KR20230012943A - Resin sheet and method for manufacturing printed wiring board - Google Patents

Abstract

Provided are a resin sheet and a method for manufacturing a printed wiring board, wherein the resin sheet has dielectric properties that are maintained or improved and a resin composition layer forming a cured product with excellent conductor adhesion and mechanical properties. The resin sheet of the present invention comprises a support body and a resin composition layer arranged on the corresponding support body, wherein the resin composition layer includes (A) a benzo cyclobutene resin, (B) an inorganic filler, and (C) a radically polymerizable resin and has oxygen permeability (α) of 70 cc/㎡·day or less that is measured when cured at 220 ℃ for 90 minutes. The resin sheet has oxygen permeability (β) of 40 cc/㎡·day or less that is measured when cured at 220 ℃ for 90 minutes, wherein the oxygen permeability (α) and oxygen permeability (β) are measured values obtained at 23 ℃ under the atmosphere of 0% RH, based on JIS K7126-2:2006 (an equal pressure method).

Description

Manufacturing method of resin sheet and printed wiring board {RESIN SHEET AND METHOD FOR MANUFACTURING PRINTED WIRING BOARD}

The present invention relates to a method for manufacturing a resin sheet and a printed wiring board. Moreover, it is related with the printed wiring board and semiconductor device obtained using the resin composition layer of the said resin sheet.

As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately piled up is known. As an insulating material of a printed wiring board used for such an insulating layer, a resin composition disclosed in Patent Literature 1 is known, for example.

Patent Document 1: Japanese Unexamined Patent Publication No. 2005-220270

As a curable resin used for an insulating material, a resin having a benzocyclobutene group (hereinafter simply referred to as "benzocyclobutene resin") is known. Since the benzocyclobutene group is a reactive functional group with low polarity, cured products of benzocyclobutene resin generally have excellent dielectric properties.

However, as examined by the present inventors, a cured product of a resin composition layer containing a benzocyclobutene resin has poor adhesion to a conductor material (eg copper) (hereinafter also referred to as “conductor adhesion”) or mechanical properties. It turned out that there is

An object of the present invention is to provide a resin sheet comprising a resin composition layer that forms a cured product having excellent dielectric properties, excellent conductor adhesion and mechanical properties, and a method for manufacturing a printed wiring board.

As a result of intensive examination to solve the above problems, the inventors of the present invention, as a resin sheet having a support and a resin composition layer, the resin composition layer, (A) benzocyclobutene resin (B) inorganic filler and (C) radicals It was found that the above problems could be solved by including in combination with a polymerizable resin and adjusting the oxygen permeability of the composition layer or resin sheet after curing to be less than or equal to a specific value, thereby completing the present invention.

That is, the present invention includes the following contents.

[1] A resin sheet comprising a support and a resin composition layer provided on the support, wherein the resin composition layer comprises (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radically polymerizable resin; , When the resin composition layer is cured at 220° C. for 90 minutes, the measured oxygen transmission rate α is 70 cc/m day or less, and the resin sheet is cured at 220° C. for 90 minutes. The measured oxygen permeability β is 40 cc/m 2 ·day or less, wherein the oxygen permeability α and the oxygen permeability β are measured in accordance with JIS K7126-2:2006 (isobaric pressure method) at 23° C. in an atmosphere of 0% RH. A resin sheet, which is a measured value.

[2] The resin sheet according to [1], wherein the content of the component (B) is 30% by mass or more and 80% by mass or less, when the non-volatile component in the resin composition is 100% by mass.

[3] The resin sheet according to [1] or [2], wherein the content of component (A) is 3% by mass or more and 40% by mass or less, when the non-volatile component in the resin composition is 100% by mass.

[4] Among [1] to [3], wherein component (A) contains a compound having two or more benzocyclobutene groups in the molecule, and component (A) has a number average molecular weight (Mn) of 2000 or less. The resin sheet described in any one.

[5] The resin sheet according to any one of [1] to [4], wherein the component (C) is at least one selected from maleimide resins, (meth)acrylic resins, and styryl resins.

[6] The support described in any one of [1] to [5], wherein the support is selected from a single-layer resin film, a multi-layer resin film, a metal foil, a release paper, and a composite film containing a support substrate and a metal foil. resin sheet.

[7] The resin sheet according to any one of [1] to [6], wherein the component (A) has a siloxane backbone.

[8] The resin sheet according to any one of [1] to [7], wherein the component (A) contains a compound represented by the following formula (A-2).

(In Formula (A-2),

R ¹ represents a divalent aliphatic group having an unsaturated bond;

R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an arylalkyl group, or an aryl group;

R ^A1 represents an alkyl group, a cyano group or a halogen atom;

R ^A2 represents an alkyl group, a trialkylsilyl group, an alkoxy group or a halogen atom;

nA1 represents an integer from 0 to 2;

nA2 represents an integer from 0 to 3;

nA4 represents an integer of 1 to 10. R ¹ , R ² , R ^A1 and R ^A2 may each independently have a substituent. A plurality of R ¹ may be the same or different, a plurality of R ² may be the same or different, when a plurality of R ^A1 are present, they may be the same or different, and when a plurality of R ^A2 are present, they may be the same or different. good.)

[9] The resin sheet according to any one of [1] to [8], wherein the component (A) contains a compound represented by the following formula.

[10] The resin sheet according to any one of [1] to [9], wherein the cured product of the resin composition layer has a dielectric constant value of 3.0 or less.

[11] The resin sheet according to any one of [1] to [10], wherein the cured product of the resin composition layer has a dielectric loss tangent value of 0.0030 or less.

[12] The resin sheet according to any one of [1] to [11], wherein one surface of the cured product of the resin composition layer is exposed when the oxygen transmission rate β is measured.

[13] The resin sheet according to any one of [1] to [12], for an insulating layer of a printed wiring board.

[14] As a method for manufacturing a printed wiring board,

The following process:

(1) Step of preparing a resin sheet comprising a support and a resin composition layer provided on the support, wherein one surface of the resin composition layer is exposed;

(2) a step of laminating the resin sheet on the substrate of the printed wiring board so that the resin composition layer is laminated on the substrate; and

(3) a step of curing the resin sheet laminated on the substrate in a state in which the support is not separated from the resin composition layer;

including,

The resin composition layer includes (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radically polymerizable resin,

The resin composition layer,

The oxygen transmission rate α measured when curing at 220 ° C. for 90 minutes is 70 cc / m 2 day or less,

The resin sheet in which one surface of the resin composition layer is exposed,

The oxygen transmission rate β measured when curing at 220 ° C. for 90 minutes is 40 cc / m 2 day or less,

Here, the oxygen permeability α and the oxygen permeability β are measured values measured in an atmosphere of 23 ° C. and 0% RH in accordance with JIS K7126-2: 2006 (isobaric method),

A method for manufacturing a printed wiring board.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the resin sheet provided with the resin composition layer which forms the hardened|cured material excellent in dielectric property, conductor adhesiveness, and mechanical property, and a printed wiring board can be provided.

<Explanation of terms>

In this specification, the term "which may have a substituent" referring to a compound or group refers to the case where the hydrogen atom of the compound or group is not substituted with a substituent, and part or all of the hydrogen atoms of the compound or group It means both when it is substituted by the substituent.

In this specification, the term "substituent" refers to a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, and a monovalent group unless otherwise specified. A heterocyclic group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group.

As a halogen atom used as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

The alkyl group used as a substituent may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 14, still more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. , and a decyl group.

The number of carbon atoms in the cycloalkyl group used as the substituent is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 6. As the said cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group etc. are mentioned, for example.

The alkoxy group used as a substituent may be linear or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 6. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and a hep group. A tyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group are mentioned.

The number of carbon atoms in the cycloalkyloxy group used as the substituent is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 6. As the said cycloalkyloxy group, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group are mentioned, for example.

The aryl group used as a substituent is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms in the aryl group used as the substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, still more preferably 6 to 10. As the said aryl group, a phenyl group, a naphthyl group, and an anthracenyl group are mentioned, for example.

The number of carbon atoms in the aryloxy group used as the substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, still more preferably 6 to 10. As an aryloxy group used as a substituent, a phenoxy group, 1-naphthyloxy group, and 2-naphthyloxy group are mentioned, for example.

The number of carbon atoms in the arylalkyl group used as the substituent is preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 15, still more preferably 7 to 11. Examples of the arylalkyl group include a phenyl-C ₁ to C ₁₂ alkyl group, a naphthyl-C ₁ to C ₁₂ alkyl group, and anthracenyl-C ₁ to C ₁₂ alkyl group.

The number of carbon atoms in the arylalkoxy group used as the substituent is preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 15, still more preferably 7 to 11. Examples of the arylalkoxy group include a phenyl-C ₁ to C ₁₂ alkoxy group and a naphthyl-C ₁ to C ₁₂ alkoxy group.

The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from the heterocycle of a heterocyclic compound. The number of carbon atoms in the monovalent heterocyclic group is preferably 3 to 21, more preferably 3 to 15, still more preferably 3 to 9. The monovalent heterocyclic group includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocycle include a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, and a piperidyl group. , quinolyl group, and isoquinol group.

The alkylidene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms in the alkylidene group is preferably 1 to 20, more preferably 1 to 14, still more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3. . Examples of the alkylidene group include a methylidene group, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, a sec-butylidene group, an isobutylidene group, a tert-butylidene group, and a pentylidene group. , hexylidene group, heptylidene group, octylidene group, nonylidene group, and decylidene group.

The acyl group used as a substituent refers to a group represented by the formula: - C(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be linear or branched. As an aryl group represented by R, a phenyl group, a naphthyl group, and an anthracenyl group are mentioned, for example. The number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 13, still more preferably 2 to 7. As the said acyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group are mentioned, for example.

The acyloxy group used as a substituent refers to a group represented by the formula: -OC(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be linear or branched. As an aryl group represented by R, a phenyl group, a naphthyl group, and an anthracenyl group are mentioned, for example. The number of carbon atoms in the acyloxy group is preferably 2 to 20, more preferably 2 to 13, still more preferably 2 to 7. Examples of the acyloxy group include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, and benzoyloxy group.

The substituent described above may further have a substituent (hereinafter sometimes referred to as "secondary substituent"). As a secondary substituent, you may use the same thing as the above-mentioned substituent unless there is a description in particular.

In the present specification, the term "aromatic ring" means a ring according to Hückel's rule in which the number of electrons contained in a cyclic π electron system is 4n+2 (n is a natural number), a monocyclic aromatic ring, and two or more monocyclic aromatic rings. A condensed aromatic ring in which a cyclic aromatic ring is condensed is included. An aromatic ring may be a carbocyclic ring or a heterocyclic ring. As an aromatic ring, for example, a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyramine ring. monocyclic aromatic rings such as ring rings; Naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzoimidazole ring, indazole ring, benzoxazole ring, benzoisooxazole ring, benzothiazole ring, quinoline ring condensed rings in which two or more monocyclic aromatic rings such as an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, and a phthalazine ring are condensed; and condensed rings in which one or more monocyclic non-aromatic rings are condensed with one or more monocyclic aromatic rings such as an indan ring, a fluorene ring, and a tetralin ring.

In this specification, the term "non-aromatic ring" means a ring other than an aromatic ring, and includes monocyclic non-aromatic rings and condensed non-aromatic rings in which two or more monocyclic non-aromatic rings are condensed. The non-aromatic ring may be a carbocyclic ring or a heterocyclic ring. The non-aromatic ring may be a saturated ring or an unsaturated ring. As a non-aromatic ring, it is a cycloalkane ring, for example; cycloalkene ring; monocyclic non-aromatic heterocycles such as pyrrolidine rings, tetrahydrofuran rings, dioxane rings and tetrahydropyran rings (preferably 3 to 10 members); and bicyclic or higher condensed non-aromatic carbocyclic rings (preferably 8 to 15 members) such as norbornane rings, decalin rings, adamantane rings, and tetrahydrodicyclopentadiene rings.

Hereinafter, the present invention will be described in detail based on its preferred embodiment. However, this invention is not limited to the following embodiment and exemplification, It can be implemented with arbitrary change in the range which does not deviate from the claim of this invention and the range of their equality.

[Resin sheet]

The resin sheet of the present invention includes a support and a resin composition layer provided on the support, wherein the resin composition layer includes (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radically polymerizable resin. . The resin composition layer in the resin sheet of the present invention has an oxygen transmission rate α of 70 cc/m 2 ·day or less when cured at 220°C for 90 minutes, and the resin sheet is cured at 220°C for 90 minutes. When cured under the conditions, the measured oxygen transmission rate β is 40 cc/m 2 ·day or less. Here, oxygen permeability α and oxygen permeability β are measured values in accordance with JIS K7126-2:2006 (isobaric method) at 23°C and 0% RH.

Benzocyclobutene resin can be cured by generating an isomeric diene (orthoquinodimethane) by heating and causing a Diels-Alder type cycloaddition reaction. Since a highly polar functional group such as a hydroxyl group is not generated by the curing reaction, it is expected that the benzocyclobutene resin forms a cured product having excellent dielectric properties. However, according to the study of the present inventors, when a cured product (insulating layer) was formed on a resin composition containing such a benzocyclobutene resin, it was found that the conductor adhesion and mechanical properties were sometimes poor. Regarding the above reaction of benzocyclobutene resin, in addition to requiring high temperature, its reactivity is poor in the presence of oxygen, so it is presumed that heat history and the difficulty in obtaining the desired crosslinkability or degree of crosslinking affect. . On the other hand, the resin sheet of the present invention, which contains a benzocyclobutene resin in combination with an inorganic filler and a radically polymerizable resin, and has an oxygen permeability as a resin composition layer or an oxygen permeability as a resin sheet in a specific range after curing According to this, a cured product having excellent conductor adhesion and mechanical properties can be formed. In addition, according to the resin sheet of the present invention that satisfies the above specific composition and oxygen permeability conditions, a cured product with further improved dielectric properties such as dielectric constant and dielectric loss tangent can be formed. In addition, the present inventors have found that the insulating properties are also improved according to the resin sheet of the present invention. As described above, the present invention is to realize a cured product having excellent dielectric properties inherent in benzocyclobutene resins, or even improving them, and having excellent conductor adhesion and mechanical properties, as well as excellent insulation properties. It makes a significant contribution to the needs of society.

As described above, the resin sheet of the present invention includes a support and a resin composition layer provided on the support, and the resin composition layer comprises (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radical polymerizable It is characterized by comprising a combination of resins and having, after curing, an oxygen permeability α as a resin composition layer and an oxygen transmittance β as a resin sheet within a specific range.

The details of the support and the resin composition layer will be described later, and oxygen transmission rates α and β will be described first.

-Oxygen permeability α-

Oxygen permeability α relates to the oxygen permeability of the resin composition layer after curing. The resin composition layer in the resin sheet of the present invention has an oxygen transmission rate α of 70 cc/m 2 ·day or less when cured at 220°C for 90 minutes.

From the viewpoint of forming a cured product exhibiting excellent dielectric properties and excellent conductor adhesion and mechanical properties, the oxygen permeability α is preferably 68 cc/m day or less, more preferably 66 cc/m day or less or 65 cc/m 2 It is less than day. The lower limit of the oxygen permeability α is not particularly limited, but is usually 1 cc/m 2 ·day or more, 5 cc/m 2 ·day or more, or 10 cc/m 2 ·day or more.

Oxygen transmission rate α can be measured according to the procedure described in the section <Measurement of oxygen transmission rate> described later, and after curing at 220° C. for 90 minutes, the resin composition layer with both main surfaces exposed is measured. Therefore, at the time of measuring the oxygen transmission rate α, both surfaces of the cured product of the resin composition layer are exposed. On the other hand, the oxygen transmission rate α can be adjusted by changing the composition or thickness of the resin composition layer. It is preferable to perform hardening of a resin composition layer together with a support body.

-Oxygen permeability β-

The oxygen transmission rate β relates to the oxygen transmission rate of the resin sheet after curing. The resin sheet of the present invention has an oxygen transmission rate β of 40 cc/m 2 ·day or less when cured at 220°C for 90 minutes.

From the viewpoint of forming a cured product exhibiting excellent dielectric properties and excellent conductor adhesion and mechanical properties, the oxygen permeability β is preferably 38 cc/m day or less, more preferably 36 cc/m day or less, 35 cc/m 2 · day or less, 34 cc/m · day or less, 32 cc/m · day or less, or 30 cc/m · day or less. The lower limit of the oxygen transmission rate β is not particularly limited, and may be 0 cc/m 2 ·day.

The oxygen transmission rate β can be measured according to the procedure described in the section <Measurement of oxygen transmission rate> described later, and is measured for the resin sheet after curing at 220°C for 90 minutes. When measuring the oxygen transmission rate β with respect to a resin sheet with a protective film, it is measured with respect to a resin sheet provided with the resin composition layer (hardened|cured material) from which the protective film was peeled off and one surface was exposed. Therefore, at the time of measuring the oxygen transmission rate β, one side of the cured product of the resin composition layer is exposed. The oxygen transmission rate β can be adjusted by changing the composition and thickness of the resin composition layer and the composition, type and thickness of the support.

From the viewpoint of forming a cured product exhibiting excellent dielectric properties and excellent conductor adhesion and mechanical properties, it is important that both oxygen transmission rates α and β satisfy the above conditions. Even if only one of the oxygen transmission rates α and β satisfies the above conditions, the effect of the present invention cannot be obtained.

Hereinafter, the support used for the resin sheet of the present invention, the resin composition layer, and the like are described.

<support>

The support is not particularly limited as long as the conditions for the oxygen transmission rate β described above are met in combination with the resin composition layer described later. The support is preferably selected from, for example, a single-layer resin film, a multi-layer resin film, a metal foil, a release paper, and a composite film containing a support base material and metal foil.

As the single-layer resin film, a single-layer film made of a plastic material is exemplified. As the plastic material, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), Polyether sulfide (PES), polyether ketone, polyimide, etc. are mentioned.

As the multi-layered resin film, a multi-layered film obtained by integrally stacking at least one selected from the examples of the single-layered resin film described above is exemplified. In the multiple-layer resin film, another material may be interposed between the two layers of single-layer resin films overlapping each other. Examples of other intervening materials include inorganic fillers, deoxidizing materials, drying agents, and ultraviolet absorbers.

As metal foil, copper foil, aluminum foil, etc. are mentioned. As the copper foil, foil made of a single metal of copper may be used, or foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good.

In the composite film containing a supporting base material and metal foil, the supporting base material is not particularly limited as long as it can support the metal foil, and examples thereof include a resin film and a metal film. Examples of the resin film used as the supporting base material include the above-described single-layer or multi-layered resin films, and examples of the metal film used as the supporting base material include copper, aluminum, stainless steel, titanium, Films made of metals such as copper alloys are exemplified. Moreover, in a composite film, as a material of metal foil, copper foil and copper alloy foil are preferable, for example. The composite film may include a peeling layer between the supporting substrate and the metal foil. The peeling layer is not particularly limited as long as the metal foil can be peeled from the supporting substrate, and examples thereof include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; An organic film etc. are mentioned. In the resin sheet of the present invention, when a composite film is used as a support, the resin composition layer may be provided on a metal foil or on a support substrate. When the resin composition layer is provided on the metal foil, it is advantageous because the conductor layer can be formed using the metal foil. In the composite film, it is also preferable that the exposed surface of the metal foil is subjected to a roughening treatment, and thereby it becomes possible to improve the fixation of the cured product of the resin composition layer formed on the upper surface.

The support may be subjected to mat treatment, corona treatment, or antistatic treatment on one or both surfaces. Such a treated surface is usually formed on a surface to be bonded to the resin composition layer.

A release layer may be further provided on one surface or both surfaces of a support body. As a release agent used for a release layer, 1 or more types chosen from the group which consists of alkyd resins, polyolefin resins, urethane resins, and silicone resins are mentioned, for example. The support with the release layer may use a commercial item, for example, "SK-1", "AL-5", "AL-5", "AL- 7", "Lumira T60" manufactured by Tore, Inc., "Purex" manufactured by Teijin, and "Uni-Peel" manufactured by Unitika Co., Ltd., and the like.

The thickness of the support is not particularly limited as long as the conditions for the oxygen transmission rate β described above are met in combination with the resin composition layer described later. Depending on the type of support, suitable thicknesses vary, but are preferably 5 μm or more, more preferably 8 μm or more, 10 μm or more, 12 μm or more, 14 μm or more, or 15 μm or more, still more preferably 20 μm or more, 25 μm or more, 30 μm or more, or 35 μm or more. or more, and the upper limit thereof is preferably 150 μm or less, more preferably 140 μm or less, 120 μm or less, 100 μm or less, or 80 μm or less. Moreover, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

<Resin composition layer>

In the resin sheet of the present invention, the resin composition layer contains (A) benzocyclobutene resin, (B) inorganic filler, and (C) radically polymerizable resin.

As described above, in the resin sheet of the present invention, the resin composition layer contains (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radically polymerizable resin in combination, and has the above oxygen permeability α and By satisfying both conditions of β, a cured product exhibiting excellent dielectric properties and excellent conductor adhesion and mechanical properties can be realized.

Hereinafter, the resin composition constituting the resin composition layer will be described.

The resin composition constituting the resin composition layer includes (A) benzocyclobutene resin, (B) inorganic filler, and (C) radically polymerizable resin. The resin composition may further contain at least one component selected from (D) a thermoplastic resin, (E) a curing accelerator, an epoxy resin, an epoxy resin curing agent, other additives, and an organic solvent.

-(A) Benzocyclobutene resin-

In the present invention, the resin composition contains benzocyclobutene resin as component (A). In this way, a cured product (insulating layer) having excellent dielectric properties can be formed. (A) component may be used individually by 1 type, and may use 2 or more types together.

The structure of component (A) is not particularly limited as long as it contains a benzocyclobutene group capable of generating an isomeric diene by heating. In combination with component (B) and component (C) described later, from the viewpoint of forming a cured product having better dielectric properties, conductor adhesion and mechanical properties, component (A) contains two or more benzocyclobutenes in the molecule It is preferable to include a compound having a group. Component (A) is further added to the benzocyclobutene group from the viewpoint of forming a cured product having better dielectric properties, conductor adhesion and mechanical properties in combination with components (B) and (C) described later, It is preferable to have an unsaturated group.

In one embodiment, component (A) contains a compound represented by the following formula (A-1).

In formula (A-1),

R ¹ represents a divalent aliphatic group having an unsaturated bond;

L represents a single bond or a divalent linking group;

R ^A1 represents an alkyl group, a cyano group or a halogen atom;

R ^A2 represents an alkyl group, a trialkylsilyl group, an alkoxy group or a halogen atom;

nA1 represents an integer from 0 to 2;

nA2 represents an integer from 0 to 3;

nA3 represents 0 or 1. R ¹ , R ^A1 and R ^A2 may each independently have a substituent. A plurality of R ¹ 's may be the same or different, when a plurality of R ^A1 's are present, they may be the same or different, and when a plurality of R ^A2 's are present, they may be the same or different. A plurality of nA1 may be the same or different. A plurality of nA2 may be the same or different.

The divalent group represented by R ¹ has preferably 1 to 3, more preferably 1 or 2, still more preferably 1 unsaturated bonds. The unsaturated bond may be a double bond or a triple bond, but is preferably a double bond. The divalent group represented by R ¹ is preferably an alkenylene group or an alkynylene group. The number of carbon atoms in the divalent group represented by R ¹ is preferably 2 to 10, more preferably 2 to 6 or 2 to 4. The number of carbon atoms in the substituent is not included in the above number of carbon atoms.

As the divalent linking group represented by L, one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and silicon atoms (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 100) It is not particularly limited as long as it is a divalent group consisting of 50) skeletal atoms, and for example, one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (for example, 1 to 3000, 1 to 1000 , 1 to 100, 1 to 50) skeletal atoms, or a siloxane skeleton may be used. Especially, it is preferable that L is a siloxane skeleton. Therefore, in one embodiment, component (A) has a siloxane backbone.

The number of carbon atoms in the alkyl group represented by R ^A1 is preferably 1 to 10, more preferably 1 to 6, 1 to 4 or 1 to 3. The number of carbon atoms in the substituent is not included in the number of carbon atoms concerned. As a halogen atom represented by R ^A1 , a chlorine atom or a bromine atom is preferable.

The number of carbon atoms in the alkyl group and alkoxy group represented by R ^A2 is preferably 1 to 10, more preferably 1 to 6, 1 to 4 or 1 to 3. The number of carbon atoms in the alkyl moiety in the trialkylsilyl group represented by R ^A2 is preferably 1 to 3, more preferably 1 or 2. The number of carbon atoms in the substituent is not included in the above number of carbon atoms. Moreover, as a halogen atom represented by R ^A2 , a chlorine atom or a bromine atom is preferable.

In combination with component (B) and component (C) described later, from the viewpoint of forming a cured product having maintained or improved dielectric properties, and from the viewpoint of forming a cured product having better conductor adhesion and mechanical properties, In the formula (A-1), nA3 is preferably 1, and L is preferably a siloxane skeleton.

In one suitable embodiment, (A) component contains the compound represented by the following formula (A-2).

In formula (A-2),

R ¹ , R ^A1 , R ^A2 , nA1 and nA2 are as described in Formula (A-1),

R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an arylalkyl group, or an aryl group;

nA4 represents an integer of 1 to 10. R ² may have a substituent. A plurality of R ² may be the same or different.

The number of carbon atoms in the alkyl group represented by R ² is preferably 1 to 10, more preferably 1 to 6, 1 to 4 or 1 to 3. The number of carbon atoms in the cycloalkyl group represented by R ² is preferably 3 to 10, more preferably 4 to 6. The number of carbon atoms in the arylalkyl group represented by R ² is preferably 7 to 20, more preferably 7 to 15 or 7 to 12. The aryl moiety in the arylalkyl group is preferably a phenyl group. The number of carbon atoms in the aryl group represented by R ² is preferably 6 to 14, more preferably 6 to 10. As the aryl group, a phenyl group is preferable. The number of carbon atoms in the substituent is not included in the above number of carbon atoms.

R ¹ , R ^A1 , R ^A2 , nA1 and nA2 are as described in Formula (A-1), and among them, it is preferable that R ¹ is an alkenylene group having 2 to 4 carbon atoms, and nA1 and nA2 are 0. .

In one particularly suitable embodiment, component (A) contains a compound represented by the following formula (A-3).

In Formula (A-3), R ² and nA4 are as described in Formula (A-2).

Component (A) can be prepared according to the procedures described in, for example, US Patent No. 4812588, US Patent No. 5138081 and the like. In addition, you may use a commercial item as (A) component, For example, as a compound represented by Formula (A-3), there exists CYCLOTENE (registered trademark) series by Dow Chemical Co., Ltd.. From the viewpoint of keeping the oxygen transmission rate after curing below the specific value described above, among the CYCLOTENE (registered trademark) series, it is preferable to use the dry etching type 3000 series. The non-volatile component contained in "CYCLOTENE (registered trademark) 3022" manufactured by Dow Chemical Co., Ltd. is represented by the following formula.

As described above, the benzocyclobutene group produces an isomeric diene and causes a Diels-Alder type cycloaddition reaction. Therefore, the component (A) may be a compound (monomer) represented by the above formulas (A-1) to (A-3) or the like, or may be a dimer or polymer formed by an addition reaction of these compounds, or a mixture thereof. good.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the component (A) are not particularly limited as long as the effect of the present invention is exhibited in combination with the component (B) and component (C) described later. In one embodiment, Mn is preferably 2000 or less, more preferably 1800 or less, and still more preferably 1600 or less, 1500 or less, 1400 or less, 1200 or less, or 1000 or less. In one embodiment, Mw is also within the above suitable range. The lower limit of the molecular weight is not particularly limited, and can be, for example, 250 or more, 300 or more, or 350 or more. (A) Mw and Mn of the component can be measured as values in terms of polystyrene by a gel permeation chromatography (GPC) method. Therefore, in a preferable aspect, component (A) contains a compound having two or more benzocyclobutene groups in the molecule, and component (A) has a number average molecular weight (Mn) of 2000 or less.

The content of the component (A) in the resin composition is preferably 3% by mass or more and 4% by mass, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of realizing a cured product with maintained or improved dielectric properties. % or more, 5 mass% or more, or 7 mass% or more. The upper limit of the content of component (A) is not particularly limited, but is preferably 40% by mass or less and 35% by mass from the viewpoint of forming a cured product having an oxygen transmission rate that satisfies the above-mentioned range, preferably the above-mentioned suitable range. % or less, 30% by mass or less, or 25% by mass or less. Therefore, in one suitable embodiment, content of (A) component is 3 mass % or more and 40 mass % or less, when the non-volatile component in a resin composition is 100 mass %.

The content of the component (A) in the resin composition is preferably 6% by mass or more and 8% by mass, when the resin component in the resin composition is 100% by mass, from the viewpoint of realizing a cured product with maintained and improved dielectric properties. or more, 10% by mass or more, or 14% by mass or more. The resin component in the resin composition represents a component excluding the (B) inorganic filler among the non-volatile components in the resin composition. The upper limit of the content of component (A) is not particularly limited, but is, for example, 90% by mass or less, and from the viewpoint of forming a cured product having a low oxygen permeability, it is preferably 80% by mass or less or 70% by mass. Therefore, in one suitable embodiment, content of component (A) is 6 mass % or more and 80 mass % or less, when the resin component in a resin composition is 100 mass %.

-(B) inorganic filler-

In the present invention, the resin composition contains an inorganic filler as component (B).

In the present invention, in addition to the component (A), the component (B) and the component (C) described later are used in combination in a resin composition, and, as described above, the resin composition layer or the resin sheet is formed with the above oxygen. By satisfying both the conditions of transmittance α and β, it has been realized that a cured product having excellent dielectric properties, conductor adhesion and mechanical properties can be formed. In addition, when the resin composition contains the component (B), a cured product having excellent thermal properties (eg linear thermal expansion coefficient) can be formed.

Examples of the component (B) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, and hydroxide. Magnesium 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, zirconate titanate Barium, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, etc. are mentioned. Among these, silica is particularly suitable. As silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica etc. are mentioned, for example. Moreover, as a silica, spherical silica is preferable. (B) component may be used individually by 1 type, and may be used in combination of 2 or more type.

As a commercial item of (B) component, it is "UFP-30" by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nittetsu Chemical &Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex; "UFP-30" by Denka Corporation; "Silent NSS-3N", "Silent NSS-4N", and "Silent NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" by the Adomatex company; "DAW-03" by Denka Corporation, "FB-105FD", etc. are mentioned.

The average particle diameter of component (B) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more. The average particle diameter of component (B) can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of the inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution analyzer, and taking the median diameter as the average particle size. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone were weighed into a vial bottle and dispersed by ultrasonic waves for 10 minutes can be used. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, using blue and red light source wavelengths, and measuring the volume-based particle size distribution of the inorganic filler by the flow cell method, and from the obtained particle size distribution, the median diameter The average particle diameter was calculated as Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba Seisakusho Co., Ltd. and the like.

The specific surface area of component (B) is not particularly limited, but is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, still more preferably 1 m 2 /g or more, 3 m 2 /g or more, or It is 5 m2/g or more. The upper limit of the specific surface area is not particularly limited, but is preferably 100 m2/g or less, more preferably 80 m2/g or less, still more preferably 60 m2/g or less, 50 m2/g or less, or 40 m2/g. /g or less. The specific surface area of the component (B) was determined by the BET method by adsorbing nitrogen gas on the surface of the sample using a specific surface area measuring device (“Macsorb HM-1210” manufactured by Mountec Co., Ltd.), and using the BET multi-point method to determine the specific surface area. It can be obtained by calculating

(B) Component is preferably surface-treated with an appropriate surface treatment agent. By surface treatment, the moisture resistance and dispersibility of component (B) can be improved. Examples of the surface treatment agent include vinyl silane coupling agents, epoxy silane coupling agents, styryl silane coupling agents, (meth)acrylic silane coupling agents, amino silane coupling agents, isocyanurate silane coupling agents, and urea. Silane coupling agents, such as a domestic silane coupling agent, a mercapto-type silane coupling agent, an isocyanate-type silane coupling agent, and an acid anhydride-type silane coupling agent; non-silane coupling-alkoxysilane compounds of methyltrimethoxysilane and phenyltrimethoxysilane; A silazane compound etc. are mentioned. A surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more type.

As a commercial item of a surface treatment agent, Shin-Etsu Chemical Co., Ltd. product "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. product "KBM803" (3-mercapto propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Industry "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) methoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), etc. are mentioned.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface treated with a surface treatment agent of preferably 0.2 to 5% by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. 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 still more preferably 0.2 mg/m 2 or more, from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the sheet form, 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 component (B) can be measured after washing the inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the surface-treated inorganic filler with a surface treatment agent, followed by ultrasonic cleaning at 25°C for 5 minutes. After removing the supernatant liquid 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 Seisakusho Co., Ltd. or the like can be used.

The content of the component (B) in the resin composition is preferably 30% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of forming a cured product having excellent dielectric properties, conductor adhesion and mechanical properties. , More preferably, it is 35 mass % or more. The upper limit of the content of component (B) is not particularly limited, but is preferably 80% by mass or less, more preferably 75% by mass or less. Therefore, in one suitable embodiment, content of (B) component is 30 mass % or more and 80 mass % or less, when the non-volatile component in a resin composition is 100 mass %.

From the viewpoint of being able to enjoy the effect of the present invention more remarkably, the compounding ratio of component (B) to component (A), that is, the mass ratio of component (B)/component (A), in terms of non-volatile components, is preferably is 1 or more, more preferably 1.5 or more, still more preferably 2.0 or more. The upper limit of the mass ratio is not particularly limited, but can be, for example, 50 or less, 40 or less, or 30 or less.

From the viewpoint of being able to enjoy the effect of the present invention more remarkably, the blending ratio of component (B) to component (A) and component (C), that is, component (B)/{component (A)+component (C)} The mass ratio of is preferably 0.5 or more in terms of non-volatile components. The upper limit of the mass ratio is not particularly limited, but can be, for example, 25 or less.

-(C) Radical polymerizable resin-

In the present invention, the resin composition contains a radically polymerizable resin as component (C). However, component (C) does not have a benzocyclobutene group and is different from component (A). That is, as for the component (C), those corresponding to the component (A) are excluded.

In the present invention, in addition to the component (A), the component (C) and the component (B) are used in combination in a resin composition, and, as described above, the resin composition layer or the resin sheet is provided with the oxygen By satisfying both the conditions of transmittance α and β, it has been realized that a cured product having excellent dielectric properties, conductor adhesion and mechanical properties can be formed.

(C) Component has a radical polymerizable unsaturated group in a molecule. (C) component may be used individually by 1 type, and may use 2 or more types together.

Component (C) is not particularly limited as long as it has a radically polymerizable unsaturated group in the molecule, but in combination with component (A) and component (B), a cured product having exceptionally excellent dielectric properties, conductor adhesion and mechanical properties is formed. From the point of view, component (C) is a radical polymerizable unsaturated group, a vinyl group, an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, and a methacryloyl group, a maleimide group, a fumaroyl group, and a maleo It is preferable to include a compound having at least one selected from group, and among them, a compound containing at least one selected from an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, and a methacryloyl group. It is more preferable to

Therefore, component (C) is preferably at least one selected from maleimide resins, styryl resins, (meth)acrylic resins, allyl resins, and butadiene resins, and maleimide resins, (meth)acrylic resins and styryl It is more preferable that it is 1 or more types chosen from resin, and it is more preferable that it is any one of a maleimide resin and a styryl resin.

Component (C) more preferably contains a compound having two or more radically polymerizable unsaturated groups in the molecule. Although there is no particular restriction on the upper limit, it can be 10 or less.

A maleimide resin contains the maleimide group represented by the following formula (C-1) in a molecule|numerator.

The number of maleimide groups per molecule of the maleimide resin is preferably 2 or more, more preferably 3 or more, and preferably 10 or less, from the viewpoint of significantly obtaining the desired effect of the present invention. More preferably, it is 6 or less, and even more preferably, it is 3 or less.

The maleimide resin preferably has either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably has an aliphatic hydrocarbon group or an aromatic hydrocarbon group, from the viewpoint of significantly obtaining the desired effect of the present invention.

As the aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferable, a divalent saturated aliphatic hydrocarbon group is more preferable, and an alkylene group is still more preferable. As an alkylene group, a C1-C10 alkylene group is preferable, a C1-C6 alkylene group is more preferable, a C1-C3 alkylene group is still more preferable, and a methylene group is especially preferable. .

As an aromatic hydrocarbon group, monovalent and divalent aromatic hydrocarbon groups are preferable, and an aryl group and an arylene group are more preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is still more preferable. Examples of such an arylene group include a phenylene group, a naphthylene group, anthracenylene group, an aralkyl group, a biphenylene group, and a biphenylaralkyl group. Among them, a phenylene group, an aralkyl group, a biphenylene group, A biphenylaralkyl group is preferable, and a phenylene group, an aralkyl group, and a biphenylene group are more preferable. The aryl group is preferably an aryl group of 6 to 30 carbon atoms, more preferably an aryl group of 6 to 20 carbon atoms, still more preferably an aryl group of 6 to 10 carbon atoms, and particularly preferably a phenyl group.

In maleimide resin, it is preferable that the nitrogen atom of maleimide group is directly bonded to the monovalent or divalent aromatic hydrocarbon group from the viewpoint of significantly obtaining the desired effect of the present invention. Here, "direct" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

It is preferable that maleimide resin contains the compound represented by the following formula (C-2), for example.

In formula (C-2), R ³¹ and R ³⁶ represent a maleimide group, R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group, and D each independently represents Represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

R ³² , R ³³ , R ³⁴ and R ³⁵ in the formula (C-2) each independently represent a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom is preferable.

As an alkyl group, a C1-C10 alkyl group is preferable, a C1-C6 alkyl group is more preferable, and a C1-C3 alkyl group is still more preferable. The alkyl group may be linear, branched or cyclic. As such an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, etc. are mentioned, for example.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring. As such an aryl group, a phenyl group, a naphthyl group, an anthracenyl group etc. are mentioned, for example.

The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited and may be the one described above. For example, a halogen atom, -OH, -OC _1-6 alkyl group, -N(C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _{6- 10} aryl groups, -NH ₂ , -CN, -C(O)OC _1-10 alkyl groups, -COOH, -C(O)H, -NO ₂ and the like. Here, the term "C _pq " (p and q are positive integers and satisfies p<q) indicates that the number of carbon atoms in the organic group described immediately after the term is p to q. For example, the expression "C _1-10 alkyl group" represents an alkyl group having 1 to 10 carbon atoms. These substituents may combine with each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring.

D in Formula (C-2) represents a divalent aromatic group. Examples of the divalent aromatic group include a phenylene group, a naphthylene group, anthracenylene group, an aralkyl group, a biphenylene group, a biphenylaralkyl group, and the like, and among these, a biphenylene group and a biphenylaralkyl group preferred, and a biphenylene group is more preferred. The divalent aromatic group may have a substituent. As a substituent, it is the same as the substituent which the alkyl group represented by ^R32 in Formula (C-2) may have.

m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, still more preferably 1 to 2, and 1 being even more preferable.

a represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, still more preferably 1 to 5.

It is preferable that maleimide resin contains the compound represented by Formula (C-3).

In Formula (C-3), R ³⁷ and R ³⁸ represent a maleimide group. a1 represents an integer from 1 to 100;

a1 is the same as a in Formula (C-2), and the preferable range is also the same.

A commercial item can be used for maleimide resin. As a commercial item, "MIR-3000-70MT" by Nippon Kayaku Co., Ltd. etc. are mentioned, for example.

It is preferable that maleimide resin contains the compound containing at least any one of the C5 or more alkyl group and the C5 or more alkylene group.

The number of carbon atoms in the alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. This alkyl group may be linear, branched or cyclic, and among these, linear is preferred. As such an alkyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group etc. are mentioned, for example. You may have the C5 or more alkyl group as a substituent for the C5 or more alkylene group. The alkyl group having 5 or more carbon atoms may be a part of an alkenyl group or a part of an alkapolyenyl group (the number of double bonds is preferably 2).

The number of carbon atoms in the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Linear, branched, or cyclic may be sufficient as this alkylene group, and a straight chain is especially preferable. Here, the cyclic alkylene group is a concept including the case where it consists only of a cyclic alkylene group and the case where it contains both a linear alkylene group and a cyclic alkylene group. Examples of such an alkylene group include a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, and a hexatriacone. and the like. The alkylene group having 5 or more carbon atoms may be a part of an alkenylene group or a part of an alkapolyenylene group (the number of double bonds is preferably 2).

It is also preferable that the maleimide resin contains a compound containing both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms from the viewpoint of significantly obtaining the desired effects of the present invention.

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may bond to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. As a ring formed by mutually bonding, a cyclohexane ring etc. are mentioned, for example.

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms preferably do not have a substituent, but may have a substituent. Although the substituent is as described above, suitable examples thereof include an unsaturated hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. A substituent may be included independently or may be included in combination of 2 or more types.

It is preferable that maleimide resin contains the compound in which the above-mentioned alkyl group of 5 or more carbon atoms and the alkylene group of 5 or more carbon atoms are directly bonded to the nitrogen atom of the maleimide group.

In one embodiment, the maleimide resin contains a compound represented by the following general formula (C-4).

In the general formula (C-4), M represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent. Preferably, M represents an alkylene group, an alkenylene group, or an alkapolyenylene group (more preferably, the number of double bonds is 2) having 5 or more carbon atoms, which may have a substituent. The alkylene group of M is the same as the above-described alkylene group having 5 or more carbon atoms. The substituent of M is the same as the substituent which the alkyl group of 5 or more carbon atoms and the alkylene group of 5 or more carbon atoms may have, and the substituent is preferably an alkyl group of 5 or more carbon atoms.

L represents a single bond or a divalent linking group. As the divalent linking group, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR ⁰ -(R ⁰ is a hydrogen atom or a carbon atom 1 to 3 alkyl group), an oxygen atom, a sulfur atom, C(=O)NR ⁰ -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a divalent group derived from two or more of these Groups composed of combinations of groups and the like are exemplified. An alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group composed of a combination of two or more types of divalent groups have a number of carbon atoms You may have 5 or more alkyl groups as a substituent. The divalent group derived from phthalimide represents a divalent group derived from phthalimide, and is specifically a group represented by general formula (C-5). The divalent group derived from pyromellitic acid diimide represents a divalent group derived from pyromellitic acid diimide, and is specifically a group represented by general formula (C-6). In the formula, "*" represents a bond.

The alkylene group as the divalent linking group in L is preferably an alkylene group of 1 to 50 carbon atoms, more preferably an alkylene group of 1 to 45 carbon atoms, particularly preferably an alkylene group of 1 to 40 carbon atoms. Do. Linear, branched, or cyclic any may be sufficient as this alkylene group. Examples of such an alkylene group include a methylethylene group, a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, and a tridecylene group. , Heptadecylene group, hexatriacontylene group, group having an octylene-cyclohexylene structure, group having an octylene-cyclohexylene-octylene structure, group having a propylene-cyclohexylene-octylene structure, etc. can be heard

The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, and particularly preferably an alkenylene group having 2 to 10 carbon atoms. Do. Any of linear, branched, and cyclic may be sufficient as this alkenylene group. As such an alkenylene group, methyl ethylene group, cyclohexenylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group etc. are mentioned, for example.

The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, and particularly preferably an alkynylene group having 2 to 10 carbon atoms. Do. Any of linear, branched, and cyclic may be sufficient as this alkynylene group. As such an alkynylene group, a methylethynylene group, a cyclohexynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group etc. are mentioned, for example.

The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, and even more preferably an arylene group having 6 to 14 carbon atoms. And, an arylene group having 6 to 10 carbon atoms is more preferable. As an arylene group, a phenylene group, a naphthylene group, an anthracenylene group etc. are mentioned, for example.

The alkylene group, alkenylene group, alkynylene group, and arylene group which are the divalent linking groups in L may have a substituent. As a substituent, it is the same as the substituent which said C5 or more alkyl group and C5 or more alkylene group may have, Preferably it is a C5 or more alkyl group.

Examples of the group consisting of a combination of two or more types of divalent groups in L include a divalent group consisting of a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group derived from phthalimide, a divalent group composed of a combination of an oxygen atom, an arylene group, and an alkylene group; a divalent group composed of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; etc. can be mentioned. A group composed of a combination of two or more types of divalent groups may form a ring such as a condensed ring by combining each group. Moreover, the repeating unit of 1-10 repeating units may be sufficient as the group which consists of a combination of 2 or more types of divalent groups.

Especially, L in general formula (C-4) is an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, an alkylene group having 1 to 50 carbon atoms which may have a substituent, and a carbon atom number. A divalent group consisting of five or more alkyl groups, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or a combination of two or more of these groups is preferable. Especially, as L, it is an alkylene group; a divalent group having a structure of an alkylene group-phthalimide-derived divalent group-oxygen atom-phthalimide-derived divalent group; a divalent group having a structure of an alkylene group-phthalimide-derived divalent group-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-phthalimide-derived divalent group; A divalent group having a structure of a divalent group derived from alkylene-pyromellitic acid diimide is more preferable.

The compound represented by the general formula (C-4) preferably includes a compound represented by the general formula (C-7).

In general formula (C-7), M ¹ each independently represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent, and Z each independently has a number of carbon atoms which may have a substituent A divalent group having an aromatic ring which may have five or more alkylene groups or substituents is shown. t represents an integer from 1 to 10.

M ¹ represents a divalent aliphatic hydrocarbon group each independently containing an alkylene group having 5 or more carbon atoms which may have a substituent. Preferably, M ¹ each independently represents an alkylene group, an alkenylene group, or an alkapolyenylene group (more preferably, the number of double bonds is 2) having 5 or more carbon atoms, which may have a substituent. M ¹ is more preferably the same as M in general formula (C-4).

Z each independently represents a divalent group having an alkylene group having 5 or more carbon atoms which may have a substituent or an aromatic ring which may have a substituent. As the alkylene group in Z, any of chain, branched, and cyclic may be used, and among these, cyclic, ie, cyclic alkylene groups having 5 or more carbon atoms which may have substituents are preferable. The number of carbon atoms in the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure. there is.

The aromatic ring in the divalent group having an aromatic ring represented by Z may be the one described above, but examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, and an aromatic heterocyclic ring. These etc. are mentioned, A benzene ring, a phthalimide ring, and a pyromellitic acid diimide ring are preferable. That is, as a divalent group having an aromatic ring, a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, a pyromellitic acid diimide ring which may have a substituent A divalent group having is preferred. Examples of the divalent group having an aromatic ring include a group composed of a combination of a divalent group derived from phthalimide and an oxygen atom; a group composed of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; divalent group derived from pyromellitic acid diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group; etc. can be mentioned. The arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in formula (C-4).

The divalent group represented by Z having an alkylene group and an aromatic ring may have a substituent. As a substituent, it is the same as the substituent which said C5 or more alkyl group and C5 or more alkylene group may have.

Specific examples of the group represented by Z include the following groups. In the formula, "*" represents a bond.

The compound represented by the general formula (C-4) is preferably either a compound represented by the general formula (C-8) or a compound represented by the general formula (C-9).

In general formula (C-8), M ² and M ³ each independently represent a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent, and R ⁴⁰ are each independently an oxygen atom; An arylene group, an alkylene group, or a divalent group composed of a combination of two or more of these groups. t1 represents an integer from 1 to 10.

In general formula (C-9), M ⁴ , M ⁶ and M ⁷ each independently represent a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent, and M ⁵ is each independently a substituent represents a divalent group having an aromatic ring which may have , and R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

M ² and M ³ each independently represent a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent. Preferably, M ² and M ³ each independently represent an alkylene group, an alkenylene group, or an alkapolyenylene group having 5 or more carbon atoms, which may have a substituent (more preferably, the number of double bonds is 2). . M ² and M ³ are more preferably the same as an alkylene group having 5 or more carbon atoms represented by M in Formula (C-4), and a hexatriacontylene group is preferable.

R ⁴⁰ each independently represents an oxygen atom, an arylene group, an alkylene group, or a group composed of a combination of two or more of these divalent groups. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (C-4). As R ⁴⁰ , it is preferably a group composed of a combination of two or more types of divalent groups or an oxygen atom.

Examples of the group consisting of a combination of two or more divalent groups in R ⁴⁰ include a combination of an oxygen atom, an arylene group, and an alkylene group. The following groups are mentioned as a specific example of the group which consists of a combination of 2 or more types of divalent groups. In the formula, "*" represents a bond.

M ⁴ , M ⁶ and M ⁷ each independently represent a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent. Preferably, M ⁴ , M ⁶ and M ⁷ are each independently an alkylene group, an alkenylene group, or an alkapolyenylene group having 5 or more carbon atoms, which may have a substituent (more preferably, the number of double bonds is 2). ). M ⁴ , M ⁶ and M ⁷ are the same as an alkylene group having 5 or more carbon atoms, which may have a substituent represented by M in formula (C-4), and are selected from a hexylene group, a heptylene group, an octylene group, a nonylene group, A decylene group is preferable, and an octylene group is more preferable.

M ⁵ represents a divalent group each independently having an aromatic ring which may have a substituent. M ⁵ is the same as a divalent group having an aromatic ring which may have a substituent represented by Z in Formula (C-7), and is a group composed of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; A group consisting of a combination of a divalent group derived from phthalimide and an alkylene group is preferable, and a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide is more preferable. The arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in formula (C-4).

Specific examples of the group represented by M ⁵ include the following groups. In the formula, "*" represents a bond.

R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. R ⁴¹ and R ⁴² are the same as the above-described alkyl group having 5 or more carbon atoms, and are preferably a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, and more preferably a hexyl group and an octyl group.

u1 and u2 each independently represent an integer of 1 to 15, preferably an integer of 1 to 10.

Specific examples of the maleimide resin include the following compounds (C1) to (C3). However, maleimide resin is not limited to these specific examples. In formula, n represents the integer of 1-10.

As a specific example of the maleimide resin, "BMI1500" (compound of formula (C1)), "BMI1700" (compound of formula (C2)), "BMI689" (compound of formula (C3)) manufactured by Designer Molecules, etc. can be heard

The maleimide group equivalent of the maleimide resin is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to 1000 g/eq., more preferably 150 g/eq. to 500 g/eq. A maleimide group equivalent is the mass of the compound containing 1 equivalent maleimide group.

The styryl resin has at least one group selected from a styryl group and a vinylphenyl group in the molecule, and preferably has a vinylphenyl group. A vinylphenyl group is a group having a structure shown below.

(* indicates a bonding hand.)

The styryl resin more preferably has two or more vinylphenyl groups from the viewpoint of obtaining a cured product having a low dielectric loss tangent.

The styryl resin preferably has a cyclic structure from the viewpoint of obtaining a cured product having a low dielectric loss tangent. As the cyclic structure, a divalent cyclic group is preferable. The divalent cyclic group may be either a cyclic group containing a non-aromatic ring such as an alicyclic structure or a cyclic group containing an aromatic ring structure. In addition, you may have a plurality of divalent cyclic groups.

The divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, preferably a 20-membered ring or less, more preferably from the viewpoint of significantly obtaining the desired effect of the present invention. It is preferably a 15-membered ring or less, more preferably a 10-membered ring or less. Moreover, as a divalent cyclic group, a monocyclic structure may be sufficient and a polycyclic structure may be sufficient.

In the ring in the divalent cyclic group, the backbone of the ring may be constituted by heteroatoms in addition to carbon atoms. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom etc. are mentioned, for example, An oxygen atom is preferable. As for the heteroatom, you may have 1 piece in said ring, and may have 2 or more.

Specific examples of the divalent cyclic group include the following divalent groups (xii) or (xiii).

(Among the divalent groups (xii) and (xiii), R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁶¹ , and R ⁶² are each independently a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R ⁵³ , R ⁵⁴ , R ⁵⁸ , R ⁵⁹ , and R ⁶⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. A methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group etc. are mentioned as a C6 or less alkyl group, It is preferable that it is a methyl group. As R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁶¹ , and R ⁶² , those representing a methyl group are preferable. R ⁵³ , R ⁵⁴ , R ⁵⁸ , R ⁵⁹ , and R ⁶⁰ are preferably hydrogen atoms or methyl groups.

Further, the divalent cyclic group may be a combination of a plurality of divalent cyclic groups. As a specific example in the case of combining a divalent cyclic group, the divalent cyclic group (divalent group (a)) represented by the following formula (C4) is mentioned.

(In formula (C4), R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ are each independently a halogen atom, an alkyl group having 6 or less carbon atoms, or represents a phenyl group, and R ⁷³ , R ⁷⁴ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. d2 represents an integer from 0 to 300, except when one of d1 and d2 is 0.)

R ⁷¹ , R ⁷² , R ⁸⁵ and R ⁸⁶ are the same as R ⁵¹ in formula (xii). R ⁷³ , R ⁷⁴ , R ⁸³ and R ⁸⁴ are the same as R ⁵³ in formula (xii). R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ , and R ⁸² are the same as R ⁵⁵ in formula (xiii). R ⁷⁸ , R ⁷⁹ , and R ⁸⁰ are the same as R ⁵⁸ in formula (xiii).

d1 and d2 represent integers from 0 to 300. However, the case where one of d1 and d2 is 0 is excluded. As d1 and d2, those representing an integer of 1 to 100 are preferred, those representing an integer of 1 to 50 are more preferred, and those representing an integer of 1 to 10 are still more preferred. d1 and d2 may be the same or different.

The divalent cyclic group may have a substituent. Examples of the substituent include 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, a nitro group, a hydroxy group, a mercapto group, and an oxo. group etc. are mentioned, and an alkyl group is preferable.

The vinylphenyl group may be bonded directly to the divalent cyclic group or through a divalent linking group. As a divalent linking group, for example, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O) N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc. may be mentioned, and groups combining a plurality of these may be used. As the alkylene group, a C1-C10 alkylene group is preferable, a C1-C6 alkylene group is more preferable, a C1-C5 alkylene group or a C1-C4 alkylene group. Ren groups are more preferred. Any of a straight-chain, branched, and cyclic|annular may be sufficient as an alkylene group. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a xylene group, a 1,1-dimethylethylene group, and the like, and a methylene group, an ethylene group, a 1,1- A dimethylethylene group is preferred. As the alkenylene group, a C2-C10 alkenylene group is preferable, a C2-C6 alkenylene group is more preferable, and a C2-C5 alkenylene group is still more preferable. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable. As a divalent linking group, an alkylene group is preferable, and a methylene group is especially preferable.

The styryl resin preferably contains a compound represented by the following formula (C-10).

(In formula (C-10), R ⁹¹ and R ⁹² each independently represent a divalent linking group. Ring B1 represents a divalent cyclic group.)

R ⁹¹ and R ⁹² each independently represent a divalent linking group. As a divalent linking group, it is the same as said divalent linking group.

Ring B1 represents a divalent cyclic group. Ring B is the same as the above divalent cyclic group.

Ring B1 may have a substituent. As a substituent, it is the same as the substituent which said divalent cyclic group may have.

Hereinafter, although the specific example of a styryl resin is shown, this invention is not limited to this.

(q1 is the same as d1 in the formula (C4), and q2 is the same as d2 in the formula (C4).)

Styryl resin may use a commercial item, and "OPE-2St" by Mitsubishi Gas Chemical Co., Ltd., etc. are mentioned, for example. A styryl resin may be used individually by 1 type, and may be used in combination of 2 or more types.

The number average molecular weight of the styryl resin is preferably 3000 or less, more preferably 2500 or less, still more preferably 2000 or less, or 1500 or less, from the viewpoint of significantly obtaining the desired effect of the present invention. The lower limit is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more, or 1000 or more. The number average molecular weight is a number average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC).

The (meth)acrylic resin includes a compound having an acryloyl group or a methacryloyl group in the molecule. As the (meth)acrylic resin, it is preferable to include a compound having two or more (meth)acryloyl groups per molecule from the viewpoint of significantly obtaining the desired effect of the present invention. The term "(meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group.

The (meth)acrylic resin preferably has a cyclic structure from the viewpoint of significantly obtaining the desired effects of the present invention. As the cyclic structure, a divalent cyclic group is preferable. The divalent cyclic group may be either a cyclic group containing a non-aromatic ring such as an alicyclic structure or a cyclic group containing an aromatic ring structure. Especially, it is preferable that it is a cyclic group containing an alicyclic structure from a viewpoint of obtaining the desired effect of this invention remarkably.

The divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, preferably a 20-membered ring or less, more preferably from the viewpoint of significantly obtaining the desired effect of the present invention. It is preferably a 15-membered ring or less, more preferably a 10-membered ring or less. Moreover, as a divalent cyclic group, a monocyclic structure may be sufficient and a polycyclic structure may be sufficient.

In the ring in the divalent cyclic group, the backbone of the ring may be constituted by heteroatoms in addition to carbon atoms. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom etc. are mentioned, for example, An oxygen atom is preferable. As for the heteroatom, you may have 1 piece in said ring, and may have 2 or more.

Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Especially, as a divalent cyclic group, (x) or (xi) is preferable.

The divalent cyclic group may have a substituent. Examples of such a substituent include 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, a nitro group, a hydroxy group, a mercapto group, An oxo group etc. are mentioned, An alkyl group is preferable.

The (meth)acryloyl group may be directly bonded to the divalent cyclic group, or may be bonded through a divalent linking group. As a divalent linking group, for example, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O) N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc. may be mentioned, and groups combining a plurality of these may be used. As the alkylene group, a C1-C10 alkylene group is preferable, a C1-C6 alkylene group is more preferable, a C1-C5 alkylene group or a C1-C4 alkylene group. Ren groups are more preferred. Any of a straight-chain, branched, and cyclic|annular may be sufficient as an alkylene group. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group, and the like, and a methylene group, an ethylene group, a 1,1 - A dimethylethylene group is preferable. As the alkenylene group, a C2-C10 alkenylene group is preferable, a C2-C6 alkenylene group is more preferable, and a C2-C5 alkenylene group is still more preferable. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and among these, a methylene group and a 1,1-dimethylethylene group are preferable.

It is preferable that the (meth)acrylic resin contains a compound represented by the following formula (C-11).

(In formula (C-11), R ¹⁰¹ and R ¹⁰⁴ each independently represent an acryloyl group or a methacryloyl group, and R ¹⁰² and R ¹⁰³ each independently represent a divalent linking group. Ring B2 is a divalent represents a fantasy period.)

R ¹⁰¹ and R ¹⁰⁴ each independently represent an acryloyl group or a methacryloyl group, and an acryloyl group is preferable.

R ¹⁰² and R ¹⁰³ each independently represent a divalent linking group. The divalent linking group is the same as the divalent linking group to which the (meth)acryloyl group may be bonded.

Ring B2 represents a divalent cyclic group. Ring B2 is the same as the above divalent cyclic group. Ring B2 may have a substituent. As a substituent, it is the same as the substituent which said divalent cyclic group may have.

Although the following are mentioned as a specific example of a (meth)acrylic resin, this invention is not limited to this.

The (meth)acrylic resin may use a commercial item, for example, "A-DOG" by Shin Nakamura Chemical Co., Ltd., "DCP-A" by Kyoeisha Chemical Co., Ltd., "NPDGA" by Nippon Kayaku Co., Ltd. ”, “FM-400”, “R-687”, “THE-330”, “PET-30”, “DPHA”, and “NK Ester DCP” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

The (meth)acryloyl group equivalent of the (meth)acrylic resin is preferably 30 g/eq. to 400 g/eq., more preferably 50 g/eq. to 300 g/eq., more preferably 75 g/eq. to 200 g/eq. The (meth)acryloyl group equivalent is the mass of a compound containing 1 equivalent of a (meth)acryloyl group.

Allyl resin has at least one allyl group in its molecule. The allyl resin more preferably has two or more allyl groups in one molecule. The upper limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

In addition, the allyl resin preferably has any one of a benzoxazine ring, a phenol ring, an isocyanuric ring, an epoxy group, and a carboxylic acid derivative having a cyclic structure, in addition to an allyl group, from the viewpoint of significantly obtaining the desired effect of the present invention. Do.

The allyl resin having a benzoxazine ring is preferably bonded to either a nitrogen atom or a benzene ring of the benzoxazine ring, and more preferably bonded to a nitrogen atom.

Examples of the allyl resin having a phenol ring include a cresol resin containing an allyl group, a novolak-type phenolic resin containing an allyl group, and a cresol novolak resin containing an allyl group.

As for the allyl resin having an isocyanuric structure, it is preferable that the nitrogen atom of an isocyanuric structure and the allyl group are directly bonded. Examples of the allyl resin having an isocyanuric structure include allyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate.

It is preferable that the allyl resin which has an epoxy group contains 2 or more epoxy groups in 1 molecule. The allyl resin having an epoxy group preferably has an aromatic structure, and when two or more types of allyl resins having an epoxy group are used, it is more preferable that at least one of them has an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles. The allyl resin having an epoxy group preferably has a bisphenol structure, and examples of the bisphenol structure include bisphenol A type, bisphenol F type, and bisphenol AF type.

As the allyl resin having a carboxylic acid derivative having a cyclic structure, allyl carboxylic acid having a cyclic structure is preferable. As the cyclic structure, any of a cyclic group containing a non-aromatic ring such as an alicyclic structure and an aromatic ring structure may be used. In addition, the skeleton of the ring may be constituted by a hetero atom in addition to carbon atoms in the cyclic group. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom etc. are mentioned, for example, A nitrogen atom is preferable. As for the heteroatom, you may have 1 piece in said ring, and may have 2 or more.

As a carboxylic acid which has a cyclic structure, isocyanuric acid, diphenic acid, phthalic acid, cyclohexane dicarboxylic acid etc. are mentioned, for example. Examples of the allyl resin having a carboxylic acid derivative having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl diphenate, allyl diphenate, ortho diallyl phthalate, Meta diallyl phthalate, para diallyl phthalate, allyl cyclohexanedicarboxylic acid, diallyl cyclohexanedicarboxylic acid, etc. are mentioned.

A commercially available product can be used as the allyl resin. As a commercial item, it is "MEH-8000H" by a Meiwa Kasei company, "MEH-8005" (allyl resin which has a phenol ring), for example; "RE-810NM" by Nippon Kayaku Co., Ltd. (allyl resin having an epoxy group); "ALP-d" by Shikoku Kasei Kogyo Co., Ltd. (allyl resin having a benzoxazine ring); "L-DAIC" by Shikoku Kasei Kogyo Co., Ltd. (allylic resin having an isocyanuric ring); "TAIC" by Nippon Kasei Co., Ltd. (allyl resin (triaryl isocyanurate) having an isocyanuric ring); "MDAC" by Osaka Soda Co., Ltd. (allyl resin having a cyclohexanedicarboxylic acid derivative); "DAD" (diallyl diphenate) by Nisshoku Technofine Chemical; Osaka Soda Co., Ltd. "Disodap monomer" (ortho diallyl phthalate), etc. are mentioned.

The allyl group equivalent of the allyl resin is preferably 20 g/eq. to 1000 g/eq., more preferably 50 g/eq. to 500 g/eq., more preferably 100 g/eq. to 300 g/eq. The allyl group equivalent is the mass of a compound containing one equivalent of an allyl group.

Butadiene resin has a butadiene skeleton. The polybutadiene structure may be contained in the main chain or in the side chain. On the other hand, part or all of the polybutadiene structure may be hydrogenated. Examples of the butadiene resin include a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl group-containing butadiene resin, a phenolic hydroxyl group-containing butadiene resin, a carboxyl group-containing butadiene resin, an acid anhydride group-containing butadiene resin, an epoxy group-containing butadiene resin, an isocyanate group-containing butadiene resin, and a urethane group. One or more resins selected from the group consisting of containing butadiene resins are more preferred.

Specific examples of the butadiene resin include "JP-100" manufactured by Nippon Soda Co., Ltd., "Ricon100" manufactured by CRAY VALLEY, "Ricon150", "Ricon130MA8", "Ricon130MA13", "Ricon130MA20", "Ricon131MA5", "Ricon131MA10", "Ricon131MA17", "Ricon131MA20", "Ricon 184MA6", etc. are mentioned.

As the content of component (C), from the viewpoint of enhancing the desired effect of the present invention, when the non-volatile component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 5% by mass or more, More preferably, it is 8 mass % or more, Preferably it is 70 mass % or less, More preferably, it is 60 mass % or less, More preferably, it is 50 mass % or less.

The content of component (C) is preferably 2% by mass or more, more preferably 10% by mass or more, when the resin component in the resin composition is 100% by mass, from the viewpoint of enhancing the desired effect of the present invention. Preferably it is 16 mass % or more, Preferably it is 90 mass % or less, More preferably, it is 87 mass % or less, More preferably, it is 85 mass % or less.

The resin sheet of the present invention comprising a resin composition layer comprising a combination of component (A), component (B) and component (C), and satisfying both conditions of the oxygen transmission rate α and β described above, (A) It is possible to realize a cured product having excellent conductor adhesion and mechanical properties while maintaining or improving the advantage of excellent dielectric properties inherent in the components. In a resin composition layer in which component (A) is combined with only component (B) or only component (C), the above effect cannot be obtained even when both conditions of oxygen transmission rate α and β are satisfied, and (A) It has been confirmed that a specific effect can be obtained when a component is formulated by combining component (B) and component (C), and both conditions of the above oxygen transmission rates α and β are satisfied.

-(D) thermoplastic resin-

In the present invention, the resin composition may further contain a thermoplastic resin as component (D).

Examples of the component (D) include, for example, phenoxy resins, polyimide resins, polycarbonate resins, polyvinyl acetal resins, polyolefin resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, and polyethersulfone resins. Phenylene ether resin, polyether ether ketone resin, polystyrene resin, polyester resin, etc. are mentioned. Among them, the component (D) is preferably at least one selected from phenoxy resins, polyimide resins, and polycarbonate resins, from the viewpoint of obtaining a cured product having excellent dielectric properties, and mechanical properties such as elongation at break. It is more preferable to use a polyimide resin from the viewpoint of obtaining a more excellent cured product by this.

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 phenoxy resins having at least one type of skeleton selected from the group consisting of skeletons, anthracene skeletons, adamantane skeletons, terpene skeletons, and trimethylcyclohexane skeletons. Any functional group, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin.

As a commercial item of a phenoxy resin, "1256" by the Mitsubishi Chemical Corporation and "4250" (both are bisphenol A frame|skeleton containing phenoxy resins); "YX8100" (bisphenol S frame|skeleton containing phenoxy resin) by Mitsubishi Chemical Corporation; "YX6954" (bisphenol acetophenone frame|skeleton containing phenoxy resin) by the Mitsubishi Chemical company; "FX280" and "FX293" manufactured by Nippon Steel Chemical &Materials; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical; etc. can be mentioned.

As the polyimide resin, a resin having an imide structure can be used. A polyimide resin can generally be obtained by imidation reaction of a diamine compound and an acid anhydride. A commercial item may be used for polyimide resin, and "Rica coat SN20" and "Rica coat PN20" by New Nippon Rica Co., Ltd. are mentioned, for example. In addition, as the polyimide resin, you may use the thermoplastic resin d in the solution prepared in <synthesis example 1> (synthesis of the solution of the thermoplastic resin d) mentioned later, or its modification.

A polycarbonate resin is a resin having a carbonate structure. Examples of such resins include carbonate resins without a reactive group, carbonate resins containing a hydroxyl group, carbonate resins containing a phenolic hydroxyl group, carbonate resins containing a carboxy group, carbonate resins containing an acid anhydride group, carbonate resins containing an isocyanate group, and carbonates containing a urethane group, as described below. A resin, an epoxy group-containing carbonate resin, etc. are mentioned. Here, a reactive group refers to a functional group capable of reacting with other components such as a hydroxyl group, a phenolic hydroxyl group, a carboxy group, an acid anhydride group, an isocyanate group, a urethane group, and an epoxy group.

A commercial item can be used for polycarbonate resin. As commercially available products, "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., "C-1090" and "C-2090" manufactured by Kuraray Co., Ltd. ”, “C-3090” (polycarbonate diol), and the like.

The weight average molecular weight (Mw) of component (D) is preferably 5000 or more, more preferably 8000 or more, still more preferably 10000, from the viewpoint of obtaining a cured product having even more excellent mechanical properties, for example, elongation at break. More than that. The upper limit of the Mw is not particularly limited, but is preferably 100000 or less, more preferably 80000 or less, still more preferably 50000 or less. (D) Mw of component can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

When the resin composition contains the component (D), the content of the component (D) in the resin composition is not particularly limited as long as the effect of the present invention is not excessively impaired, but the non-volatile component in the resin composition is 100% by mass. In one case, it can be 0.1 mass % or more, 0.3 mass % or more, or 0.5 mass % or more. The lower limit of the content of component (D) is preferably 0.7% by mass or more, 0.8% by mass or more, or 1.0% by mass or more from the viewpoint of obtaining a cured product having even more excellent mechanical properties, for example, elongation at break. The upper limit of the content of component (D) is not particularly limited, but is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less.

-(E) Curing Accelerator-

In the present invention, the resin composition may further contain a curing accelerator as component (E). (E) A typical example of the curing accelerator as component is a peroxide-based curing accelerator.

As component (E), for example, t-butylcumyl peroxide, t-butylperoxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butylperoxylaurate, and peroxides such as t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butylperoxybenzoate.

(E) As a commercial item of a component, for example, "Perbutyl (registered trademark) C", "Perbutyl (registered trademark) A", "Perbutyl (registered trademark) P", "Perbutyl ( "Perbutyl (registered trademark) O", "Perbutyl (registered trademark) ND", "Perbutyl (registered trademark) Z", "Perhexyl (registered trademark) D", "Percumyl (registered trademark) Registered trademark) P", "Percumyl (registered trademark) D", etc. are mentioned.

When the resin composition contains the component (E), the content of the component (E) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, when the non-volatile component in the resin composition is 100% by mass. , More preferably, it is 0.05 mass% or more, preferably 1 mass% or less, more preferably 0.5 mass% or less, still more preferably 0.3 mass% or less.

-Other Ingredients-

In the present invention, the resin composition may further contain an epoxy resin and an epoxy resin curing agent.

Examples of the epoxy resin include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxies. Resin, naphthol novolac type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycy Diyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane type Epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, and the like are exemplified. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

Epoxy resins include liquid epoxy resins at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and solid epoxy resins at a temperature of 20°C (hereinafter referred to as "solid epoxy resins"). The resin composition for a resin sheet of the present invention may contain only a liquid 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 a specific example of a liquid epoxy resin, "HP4032" by DIC Corporation, "HP4032D", "HP4032SS" (naphthalene type epoxy resin); “828US”, “jER828EL”, “825”, and “Epicoat 828EL” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "jER807", "1750" (bisphenol F-type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" by Mitsubishi Chemical Corporation, "630LSD" (glycidylamine type|mold epoxy resin); "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "EX-721" by Nagase ChemteX Co., Ltd. (glycidyl ester type epoxy resin); "Celoxide 2021P" by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton); "PB-3600" by the Daicel company (epoxy resin which has a butadiene structure); “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon-Stetsu Chemical & Materials Co., Ltd., and the like are exemplified.

As a specific example of a solid-state epoxy resin, "HP4032H" by DIC Corporation (naphthalene-type epoxy resin); "HP-4700" by DIC Corporation, "HP-4710" (naphthalene type tetrafunctional epoxy resin); "N-690" by DIC Corporation (cresol novolak-type epoxy resin); "N-695" by DIC Corporation (cresol novolak-type epoxy resin); "HP-7200HH" by DIC, "HP-7200H", "HP-7200" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC; Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd. "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN485" (naphthol novolak-type epoxy resin) by the Nippon Steel Chemical & Materials company; Mitsubishi Chemical Corporation "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical Corporation "YX4000HK" (bixylenol type epoxy resin); Mitsubishi Chemical Corporation "YX8800" (anthracene-type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; Mitsubishi Chemical Corporation "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) by the Mitsubishi Chemical Corporation etc. are mentioned.

The epoxy equivalent of the epoxy resin is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., more preferably 80 g/eq. to 2000 g/eq., even more preferably 110 g/eq. to 1000 g/eq. Epoxy equivalent is the mass of the compound containing 1 equivalent of an 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 5000, more preferably 250 to 3000, still more preferably 400 to 1500. Mw of an epoxy resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

When the resin composition contains an epoxy resin, the content of the epoxy resin in the resin composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, when the non-volatile component in the resin composition is 100% by mass, More preferably, it is 0.5 mass % or more, 1 mass % or more, or 1.5 mass % or more, Preferably it is 10 mass % or less, More preferably, it is 5 mass % or less, or 3 mass % or less.

Examples of the epoxy resin curing agent include an active ester curing agent, a phenol curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate ester curing agent, a carbodiimide curing agent, an amine curing agent, an acid anhydride curing agent, and the like. can These may be used individually by 1 type, or may be used in combination of 2 or more types.

The content of the epoxy resin curing agent is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, when the non-volatile component in the resin composition is 100% by mass. is 10% by mass or less, more preferably 5% by mass or less.

The resin composition may further contain optional additives. Examples of such additives include: phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators other than the above-described peroxide-based hardening accelerators; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; coloring agents 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 antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet 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-based antioxidants and hindered amine-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (eg, phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red), nitrogen-based flame retardants (eg, melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (eg, antimony trioxide); dispersants such as phosphoric acid ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic acid anhydride stabilizers. These additives may be used individually by 1 type, and may be used in combination of 2 or more type. Each content can be appropriately set by those skilled in the art.

The resin composition may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile component described above. As an organic solvent, a well-known thing can be used suitably, and the kind is not specifically limited. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether and diphenyl ether; alcohol 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 solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide-based solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

In the present invention, the resin composition, for example, (A) component, (B) component, (C) component, and, if necessary, (D) component, (E) component, epoxy resin in an arbitrary preparation container , an epoxy resin curing agent, and other additives or organic solvents, in any order and/or partially or all simultaneously added and mixed. In addition, in the process of adding and mixing each component, the temperature can be set appropriately, and you may heat and/or cool temporarily or continuously. In addition, in the process of adding and mixing, or after that, the resin composition may be stirred or shaken using a stirring device such as a mixer or a shaking device to uniformly disperse the resin composition. Moreover, you may perform defoaming under low-pressure conditions, such as under vacuum, simultaneously with stirring or shaking.

For the resin sheet of the present invention, for example, the above resin composition is prepared, the liquid resin composition is prepared as it is, or a resin varnish obtained by dissolving the resin composition in an organic solvent is prepared, and this is coated on a support using a die coater or the like. It can be manufactured by applying and further drying to form a resin composition layer. What is necessary is just to use the thing mentioned above as an organic solvent, when preparing a resin varnish.

You may perform drying by a well-known method, such as heating and hot air spray. Drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although different depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 15% by mass to 60% by mass of the organic solvent, at 50°C to 150°C for 1 minute to 10 minutes A resin composition layer can be formed by drying.

In the resin sheet of the present invention, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. The lower limit of the thickness of the resin composition layer is not particularly limited, but is usually 5 μm or more, 10 μm or more, and the like.

<any floor>

The resin sheet of this invention may contain arbitrary layers. As an arbitrary layer, a protective film, a barrier film, metal foil, etc. are mentioned. As the material of the protective film, the barrier film, and the metal foil, those selected arbitrarily from the group of materials of the support body enumerated as described above are preferable. It is preferable that arbitrary layers are provided so that exfoliation is possible from the resin sheet. The optional layer is preferably provided on the surface of the resin sheet that is not bonded to the support of the resin composition layer (that is, the surface opposite to the support), thereby preventing dust and the like from adhering to the surface of the resin composition layer. or scratches can be suppressed. The thickness of the arbitrary layer is not particularly limited, but is, for example, 1 μm to 100 μm.

The resin sheet can be wound up in a roll shape and stored. When a resin sheet has a protective film, a barrier film, metal foil, etc. as an arbitrary layer, it becomes usable by peeling off these arbitrary layers.

The resin sheet of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and is more suitable for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board). can be used appropriately. Since the resin sheet of the present invention forms an insulating layer with good component embedding properties, it can be suitably used even when the printed wiring board is a circuit board with built-in components. The resin sheet of the present invention can be suitably used also as an insulating layer (for an insulating layer for forming a conductor layer) in order to form an insulating layer on which a conductor layer (including a redistribution layer) is provided. The resin sheet of the present invention can also be used in a wide range of applications, such as solder resist, underfill material, die bonding material, semiconductor sealing material, hole filling resin, and parts embedding resin.

In one embodiment, a cured product formed using the resin sheet of the present invention is characterized by low dielectric constant (Dk). For example, when measured at 5.8 GHz and 23° C. as described in the section <Evaluation of dielectric properties> described later, the dielectric constant (Dk) of the cured product of the resin composition layer for a resin sheet of the present invention is preferably It can be less than 3.0 or less than 2.9.

In one embodiment, a cured product formed using the resin sheet of the present invention is characterized by a low dielectric loss tangent (Df). For example, when measured at 5.8 GHz and 23° C. as described in the section <Evaluation of Dielectric Characteristics> described later, the dielectric loss tangent (Df) of the cured product of the resin composition layer for a resin sheet of the present invention is preferably may be 0.0030 or less, 0.0029 or less, or 0.0028 or less.

In one embodiment, a cured product formed using the resin sheet of the present invention is characterized by excellent conductor adhesion. For example, the conductor adhesion strength measured by the method described in the <Evaluation of Conductor Adhesion> column described later can be preferably 0.50 kgf/cm or more, 0.52 kgf/cm or more, or 0.54 kgf/cm or more.

In one embodiment, a cured product formed using the resin sheet of the present invention is characterized by excellent mechanical properties. For example, the maximum point stress measured by the method described in the section <Evaluation of mechanical properties (maximum point stress and elongation at break)> described later may be preferably 100 MPa or more, 101 MPa or more, 102 MPa or more, or 105 MPa or more. . Further, the elongation at break may be preferably 1.4% or more or 1.5% or more.

In one embodiment, a cured product formed using the resin sheet of the present invention tends to exhibit characteristics of excellent insulation reliability. For example, when the HAST test is conducted under conditions of 130°C and 85% RH by the method described in the <Evaluation of insulation reliability> section described later, the insulation resistance value after 300 hours is preferably 50% of the initial insulation resistance value. Excess, more preferably 51% or more of the initial insulation resistance value, or 52% or more of the initial insulation resistance value.

[printed wiring board]

A printed wiring board can be manufactured using the resin sheet of this invention. In this case, the printed wiring board includes an insulating layer made of a cured product of the resin composition layer in the resin sheet of the present invention.

A printed wiring board can be manufactured by the method including the process of following (I) and (II) using said resin sheet, for example.

(I) Step 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 step of forming an insulating layer by curing (for example, thermal curing) the resin composition layer

The "inner layer substrate" used in step (I) is a member to be a substrate of a printed wiring board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene An ether substrate etc. are mentioned. In addition, the board|substrate may have a conductor layer on one side or both sides thereof, and this conductor layer may be patterned. An inner-layer board in which a conductor layer (circuit) is formed on one or both surfaces of the board is sometimes referred to as an "inner-layer circuit board". In addition, when manufacturing a printed wiring board, an intermediate product in which an insulating layer and/or a conductor layer is to be further formed is also included in the "inner layer substrate" as used in the present invention. In the case where the printed wiring board is a component-embedded circuit board, an inner-layer board having components embedded 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 body side. Examples of the member for heat-pressing the resin sheet to the inner-layer substrate (hereinafter also referred to as "heat-compression member") include a heated metal plate (SUS head plate, etc.) or a metal roll (SUS roll). On the other hand, the thermocompression bonding member may be pressed directly onto the resin sheet, or may be pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the irregularities on the surface 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 compression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the heat compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat pressing time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. Lamination can be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, a vacuum pressurization type laminator made by Meiki Sesakusho, a vacuum applicator made by Nikko Materials, a batch type vacuum pressurization laminator, etc. are mentioned, for example.

After lamination, the laminated resin sheets may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing the hot-compression bonding member from the support body side. The press conditions for the smoothing treatment can be the same conditions as the thermal compression conditions for the above laminate. The smoothing process can be performed with a commercially available laminator. On the other hand, you may perform lamination|stacking and a smoothing process continuously using the said commercially available vacuum laminator.

The support may be removed between the steps (I) and the step (II), but is preferably removed or peeled after the step (II).

One of the preferable embodiments of the manufacturing method of a printed wiring board is as follows.

As a manufacturing method of a printed wiring board,

The following process:

(1) Step of preparing a resin sheet comprising a support and a resin composition layer provided on the support, wherein one surface of the resin composition layer is exposed;

(2) a step of laminating the resin sheet on the substrate of the printed wiring board so that the resin composition layer is laminated on the substrate; and

(3) a step of curing the resin sheet laminated on the substrate in a state in which the support is not separated from the resin composition layer;

including,

The resin composition layer includes (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radically polymerizable resin,

The resin composition layer,

The oxygen transmission rate α measured when curing at 220 ° C. for 90 minutes is 70 cc / m 2 day or less,

The resin sheet in which one surface of the resin composition layer is exposed,

The oxygen transmission rate β measured when curing at 220 ° C. for 90 minutes is 40 cc / m 2 day or less,

Here, the oxygen permeability α and the oxygen permeability β are measured values measured in an atmosphere of 23 ° C. and 0% RH in accordance with JIS K7126-2: 2006 (isobaric method),

A method for manufacturing a printed wiring board.

On the other hand, when using a metal foil as a support body, you may form a conductor layer using the said metal foil, without peeling off a support body. Moreover, what is necessary is just to peel a support base material (and a peeling layer), when metal foil with a support base material is used as a support body. And a conductor layer can be formed using metal foil.

In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. Curing conditions for the resin composition layer are not particularly limited, and conditions usually employed when forming an insulating layer of a printed wiring board may be used.

For example, the thermal curing conditions of the resin composition layer vary depending on the type of resin composition and the like, but in one embodiment, the curing temperature is preferably 120°C to 250°C, more preferably 150°C to 240°C, and furthermore Preferably it is 180 °C to 230 °C. The curing time can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, still more preferably 15 minutes to 120 minutes.

Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer is heated for 5 minutes or more at a temperature of 50 ° C to 120 ° C, preferably 60 ° C to 115 ° C, more preferably 70 ° C to 110 ° C, You may preheat 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.

When manufacturing a printed wiring board, you may further perform (III) the process of making a hole in an insulating layer, the process of roughening (IV) an insulating layer, and the process of forming a (V) conductor layer. You may carry out these process (III) - process (V) according to the various methods known to those skilled in the art used for manufacture of a printed wiring board. On the other hand, when the support is removed after step (II), the removal of the support is between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). ) may be performed between Moreover, if necessary, you may form a multilayer wiring board by repeating formation of the insulating layer and the conductor layer of a process (I) - process (V).

Step (III) is a step of perforating the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) depends on the composition of the resin composition used for forming the insulating layer, and may be performed using, for example, a drill, laser, plasma, or the like. You may determine the size and shape of a hole suitably according to the design of a printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, smear is also removed in this step (IV). The procedures and conditions of the roughening treatment are not particularly limited, and known procedures and conditions normally used when forming the insulating layer of a printed wiring board are employable. For example, the insulation layer can be roughened by performing the swelling process by swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralization liquid in this order.

Although it does not specifically limit as a swelling liquid used for a roughening process, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As a swelling liquid marketed, "Swelling Deep Securiganth P" by the Atotech Japan company, "Swelling Deep Securiganth SBU", etc. are mentioned, for example. The swelling treatment by the swelling solution is not particularly limited, but can be performed by, for example, immersing the insulating layer in a swelling solution at 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 solution at 40°C to 80°C for 5 minutes to 15 minutes.

Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment by 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 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As an oxidizing agent marketed, alkaline permanganic acid solutions, such as "Concentrate Compact CP" by the Atotech Japan company and "Dosing Solution Securiganth P", are mentioned, for example.

Moreover, as a neutralization liquid used for a roughening process, an acidic aqueous solution is preferable, and as a commercial item, "Reduction Solution Securigant P" by Atotech Japan Co., Ltd. is mentioned, for example.

The treatment with the neutralization liquid can be performed by immersing the treated surface subjected to the roughening treatment by the oxidizing agent in the neutralization liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the standpoint of workability and the like, a method of immersing the object subjected to the roughening treatment with an oxidizing agent in a neutralization solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In suitable embodiments, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more types of metals selected from the above groups (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium) alloy). Among them, from the viewpoint of versatility of formation of a conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, a nickel-chromium alloy, or a copper-nickel alloy , An alloy layer of a copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper this is more preferable

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

The thickness of the conductor layer depends on the design of the desired 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 on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method. It is preferable to form by an additive method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After forming a metal layer by electroplating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

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

Metal foil can be manufactured by well-known methods, such as an electrolysis method and a rolling method, for example. As a commercial item of metal foil, HLP foil by the JX Nikko Nisseki Kinzoku company, JXUT-III foil, 3EC-III foil by the Mitsui Kinzokukozan company, TP-III foil, etc. are mentioned, for example.

Alternatively, when a metal foil or a metal foil with a support substrate is used as the support of the resin sheet, it is as described above that the metal foil may be used to form the conductor layer.

Further, the resin composition layer for a resin sheet of the present invention is a resin composition layer (resin composition layer for forming a redistribution layer) for forming an insulating layer for forming a redistribution layer when manufacturing a semiconductor chip package, and a semiconductor It can also be suitably used as a resin composition layer for sealing chips (resin composition layer for sealing semiconductor chips). A technique for manufacturing a semiconductor chip package using a resin composition layer (resin sheet) is widely known in the art, and the resin sheet or the resin composition layer of the present invention can be applied to any method or technique.

[Semiconductor device]

The semiconductor device can be manufactured to include an insulating layer made of a cured product of the layer of the resin composition for a resin sheet according to the present invention. Such a semiconductor device can be manufactured using the above printed wiring board or semiconductor package.

Examples of the semiconductor device include various semiconductor devices provided for electric appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, electric cars, ships, aircraft, etc.). there is.

[Example]

Hereinafter, the present invention will be specifically described by examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In particular, temperature conditions and pressure conditions in the case where there is no designation of temperature are room temperature (25°C) and atmospheric pressure (1 atm).

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

[Preparation of samples for measurement and evaluation]

1. Preparation of cured products for evaluation

The protective film was peeled off from the resin sheet A with a protective film prepared in Examples and Comparative Examples, and one surface of the resin composition layer was exposed. Subsequently, the resin composition layer was thermally cured by rapidly heating in a nitrogen atmosphere at 220°C for 90 minutes. Thus, a resin sheet B composed of a support and a cured material provided on the support was obtained.

Further, both sides of the resin composition layer were exposed by cutting a part of the resin sheet B and peeling off the support to obtain a film-like cured product C composed of a cured product of the resin composition layer.

2. Production of substrate for first evaluation

(1) Copper foil base treatment

The polished surface of "3EC-III" (electrolytic copper foil, 35 μm) manufactured by Mitsui Kinzokukozan Co., Ltd. is immersed in MAC Etch Bond "CZ-8201" manufactured by Mack Co., Ltd., thereby roughening the copper surface so that the Ra value becomes 0.5 μm. did Then, rust prevention treatment (CL8300) was performed, and further heat treatment was performed in an oven at 130°C for 30 minutes. In this way, a copper foil having a low surface roughness (hereinafter, referred to as "CZ copper foil") was obtained.

(2) Fabrication of substrate

The protective film was peeled off from the resin sheet A with a protective film prepared in Examples and Comparative Examples, and one surface of the resin composition layer was exposed. Then, using a batch-type vacuum pressure laminator (“MVLP-500” manufactured by Makeki), the glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness of 18 μm, substrate The resin sheet from which the protective film was peeled was laminated on both sides of the laminated board so as to bond to a thickness of 0.4 mm, manufactured by Panasonic Corporation "R1515A"). The lamination process was performed by reducing the pressure for 30 seconds, adjusting the air pressure to 13 hPa or less, and then press-bonding at 100°C and a pressure of 0.74 MPa for 30 seconds. After the lamination process, the support was peeled off from the resin sheet. Then, the treated surface of the CZ copper foil was laminated on the exposed surface of the resin composition layer under the same conditions as above. After the lamination process, the resin composition layer was thermally cured at 220°C for 90 minutes to form a cured product (insulating layer). In this way, a substrate D in which CZ copper foils were laminated on both sides was produced.

3. Production of substrate for second evaluation

An imide film having a comb-shaped electrode (line/space: 15 μm/15 μm) formed on one surface was prepared. The protective film was peeled off from the resin sheet A with a protective film, and one surface of the resin composition layer was exposed. Then, using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Sesakusho Co., Ltd.), the resin composition layer was laminated so that the exposed surface was bonded to the circuit formation surface (electrode formation surface) of the imide film. The lamination was carried out by reducing the pressure for 30 seconds to reduce the air pressure to 13 hPa or less, and then pressing at 100°C and a pressure of 0.74 MPa for 30 seconds. Thereafter, the resin composition layer was cured by heating at 100°C for 30 minutes and then at 220°C for 90 minutes under a nitrogen atmosphere. In this way, substrate E provided with the imide film and the cured product of the resin composition layer provided on the imide film was produced.

<Measurement of oxygen transmission rate>

Oxygen permeability was measured for the resin sheet B and the cured product C. It was measured in accordance with teJIS K7126-2:2006 (isobaric method) using an oxygen transmission rate measuring device (“OX-TRAN2/21” manufactured by MOCON) at 23° C. in an atmosphere of 0% RH. The oxygen permeability of the resin sheet B is referred to as "oxygen permeability β", and the oxygen permeability of the cured product C is referred to as "oxygen permeability α".

In addition, the oxygen transmission rate was measured as described above with respect to the support used at the time of production of the resin sheet A with a protective film. The oxygen permeability of each support used in Examples and Comparative Examples is shown below.

Oxygen transmission rate of support A: 40 cc/m day

Oxygen transmission rate of support B: 0.1 cc/m day

Oxygen transmission rate of support C: 0.1 cc/m 2 day

<Evaluation of dielectric properties>

Cured product C was used to evaluate dielectric properties.

In detail, the cured material C was cut out to a width of 2 mm and a length of 80 mm to obtain a test piece. About the obtained test piece, the permittivity (Dk value) and the dielectric loss tangent (Df value) were measured by the cavity resonance perturbation method using "HP8362B" by Agilent Technologies, at a measurement frequency of 5.8 GHz, and a measurement temperature of 23 degreeC. Measurements were made on three test pieces (n = 3), and the average value was calculated. The dielectric properties of the cured product C were evaluated according to the following evaluation criteria.

Criteria for evaluating dielectric properties:

○: The average value of dielectric constant satisfies 3.0 or less, and the average value of dielectric loss tangent satisfies 0.0030 or less (dielectric properties are excellent)

×: One or both of the average value of the dielectric constant and the average value of the dielectric loss tangent do not satisfy the above criteria (dielectric properties are poor)

<Evaluation of conductor adhesion>

Conductor adhesion was evaluated using the substrate D for evaluation.

Specifically, the substrate D for evaluation was cut into small pieces of 150 x 30 mm. An incision of 10 mm in width and 100 mm in length was made in the copper foil portion of the small piece using a cutter. Then, one end of the copper foil was peeled off, picked up with a tool attached to the tensile tester described later, and the load [kgf/cm] when peeled off 35 mm in the vertical direction at a rate of 50 mm/min in room temperature (room temperature) was measured. For the measurement, a tensile tester (Autocom Universal Tester "AC-50C-SL" manufactured by TSE Co., Ltd.) was used. The measurement was performed based on Japanese Industrial Standards JIS C6481. The value of the load obtained as a result of the measurement is hereinafter referred to as "conductor adhesion strength". Conductor adhesion was evaluated according to the following evaluation criteria.

Conductor adhesion evaluation criteria:

○: Value of conductor adhesion strength is 0.50 kgf/cm or more (conductor adhesion is excellent)

×: Value of conductor adhesion strength is less than 0.50 kgf/cm (conductor adhesion is inferior)

<Evaluation of mechanical properties (maximum point stress and elongation at break)>

Cured product C was used to evaluate mechanical properties.

In detail, the cured material C was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. About the obtained test piece, the tensile strength was measured at the test speed of 5 mm/min using the tensile tester "RTC-1250A" by Orientec, and the breaking elongation and maximum point stress at 23 degreeC were measured. The measurement was performed based on JIS K7127. The measurement was performed 5 times (n = 5), and the average value of the top 3 points was calculated. The mechanical properties of the cured product were evaluated according to the following evaluation criteria.

Criteria for evaluating machine characteristics:

○: The average value of elongation at break satisfies 1.4% or more and the average value of maximum point stress satisfies 100 MPa or more (excellent mechanical properties)

×: One or both of the average value of the maximum point stress and the average value of the elongation at break do not satisfy the above criteria (mechanical properties are poor)

<Evaluation of insulation reliability>

Using substrate E, insulation reliability was evaluated.

Specifically, first, the initial insulation resistance value of the substrate E was measured. Thereafter, the substrate E was placed in a high-temperature, high-humidity tank under an atmosphere of 130° C. and 85% humidity, and a voltage of 3.3 V was charged, and the HAST test was performed in the tank for 300 hours under conditions of 130° C. and 85% RH. The insulation resistance value of the board|substrate F after 300 hours passed was measured and evaluated according to the following criteria.

Insulation Reliability Evaluation Criteria:

○: The insulation resistance value after 300 hours exceeds the initial insulation resistance value by 50% (insulation reliability is excellent)

×: The insulation resistance value after 300 hours is 50% or less of the initial insulation resistance value (insulation reliability is poor)

<Synthesis Example 1> (Synthesis of solution of thermoplastic resin d)

A 500 mL separable flask equipped with a moisture meter connected to a reflux condenser, a nitrogen inlet pipe, and a stirrer was prepared. To this flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5-(4-aminophenoxy)-3-[4-(4-amino) 29.6 g of phenoxy)phenyl]-1,1,3-trimethylindane was added, and the mixture was stirred for 2 hours at 45°C under a nitrogen stream to react. Next, the temperature of this reaction solution was raised, and the condensation water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160°C. It was confirmed that a predetermined amount of water was stagnant in the water-determination receiver and that the outflow of water was not visible. After confirmation, the temperature of the reaction solution was further raised and stirred at 200°C for 1 hour. It was then cooled to obtain a solution (20% by mass of non-volatile components) containing a thermoplastic resin having a 1,1,3-trimethylindan skeleton (hereinafter also referred to as "thermoplastic resin d"). The obtained thermoplastic resin d was a polyimide compound having a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). In addition, the weight average molecular weight of said thermoplastic resin d was 12,000.

-Examples 1 to 6, Comparative Examples 1 to 5-

Hereinafter, Examples and Comparative Examples are illustratively shown regarding aspects of a resin sheet comprising a resin composition layer containing a component selected from (A) component, (B) component, and (C) component, and a support.

[Example 1]

(1) Preparation of a resin composition constituting a resin composition layer

(C) Radical polymerizable resin c1 as component ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.; MEK/toluene mixed solution of 70% by mass of non-volatile component) 28.6 parts (20 parts as non-volatile component), (A) Benzocyclobutene resin a as a component ("CYCLOTEN (registered trademark) 3022" by Dow Chemical Co., Ltd.; number average molecular weight: 390, mesitylene solution of 35% by mass of non-volatile components) 28.6 parts (10 parts as non-volatile components), It was heated and dissolved while stirring in 10 parts of methyl ethyl ketone (MEK). In this way, a solution was obtained.

On the other hand, the non-volatile component contained in radically polymerizable resin c1 ("MIR-3000-70MT") is represented by the following structural formula. In formula, e1 is an integer of 1-100.

The resulting solution was cooled to room temperature. Then, to the solution, radically polymerizable resin c2 as component (C) ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd. (oligophenylene ether styrene resin); number average molecular weight: 1200, non-volatile component 65% by mass of toluene solution) 13.8 parts (9 parts as non-volatile component), (B) inorganic filler b as component (Spherical silica manufactured by Adomatex, surface-treated with Shin-Etsu Chemical Co., Ltd. amine silane coupling agent "KBM573") "SO-C2" (average particle diameter: 0.5 μm, specific surface area: 5.8 m2/g)) 60 parts, (D) 5 parts of thermoplastic resin d as component (1 part as non-volatile component), (E) curing as component 0.05 part of accelerator e (“Perhexyl (registered trademark) D” by Nichiyu Co., Ltd.) was added, mixed, and further uniformly dispersed with a high-speed rotary mixer. In this way, a dispersion liquid was obtained. Thus, a resin varnish (amount of non-volatile components: 69% by mass) of a resin composition containing components (A) to (E) was prepared.

(2) Preparation of resin sheet with protective film

As the support A, a PET film ("Lumira R80" manufactured by Toray Corporation; thickness: 38 µm, softening point: 130°C) was prepared by subjecting one main surface to release treatment with an alkyd resin-based release agent ("AL-5" manufactured by Lintec). The thickness of the whole support A (total thickness) was 38 μm.

The resin varnish of the resin composition prepared in the above (1) was uniformly applied with a die coater on the release-treated surface of the support A so that the thickness of the resin composition layer after drying was 40 μm, and dried at 90 ° C. for 3 minutes. Thus, a resin sheet containing the support A and the resin composition layer provided on the support A was obtained.

Next, the support A as a protective film was laminated on the exposed surface of the resin composition layer (the surface not bonded to the support A) so that the release-treated surface was bonded to the resin composition layer. Thus, a resin sheet provided with a support, a resin composition layer provided on the support, and a protective film provided on the resin composition layer was obtained. The resin sheet obtained in this way is generically called also "resin sheet A with a protective film."

[Example 2]

1) Change the compounding amount of benzocyclobutene resin a from 28.6 parts to 38.5 parts (25 parts as a non-volatile component), 2) Change the compounding amount of radically polymerizable resin c1 from 28.6 parts to 0 parts (i.e., no compounding), In addition, a resin varnish was prepared in the same manner as in Example 1, except that the blending amount of the radically polymerizable resin c2 was changed from 13.8 parts to 21.5 parts (14 parts as a non-volatile component), and a resin varnish was prepared using the support A. sheet was made.

[Example 3]

1) Change the blending amount of inorganic filler b from 60 parts to 40 parts, 2) Change the blending amount of radically polymerizable resin c1 from 28.6 parts to 42.9 parts (19 parts as non-volatile component), and also radically polymerizable resin c2 A resin varnish was prepared in the same manner as in Example 1, except that the blending amount of was changed from 13.8 parts to 29.2 parts (14 parts as a non-volatile component), and a resin sheet was produced using the support A.

[Example 4]

A resin varnish was prepared in the same manner as in Example 3, except that the support A was changed to the support B, and a resin sheet was produced using the support B. As the support B, an alkyd release treatment (“AL-5” manufactured by Lintec) was applied to one main surface of a PET film ("Lumira R80" manufactured by Tore, Inc.; thickness 38 μm), and an adhesive layer (thickness 3 μm) was applied to the other main surface. A PET film (“Tech Barrier (registered trademark) HX” manufactured by Mitsubishi Chemical Corporation; thickness: 12 μm) bonded to each other with a 300 nm silica deposition layer formed therebetween was used. The thickness of the entire support B (total thickness) was 53 µm.

[Example 5]

Except having changed the support body A to the support body C, it carried out similarly to Example 3, prepared the resin varnish, and produced the resin sheet using the support body C.

Support body C was prepared as follows. First, the same film with a metal film as the film with a metal film described in Example 1 of Patent No. 5500074 (Layer configuration: 38 μm-thick PET film/2-μm-thick water-soluble resin layer/1000 nm-thick copper layer) was prepared. Then, an alkyd type release treatment (“AL-5” manufactured by Lintec Corporation) was applied to the exposed surface of the PET film of this film with a metal film. The overall thickness (total thickness) of the support body C obtained in this way was 41 µm.

[Example 6]

1) The blending amount of inorganic filler b is changed from 60 parts to 50 parts, 2) The blending amount of radically polymerizable resin c1 is changed from 28.6 parts to 0 part (i.e., no blending), and the blending amount of radical reactive resin c2 is changed to 13.8 parts. part to 15.4 parts (10 parts as a non-volatile component), 3) the blending amount of thermoplastic resin d was changed from 5 parts to 150 parts (30 parts as a non-volatile component), and 4) Support A was changed to Support B A resin varnish was prepared in the same manner as in Example 1, except for changing to, and a resin sheet was produced using the support B.

[Comparative Example 1]

1) The blending amount of radically polymerizable resin c1 is changed from 28.6 parts to 0 part (i.e., no blending), and the blending amount of radically polymerizable resin c2 is changed from 13.8 parts to 0 part (ie, no blending) (that is, ( component C) was not used), and 3) resin varnish was prepared in the same manner as in Example 1, except that the blending amount of thermoplastic resin d was changed from 5 parts to 150 parts (30 parts as a non-volatile component). prepared, and a resin sheet was produced using the support body A.

[Comparative Example 2]

1) Change the blending amount of inorganic filler b from 60 parts to 40 parts, 2) Change the blending amount of radical polymerizable resin c1 from 28.6 parts to 0 part (i.e. no blending), and also change the blending amount of radical polymerizable resin c2 Except for changing from 13.8 parts to 15.4 parts (10 parts as non-volatile components) and also changing the blending amount of 3) thermoplastic resin d from 5 parts to 200 parts (40 parts as non-volatile components), Example 1 and Similarly, a resin varnish was prepared and a resin sheet was produced using the support A.

[Comparative Example 3]

1) Same as Comparative Example 2 except that the blending amount of benzocyclobutene resin a was changed from 28.6 parts to 85.7 parts (30 parts as a non-volatile component), and 2) the blending amount of inorganic filler b was changed from 40 parts to 20 parts. Thus, a resin varnish was prepared, and a resin sheet was produced using the support A.

[Comparative Example 4]

A resin varnish was prepared in the same manner as in Comparative Example 3, except that the support A was changed to the support B, and a resin sheet was produced using the support B.

[Comparative Example 5]

Except having changed the support body B to the support body A, it carried out similarly to Example 6, prepared the resin varnish, and produced the resin sheet using the support body A.

The results of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 1 and Table 2.

Claims (14)

A resin sheet comprising a support and a resin composition layer provided on the support,
The resin composition layer includes (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radically polymerizable resin,
The resin composition layer,
The oxygen transmission rate α measured when curing at 220 ° C. for 90 minutes is 70 cc / m 2 day or less,
The resin sheet,
The oxygen transmission rate β measured when curing at 220 ° C. for 90 minutes is 40 cc / m 2 day or less,
Here, the oxygen permeability α and the oxygen permeability β are measured values measured in an atmosphere of 23 ° C. and 0% RH in accordance with JIS K7126-2: 2006 (isobaric method),
resin sheet. The resin sheet according to claim 1, wherein the content of the component (B) is 30% by mass or more and 80% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin sheet according to claim 1, wherein the content of the component (A) is 3% by mass or more and 40% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin sheet according to claim 1, wherein component (A) contains a compound having two or more benzocyclobutene groups in a molecule, and component (A) has a number average molecular weight (Mn) of 2000 or less. The resin sheet according to claim 1, wherein the component (C) is at least one selected from maleimide resins, (meth)acrylic resins, and styryl resins. The resin sheet according to claim 1, wherein the support is selected from a single-layer resin film, a multi-layer resin film, a metal foil, a release paper, and a composite film comprising a support substrate and a metal foil. The resin sheet according to claim 1, wherein the component (A) has a siloxane skeleton. The resin sheet according to claim 1, wherein component (A) contains a compound represented by the following formula (A-2).

(In Formula (A-2),
R ¹ represents a divalent aliphatic group having an unsaturated bond;
R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an arylalkyl group, or an aryl group;
R ^A1 represents an alkyl group, a cyano group or a halogen atom;
R ^A2 represents an alkyl group, a trialkylsilyl group, an alkoxy group or a halogen atom;
nA1 represents an integer from 0 to 2;
nA2 represents an integer from 0 to 3;
nA4 represents an integer of 1 to 10. R ¹ , R ² , R ^A1 and R ^A2 may each independently have a substituent. A plurality of R ¹ may be the same or different, a plurality of R ² may be the same or different, when a plurality of R ^A1 are present, they may be the same or different, and when a plurality of R ^A2 are present, they may be the same or different. good.) The resin sheet according to claim 1, wherein the component (A) contains a compound represented by the following formula.

The resin sheet according to claim 1, wherein the cured product of the resin composition layer has a dielectric constant value of 3.0 or less. The resin sheet according to claim 1, wherein the cured product of the resin composition layer has a dielectric loss tangent value of 0.0030 or less. The resin sheet according to claim 1, wherein one side of the cured product of the resin composition layer is exposed when the oxygen transmission rate β is measured. The resin sheet according to claim 1, which is for an insulating layer of a printed wiring board. As a manufacturing method of a printed wiring board,
The following process:
(1) Step of preparing a resin sheet comprising a support and a resin composition layer provided on the support, wherein one surface of the resin composition layer is exposed;
(2) a step of laminating the resin sheet on the substrate of the printed wiring board so that the resin composition layer is laminated on the substrate; and
(3) a step of curing the resin sheet laminated on the substrate in a state in which the support is not separated from the resin composition layer;
including,
The resin composition layer includes (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radically polymerizable resin,
The resin composition layer,
The oxygen transmission rate α measured when curing at 220 ° C. for 90 minutes is 70 cc / m 2 day or less,
The resin sheet in which one surface of the resin composition layer is exposed,
The oxygen transmission rate β measured when curing at 220 ° C. for 90 minutes is 40 cc / m 2 day or less,
Here, the oxygen permeability α and the oxygen permeability β are measured values measured in an atmosphere of 23 ° C. and 0% RH in accordance with JIS K7126-2: 2006 (isobaric method),
A method for manufacturing a printed wiring board.