition according to the second embodiment may have a low dielectric loss tangent. Therefore, an insulating layer with a low dielectric loss tangent can be formed with a cured product of these resin compositions. In one example, the dielectric loss tangent of the cured product is preferably 0.020 or less, more preferably 0.018 or less, and particularly preferably 0.016 or less. The lower limit is not particularly limited and may be, for example, 0.001 or more, 0.002 or more, etc.

When the resin composition is thermosetting, the relative dielectric constant and dielectric loss tangent can be measured, for example, using a cured product obtained by thermally curing the resin composition at 180°C for 90 minutes. In addition, when the resin composition is photocurable, the relative dielectric constant and dielectric loss tangent can be measured using a cured product obtained by irradiating the resin composition with ultraviolet rays at 1 J/cm2 and then heating it at 180°C for 90 minutes. The relative dielectric constant and dielectric loss tangent of the cured product can be measured using the cavity resonance perturbation method under the conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. The specific operation of the measurement method for relative dielectric constant and dielectric loss tangent can be performed using the method described in the examples described later.

The cured product of the resin composition according to the first embodiment and the resin composition according to the second embodiment may have a large elongation at break. Therefore, an insulating layer with a large fracture elongation can be formed with a cured product of these resin compositions. In one example, the elongation at break of the cured product is preferably 0.5% or more, more preferably 1.0% or more, and particularly preferably 1.2% or more. The upper limit is not particularly limited and may be, for example, 10% or less, 5.0% or less, etc.

When the resin composition is thermosetting, the elongation at break can be measured, for example, using a cured product obtained by thermosetting the resin composition at 180°C for 90 minutes. In addition, when the resin composition is photocurable, the breaking elongation can be measured using a cured product obtained by irradiating the resin composition with ultraviolet rays at 1 J/cm2 and then heating it at 180°C for 90 minutes. Elongation at break can be measured as elongation at the time of fracture by performing a tensile test at a temperature of 25°C (room temperature) and a tensile speed of 50 mm/min. The specific operation of the method for measuring the elongation at break can employ the method explained in the Examples described later.

[15. [Use of resin composition]

The above resin composition can be used as a resin composition for insulation purposes, and can be particularly suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer). For example, the above resin composition can be used as a resin composition for forming an insulating layer of a printed wiring board, and can be suitably used as a resin composition for forming an interlayer insulating layer (resin composition for interlayer insulation).

Additionally, the above resin composition may be used as a resin composition for forming a redistribution forming layer (resin composition for forming a redistribution forming layer). The redistribution forming layer refers to an insulating layer for forming a rewiring layer. In addition, the rewiring layer refers to a conductor layer formed on the rewiring forming layer as an insulating layer. For example, when a semiconductor chip package is manufactured through the following processes (1) to (6), the resin composition may be used as a resin composition for forming a redistribution formation layer. Additionally, when a semiconductor chip package is manufactured through the following processes (1) to (6), a rewiring layer may be additionally formed on the sealing layer.

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

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

(3) Process of forming a sealing layer on the semiconductor chip,

(4) A process of peeling the base material and temporarily fixed film from the semiconductor chip,

(5) A process of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and temporarily fixed film are peeled, and

(6) A process of forming a redistribution layer as a conductor layer on the redistribution forming layer.

In addition, the resin composition is used for applications such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor sealants, hole filling resins, and component embedding resins. It can be used widely in

[16. Sheet-like laminated material]

The resin composition may be applied and used in a varnish state, but industrially, it is suitable to be used in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminated material, the resin sheets and prepregs shown below are preferable.

In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support. The resin composition layer is formed from the above resin composition. Therefore, the resin composition layer usually contains the resin composition, and preferably contains only the resin composition.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. 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, metal foils, and release papers made of plastic materials, 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 abbreviated as “PEN”) ), polyester such as polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (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 bonded to the resin composition layer.

As a 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 one or more types of release agents 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. On the other hand, 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.

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 (i.e., 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. By laminating a protective film, adhesion of dust and scratches to the surface of the resin composition layer can be suppressed.

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

Examples of the solvent include the same solvents as those described as components 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 methods 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.

In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition.

The sheet-like fiber substrate used in the prepreg can be, for example, a material commonly used as a prepreg substrate such as glass cloth, aramid nonwoven fabric, or liquid crystal polymer nonwoven fabric. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like substrate is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited and is usually 10 μm or more.

Prepreg can be manufactured by methods such as hot melt method and solvent method.

The thickness of the prepreg may be in the same range as the resin composition layer in the resin sheet.

The sheet-like laminated material can be suitably used to form an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more suitably used to form an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board). You can.

[17. Printed wiring board]

A printed wiring board according to an embodiment of the present invention includes an insulating layer containing a cured product obtained by curing the resin composition. The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the resin sheet.

(I) A process of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate.

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

The “inner layer substrate” used in step (I) is a member that becomes the substrate of the printed wiring board, for example, glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, and thermosetting polyphenylene. Ether substrates, etc. can be mentioned. Additionally, the substrate may have a conductor layer on one or both sides, and the conductor layer may be pattern-processed. An inner layer substrate on 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 printed wiring 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 printed wiring board is a circuit board with embedded components, an inner layer board with embedded components may be used.

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. Examples of members that heat and press the resin sheet to the inner layer substrate (hereinafter also referred to as “heat and press members”) include heated metal plates (SUS head plates, etc.) or metal rolls (SUS rolls, etc.). On the other hand, it is preferable not to press the heat-compression member directly on 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 pressurized 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-described lamination. Smoothing treatment can be performed using a commercially available laminator. Meanwhile, the lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator.

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. Curing of the resin composition layer can be performed by a method suitable for the resin composition, such as heat curing or photo curing. The specific curing conditions for the resin composition layer may be those normally employed when forming the insulating layer of a printed wiring board.

When a thermosetting resin composition is used, curing of the resin composition can proceed as thermal curing. Therefore, in this case, step (II) may include thermosetting the resin composition layer. Thermal curing conditions of the resin composition layer may also vary depending on the type of resin composition. For 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. Additionally, 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.

In addition, when the resin composition layer is thermally cured, the method for producing a printed wiring board preferably includes preheating the resin composition layer at a temperature lower than the curing temperature before the thermal curing. For example, prior to heat curing the resin composition layer, the resin composition layer is usually cured at a temperature of 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°C, usually for 5 minutes. Preheating may be performed above, preferably for 5 minutes to 150 minutes, more preferably for 15 minutes to 120 minutes, and even more preferably for 15 minutes to 100 minutes.

On the other hand, when a photocurable resin composition is used, curing of the resin composition can proceed through photocuring. Therefore, in this case, step (II) may include photocuring the resin composition layer. Photocuring conditions for the resin composition may vary depending on the type of the resin composition. For example, the resin composition layer in the irradiated area can be photocured by exposure treatment in which actinic light is irradiated to the resin composition layer. Actinic rays include, for example, ultraviolet rays, visible rays, electron beams, X-rays, etc., and ultraviolet rays are particularly preferable. The irradiation amount of ultraviolet rays is, for example, 10 mJ/cm2 to 1,000 mJ/cm2. When a resin sheet provided with a support is used, exposure may be performed through the support, or exposure may be performed after peeling off the support.

In the exposure treatment, actinic light may be irradiated to the resin composition layer through a mask on which a pattern is formed. Exposure methods using a mask include a contact exposure method in which exposure is performed by bringing the mask into contact with the workpiece, and a non-contact exposure method in which exposure is performed using parallel light without bringing the mask into contact with the work, and either may be used.

Process (II) may include performing development treatment after exposure treatment. According to the development treatment, the portion that has not been photocured (unexposed portion) can be removed, and a pattern can be formed in the cured layer. Development is usually performed by wet development. In wet development, a developer that is safe, stable, and has good operability, such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, is used. Among these, a development process using an aqueous alkaline solution is preferable. As a developing method, for example, spraying, shaking immersion, brushing, scraping, etc. can be employed.

In addition, when the resin composition layer is photocured, post-bake treatment may be performed as needed after photocuring and development. Post-bake treatment includes, for example, ultraviolet irradiation treatment using a high-pressure mercury lamp, heat treatment using a clean oven, etc. Ultraviolet irradiation treatment can be performed, for example, at an irradiation amount of about 0.05 J/cm2 to 10 J/cm2. In addition, heat treatment can be performed, for example, preferably at 150°C to 250°C for 20 minutes to 180 minutes, more preferably at 160°C to 230°C for 30 minutes to 120 minutes.

When manufacturing a printed wiring board, (III) a step of perforating the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be additionally performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. On the other hand, when the support is removed after step (II), the support is removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). It can be done in between. Additionally, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

In another embodiment, a printed wiring board can be manufactured using the prepreg. The manufacturing method may be basically the same as when using a resin sheet.

Process (III) is a process of drilling into the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the hole may be appropriately determined depending on the design of the printed wiring board.

Process (IV) is a process of roughening the insulating layer. Usually, the smear is also removed in the above step (IV). The procedures and conditions of the roughening process are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and 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, sodium hydroxide solution and 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 insulating layer 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 insulating layer to an appropriate level, it is preferable to immerse the insulating layer 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 insulating layer 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 permanganic acid 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 an 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.

Step (V) 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 includes 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 alloy) ) can include a layer formed of. 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, copper-nickel alloy, An alloy layer of a copper-titanium alloy is preferable, and a single 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 single metal layer of copper is even more preferable. desirable.

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 depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

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 the 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. Hereinafter, an example of forming a conductor layer by a semi-additive method will be shown.

First, a plating seed 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 a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer with a desired wiring pattern.

In another embodiment, the conductor layer may be formed using metal foil. When forming a conductor layer using metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The conditions for lamination may be the same as those described for step (I). Next, process (II) is performed to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventionally known techniques such as the subtractive method and the modified semiadditive method.

Metal foil can be manufactured by known methods such as electrolysis and rolling, for example. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Kinzoku Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Kogyo Co., Ltd.

[18. semiconductor device]

A semiconductor device according to an embodiment of the present invention includes the printed wiring board. Semiconductor devices can be manufactured using printed wiring boards.

Semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.). there is.

[Example]

Hereinafter, the present invention will be described in detail with reference to 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, in cases where there was no specific temperature designation, the temperature and pressure conditions were room temperature (25°C) and atmospheric pressure (1 atm).

[Synthesis Example 1: Synthesis of resin (a1) containing an ethylenically unsaturated bond and a carboxyl group]

A naphthol aralkyl type epoxy resin (“ESN-475V” manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., epoxy equivalent weight of approximately 325 g/eq.) shown in the following formula (1) was prepared.

[Formula 1]

In Formula 1, Z is a glycidyl group (Gl) or a hydrocarbon group (R6) having 1 to 8 carbon atoms, and the ratio of R6/Gl is 0.05 to 2.0. Additionally, n is an average value and represents a number from 1 to 6.

325 parts of the naphthol aralkyl type epoxy resin (“ESN-475V” manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., epoxy equivalent weight of about 325 g/eq.) were placed in a flask equipped with a gas introduction pipe, a stirring device, a cooling pipe, and a thermometer, 340 parts of carbitol acetate was added and dissolved by heating, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. This mixture was heated to 95°C to 105°C, 72 parts of acrylic acid was gradually added dropwise, and reaction was carried out for 16 hours. This reaction product was cooled to 80°C to 90°C, 80 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. In this way, a resin solution (non-volatile matter 70%, hereinafter sometimes abbreviated as “resin (a1) solution”) with a solid acid value of 60 mg KOH/g was obtained. It was confirmed that this resin (a1) solution contains at least resin (a1) containing the structure shown in the following formula (2).

[Formula 2]

[Example 1]

Bisphenol A type epoxy resin (“828EL” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight approximately 180 g/eq.) to 10 parts, biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Corporation, epoxy equivalent weight approximately 269 g/eq.) to 25 parts. 50 parts of methyl ethyl ketone were added and dissolved by heating while stirring. This was cooled to room temperature to prepare an epoxy resin dissolution composition. To this epoxy resin dissolution composition, 10 parts of a phenol-based curing agent containing a triazine skeleton (“LA-3018-50P” manufactured by DIC, an active group equivalent of about 151 g/eq., a 2-methoxypropanol solution with a non-volatile component rate of 50%) , 10 parts of naphthol-type curing agent (“SN-485” manufactured by Nittetsu Chemical & Materials, hydroxyl equivalent weight approximately 205 g/eq.), phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK with 30% by mass of non-volatile matter and cyclo 15 parts of hexanone (1:1 solution), spherical silica as a solid inorganic filler surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Adomatex, average particle) 50 parts of diameter 0.5㎛, BET specific surface area 5.8㎡/g, 1 hollow silica particle (average particle diameter 1.6㎛, BET specific surface area 12) surface-treated with silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) ㎡/g, porosity 50% by volume) 25 parts, rubber particles (“PARALOID EXL2655” manufactured by Dow Chemical Nippon Co., Ltd.; a core portion formed of a polymer of butadiene (specific gravity 0.91), styrene (specific gravity 1.06) and methyl methacrylate (specific gravity 1.18) 3 parts of core-shell particles having a shell portion formed of a copolymer; average particle diameter of 0.2 ㎛) and 4 parts of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) are mixed. and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish. The average particle diameter of the inorganic filler contained in this resin varnish was 1.1 ㎛, and the BET specific surface area was 9.0 m 2 /g.

Next, a resin varnish was uniformly applied on the release surface of the release-treated polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm) as a support so that the thickness of the resin composition layer was 40 μm, and 80 μm was applied. It was dried at ℃ to 120℃ (average 100℃) for 5 minutes to produce a resin sheet.

[Example 2]

Spherical silica (“SO-C2” manufactured by Adomatex) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was not used.

Additionally, the amount of hollow silica particles 1 (average particle diameter 1.6 μm, BET specific surface area 12 m 2 /g, porosity 50 vol%) was changed from 25 parts to 50 parts.

Additionally, 3 parts of biphenyl aralkyl novolak type maleimide (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., a MEK/toluene mixed solution with a non-volatile component ratio of 70%) was added to the resin varnish.

Resin varnish and resin sheets were manufactured in the same manner as in Example 1 except for the above. The average particle diameter of the inorganic filler contained in the resin varnish was 1.6 μm, and the BET specific surface area was 12 m 2 /g.

[Example 3]

Spherical silica (“SO-C2” manufactured by Adomatex) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was not used.

In addition, instead of 25 parts of hollow silica particles (average particle diameter 1.6 ㎛, BET specific surface area 12 m2/g, porosity 50 volume%), surface treatment was performed with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) 80 parts of hollow silica particles 2 (average particle diameter 2.0 ㎛, BET specific surface area 3.8 m2/g, porosity 20 volume%) were used.

Additionally, instead of three parts of rubber particles (“PARALOID EXL2655” manufactured by Dow Chemical Nippon Co., Ltd.), hollow acrylic particles (“XX-5598Z” manufactured by Sekisui Kaseihin Kogyo Co., Ltd.; styrene (specific gravity 1.06) and methyl methacrylate (specific gravity 1.18 ) 3 parts of hollow particles having a shell formed of a copolymer and a hollow part formed within the shell; average particle diameter 0.5 ㎛, porosity 35% by volume) were used.

Additionally, 5 parts of vinylbenzyl-modified polyphenylene ether (“OPE-2St 2200” manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a non-volatile content of 65%) was added to the resin varnish.

Resin varnish and resin sheets were manufactured in the same manner as in Example 1 except for the above. The average particle diameter of the inorganic filler contained in the resin varnish was 2.0 μm, and the BET specific surface area was 3.8 m 2 /g.

[Example 4]

Instead of 25 parts of biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd.), 25 parts of naphthylene ether-type epoxy resin (epoxy equivalent weight of about 250 g/eq., “HP6000” manufactured by DIC Co., Ltd.) was used.

In addition, instead of 25 parts of hollow silica particles (average particle diameter 1.6 ㎛, BET specific surface area 12 m2/g, porosity 50 volume%), surface treatment was performed with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) 22 parts of hollow alumina borosilicate glass particles (“MG-005” manufactured by Taiheyo Cement Co., Ltd., average particle diameter 1.6 μm, BET specific surface area 6.5 m2/g, porosity 80% by volume) were used.

Additionally, the amount of rubber particles (“PARALOID EXL2655” manufactured by Dow Chemical Nippon Co., Ltd.) was changed from 3 parts to 5 parts.

Resin varnish and resin sheets were manufactured in the same manner as in Example 1 except for the above. The average particle diameter of the inorganic filler contained in the resin varnish was 1.1 μm, and the BET specific surface area was 6.2 m 2 /g.

[Example 5]

5 parts of rubber particles (“PARALOID EXL2655” manufactured by Dow Chemical Nippon Co., Ltd.), a core portion formed of a polymer of rubber particles (“Starpilod AC3816N” manufactured by Aika Kogyo Co., Ltd.; butyl acrylate (specific gravity 1.09), and methyl methacrylate ( Core-shell particles having a shell portion formed of a polymer with a specific gravity of 1.18; average particle diameter of 0.5 μm) were changed to 5 parts.

Resin varnish and resin sheets were manufactured in the same manner as in Example 4 except for the above. The average particle diameter of the inorganic filler contained in the resin varnish was 1.1 μm, and the BET specific surface area was 6.2 m 2 /g.

[Example 6]

50 parts of methyl ethyl ketone were added to 10 parts of naphthalene type epoxy resin (“HP-4032-SS” manufactured by DIC, epoxy equivalent weight approximately 144 g/eq.), and heated with stirring to homogenize. This was cooled to room temperature to prepare an epoxy resin dissolution composition. To the above epoxy resin dissolution composition, 30 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, active ester group equivalent of about 223 g/eq., toluene solution with a non-volatile component ratio of 65%), a phenolic compound containing a triazine skeleton 2 parts of curing agent (“LA-3018-50P” manufactured by DIC, active group equivalent of about 151 g/eq., 2-methoxypropanol solution with 50% non-volatile content), 2 parts carbodiimide-based curing agent (manufactured by Nisshinbo Chemicals) V-03”, 5 parts of toluene solution with an active group equivalent of about 216 g/eq. and a non-volatile component ratio of 50%), 1 part of hollow silica particles surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter 1.6㎛, BET specific surface area 12㎡/g, porosity 50% by volume) 45 parts, rubber particles (“PARALOID EXL2655” manufactured by Dow Chemical Nippon Co., Ltd.) 5 parts, imidazole-based curing accelerator (manufactured by Shikoku Kaseiko Co., Ltd.) 0.1 part of "1B2PZ", 1-benzyl-2-phenylimidazole) was mixed and dispersed uniformly with a high-speed rotating mixer to prepare a resin varnish. The average particle diameter of the inorganic filler contained in the resin varnish was 1.6 ㎛, The BET specific surface area was 12 m2/g.

Next, resin varnish was uniformly applied on the release surface of the release-treated polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm) as a support so that the thickness of the resin composition layer was 40 μm, and 80 μm was applied. It was dried at ℃ to 120℃ (average 100℃) for 5 minutes to produce a resin sheet.

[Example 7]

To 10 parts of naphthalene type epoxy resin (“HP-4032-SS” manufactured by DIC, epoxy equivalent approximately 144 g/eq.), bisphenol A type epoxy resin (“828EL” manufactured by Mitsubishi Chemical Company, epoxy equivalent approximately 180 g/eq.) 10 parts of naphthylene ether type epoxy resin (“HP6000” manufactured by DIC, epoxy equivalent weight: approximately 250 g/eq.), 15 parts, and 50 parts of methyl ethyl ketone were added and heated and dissolved while stirring. This was cooled to room temperature, and an epoxy resin dissolution composition was prepared. To this epoxy resin dissolution composition, 15 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, active ester group equivalent of about 223 g/eq., toluene solution with a non-volatile component ratio of 65%), bisphenol A dicyanate 20 parts of prepolymer (“BA230S75” manufactured by Lonza Japan, MEK solution with a cyanate equivalent of about 232 g/eq. and 75% by mass of non-volatile matter), surface treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) 60 parts of spherical silica as a solid inorganic filler (“SO-C2” manufactured by Adomatex, BET specific surface area of 5.8 m2/g, average particle diameter of 0.5 μm), silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd. ") 30 parts of hollow silica particles surface treated with 1 (average particle diameter 1.6㎛, BET specific surface area 12㎡/g, porosity 50% by volume), 5 parts rubber particles ("PARALOID EXL2655" manufactured by Dow Chemical Nippon Co., Ltd.), amine 4 parts of a system curing accelerator (4-dimethylaminopyridine (DMAP), a MEK solution with a solid content of 5% by mass), 1 part of a 1% by mass MEK solution of cobalt (III) acetylacetonate (manufactured by Tokyo Kasei), and phenoxy resin ( 8 parts (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., a 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass) were mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish. The average particle diameter of the filler was 1.1㎛, and the BET specific surface area was 9.0㎡/g.

Next, a resin varnish was uniformly applied on the release surface of the release-treated polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm) as a support so that the thickness of the resin composition layer was 40 μm, and 80 μm was applied. It was dried at ℃ to 120℃ (average 100℃) for 5 minutes to produce a resin sheet.

[Example 8]

5 parts of naphthalene-type epoxy resin (“HP-4032-SS” manufactured by DIC, epoxy equivalent of approximately 144), 10 parts of biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku, epoxy equivalent of approximately 269 g/eq.), 7 parts of biphenyl aralkyl novolac type maleimide (“MIR-3000-70MT” manufactured by Nippon Kayaku, MEK/toluene mixed solution with 70% non-volatile content), 10 parts of methyl ethyl ketone, and diethylene glycol monoethyl ether 10 parts of acetate were added and dissolved by heating while stirring. This was cooled to room temperature to prepare an epoxy resin dissolution composition. To this epoxy resin dissolution composition, spherical silica as a solid inorganic filler (“SO-C2” manufactured by Adomatex Co., Ltd., BET specific surface area of 5.8 m2) was surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.). /g, average particle diameter 0.5㎛) 56 parts, 28 parts of hollow silica particles surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.), an imidazole-based curing accelerator (Shikoku Chemical Co., Ltd.) 0.02 part of "1B2PZ", 1-benzyl-2-phenylimidazole) and 5 parts of rubber particles ("PARALOID EXL2655" manufactured by Dow Chemical Nippon Co., Ltd.) were mixed and uniformly dispersed with a high-speed rotating mixer. Subsequently, 50 parts of the resin (a1) solution prepared in Synthesis Example 1 and 5 parts of a photopolymerization initiator (“IrgacureTPO” manufactured by BASF, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) were added, and the mixture was incubated at room temperature. was stirred until uniformity was obtained, and a resin varnish was prepared. The average particle diameter of the inorganic filler contained in the resin varnish was 1.1 μm, and the BET specific surface area was 9.0 m 2 /g.

Next, a resin varnish was uniformly applied on the release surface of the release-treated polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm) as a support so that the thickness of the resin composition layer was 40 μm, and 80 μm was applied. It was dried at ℃ to 120℃ (average 100℃) for 5 minutes to produce a resin sheet.

[Comparative Example 1]

The amount of spherical silica (“SO-C2” manufactured by Adomatex, average particle diameter 0.5 μm) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 50 parts to 100 parts. did.

In addition, hollow silica particles 1 (average particle diameter 1.6 ㎛, BET specific surface area 12 m2/g, porosity 50 volume%) were not used.

Additionally, the amount of rubber particles (“PARALOID EXL2655” manufactured by Dow Chemical Nippon Co., Ltd.) was changed from 3 parts to 5 parts.

Resin varnish and resin sheets were manufactured in the same manner as in Example 1 except for the above.

[Comparative Example 2]

Spherical silica (“SO-C2”, manufactured by Adomatex, average particle diameter 0.5 μm) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) and rubber particles (“KBM-573” manufactured by Dow Chemical Nippon Corporation) PARALOID EXL2655”) was not used.

In addition, instead of 25 parts of hollow silica particles (average particle diameter 1.6 ㎛, BET specific surface area 12 m2/g, porosity 50 volume%), surface treatment was performed with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) 80 parts of hollow silica particles 2 (average particle diameter 2.0 ㎛, BET specific surface area 3.8 m2/g, porosity 20 volume%) were used.

Resin varnish and resin sheet were manufactured in the same manner as in Example 1 except for the above.

[Measurement of dielectric loss tangent]

(1-1) Production of cured product for evaluation (Examples 1 to 7, Comparative Examples 1 and 2):

Prepare a PET film (“501010” manufactured by Lintech, 50 μm thick, 240 mm square) having a side on which release agent treatment was applied (release agent treated side) and a side on which release agent treatment was not applied (release agent untreated side). did. A glass cloth-based epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Panasonic, thickness 0.7 mm, 255 mm square) was placed on the untreated side of the PET film, and the four sides were fixed with polyimide adhesive tape (width 10 mm). The PET film fixed to the glass cloth-based epoxy resin double-sided copper-clad laminate in this way may hereinafter be referred to as “fixed PET film.”

The resin varnishes produced in Examples 1 to 7 and Comparative Examples 1 and 2 were applied on the release-treated surface of the fixed PET film with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and the mixture was coated at 80° C. to 120° C. It was dried at ℃ (average 100℃) for 10 minutes to form a resin composition layer. Next, the resin composition layer was heat-cured by placing it in an oven at 180°C and heating it for 90 minutes. After heat curing, the polyimide adhesive tape was peeled off, the glass cloth base epoxy resin double-sided copper clad laminate was peeled off, and the PET film (“501010” manufactured by Lintec) was also peeled to obtain a sheet-like cured product. The obtained cured product is sometimes referred to as a “cured product for evaluation.”

(1-2) Production of cured product for evaluation (Example 8):

The resin varnish produced in Example 8 was applied on the release-treated surface of the fixed PET film with a die coater so that the thickness of the resin composition layer after drying was 40 ㎛, and applied at 80 to 120 ° C. (average 100 ° C.) for 10 days. It was dried for a minute to form a resin composition layer. Next, after irradiation with ultraviolet rays at 1 J/cm2, it was placed in an oven at 180°C and heated for 90 minutes to cure the resin composition layer. After curing, the polyimide adhesive tape was peeled off, the glass cloth-based epoxy resin double-sided copper-clad laminate was peeled off, and the PET film (“501010” manufactured by Lintech Co., Ltd.) was also peeled to obtain a sheet-like cured product. The obtained cured product is referred to as “cured product for evaluation.”

(2) Measurement of relative permittivity and dielectric loss tangent:

The cured product for evaluation was cut to 80 mm in length and 2 mm in width to obtain an evaluation sample. For this evaluation sample, the relative dielectric constant and dielectric loss tangent were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by a cavity resonance perturbation method using an HP8362B device manufactured by Agilent Technologies. Measurements were made on two test pieces, and the average value was calculated.

[Evaluation of linear thermal expansion coefficient of hardened material]

The cured product for evaluation was cut into pieces about 15 mm in length and 5 mm in width to obtain test pieces. Thermomechanical analysis of the test piece was performed using a thermomechanical analysis device (“Thermo Plus TMA8310” manufactured by Rigaku Corporation) by the tensile weighting method. Specifically, after the test piece was mounted on the above device, it was measured twice in succession under the measurement conditions of a load of 1 g and a temperature increase rate of 5°C/min. In the second measurement, the glass transition temperature and the average coefficient of linear thermal expansion (coefficient of thermal expansion) in the temperature range from 25°C to 150°C were calculated.

[Measurement of specific gravity of hardened product]

The cured product for evaluation was cut into pieces about 3 cm in length and 3 cm in width to obtain test pieces. The specific gravity of the test piece was measured using an analytical balance "XP105" manufactured by Mettler Toledo (using a specific gravity measurement kit). Measurements were made on five test pieces, and the average value was calculated.

[Measurement of fracture elongation of hardened material]

For the cured product for evaluation, a tensile test was performed using a Tensiron universal testing machine (manufactured by A & D) in accordance with Japanese Industrial Standards (JIS K7161) at a temperature of 25°C (room temperature) and a tensile speed of 50 mm/min. The elongation rate (elongation at break) at the time of fracture was measured.

[Evaluation of impact peeling resistance and impact crack resistance]

(1) Preparation of inner layer substrate:

Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 ㎛, substrate thickness 0.8 mm, “R1515A” manufactured by Panasonic) were etched 1 ㎛ with a microetchant (“CZ8101” manufactured by Mack) to remove the copper surface. Roughening treatment was performed to obtain an inner layer substrate.

(2) Laminate of resin sheets:

Using a batch-type vacuum pressurized laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials), the resin sheets obtained in the examples and comparative examples were spread on both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. It was laminated. The lamination was performed by reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then pressing at 100°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 to obtain an intermediate substrate having the layer structure of support/resin composition layer/inner layer substrate/resin composition layer/support.

(3-1) Curing of the resin composition layer (Examples 1 to 7, Comparative Examples 1 and 2):

The resin composition layer was cured under heat curing conditions of 180°C for 90 minutes to form an insulating layer. Thereafter, the support was peeled off to obtain a substrate for evaluation having a layer structure of insulating layer/inner layer substrate/insulating layer.

(3-2) Curing of the resin composition layer (Example 8):

The resin composition layer was irradiated with 1 J/cm2 of ultraviolet rays, and then heated at 180°C for 90 minutes to cure the resin composition layer, thereby forming an insulating layer. Thereafter, the support was peeled off to obtain a substrate for evaluation having a layer structure of insulating layer/inner layer substrate/insulating layer.

(4) Drop test:

The substrate for evaluation was cut into 10 mm x 10 mm, and a plurality of substrate pieces were obtained. As shown in FIG. 1, a substrate piece as a sample 11 was fixed to the bottom of a cylindrical weight 12 weighing 200 g using an adhesive tape (not shown), and five test specimens 13 were formed. Ready. Each of the test specimens 13 was freely dropped three times with the substrate piece as the sample 11 facing down from a height H of 1.5 m onto a steel plate 14 made of SS400 with a thickness of 20 mm and a diameter of 200 mm.

(5) Evaluation of impact peel resistance:

The substrate piece after the drop test was observed, and the impact peeling resistance of the substrate piece was determined based on the following criteria. Excellent impact peeling resistance indicates that peeling of the insulating layer is unlikely to occur even due to an impact applied by dropping. Therefore, excellent impact peeling resistance indicates that the insulating layer has high resistance to peeling due to impact.

“Excellent”: No peeling is observed on all five substrate pieces after the drop test.

“Possible”: Of the five substrate pieces after the drop test, only one sample shows peeling.

“Impossible”: Among the five substrate pieces after the drop test, peeling is visible in two or more samples.

(6) Evaluation of impact crack resistance:

The substrate piece after the drop test was observed, and the impact crack resistance of the substrate piece was determined based on the following criteria. Excellent impact crack resistance indicates that cracks are unlikely to occur in the insulating layer even from an impact applied by dropping. Therefore, excellent impact crack resistance indicates that the insulating layer has high resistance to the occurrence of cracks due to impact.

“Excellent”: No cracks or cracks are visible on all five substrate pieces after the drop test.

“Possible”: Among the five substrate pieces after the drop test, only one sample showed cracks and some cracks.

“Impossible”: Among the five substrate pieces after the drop test, cracks or partial cracks are visible in two or more samples.

[result]

The composition and evaluation results of the resin compositions in Examples and Comparative Examples are shown in the table below. In the “Impact Peel Resistance” column of Table 3, the numerical value shown together with the evaluation result represents the number of pieces in which peeling was observed among the five substrate pieces. In addition, in the “Impact Crack Resistance” column of Table 3, the numerical value shown together with the evaluation result represents the number of pieces that showed cracks or partial cracks among the five substrate pieces.

In the table below, the meanings of the abbreviations are as follows.

a1: Resin (a1) prepared in Synthesis Example 1.

Hollow glass particles: Hollow alumina borosilicate glass particles.

11 samples
12 pendulum
13 test specimen
14 Steel disc

Claims (18)

A resin composition comprising (A) a curable resin and (B) an inorganic filler,
The specific gravity of the cured product obtained by curing the resin composition is 1.6 g/cm3 or less,
A resin composition wherein the cured product obtained by curing the resin composition has a thermal expansion coefficient of 40 ppm/°C or less. The resin composition according to claim 1, wherein (B) the inorganic filler has an average particle diameter of 0.01 μm or more and 5 μm or less. The resin composition according to claim 1, wherein the BET specific surface area of the (B) inorganic filler is 1 m 2 /g or more and 100 m 2 /g or less. The resin composition according to claim 1, wherein the inorganic filler (B) contains a hollow inorganic filler (B-1) having voids therein. The resin composition according to claim 4, wherein (B-1) the hollow inorganic filler has a porosity of 10% by volume or more. The resin composition according to claim 1, further comprising (C) organic particles. The resin composition according to claim 6, wherein the amount of (C) organic particles is 2% by mass or more based on 100% by mass of non-volatile components of the resin composition. The method of claim 6, wherein (C) the organic particles have a shell portion and an interior portion formed within the shell portion,
A resin composition in which the interior part contains a rubber component or is hollow. The resin composition according to claim 1, wherein (A) the curable resin is selected from the group consisting of thermosetting resin and photocurable resin. The resin composition according to claim 9, wherein the thermosetting resin contains at least one type selected from the group consisting of epoxy resin, phenol resin, activated ester resin, cyanate resin, and radical polymerizable resin. The resin composition according to claim 9, wherein the photocurable resin contains a radically polymerizable resin. A resin composition comprising (A) a curable resin, (B) an inorganic filler, and (C) an organic particle,
(B) the inorganic filler includes a hollow inorganic filler (B-1) having voids therein,
(B-1) The hollow inorganic filler has a porosity of 10% by volume or more,
With respect to 100 volume% of non-volatile components of the resin composition, (B) the amount of inorganic filler is 40 volume% or more,
A resin composition in which the amount of (B-1) hollow inorganic filler is 10 volume% or more based on 100 volume% of non-volatile components of the resin composition. The resin composition according to claim 1, which is used for forming an insulating layer. A cured product of the resin composition according to any one of claims 1 to 13. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 13. A resin sheet comprising a support and a resin composition layer formed on the support from the resin composition according to any one of claims 1 to 13. A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 13. A semiconductor device comprising the printed wiring board according to claim 17.

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