JP2024030949A - resin composition - Google Patents

Abstract

The present invention provides a resin composition capable of obtaining a cured product with a low dielectric loss tangent and suppressing the haloing phenomenon. [Solution] (A) A compound containing a secondary carbon atom, an oxygen atom bonded to the secondary carbon atom with a single bond, and an aliphatic unsaturated bond; and (B) a secondary carbon atom. A resin composition comprising a radically polymerizable resin that does not contain an oxygen atom bonded to by a single bond and contains an aliphatic unsaturated bond. [Selection diagram] None

Description

The present invention relates to a resin composition.

In recent years, demand for small, high-performance electronic devices such as smartphones and tablet devices has been increasing. Accordingly, there is a demand for even higher functionality in insulating layers for printed wiring boards and semiconductor packages used in these small electronic devices. Such an insulating layer is known to be formed by curing a resin composition (for example, see Patent Document 1).

JP2020-023714A

With the advancement of high-speed communications, the material for the insulating layer is required to have a lower dielectric loss tangent. As methods for lowering the dielectric loss tangent, the present inventor has proposed a method of using a resin with low polarity as a material for the insulating layer, a method of using a large amount of resin with a low proportion of functional groups, and a method of using a large amount of inorganic filler. investigated. However, although these methods can lower the dielectric loss tangent of the insulating layer, they tend to cause a large haloing phenomenon.

The haloing phenomenon refers to a phenomenon in which when a hole is formed in an insulating layer provided on a base material, the resin of the insulating layer changes color around the hole. Such a haloing phenomenon usually occurs due to deterioration of the resin around the hole when the hole is formed. Therefore, since the resin tends to be easily eroded in the discolored portion, when the insulating layer is subjected to roughening treatment, peeling is likely to occur between the insulating layer and the base material.

Due to the above-mentioned circumstances, it has conventionally been difficult to achieve both lowering the dielectric loss tangent of the insulating layer and suppressing the haloing phenomenon.

The present invention was created in view of the above-mentioned problems, and provides a resin composition capable of obtaining a cured product having a low dielectric loss tangent and suppressing the haloing phenomenon; a cured product of the resin composition layer described above. ; A sheet-like laminate material and a resin sheet comprising the above resin composition; a printed wiring board comprising an insulating layer comprising a cured product of the resin composition; and a semiconductor device comprising the printed wiring board. The purpose is to

The inventors of the present invention have made extensive studies to solve the above problems. As a result, the present inventor discovered that (A) a compound containing a secondary carbon atom, an oxygen atom bonded to the secondary carbon atom with a single bond, and an aliphatic unsaturated bond, and (B) a secondary hydroxyl group. The present inventors have discovered that a resin composition containing a combination of a radically polymerizable resin containing no aliphatic unsaturated bond can solve the above-mentioned problems, and has completed the present invention.
That is, the present invention includes the following.

（式（Ａ－１）において、
Ｒ^０は、水素原子又は１価の有機基を表し、
Ｒ^１は、それぞれ独立に、置換基を有していてもよい２価の炭化水素基を表し、
Ｒ^２は、それぞれ独立に、置換基を有していてもよい２価の炭化水素基を表し、
Ｒ^３は、それぞれ独立に、水素原子、又は、置換基を有していてもよい１価の炭化水素基を表し、
Ｒ^４は、それぞれ独立に、水素原子、又は、置換基を有していてもよい１価の炭化水素基を表し、
Ｒ^５は、それぞれ独立に、水素原子、又は、置換基を有していてもよい１価の炭化水素基を表し、
ｎは、それぞれ独立に、０以上６以下の整数を表す。）
＜３＞ （Ｂ）成分が、マレイミド樹脂を含む、＜１＞又は＜２＞に記載の樹脂組成物。
＜４＞ （Ｃ）エポキシ樹脂を含む、＜１＞～＜３＞の何れか一項に記載の樹脂組成物。
＜５＞ （Ｄ）硬化剤を含む、＜１＞～＜４＞の何れか一項に記載の樹脂組成物。
＜６＞ （Ｅ）無機充填材を含む、＜１＞～＜５＞の何れか一項に記載の樹脂組成物。
＜７＞ （Ｅ）無機充填材の量が、樹脂組成物中の不揮発成分１００質量％に対して、５０質量％以上である、＜６＞に記載の樹脂組成物。
＜８＞ （Ｆ）熱可塑性樹脂を含む、＜１＞～＜７＞の何れか一項に記載の樹脂組成物。
＜９＞ 絶縁層形成用である、＜１＞～＜８＞の何れか一項に記載の樹脂組成物。
＜１０＞ ＜１＞～＜９＞の何れか１項に記載の樹脂組成物の硬化物。
＜１１＞ ＜１＞～＜９＞の何れか１項に記載の樹脂組成物を含む、シート状積層材料。
＜１２＞ 支持体と、当該支持体上に形成された樹脂組成物層と、を備え、
前記樹脂組成物層が、＜１＞～＜９＞の何れか１項に記載の樹脂組成物を含む、樹脂シート。
＜１３＞ ＜１＞～＜９＞の何れか１項に記載の樹脂組成物の硬化物を含む絶縁層を備える、プリント配線板。
＜１４＞ ＜１３＞に記載のプリント配線板を備える、半導体装置。 <1> (A) A compound containing a secondary carbon atom, an oxygen atom bonded to the secondary carbon atom with a single bond, and an aliphatic unsaturated bond, and
(B) A resin composition comprising a radically polymerizable resin that does not contain an oxygen atom bonded to a secondary carbon atom through a single bond and contains an aliphatic unsaturated bond.
<2> The resin composition according to <1>, wherein the component (A) contains a compound represented by the following formula (A-1).

(In formula (A-1),
R ⁰ represents a hydrogen atom or a monovalent organic group,
R ¹ each independently represents a divalent hydrocarbon group which may have a substituent,
R ² each independently represents a divalent hydrocarbon group which may have a substituent,
R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent,
R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent,
R ⁵ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent,
n each independently represents an integer of 0 or more and 6 or less. )
<3> The resin composition according to <1> or <2>, wherein the component (B) contains a maleimide resin.
<4> (C) The resin composition according to any one of <1> to <3>, comprising an epoxy resin.
<5> (D) The resin composition according to any one of <1> to <4>, which contains a curing agent.
<6> (E) The resin composition according to any one of <1> to <5>, containing an inorganic filler.
<7> The resin composition according to <6>, wherein the amount of the inorganic filler (E) is 50% by mass or more based on 100% by mass of nonvolatile components in the resin composition.
<8> (F) The resin composition according to any one of <1> to <7>, comprising a thermoplastic resin.
<9> The resin composition according to any one of <1> to <8>, which is for forming an insulating layer.
<10> A cured product of the resin composition according to any one of <1> to <9>.
<11> A sheet-like laminate material comprising the resin composition according to any one of <1> to <9>.
<12> Comprising a support and a resin composition layer formed on the support,
A resin sheet, wherein the resin composition layer contains the resin composition according to any one of <1> to <9>.
<13> A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of <1> to <9>.
<14> A semiconductor device comprising the printed wiring board according to <13>.

According to the present invention, a resin composition that can obtain a cured product with a low dielectric loss tangent and suppress the haloing phenomenon; a cured product of the resin composition layer; It is possible to provide a sheet-like laminate material and a resin sheet; a printed wiring board comprising an insulating layer containing a cured product of the resin composition; and a semiconductor device comprising the printed wiring board.

FIG. 1 is a cross-sectional view schematically showing, together with an inner layer substrate, an insulating layer formed of a cured product of a resin composition according to an embodiment of the present invention after a roughening treatment is performed. FIG. 2 schematically shows the surface of the insulating layer opposite to the inner layer substrate after roughening treatment has been performed on the insulating layer formed of the cured product of the resin composition according to one embodiment of the present invention. FIG.

Hereinafter, the present invention will be explained by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be implemented with arbitrary changes within the scope of the claims and equivalents thereof.

<Summary of resin composition>
The resin composition according to one embodiment of the present invention includes (A) a compound containing a secondary carbon atom, an oxygen atom bonded to the secondary carbon atom with a single bond, and an aliphatic unsaturated bond; , (B) a radically polymerizable resin that does not contain an oxygen atom bonded to a secondary carbon atom with a single bond and contains an aliphatic unsaturated bond. Hereinafter, the above-mentioned "(A) compound containing a secondary carbon atom, an oxygen atom bonded to the secondary carbon atom with a single bond, and an aliphatic unsaturated bond" will be referred to as "(A) specific compound". Sometimes. In addition, the above-mentioned "(B) radically polymerizable resin that does not contain an oxygen atom bonded to a secondary carbon atom through a single bond and contains an aliphatic unsaturated bond" is referred to as "(B) radically polymerizable resin". Sometimes.

According to the resin composition of this embodiment containing (A) a specific compound and (B) a radically polymerizable resin, a cured product with a low dielectric loss tangent can be obtained. Further, when an insulating layer is formed using the cured product of the resin composition of the present embodiment and holes such as via holes are formed in the insulating layer, the haloing phenomenon can be suppressed. Therefore, according to the resin composition of this embodiment, it is possible to achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon.
Furthermore, the cured product of the resin composition of the present embodiment usually has excellent crack resistance. Further, the cured product of the resin composition of the present embodiment can usually have excellent adhesion to the conductor layer.

The present inventor conjectures the mechanism by which the excellent advantages described above are obtained by the resin composition of the present embodiment as follows. However, the technical scope of the present invention is not limited by the mechanism described below.

Since the radically polymerizable resin (B) contained in the resin composition of the present embodiment contains an aliphatic unsaturated bond, a radical polymerization reaction using the aliphatic unsaturated bond is possible. Moreover, since the specific compound (A) contains an aliphatic unsaturated bond, it may undergo a radical polymerization reaction. The resin composition of this embodiment can be cured by causing the above-mentioned radical polymerization reaction when heat is applied. Although the cured product of the resin composition contains bonds generated by a radical polymerization reaction, these bonds usually do not contain polar groups and therefore can have low polarity. Therefore, since the cured product itself can have low polarity, a low dielectric loss tangent can be achieved.

However, bonds generated by radical polymerization reactions generally tend to be easily broken by oxidation. Therefore, when a hole is formed in an insulating layer containing a cured product, a haloing phenomenon tends to occur around the hole. Specifically, when forming a hole in an insulating layer, optical or thermal energy may be applied to the insulating layer to form the hole. When energy is applied, the bonds formed by the radical polymerization reaction are broken by oxidation, resulting in the deterioration of the cured product and the cured product may easily change color. Furthermore, in general, when holes are formed in an insulating layer, a roughening treatment is performed to remove resin residue (smear) that may remain in the holes. At this time, if the cured product has deteriorated, the boundary between the insulating layer and the base material as its base will be greatly eroded during the roughening treatment, resulting in peeling between the insulating layer and the base material. It was possible.

On the other hand, in this embodiment, since the specific compound (A) can trap oxygen, oxidation of the cured product of the resin composition can be suppressed. Therefore, since deterioration of the cured product can be suppressed, the haloing phenomenon can be suppressed. Moreover, the roughening treatment may be performed using an oxidizing agent. Even when roughening treatment using an oxidizing agent is performed in this way, it is possible to suppress the haloing phenomenon because the specific compound (A) can suppress oxidation. In addition, if the haloing phenomenon can be suppressed in this way, erosion of the boundary between the insulating layer and the base material during roughening treatment can be suppressed, so that the intended separation between the insulating layer and the base material can be suppressed. It is possible to suppress undesirable peeling.

Furthermore, since the specific compound (A) traps oxygen, it is possible to suppress the introduction of polar groups into the cured product due to the infiltration of oxygen. Therefore, since an increase in the polarity of the cured product due to the introduction of polar groups can be suppressed, the resin composition of the present embodiment can particularly effectively lower the dielectric loss tangent of the cured product. It has been common knowledge among those skilled in the art that resins containing oxygen atoms, such as hydroxyl group-containing compounds, generally increase the polarity of the cured product and increase the dielectric loss tangent. In view of this common technical knowledge, it is a surprising effect that the resin composition of this embodiment can lower the dielectric loss tangent of the cured product.

Furthermore, since deterioration of the resin can be suppressed by suppressing oxidation as described above, the cured product of the resin composition can usually have high mechanical strength. Therefore, the cured product of the resin composition of this embodiment can usually have high crack resistance.

In addition, (A) a specific compound introduces a partial structure containing oxygen atoms (for example, a hydroxyl group) into the cured product, so when the cured product and the conductor layer come into contact, the interface contains a portion containing oxygen atoms. structure can exist. The effect of the partial structure containing oxygen atoms can improve the adhesion between the cured product and the conductor layer.

The resin composition of this embodiment may further contain arbitrary components in combination with (A) the specific compound and (B) the radically polymerizable resin. Examples of the optional components include (C) an epoxy resin, (D) a curing agent, (E) an inorganic filler, (F) a thermosetting resin, and (G) a curing accelerator.

<(A) Specific compound (compound containing a secondary carbon atom, an oxygen atom bonded to the secondary carbon atom with a single bond, and an aliphatic unsaturated bond)>
The resin composition according to one embodiment of the present invention contains the (A) specific compound as the (A) component. (A) The specific compound contains a secondary carbon atom, an oxygen atom bonded to the secondary carbon atom through a single bond, and an aliphatic unsaturated bond. The resin composition of the present embodiment contains (A) a specific compound containing in its molecule a secondary carbon atom, an oxygen atom bonded to the secondary carbon atom through a single bond, and an aliphatic unsaturated bond. B) By including it in combination with a radically polymerizable resin, it is possible to achieve both a reduction in the dielectric loss tangent of the cured product of the resin composition and suppression of the haloing phenomenon.

(A) The number of secondary carbon atoms contained in one molecule of the specific compound may be two or more, but is preferably one.

(A) The specific compound contains an oxygen atom bonded to the secondary carbon atom through a single bond. An oxygen atom bonded to a secondary carbon atom through a single bond may be hereinafter referred to as a "specific oxygen atom." (A) The number of specific oxygen atoms contained in one molecule of the specific compound may be two or more, but is preferably one. Further, the number of specific oxygen atoms bonded to one secondary carbon atom may be two, but is preferably one.

One of the two bonds that the specific oxygen atom has is bonded to a secondary carbon atom. The other bond of the specific oxygen atom may be bonded to a carbon atom other than the secondary carbon atom. For example, by bonding a (meth)acryloyloxy group to a secondary carbon atom, a specific oxygen atom may be bonded to the secondary carbon atom through a single bond. The term "(meth)acryloyloxy group" includes acryloyloxy groups, methacryloyloxy groups and combinations thereof. Further, the other bond of the specific oxygen atom may be bonded to any atom other than the carbon atom. For example, by bonding a hydroxyl group to a secondary carbon atom, a specific oxygen atom may be bonded to the secondary carbon atom through a single bond. A hydroxyl group bonded to a secondary carbon atom is sometimes referred to as a "secondary hydroxyl group."

(A) The aliphatic unsaturated bond contained in the specific compound represents a non-aromatic carbon-carbon unsaturated bond, and specifically represents a carbon-carbon double bond and a carbon-carbon triple bond. Among these, the aliphatic unsaturated bond is preferably a carbon-carbon double bond (ie, an ethylenically unsaturated bond). (A) The number of aliphatic unsaturated bonds contained in one molecule of the specific compound may be one, but preferably two or more.

(A) The specific compound preferably contains an ether bond in its molecule. Moreover, it is preferable that this ether bond is not directly bonded to a secondary carbon atom. The ether bond can particularly effectively enhance the adhesion between the cured resin composition and the conductor layer. (A) The number of ether bonds contained in one molecule of the specific compound may be one, but preferably two or more.

(A) The molecular weight of the specific compound is not limited as long as it does not significantly impair the effects of the present invention. (A) From the viewpoint of significantly obtaining the effects of the present invention, the molecular weight of the specific compound is preferably 58 or more, more preferably 112 or more, particularly preferably 168 or more, and preferably 1000 or less, more preferably 500 or less, Particularly preferably, it is 300 or less.

Preferred specific compounds (A) include, for example, compounds represented by the following formula (A-1). Therefore, (A) the specific compound preferably contains a compound represented by the following formula (A-1), and more preferably contains only a compound represented by the following formula (A-1).

(In formula (A-1),
R ⁰ represents a hydrogen atom or a monovalent organic group,
R ¹ each independently represents a divalent hydrocarbon group which may have a substituent,
R ² each independently represents a divalent hydrocarbon group which may have a substituent,
R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent,
R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent,
R ⁵ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent,
n each independently represents an integer of 0 or more and 6 or less. )

In formula (A-1), R ⁰ represents a hydrogen atom or a monovalent organic group. The number of carbon atoms in the monovalent organic group is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 6 or less, still more preferably 4 or less. Moreover, it is preferable that the monovalent organic group contains an aliphatic unsaturated bond. Examples of preferable monovalent organic groups include (meth)acryloyl groups such as acryloyl and methacryloyl groups. Among these, R ⁰ is particularly preferably a hydrogen atom.

In formula (A-1), R ¹ each independently represents a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aliphatic hydrocarbon group is preferable. Further, the aliphatic hydrocarbon group may be a linear or branched chain hydrocarbon group, or a cyclic hydrocarbon group (namely, an alicyclic hydrocarbon group). Further, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferable. The number of carbon atoms in R ¹ is usually 1 or more, preferably 12 or less, more preferably 10 or less, and still more preferably 6 or less. Examples of R ¹ include alkylene groups such as methylene group, ethylene group and propylene group; cycloalkylene groups such as cyclopentylene group and cyclohexylene group; arylene groups such as phenylene group and naphthylene group; and the like. Among these, an alkylene group is preferred.

The divalent hydrocarbon group represented by R ¹ may have a substituent. There are no restrictions on the substituents as long as they do not significantly impair the effects of the present invention. Examples of substituents include alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups (alkyl groups substituted with aryl groups), alkyl-aryl groups (aryl groups substituted with alkyl groups), and alkyl-oxy groups. , alkenyl-oxy group, aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl group Examples include monovalent substituents such as -oxy group, alkenyl-carbonyl-oxy group, and aryl-carbonyl-oxy group, and if substitutable, divalent substituents such as oxo group (=O) may also be included. . The number of substituents that R ¹ has may be 1 or 2 or more. Among these, it is preferable that R ¹ has no substituent.

R ¹ in formula (A-1) may be different from each other, but are preferably the same.

In formula (A-1), R ² each independently represents a divalent hydrocarbon group which may have a substituent. The range of R ² and its preferred range can be the same as R ¹ . Furthermore, R ² in formula (A-1) may be different from each other, but are preferably the same.

In formula (A-1), R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent. The monovalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aliphatic hydrocarbon group is preferable. Further, the aliphatic hydrocarbon group may be a linear or branched chain hydrocarbon group, or a cyclic hydrocarbon group (namely, an alicyclic hydrocarbon group). Further, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferable. When R ³ is a monovalent hydrocarbon group which may have a substituent, the number of carbon atoms in R ³ is usually 1 or more, preferably 12 or less, more preferably 10 or less, and even more preferably is 6 or less. Examples of ^R3 include chain alkyl groups such as methyl, ethyl, and propyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; and aryl groups such as phenyl and naphthyl groups. It will be done. Among these, alkyl groups are preferred, and chain alkyl groups are particularly preferred.

The monovalent hydrocarbon group represented by R ³ may have a substituent. There are no restrictions on the substituents as long as they do not significantly impair the effects of the present invention. Examples of the substituent include the same substituents as those of the divalent hydrocarbon group represented by R ¹ . The number of substituents that R ³ has may be 1 or 2 or more. Among these, R ³ preferably has no substituent.

Among those mentioned above, R ³ is preferably a hydrogen atom. Furthermore, R ³ in formula (A-1) may be different from each other, but are preferably the same.

In formula (A-1), R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent. The range of ^R4 can be the same as ^R3 . Among these, R ⁴ is preferably a monovalent hydrocarbon group that may have a substituent, more preferably a monovalent hydrocarbon group that does not have a substituent, and R 4 is a saturated aliphatic hydrocarbon group that does not have a substituent. Hydrogen groups are more preferred, and alkyl groups without substituents are particularly preferred. Furthermore, R ⁴ in formula (A-1) may be different from each other, but are preferably the same.

In formula (A-1), R ⁵ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent. The range of R ⁵ can be the same as R ³ . Among these, R ⁵ is preferably a monovalent hydrocarbon group that may have a substituent, more preferably a monovalent hydrocarbon group that does not have a substituent, and a saturated aliphatic hydrocarbon group that does not have a substituent. Hydrogen groups are more preferred, and alkyl groups without substituents are particularly preferred. Further, R ⁵ in formula (A-1) may be different from each other, but are preferably the same.

In formula (A-1), n each independently represents an integer from 0 to 6. Specifically, n is usually 0 or more, preferably 1 or more, and usually 6 or less, preferably 2 or less. n in formula (A-1) may be different from each other, but preferably the same.

(A) Examples of specific compounds include 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane, 1,3-bis(3-methyl-2-butenoxy)-2-methacryloyl Examples include oxypropane.

(A) Specific compounds may be used alone or in combination of two or more.

(A) The amount of the specific compound is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.2% by mass, based on 100% by mass of the nonvolatile components in the resin composition. The content is preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 1% by mass or less. (A) When the amount of the specific compound is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

(A) The amount of the specific compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, based on 100% by mass of the resin component in the resin composition. The content is preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less. The resin component of the resin composition refers to the nonvolatile components of the resin composition excluding (E) the inorganic filler. (A) When the amount of the specific compound is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

The mass ratio of (A) specific compound to (B) radically polymerizable resin ((A) specific compound/(B) radically polymerizable resin) is preferably within a specific range. Specifically, the mass ratio ((A) specific compound/(B) radically polymerizable resin) is preferably 0.01 or more, more preferably 0.02 or more, particularly preferably 0.03 or more, and preferably is 0.8 or less, more preferably 0.5 or less, particularly preferably 0.3 or less. When the mass ratio ((A) specific compound/(B) radically polymerizable resin) is within the above range, both reduction in dielectric loss tangent and suppression of the haloing phenomenon can be effectively achieved. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

<(B) Radical polymerizable resin>
The resin composition according to one embodiment of the present invention includes (B) a radically polymerizable resin as the (B) component. (B) The radically polymerizable resin contains an aliphatic unsaturated bond. Moreover, the radically polymerizable resin (B) may or may not contain a secondary carbon atom. However, the radically polymerizable resin (B) does not contain an oxygen atom bonded to a secondary carbon atom through a single bond. Therefore, this (B) radically polymerizable resin does not include those corresponding to the above-mentioned (A) specific compounds. (B) The radically polymerizable resin can form bonds through a radical polymerization reaction and cure the resin composition. Therefore, when the resin composition is heated, the radically polymerizable resin (B) reacts with the thermal radicals generated during the heating, and a cured product can be obtained.

(B) The aliphatic unsaturated bond contained in the radically polymerizable resin represents a non-aromatic carbon-carbon unsaturated bond, and specifically includes a carbon-carbon double bond and a carbon-carbon double bond. Represents a carbon triple bond. Among these, the aliphatic unsaturated bond is preferably a carbon-carbon double bond (ie, an ethylenically unsaturated bond). (B) The number of aliphatic unsaturated bonds contained in one molecule of the radically polymerizable resin may be one, but preferably two or more.

Since the radically polymerizable resin (B) contains an aliphatic unsaturated bond, the radically polymerizable resin (B) may contain a radically polymerizable unsaturated group. The radically polymerizable unsaturated group represents a group that contains an aliphatic unsaturated bond and can undergo radical polymerization. Examples of the radically polymerizable unsaturated group include a maleimide group, a vinyl group, an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, and a maleoyl group. The number of radically polymerizable unsaturated groups may be one type or two or more types.

(B) A preferable example of the radically polymerizable resin is a maleimide resin. Maleimide resin refers to a compound having a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) in the molecule. (B) When the radically polymerizable resin contains a maleimide resin, both a reduction in dielectric loss tangent and suppression of the haloing phenomenon can be effectively achieved. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

An example of a preferable maleimide resin is a maleimide resin having a partial structure represented by formula (B-1-1).

(In formula (B-1-1), ring A represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent; a and b are , each independently represents an integer of 0 or 1 or more, and the sum of a and b is 6 or more; * represents a binding site.)

In formula (B-1-1), ring A represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent.
A monocycloalkane ring means a monocyclic aliphatic saturated hydrocarbon ring. The monocycloalkane ring is preferably a monocycloalkane ring having 4 to 14 carbon atoms, more preferably a monocycloalkane ring having 4 to 10 carbon atoms, and particularly preferably a monocycloalkane ring having 5 or 6 carbon atoms. Examples of the monocycloalkane ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring.
Monocycloalkene ring means a monocyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond. The monocycloalkene ring is preferably a monocycloalkene ring having 4 to 14 carbon atoms, more preferably a monocycloalkene ring having 4 to 10 carbon atoms, and particularly preferably a monocycloalkene ring having 5 or 6 carbon atoms. Examples of the monocycloalkene ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, and a cyclohexadiene ring.

Examples of substituents on monocycloalkane rings and monocycloalkene rings include alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups (alkyl groups substituted with an aryl group), alkyl-aryl groups (alkyl groups substituted with an alkyl group), aryl group), alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, Examples include monovalent substituents such as aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, and aryl-carbonyl-oxy group, and if substitutable, oxo group (=O) It may also contain divalent substituents such as. In these substituents, the number of carbon atoms in the alkyl group is preferably 1 to 14, more preferably 1 to 10, particularly preferably 1 to 8. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Examples include decyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group, cyclopentylmethyl group, and cyclohexylmethyl group. The alkenyl group can also be a linear, branched or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl group preferably has 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms. Examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a cyclohexenyl group, and the like. Further, the aryl group may be a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. The number of carbon atoms in the aryl group is preferably 6 to 14, more preferably 6 to 10. Examples of the aryl group include phenyl group, 1-naphthyl group, and 2-naphthyl group.

Ring A is preferably a monocycloalkane ring which may be substituted with a group selected from an alkyl group and an alkenyl group; or a monocycloalkene ring which may be substituted with a group selected from an alkyl group and an alkenyl group. represent. Ring A is more preferably a monocycloalkane ring optionally substituted with a group selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms; or a monocycloalkane ring having 1 to 14 carbon atoms. represents a monocycloalkene ring optionally substituted with a group selected from an alkyl group and an alkenyl group having 2 to 14 carbon atoms.

In formula (B-1-1), a and b each independently represent an integer of 0 or 1 or more, and the sum of a and b is 6 or more. In detail, a and b are each independently usually 0 or more, preferably 1 or more, and preferably 20 or less. Further, the sum of a and b is usually 6 or more, preferably 8 or more, and more preferably 10 or more. More preferably, a and b are each independently an integer of 5 to 10. a and b are particularly preferably 8.

Specific examples of maleimide resins having partial structures combined by formula (B-1-1) include maleimide resins represented by formula (B-1) below.

(In formula (B-1), R ^b1 each independently represents a substituent; Ring B each independently represents an aromatic ring that may have a substituent; L ¹ and L ² each independently represents a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, - COO- or -OCO-; R ^x each independently represents a hydrogen atom or an alkyl group; c each independently represents 0 or 1; d each independently, represents an integer of 0 or 1 or more; e each independently represents 0, 1, or 2; m1 represents an integer of 0 or 1 or more; other symbols are the same as above; d unit; The e unit and m1 unit may be the same or different for each unit.)

In formula (B-1), R ^b1 each independently represents a substituent. Examples of this substituent include those in the same range as the monovalent substituent that the monocycloalkane ring or monocycloalkene ring represented by ring A in formula (B-1-1) may have. Among these, R ^b1 is preferably an alkyl group.

In formula (B-1), each ring B independently represents an aromatic ring which may have a substituent. As the aromatic ring, a benzene ring is preferred. In addition, examples of the substituent bonded to the aromatic ring include those in the same range as the substituents that the monocycloalkane ring or monocycloalkene ring represented by ring A in formula (B-1-1) can have. . Preferably, ring B represents a benzene ring optionally substituted with an alkyl group.

In formula (B-1), L ¹ and L ² each independently represent a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ represents -, -CONH-, -NHCO-, -COO-, or -OCO-. L ¹ and L ² preferably each independently represent a single bond, -C(R ^x ) ₂ -, or -O-. R ^x each independently represents a hydrogen atom or an alkyl group. When R ^x is an alkyl group, the range of the alkyl group is the alkyl group as a monovalent substituent that the monocycloalkane ring or monocycloalkene ring represented by ring A in formula (B-1-1). It can be the same as the base. R ^x preferably represents a hydrogen atom or a methyl group.

In formula (B-1), c each independently represents 0 or 1, preferably represents 0.
In formula (B-1), d each independently represents 0 or an integer of 1 or more, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2.
In formula (B-1), e each independently represents 0, 1 or 2, preferably 0.
In formula (B-1), m1 represents an integer of 0 or 1 or more, preferably an integer of 0 to 10, more preferably an integer of 0 to 2, and even more preferably 0 or 1.

The partial structure represented by formula (B-1-2) contained in formula (B-1) is not particularly limited, but for example, formula (B-1-3), formula (B-1-4) ) or (B-1-5).

(In formula (B-1-2), * indicates a binding site; other symbols are the same as above.)

(In formula (B-1-3), formula (B-1-4) and formula (B-1-5), * represents a binding site.)

Commercially available maleimide resins represented by formula (B-1) include, for example, "BMI-689", "BMI-1400", and "BMI-1500" manufactured by Designer Molecules (the following formula (b- 1), "BMI-1700", "BMI-3000J", "BMI-5000", etc. These maleimide resins may be maleimide resins containing a 36-carbon aliphatic skeleton derived from a dimer diamine.

Another example of a preferable maleimide resin is a maleimide resin represented by formula (B-2).

(In formula (B-2), R ^b2 each independently represents an alkyl group; Ring C and Ring D each independently represent an aromatic ring which may have a substituent; f indicates an integer greater than or equal to 1.The f units may be the same or different for each unit.)

In formula (B-2), R ^b2 each independently represents an alkyl group. The range of this alkyl group may be the same as the alkyl group as a monovalent substituent that the monocycloalkane ring or monocycloalkene ring represented by ring A in formula (B-1-1). Among these, R ^b2 preferably represents a methyl group.

In formula (B-2), each ring C independently represents an aromatic ring which may have a substituent. As the aromatic ring, a benzene ring is preferred. In addition, examples of the substituent bonded to the aromatic ring include those in the same range as the substituents that the monocycloalkane ring or monocycloalkene ring represented by ring A in formula (B-1-1) can have. . Preferably, ring C represents a benzene ring optionally substituted with an alkyl group. More preferably, ring C represents a benzene ring substituted with an alkyl group.

In formula (B-2), each ring D independently represents an aromatic ring which may have a substituent. The range of ring D can be the same as ring C. Preferably, ring D represents an unsubstituted benzene ring.

In formula (B-2), f represents an integer of 1 or more, preferably an integer of 1 to 20.

Examples of maleimide resins represented by formula (B-2) include maleimide resins having an indane skeleton, and specific examples thereof include compounds represented by formula (b-2) below.

The maleimide resin represented by formula (B-2) can be produced, for example, using the method described in Japan Institute of Invention and Innovation Publication No. 2020-500211.

One type of maleimide resin may be used alone, or two or more types may be used in combination.

The amount of maleimide resin is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. is 50% by mass or less, more preferably 30% by mass or less, particularly preferably 10% by mass or less. When the amount of maleimide resin is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

The amount of maleimide resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, particularly preferably 5% by mass or more, and preferably 70% by mass or more, based on 100% by mass of the resin component in the resin composition. It is at most 50% by mass, more preferably at most 30% by mass, particularly preferably at most 20% by mass. When the amount of maleimide resin is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

The amount of maleimide resin is preferably 1% by mass or more, more preferably 5% by mass or more, particularly preferably 10% by mass or more, and usually 100% by mass or less, based on 100% by mass of the (B) radically polymerizable resin. It is. When the amount of maleimide resin is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

(B) Other examples of the radically polymerizable resin include styryl resin and (meth)acrylic resin.

Styryl resin refers to a compound containing a styryl group or a vinylphenyl group in the molecule. Examples of the styryl resin include "OPE-2St", "OPE-2St 1200" (resin of the following formula (b-3)), and "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Co., Ltd.). . In formula (b-3), q and r each independently represent an integer from 1 to 200.

The (meth)acrylic resin refers to a compound having a (meth)acryloyl group in the molecule. The term "(meth)acryloyl group" includes acryloyl groups, methacryloyl groups and combinations thereof. Examples of (meth)acrylic resins include "A-DOG" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.); "NPDGA", "FM-400", and "R-687". ”, “THE-330”, “PET-30”, and “DPHA” (all manufactured by Nippon Kayaku Co., Ltd.).

(B) The radically polymerizable resin may be used alone or in combination of two or more.

When the resin composition of this embodiment contains (C) an epoxy resin, it is preferable that (B) radically polymerizable resin contains (B) radically polymerizable resin containing an active group that can react with an epoxy group. "(B) Radical polymerizable resin containing an active group that can react with an epoxy group" is sometimes referred to as "radical polymerizable curing agent" hereinafter. When the radically polymerizable curing agent is used in combination with the epoxy resin (C), the dielectric loss tangent of the cured product can be effectively reduced. Furthermore, the mechanical strength of the cured product can be increased by incorporating the bond network of (B) the radically polymerizable resin into the crosslinked structure of the (C) epoxy resin. Point strength, elongation, and adhesion to the conductor layer can be significantly improved.

As the radically polymerizable curing agent, a compound containing an active ester group is preferable from the viewpoint of realizing a high level of reduction in dielectric loss tangent and suppression of haloing phenomenon. Examples of the radically polymerizable curing agent containing an active ester group include a compound represented by the following formula (B-3).

(In formula (B-3), s represents an integer of 1 to 6, preferably an integer of 1 to 3. Also, t represents an integer of 1 to 20, more preferably 1 to 10. represents an integer, more preferably an integer from 1 to 5, particularly preferably an integer from 1 to 3.)

As a commercially available product of the radically polymerizable curing agent represented by formula (B-3), for example, "PC1300-02-65MA" (manufactured by Air Water Co., Ltd.) may be mentioned.

The active group equivalent of the radically polymerizable curing agent is preferably 50 g/eq. ～3000g/eq. , more preferably 100g/eq. ～1000g/eq. , more preferably 100g/eq. ～500g/eq. , particularly preferably 100 g/eq. ～300g/eq. It is. The active group equivalent represents the mass of resin per equivalent of active group.

The mass ratio of the radically polymerizable curing agent to the (C) epoxy resin (radical polymerizable curing agent/(C) epoxy resin) is preferably within a specific range. Specifically, the mass ratio (radical polymerizable curing agent/(C) epoxy resin) is preferably 0.1 or more, more preferably 0.5 or more, particularly preferably 1.0 or more, and preferably 50 Below, it is more preferably 30 or less, particularly preferably 10 or less. When the mass ratio (radical polymerizable curing agent/(C) epoxy resin) is within the above range, both a reduction in dielectric loss tangent and suppression of the haloing phenomenon can be effectively achieved. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

The amount of the radically polymerizable curing agent is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 50% by mass or more, based on 100% by mass of the radically polymerizable resin (B). It is 100% by mass or less, more preferably 95% by mass or less, particularly preferably 90% by mass or less. When the amount of the radically polymerizable curing agent is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

(B) The amount of radically polymerizable resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass, based on 100% by mass of the nonvolatile components in the resin composition. The content is preferably 50% by mass or less, more preferably 30% by mass or less, particularly preferably 20% by mass or less. (B) When the amount of the radically polymerizable resin is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

(B) The amount of radically polymerizable resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, particularly preferably 5% by mass or more, based on 100% by mass of the resin component in the resin composition. The content is preferably 90% by mass or less, more preferably 80% by mass or less, particularly preferably 70% by mass or less. (B) When the amount of the radically polymerizable resin is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

<(C) Epoxy resin>
The resin composition according to one embodiment of the present invention may include (C) an epoxy resin as an optional component. The epoxy resin (C) as the component (C) may be a curable resin having an epoxy group. Normally, when the resin composition (C) is heated, the epoxy groups of the epoxy resin react to form bonds, thereby curing the resin composition. This (C) epoxy resin does not include those corresponding to the above-mentioned components (A) to (B) unless otherwise specified.

(C) Epoxy resins include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane di Examples include methanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin. (C) Epoxy resins may be used alone or in combination of two or more.

(C) The epoxy resin preferably contains an epoxy resin containing an aromatic structure from the viewpoint of obtaining a cured product with excellent heat resistance. The aromatic structure is a chemical structure that is generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. Examples of the epoxy resin containing an aromatic structure include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, Naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bishkylenol type epoxy resin, glycidylamine type epoxy resin with aromatic structure Resin, glycidyl ester type epoxy resin with aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with aromatic structure, alicyclic epoxy resin with aromatic structure, heterocyclic type Epoxy resin, spiro ring-containing epoxy resin with aromatic structure, cyclohexanedimethanol type epoxy resin with aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin with aromatic structure, tetramer with aromatic structure Examples include phenylethane type epoxy resin.

It is preferable that the resin composition contains, as the epoxy resin (C), an epoxy resin having two or more epoxy groups in one molecule. (C) The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably is 70% by mass or more.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). ). The resin composition may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. good.

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

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, and ester skeleton. Alicyclic epoxy resins, cyclohexane-type epoxy resins, and cyclohexanedimethanol-type epoxy resins are preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. ", "Epicote 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical's "630", "630LSD", "604" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycyol type epoxy resin); ADEKA's "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (bisphenol A type epoxy resin) manufactured by Nippon Steel Chemical & Material Chemical Co., Ltd. Bisphenol F type epoxy resin mixture); “EX-721” manufactured by Nagase ChemteX (glycidyl ester type epoxy resin); “Celoxide 2021P” manufactured by Daicel Corporation (alicyclic epoxy resin having an ester skeleton); Examples include "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Tetsu Chemical & Materials. These may be used alone or in combination of two or more.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalyl Midine type epoxy resins are preferred.

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

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

(C) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ～5,000g/eq. , more preferably 60g/eq. ～3,000g/eq. , more preferably 80g/eq. ~2,000g/eq. , particularly preferably 110 g/eq. ～1,000g/eq. It is. Epoxy equivalent represents the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

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

The amount of the epoxy resin (C) in the resin composition may be 0% by mass or more than 0% by mass, preferably 1% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The content is more preferably 2% by mass or more, particularly preferably 4% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less. (C) When the amount of epoxy resin is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

The amount of the epoxy resin (C) in the resin composition may be 0% by mass or more than 0% by mass, preferably 5% by mass or more, based on 100% by mass of the resin component in the resin composition. The content is more preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, particularly preferably 40% by mass or less. (C) When the amount of epoxy resin is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

<(D) Curing agent>
The resin composition according to one embodiment of the present invention may include (D) a curing agent as an optional component. The curing agent (D) as the component (D) may have a function of curing the resin composition by reacting with the epoxy resin (C). Therefore, it is preferable that the resin composition contains (D) a curing agent in combination with (C) the epoxy resin. This (D) curing agent does not include those corresponding to the above-mentioned components (A) to (C) unless otherwise specified. Therefore, unless otherwise specified, the curing agent (D) does not include a radically polymerizable curing agent. (D) The curing agent may be used alone or in combination of two or more.

Preferred curing agents (D) include, for example, phenolic curing agents, active ester curing agents, cyanate curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, Examples include thiol-based curing agents. Among these, phenolic curing agents, active ester curing agents and carbodiimide curing agents are preferred.

As the phenolic curing agent, a compound having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. From the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolak structure is preferred. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred. Among these, triazine skeleton-containing phenol novolac curing agents are preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenolic curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN", "CBN", and "manufactured by Nippon Kayaku Co., Ltd." GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495”, “SN-” manufactured by Nippon Steel Chemical & Materials. 375'', ``SN-395'', DIC's ``LA-7052'', ``LA-7054'', ``LA-3018'', ``LA-3018-50P'', ``LA-1356'', ``TD2090'', `` TD-2090-60M” and the like.

Active ester curing agents generally have two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. compounds are preferably used. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester curing agents obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester curing agents obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound are more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples include benzenetriol, dicyclopentadiene type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, active ester curing agents include dicyclopentadiene-type active ester curing agents, naphthalene-type active ester curing agents containing a naphthalene structure, active ester curing agents containing acetylated products of phenol novolak, and phenol novolacs. An active ester curing agent containing a benzoylated product is preferable, and at least one selected from a dicyclopentadiene type active ester curing agent and a naphthalene type active ester curing agent is more preferable. As the dicyclopentadiene type active ester curing agent, an active ester type curing agent containing a dicyclopentadiene type diphenol structure is preferable.

Commercially available active ester curing agents include "EXB9451," "EXB9460," "EXB9460S," "EXB-8000L," and "EXB-" as active ester curing agents containing a dicyclopentadiene diphenol structure. 8000L-65M”, “EXB-8000L-65TM”, “HPC-8000L-65TM”, “HPC-8000”, “HPC-8000-65T”, “HPC-8000H”, “HPC-8000H-65TM” (DIC HPB-8151-62T, EXB-8100L-65T, EXB-8150-60T, EXB-8150-62T, EXB-9416 as active ester curing agents containing naphthalene structure -70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); as a phosphorus-containing active ester curing agent, "EXB9401" (manufactured by DIC Corporation); phenol “DC808” (manufactured by Mitsubishi Chemical Corporation) is an active ester curing agent that is an acetylated novolac; (manufactured by Air Water Co., Ltd.); "PC1300-02-65MA" (manufactured by Air Water Co., Ltd.) is an active ester curing agent containing a styryl group and a naphthalene structure.

As the carbodiimide curing agent, a compound having one or more, preferably two or more carbodiimide structures in one molecule can be used. Specific examples of carbodiimide curing agents include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); Biscarbodiimides such as biscarbodiimide; aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), Poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide) , poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylene diphenylenecarbodiimide), poly[methylenebis(methylphenylene)carbodiimide], and other aromatic polycarbodiimides. Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Co., Ltd. "Stavaxol P", "Stavaxol P400", "Hikasil 510", etc. manufactured by Rhein Chemie.

As the cyanate curing agent, a compound having one or more, preferably two or more cyanate groups in one molecule can be used. Examples of the cyanate curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate curing agents such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether , polyfunctional cyanate curing agents derived from phenol novolaks, cresol novolacs, etc., prepolymers in which these cyanate curing agents are partially triazine-formed, and the like. Specific examples of cyanate-based curing agents include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate-based curing agents) manufactured by Lonza Japan, "BA230" and "BA230S75" (part of bisphenol A dicyanate). or a prepolymer completely triazinated to form a trimer).

As the acid anhydride curing agent, a compound having one or more, preferably two or more acid anhydride groups in one molecule can be used. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. Anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride Mellitic acid, pyromellitic anhydride, bensophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. Commercially available acid anhydride curing agents include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Chemical Co., Ltd.; and "OSA" manufactured by Mitsubishi Chemical Corporation. "YH-306", "YH-307"; "HN-2200", "HN-5500" manufactured by Hitachi Chemical; "EF-30", "EF-40", "EF-60" manufactured by Clay Valley; Examples include "EF-80".

As the amine curing agent, a compound having one or more, preferably two or more amino groups in one molecule can be used. Examples of the amine curing agent include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like, with aromatic amines being preferred. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. , m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4' -diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2, 2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4- (3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine curing agents include, for example, "SEIKACURE-S" manufactured by Seika; "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", and "Kayahard" manufactured by Nippon Kayaku Co., Ltd. Examples include "A-B", "Kayahard AS"; "Epicure W" manufactured by Mitsubishi Chemical; and "DTDA" manufactured by Sumitomo Seika.

Specific examples of benzoxazine curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical; "HFB2006M" manufactured by Showa Kobunshi Co., Ltd.; "P-d" manufactured by Shikoku Kasei Kogyo Co., Ltd.; Examples include "Fa".

Examples of the thiol curing agent include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)isocyanurate, and the like.

(D) The active group equivalent of the curing agent is preferably 50 g/eq. ～3000g/eq. , more preferably 100g/eq. ～1000g/eq. , more preferably 100g/eq. ～500g/eq. , particularly preferably 100 g/eq. ～300g/eq. It is. The active group equivalent represents the mass of resin per equivalent of active group.

When the number of epoxy groups in the epoxy resin (C) is 1, the number of active groups in the curing agent (D) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably is 5.0 or less, more preferably 4.0 or less, particularly preferably 3.0 or less. "Number of epoxy groups in (C) epoxy resin" refers to the total value of all the values obtained by dividing the mass of nonvolatile components of (C) epoxy resin present in the resin composition by the epoxy equivalent. Moreover, "the number of active groups of the curing agent (D)" represents the total value of all the values obtained by dividing the mass of the nonvolatile components of the curing agent (D) present in the resin composition by the active group equivalent.

When the number of epoxy groups in the epoxy resin (C) is 1, the total number of active groups in the radically polymerizable curing agent and the number of active groups in the curing agent (D) preferably falls within a specific range. Specifically, the total number is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1.0 or more, and preferably 5.0 or less, more preferably 4.0 or less. , particularly preferably 3.0 or less. The "number of active groups of the radically polymerizable curing agent" refers to the total value of all the values obtained by dividing the mass of the nonvolatile components of the radically polymerizable curing agent present in the resin composition by the active group equivalent.

The amount of the curing agent (D) in the resin composition may be 0% by mass or more than 0% by mass, preferably 0.1% by mass, based on 100% by mass of the nonvolatile components in the resin composition. The content is more preferably 1% by mass or more, particularly preferably 2% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, particularly preferably 30% by mass or less. (D) When the amount of the curing agent is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

The amount of the curing agent (D) in the resin composition may be 0% by mass or more than 0% by mass, preferably 1% by mass or more, based on 100% by mass of the resin component in the resin composition. The content is more preferably 3% by mass or more, particularly preferably 5% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, particularly preferably 70% by mass or less. (D) When the amount of the curing agent is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

<(E) Inorganic filler>
The resin composition according to one embodiment of the present invention may include (E) an inorganic filler as an optional component. (E) The inorganic filler is usually contained in the resin composition in the form of particles.

(E) An inorganic compound is used as the material for the inorganic filler. (E) Materials for the inorganic filler include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. (E) One type of inorganic filler may be used alone, or two or more types may be used in combination.

(E) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical &Materials; "YC100C", "YA050C" and "YA050C-" manufactured by Admatex. "MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1"; Denka's "UFP-30", "DAW-03", "FB-105FD" ; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama; "Selfias" and "MGH-005" manufactured by Taiheiyo Cement; ” and “BA-S”.

(E) The average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm. or more, preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, particularly preferably 1 μm or less. (E) When the average particle size of the inorganic filler is within the above range, it becomes possible to effectively suppress the haloing phenomenon. In addition, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured resin composition.

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

(E) The specific surface area of the inorganic filler is not particularly limited, but is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, particularly preferably 5 m ² /g or more, and preferably It is 100 m ² /g or less, more preferably 50 m ² /g or less, particularly preferably 30 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multipoint method. You can get it by doing that.

(E) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate-based coupling agents. Coupling agents and the like can be mentioned. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

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

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 0.2% by mass to 5% by mass of a surface treatment agent, and preferably 0.2% by mass to 3% by mass of a surface treatment agent. It is more preferable that the surface be treated, and it is even more preferable that the surface be treated with 0.3% by mass to 2% by mass of a surface treatment agent.

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 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m ² The following are more preferred.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler whose surface has been treated with a surface treatment agent, and the mixture is subjected to 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 the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.

The amount of the inorganic filler (E) in the resin composition may be 0% by mass or more than 0% by mass, preferably 50% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. , more preferably 60% by mass or more, particularly preferably 70% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, particularly preferably 80% by mass or less. (E) When the amount of the inorganic filler is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

<(F) Thermoplastic resin>
The resin composition according to one embodiment of the present invention may include (F) a thermoplastic resin as an optional component. The thermoplastic resin (F) as component (F) does not include those corresponding to components (A) to (E) described above, unless otherwise specified.

(F) Thermoplastic resins include, for example, phenoxy resin, aromatic hydrocarbon resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether Examples include resins, polycarbonate resins, polyetheretherketone resins, polyester resins, and the like. (F) The thermoplastic resin may be used alone or in combination of two or more.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. Examples include phenoxy resins having one or more types of skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both phenoxy resins containing bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol S skeleton); "YX6954" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (phenoxy resin containing bisphenolacetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation; Examples include "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", "YL7891BH30", "YL7891T30", and the like.

Examples of the aromatic hydrocarbon resin include homopolymers and copolymers of aromatic hydrocarbon monomers such as styrene, methylstyrene, dimethylstyrene, indene, and divinylbenzene. Specific examples of the aromatic hydrocarbon resin include "FMR0150" (a copolymer of 4-methyl-α-methyl-styrene and indene) manufactured by Mitsui Chemicals.

Specific examples of polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shinnihon Rika Co., Ltd., and the like.

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

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

Specific examples of the polyamide-imide resin include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo. Specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical.

A specific example of the polyether sulfone resin includes "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

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

A specific example of the polyphenylene ether resin includes "NORYL SA90" manufactured by SABIC. A specific example of the polyetherimide resin includes "Ultem" manufactured by GE.

Examples of the polycarbonate resin include hydroxy group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, and the like. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090" and "C-2090" manufactured by Kuraray Corporation. , "C-3090" (polycarbonate diol), and the like. A specific example of the polyetheretherketone resin is "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexane dimethyl terephthalate resin, and the like.

(F) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 2,000 or more, more preferably larger than 5,000, even more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably It is 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, particularly preferably 50,000 or less. In particular, when the thermoplastic resin (F) contains an epoxy group or an active group, it is particularly preferable that the weight average molecular weight (Mw) of the thermoplastic resin (F) is greater than 5,000.

The amount of the thermoplastic resin (F) in the resin composition may be 0% by mass or more than 0% by mass, preferably 0.01% by mass, based on 100% by mass of the nonvolatile components in the resin composition. % or more, more preferably 0.1% by mass or more, particularly preferably 0.3% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, particularly preferably 1% by mass or less. (F) When the amount of the thermoplastic resin is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

The amount of the thermoplastic resin (F) in the resin composition may be 0% by mass or more than 0% by mass, preferably 0.1% by mass, based on 100% by mass of the resin component in the resin composition. % or more, more preferably 1% by mass or more, particularly preferably 2% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, particularly preferably 5% by mass or less. (F) When the amount of the thermoplastic resin is within the above range, it is possible to effectively achieve both a reduction in dielectric loss tangent and suppression of the haloing phenomenon. Furthermore, it is usually possible to effectively improve the crack resistance, strength at break, elongation, and adhesion to the conductor layer of the cured product of the resin composition.

<(G) Curing accelerator>
The resin composition according to one embodiment of the present invention may further contain (G) a curing accelerator as an optional component in combination with the above-mentioned components (A) to (F). The curing accelerator (G) as the component (G) may function as a curing catalyst that promotes curing of the epoxy resin. Therefore, it is preferable that the resin composition contains (G) a curing accelerator in combination with (C) the epoxy resin. This (G) curing accelerator does not include those corresponding to the above-mentioned components (A) to (F) unless otherwise specified.

(G) Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. . (G) The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, and tetrabutylphosphonium hydro Aliphatic phosphonium salts such as denhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl Phosphonium tetraphenylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 - Aromatic phosphonium salts such as methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl- Aliphatic phosphine such as 2-butenyl)phosphine, tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o -Tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris( 3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4- methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis( Examples include aromatic phosphines such as diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. It will be done.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl) )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea] etc.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide and the like.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , imidazole compounds such as 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. Commercially available imidazole curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", and "2MA-OK-" manufactured by Shikoku Kasei Kogyo Co., Ltd. PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A"; "P200-H50" manufactured by Mitsubishi Chemical Corporation, and the like.

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

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo. Examples include (5,4,0)-undecene and the like. As the amine curing accelerator, commercially available products may be used, such as "MY-25" manufactured by Ajinomoto Fine Techno.

The amount of the curing accelerator (G) in the resin composition may be 0% by mass or greater than 0% by mass, preferably 0% by mass, based on 100% by mass of the nonvolatile components in the resin composition. .01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.05% by mass or more, preferably 1.0% by mass or less, more preferably 0.5% by mass or less, particularly preferably It is 0.2% by mass or less.

The amount of the curing accelerator (G) in the resin composition may be 0% by mass or greater than 0% by mass, preferably 0% by mass, based on 100% by mass of the resin component in the resin composition. .01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, particularly preferably 1% by mass or less. It is.

<(H) Optional additive>
The resin composition according to one embodiment of the present invention may further contain (H) any additive in combination with the above-mentioned components (A) to (G) as an optional non-volatile component. The (H) optional additives as the (H) component do not include those corresponding to the above-mentioned components (A) to (G).

(H) Optional additives include, for example, organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators. 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; Silicone leveling agents, acrylic polymer leveling agents Leveling agents such as bentone and montmorillonite; Antifoaming agents such as silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; Benzotriazole ultraviolet absorbers UV absorbers such as; adhesion improvers such as urea silane; adhesion agents such as triazole adhesion agents, tetrazole adhesion agents, and triazine adhesion agents; fluorescent brighteners such as stilbene derivatives. ; Surfactants such as fluorine surfactants and silicone surfactants; Phosphorus flame retardants (e.g. phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g. melamine sulfate), Flame retardants such as halogen flame retardants, inorganic flame retardants (e.g. antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, cations Dispersants such as oleaginous dispersants; stabilization of borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic acid anhydride stabilizers, etc. agents; (H) The optional additives may be used alone or in combination of two or more.

<(I) Solvent>
The resin composition according to one embodiment of the present invention may further contain (I) a solvent as an optional volatile component in combination with the non-volatile components such as the components (A) to (H) described above.

(I) As the solvent, an organic solvent is usually used. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone. Ester solvents; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol; acetic acid Ether ester solvents such as 2-ethoxyethyl, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, etc. Ester alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide, N, Amide solvents such as N-dimethylacetamide and N-methyl-2-pyrrolidone; Sulfoxide solvents such as dimethyl sulfoxide; Nitrile solvents such as acetonitrile and propionitrile; Aliphatic solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane Hydrocarbon solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The solvent (I) may be used alone or in combination of two or more.

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

<Method for manufacturing resin composition>
The resin composition according to one embodiment of the present invention can be manufactured, for example, by mixing components that can be included in the resin composition. The above-mentioned components may be mixed in part or in whole at the same time, or in order. During the process of mixing each component, the temperature may be set as appropriate, and thus may be heated and/or cooled temporarily or throughout. Moreover, in the process of mixing each component, stirring or shaking may be performed.

<Characteristics of resin composition>
The resin composition described above can be cured by heat. Therefore, by thermosetting the resin composition, a cured product of the resin composition can be obtained. Generally, among the components contained in a resin composition, volatile components such as (I) solvent can be volatilized by the heat during thermosetting, but non-volatile components such as components (A) to (H) can be volatile during thermosetting. It does not evaporate due to heat. Therefore, the cured product of the resin composition may contain the nonvolatile components of the resin composition or a reaction product thereof.

According to the resin composition according to one embodiment of the present invention, a cured product having a low dielectric loss tangent can be obtained. In one example, the dielectric loss tangent of the cured product obtained by thermosetting the resin composition at 190° C. for 90 minutes is preferably 0.0050 or less, more preferably 0.0040 or less, still more preferably 0.0032 or less, Particularly preferably, it is 0.0030 or less. The lower limit is not particularly limited, and may be, for example, 0.0001 or more. The dielectric loss tangent of the cured product of the resin composition can be measured by a cavity resonance perturbation method (frequency: 5.8 GHz, temperature: 23° C.). As a specific method for measuring the dielectric loss tangent, the method described in <Measurement of the dielectric loss tangent> in Examples can be adopted.

According to the resin composition according to one embodiment of the present invention, an insulating layer that can suppress the haloing phenomenon can be obtained. The ability to suppress the haloing phenomenon in this manner will be described below with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing, together with an inner layer substrate, an insulating layer formed of a cured product of a resin composition according to an embodiment of the present invention after a roughening treatment is performed. FIG. 1 shows a cross section of the insulating layer 100 taken along a plane that passes through the center 120C of the bottom 120 of the via hole 110 and is parallel to the thickness direction of the insulating layer 100. Further, FIG. 2 shows a surface 100U of the insulating layer 100 opposite to the inner layer substrate after roughening treatment has been performed on the insulating layer formed of the cured product of the resin composition according to an embodiment of the present invention. FIG. 2 is a schematic plan view.

As shown in FIG. 1, consider a case where an insulating layer 100 is formed on an inner layer substrate 200 including a conductor layer 210, and a via hole 110 is formed as a hole in the insulating layer 100. The via hole 110 is generally formed in a tapered shape such that the closer it is to the surface 100U of the insulating layer 100 opposite to the inner layer substrate 200, the larger the diameter is, and the closer it is to the inner layer substrate 200, the smaller the diameter. Therefore, the diameter of the via bottom 120 is usually less than or equal to the diameter of the via top 130. Here, the via bottom 120 represents the bottom of the via hole 110 on the circuit board 200 side, and the via top 130 represents an opening formed on the side of the via hole 110 opposite to the inner layer substrate 200. Hereinafter, the diameter of the via top 130 may be referred to as "top diameter" Lt. The via hole 110 is formed, for example, by irradiating the surface 100U of the insulating layer 100 with a laser beam and removing a portion of the insulating layer 100. The via bottom 120 and the via top 130 are generally formed to have a circular planar shape when viewed from the thickness direction of the insulating layer 100, but may have an elliptical shape. When the planar shape of the via top 130 is an ellipse, the top diameter Lt represents the long axis of the ellipse.

When looking at the insulating layer 100 in which the via hole 110 is formed, a discolored portion 140 in which the insulating layer 100 is discolored can be observed around the via hole 110 due to the haloing phenomenon. This discolored portion 140 is formed due to resin deterioration during the formation of the via hole 110, and is usually formed continuously from the via hole 110. Further, in many cases, the discolored portion 140 is a whitened portion.

When the insulating layer 100 in which the via hole 110 is formed is subjected to the roughening treatment, the discolored portion 140 is eroded, and the insulating layer 100 in the discolored portion 140 may peel off from the conductive layer 210 on the surface of the circuit board 200. Therefore, a gap 160 may be formed between the insulating layer 100 and the circuit board 200, continuing from the edge 150 of the via bottom 120. The size of this gap 160 is represented by the distance Wb from the edge 150 of the via bottom 120 to the outer peripheral end 170 of the gap 160 (that is, the end farthest from the center 120C of the via bottom 120). When a conductor layer (not shown) is formed on the insulating layer 100, the gap 160 is Preferably, the size is small.

The size of gap 160 generally correlates to the size of discoloration 140. Therefore, if the size of the discolored portion 140 can be reduced by suppressing the haloing phenomenon, the size of the gap portion 160 can be reduced to improve conduction reliability. As shown in FIG. 2, the size of the discolored portion 140 can be expressed by the distance Wt from the edge 180 of the via top 130 to the outer peripheral edge 190 of the discolored portion 140. When using the resin composition according to the present embodiment, the size of the discolored portion 140 can be reduced to achieve suppression of the haloing phenomenon.

When the top diameter Lt is constant, the smaller the diameter of the outer edge 190 of the discolored part 140, the smaller the size of the discolored part 140, and therefore the haloing phenomenon can be effectively suppressed. represent. In the following description, the diameter of the outer circumferential edge 190 of the discolored portion 140 may be referred to as the "diameter of the harrowing portion." In one example, when a via hole with a top diameter Lt of 50 μm is formed in an insulating layer formed of a cured product of the resin composition according to the present embodiment, the diameter of the harrowing portion can be made 89 μm or less. The diameter of the haloing part can be measured by the method described in <Evaluation of haloing phenomenon> in Examples.

According to the resin composition according to one embodiment of the present invention, a cured product with excellent elongation can usually be obtained. Specifically, the cured product of the resin composition can usually have a high elongation at break. In one example, the elongation at break of a cured product obtained by thermosetting the resin composition at 190° C. for 90 minutes is preferably 1.0% or more. The upper limit is not particularly limited and may be, for example, 100% or less. The elongation at break can be measured in accordance with Japanese Industrial Standards (JIS K7127). As a specific method for measuring elongation at break, the method described in <Evaluation of elongation> in Examples can be adopted.

According to the resin composition according to one embodiment of the present invention, a cured product having excellent strength at break can usually be obtained. Specifically, when a cured product is subjected to a tensile test in accordance with JIS K7127, a large strength at break can be obtained. In one example, the strength at break of a cured product having a thickness of 40 μm obtained by thermosetting the resin composition at 190° C. for 90 minutes is preferably 80 MPa or more.

According to the resin composition according to one embodiment of the present invention, a cured product having excellent crack resistance can usually be obtained. Specifically, when cuts are made in the layer of the cured resin composition in a checkerboard pattern according to JIS K 5600-5-6, the rate of crack generation can be suppressed. In one example, when cuts are made in a checkerboard pattern in the layer of the cured product of the resin composition according to the present embodiment, the proportion of cured pieces in which cracks occur is preferably less than 15%, more preferably less than 5%. can. Here, the term "cured piece" refers to each portion of a layer of cured material that is divided by cuts. The proportion of cured pieces in which cracks occur can be measured by the method described in <Evaluation of crack resistance> in Examples.

According to the resin composition according to one embodiment of the present invention, a cured product that has excellent adhesion to a conductor layer can usually be obtained. Specifically, when a conductor layer is formed on a cured product of a resin composition by a plating method, the peel strength of the conductor layer can be increased. Here, the peel strength represents the force required to peel the conductor layer from the cured product, and the higher the peel strength, the better the adhesion. In one example, when a conductor layer is formed on a cured product of the resin composition according to this embodiment, a peel strength of 0.3 kgf/cm or more can be obtained. Peel strength can be measured by the method described in <Evaluation of Adhesion> in Examples.

<Applications of resin composition>
The above-mentioned resin composition can be used as a resin composition for insulation purposes, and particularly can be suitably used as a resin composition for forming an insulation layer (resin composition for forming an insulation layer). For example, the above-mentioned resin composition can be used as a resin composition for forming an insulating layer of a printed wiring board, and is suitable as a resin composition for forming an interlayer insulating layer (resin composition for interlayer insulation). Can be used.

Moreover, the resin composition mentioned above may be used as a resin composition for forming a rewiring formation layer (resin composition for forming a rewiring formation layer). The rewiring formation layer represents an insulating layer for forming a rewiring layer. Further, the rewiring layer refers to a conductor layer formed on the rewiring formation layer as an insulating layer. For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the above-mentioned resin composition may be used as a resin composition for forming a rewiring formation layer. Further, when a semiconductor chip package is manufactured by the following steps (1) to (6), a rewiring layer may be further formed on the sealing layer.
(1) The step of laminating a temporary fixing film on the base material,
(2) Temporarily fixing the semiconductor chip on the temporary fixing film,
(3) forming a sealing layer on the semiconductor chip;
(4) Peeling the base material and temporary fixing film from the semiconductor chip,
(5) Forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled; and (6) Forming a rewiring layer as a conductive layer on the rewiring layer. Forming process

Furthermore, the above-mentioned resin compositions can be used, for example, in sheet-like laminated materials such as resin sheets, prepregs, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole filling resins, component embedding resins, etc. Can be used in a wide range of applications.

<Sheet-like laminated material>
The above-mentioned resin composition may be applied in the form of a varnish, but industrially it is preferable to use it in the form of a sheet-like laminate material containing the resin composition.

As the sheet-like laminated material, the following resin sheets and prepregs are preferred.

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

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 50 μm or less, from the viewpoint of making the printed wiring board thinner and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film. Preferably it is 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be 5 μm or more, 10 μm or more, etc.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polyesters such as polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using metal foil as the support, examples of the metal foil include copper foil, aluminum foil, etc., with copper foil being preferred. As the copper foil, a foil made of a single metal such as copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. May be used.

The surface of the support to be bonded to the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

As the support, a support with a release layer may be used, which has a release layer on the surface to be bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . The support with a release layer may be a commercially available product, such as "SK-1" manufactured by Lintec Corporation, which is a PET film having a release layer containing an alkyd resin mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin, and "Unipeel" manufactured by Unitika.

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

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

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

Examples of the solvent include the same solvents as those described as components of the resin composition. One type of solvent may be used alone, or two or more types may be used in combination.

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

The resin sheet can be stored by winding it up into a roll. When the resin sheet has a protective film, it can usually be used by peeling off the protective film.

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

As the sheet-like fiber base material used for the prepreg, those commonly used as base materials for prepregs, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of making the printed wiring board thinner, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited, and is usually 10 μm or more.

Prepreg can be manufactured by a method such as a hot melt method or a solvent method.

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

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

<Printed wiring board>
A printed wiring board according to an embodiment of the present invention includes an insulating layer containing a cured product obtained by curing the resin composition described above. This printed wiring board can be manufactured, for example, using the above-mentioned resin sheet by a method including the following steps (I) and (II).
(I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate.
(II) A step of curing the resin composition layer to form an insulating layer.

The "inner layer substrate" used in step (I) is a member that becomes a substrate of a printed wiring board, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. Further, the substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer board in which a conductor layer (circuit) is formed on one or both sides of the board is sometimes referred to as an "inner layer circuit board." Further, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and/or a conductive layer is further formed is also included in the above-mentioned "inner layer board". If the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for hot-pressing the resin sheet to the inner layer substrate (hereinafter also referred to as "heat-pressing member") include a heated metal plate (SUS mirror plate, etc.), a metal roll (SUS roll), and the like. Note that, instead of pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the resin sheet may be laminated by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the heat-pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0. The pressure is in the range of .29 MPa to 1.47 MPa, and the heat-pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

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

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

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

In step (II), the resin composition layer is cured to form an insulating layer containing a cured product of the resin composition. The resin composition layer is usually cured by heat curing. As specific curing conditions for the resin composition layer, conditions that are normally employed when forming an insulating layer of a printed wiring board may be used.

Thermal curing conditions for the resin composition layer may vary depending on the type of resin composition. For example, the curing temperature may be preferably 120°C to 240°C, more preferably 150°C to 220°C, even more preferably 170°C to 210°C. Further, the curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 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 thermosetting the resin composition layer, the resin composition layer is cured for 5 minutes or more at a temperature of 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°C. Preheating may be performed preferably for 5 minutes to 150 minutes, more preferably for 15 minutes to 120 minutes, even more preferably for 15 minutes to 100 minutes.

When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be performed according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. Note that when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or during step (IV). IV) and step (V). Furthermore, if necessary, the steps (I) to (V) for forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.

In other embodiments, printed wiring boards can be manufactured using the prepregs described above. The manufacturing method can be basically the same as when using a resin sheet.

Step (III) is a step of drilling a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be determined as appropriate depending on the design of the printed wiring board.

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

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

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

The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product includes, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing liquid can be carried out by immersing the treated surface, which has been roughened with an oxidizing agent, in the neutralizing liquid at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability, it is preferable to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, etc. Further, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer includes one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-chromium alloy, a copper-chromium alloy, etc.). nickel alloys and copper-titanium alloys). Among these, from the viewpoint of versatility in forming conductor layers, cost, ease of patterning, etc., monometallic layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, nickel-chromium alloys, copper, etc. An alloy layer of nickel alloy or copper/titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel/chromium alloy is more preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is more preferable. A metal layer is more preferred.

The conductor layer may have a single layer structure, or may have a multilayer 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 multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a fully additive method. From the viewpoint of ease of production, a semi-additive method is preferred. An example of forming a conductor layer by a semi-additive method will be shown below.

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

In other embodiments, the conductive layer may be formed using metal foil. When forming a conductor layer using metal foil, step (V) is preferably carried out between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer. The resin composition layer and the metal foil may be laminated by vacuum lamination. The 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 using the metal foil on the insulating layer by a conventional known technique such as a subtractive method or a modified semi-additive method.

Metal foil can be manufactured by a known method such as an electrolytic method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining Co., Ltd., and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Mining Co., Ltd.

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

Examples of semiconductor devices include various semiconductor devices used in electrical products (eg, computers, mobile phones, digital cameras, televisions, etc.), vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.), and the like.

The present invention will be specifically described below with reference to Examples. However, the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the temperature conditions and pressure conditions when there was no particular temperature specification were room temperature (25° C.) and atmospheric pressure (1 atm).

<Synthesis Example 1: Synthesis of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane>
A reactor equipped with a stirrer, thermometer and addition funnel was prepared. 61.8 g (0.717 mol) of 3-methyl-2-buten-1-ol and 36.84 g (0.657 mol) of potassium hydroxide were charged into this reactor under a nitrogen stream. While keeping the internal temperature at 10°C or lower, 19.34 g (0.209 mol) of epichlorohydrin was added dropwise while stirring, and after the completion of the dropwise addition, the temperature was raised to 50°C. The mixture was stirred at an internal temperature of 50°C for 6 hours, and then cooled to 25°C. The reaction solution was neutralized with a 4M aqueous hydrochloric acid solution, and the upper layer was washed with 310 mL of ion-exchanged water. The obtained organic layer was purified by distillation to obtain 28.77 g (0.126 mol; yield of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane represented by formula (a-1) 60.3%).

<Example 1>
(Manufacture of resin composition)
10 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: approximately 185 g/eq.), 10 parts of naphthalene type epoxy resin ("HP4032SS", manufactured by DIC Corporation, epoxy equivalent: approximately 144 g/eq.), 3', 10 parts of 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate ("Celoxide 2021P" manufactured by Daicel Corporation, epoxy equivalent: approx. 175 g/eq.), cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: approx. 135 g/eq.), 10 parts of phenoxy resin (YL7891T30 manufactured by Mitsubishi Chemical Corporation, toluene solution with solid content of 30% by mass, weight average molecular weight Mw = 30000) were dissolved by heating in 50 parts of methyl ethyl ketone with stirring. , a solution was obtained. After cooling to room temperature, a triazine skeleton-containing cresol novolak resin (DIC "LA-3018-50P", hydroxyl equivalent: about 151 g/eq., 2-methoxypropanol solution with solid content of 50%) was added to the solution. 120 parts of active ester resin (HPB-8151-62T manufactured by DIC, active group equivalent: approximately 238 g/eq., toluene solution containing 62% by mass of non-volatile components), inorganic filler (spherical silica (manufactured by Admatex)) 1 part of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) was applied to 100 parts of "SC2500SQ", average particle size 0.63 μm, specific surface area 11.2 m ² /g). treated particles), 400 parts of polycarbodiimide compound (V-03, manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent: approximately 216 g/eq., toluene solution with solid content of 50%), aliphatic group-containing maleimide resin (designer mole) 15 parts of a toluene solution with a solid content of 80% solid content of "BMI-1500" manufactured by Kuels, 0.1 part of an amine curing accelerator (4-dimethylaminopyridine (DMAP)), and 1 synthesized in Synthesis Example 1. , 2.5 parts of 3-bis(3-methyl-2-butenoxy)-2-hydroxypropane were mixed and uniformly dispersed using a high-speed rotating mixer to obtain a mixture. Thereafter, this mixture was filtered through a cartridge filter ("SHP020" manufactured by ROKITECHNO) to obtain a resin composition.

(Manufacture of resin sheet)
PET film ("501010" manufactured by Lintec Corporation, thickness 38 μm, having a surface treated with a mold release agent (mold release treated surface) and a surface not subjected to mold release treatment (mold release agent untreated surface) 240 mm square) was prepared. A glass cloth-based epoxy resin double-sided copper-clad laminate (R5715ES manufactured by Matsushita Electric Works, thickness 0.7 mm, 255 mm square) was placed on the untreated side of the PET film, and the four sides were covered with polyimide adhesive tape (width 10 mm).

The resin composition was applied onto the release-treated surface of the PET film using a die coater so that the thickness of the resin composition layer after drying was 40 μm, and the mixture was applied at 80°C to 120°C (average 100°C). The resin sheet was dried for 10 minutes to obtain a resin sheet.

(Manufacture of cured product)
Next, the resin sheet was placed in an oven at 190° C. and heated for 90 minutes to thermally cure it. After thermosetting, the PET film was peeled off to obtain a sheet-like cured product.

<Example 2>
Instead of 120 parts of active ester resin ("HPB-8151-62T" manufactured by DIC Corporation), radical polymerizable resin containing active ester groups ("PC1300-02-65MA" manufactured by Air Water Corporation, active ester group equivalent) A resin composition, a resin sheet, and a cured product were produced in the same manner as in Example 1, except that 100 parts of a methyl amyl ketone solution with a nonvolatile content of 65% (approximately 199 g/eq.) was used.

<Example 3>
Instead of 10 parts of phenoxy resin ("YL7891T30" manufactured by Mitsubishi Chemical Corporation), 10 parts of styrene-modified polyphenylene ether resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight Mn = 1200, solid content 65% toluene solution) A resin composition, a resin sheet, and a cured product were produced in the same manner as in Example 1, except that the same procedure as Example 1 was used.

<Example 4>
Example except that 10 parts of maleimide resin b (methyl ethyl ketone solution containing 70% by mass of non-volatile components) represented by the following formula (b-2) was used instead of 10 parts of phenoxy resin (YL7891T30 manufactured by Mitsubishi Chemical Corporation). A resin composition, a resin sheet, and a cured product were manufactured by the same method as in Example 1. The maleimide compound b represented by the formula (b-2) is a maleimide compound synthesized by the method described in Synthesis Example 1 of Japan Institute of Invention and Innovation Publication No. 2020-500211.

<Example 5>
Instead of 10 parts of phenoxy resin (YL7891T30, manufactured by Mitsubishi Chemical Corporation), aromatic hydrocarbon resin (FMR0150, manufactured by Mitsui Chemicals, a copolymer of 4-methyl-α-methyl-styrene and indene, number average A resin composition, a resin sheet, and a cured product were produced in the same manner as in Example 1, except that 5 parts (molecular weight Mn = 1190, weight average molecular weight Mw = 2040) were used.

<Comparative example 1>
A resin composition, a resin sheet, and a cured product were produced in the same manner as in Example 1, except that 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane was not used.

<Comparative example 2>
1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane and aliphatic group-containing maleimide resin (80% solids toluene solution of "BMI-1500" manufactured by Designer Molecules) were used. A resin composition, a resin sheet, and a cured product were manufactured by the same method as in Example 3 except that there was no.

<Measurement of dielectric loss tangent>
The cured products (sheet-like) produced in the Examples and Comparative Examples were cut out to a width of 2 mm and a length of 80 mm, and measured using a cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. The dielectric loss tangent was measured.

<Evaluation of haloing phenomenon>
A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, board thickness 0.8 mm, “R1766” manufactured by Panasonic Corporation) was prepared as an inner layer circuit board having copper layers on both sides. Both surfaces of this inner layer circuit board were etched by 0.5 μm using "CZ8201" manufactured by MEC Co., Ltd. to roughen the surface of the copper layer.

Thereafter, the resin sheets produced in Examples and Comparative Examples were bonded to the inner layer circuit board using a batch vacuum pressure laminator (manufactured by Nikko Materials, 2-stage build-up laminator, CVP700). Both sides of the above inner layer circuit board were laminated as shown. The lamination process was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then press-bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds. Thereafter, the resin composition layer was thermally cured at 100° C. for 30 minutes and then at 180° C. for 30 minutes to form an insulating layer. Then, it was cooled to room temperature.

After that, without peeling the PET film of the resin sheet, a carbon dioxide laser device (Mitsubishi Electric "ML605GTWII-P") irradiates laser light through the PET film with a pulse width of 4 μs to make holes in the insulating layer. A blind via (top diameter of 50 μm) was formed as a via hole. Thereafter, the PET film of the resin sheet was peeled off to obtain an evaluation board having a layer structure of insulating layer/interior circuit board/insulating layer.

The evaluation board described above was subjected to a roughening treatment. Specifically, the evaluation board was immersed in a swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous sodium hydroxide solution containing diethylene glycol monobutyl ether) at 60°C for 10 minutes, and then immersed in an oxidizing agent (Atotech Japan Co., Ltd.). "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., an aqueous solution with a potassium permanganate concentration of about 6% by mass and a sodium hydroxide concentration of about 4% by mass) for 20 minutes at 80°C, and then a neutralizing solution ("Reduction" manufactured by Atotech Japan Co., Ltd.) Solution Securigant P" (hydroxylamine sulfate aqueous solution) was immersed at 40° C. for 5 minutes. Thereafter, it was dried at 80° C. for 15 minutes.

The evaluation substrate after the roughening treatment was observed using an optical microscope (“KH8700” manufactured by Hirox Corporation). Specifically, the insulating layer around the via hole was observed from above the evaluation board using an optical microscope (CCD). The via hole was observed by focusing an optical microscope on the via top. The top diameter (Lt) of the via hole was measured from the observed image. Furthermore, as a result of observation, a donut-shaped haloing part in which the insulating layer turned white was observed around the via hole, continuing from the edge of the via top of the via hole. Therefore, the diameter of the haloing part was measured from the observed image. When the diameter of the haloing part was 90 μm or more, it was marked as “×”, and when it was 89 μm or less, it was marked as “○”.

<Evaluation of elongation>
The cured products produced in Examples and Comparative Examples may be hereinafter referred to as "cured products for evaluation c." The cured product c for evaluation was subjected to a tensile test in accordance with the Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec), and the elongation at break (%) was measured. If the elongation at break was less than 1.0%, it was rated "x", and if it was 1.0% or more, it was rated "○".

<Evaluation of strength at break>
The cured product c for evaluation was subjected to a tensile test in accordance with the Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec) to measure the strength at break. When the strength at break was less than 80 MPa, it was marked as "x", and when it was 80 MPa or more, it was marked as "○".

<Evaluation of adhesion>
A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, board thickness 0.8 mm, “R1766” manufactured by Panasonic Corporation) was prepared as an inner layer circuit board having copper layers on both sides. Both surfaces of this inner layer circuit board were etched by 0.5 μm using "CZ8201" manufactured by MEC Co., Ltd. to roughen the surface of the copper layer.

Thereafter, the resin sheets produced in Examples and Comparative Examples were bonded to the inner layer circuit board using a batch vacuum pressure laminator (manufactured by Nikko Materials, 2-stage build-up laminator, CVP700). Both sides of the above inner layer circuit board were laminated as shown. The lamination process was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then press-bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds. Thereafter, the resin composition layer was thermally cured at 100° C. for 30 minutes and then at 180° C. for 30 minutes to form an insulating layer. Then, it was cooled to room temperature.

Thereafter, the PET film of the resin sheet was peeled off to obtain an evaluation board having a layer structure of insulating layer/interior circuit board/insulating layer. This evaluation substrate was subjected to a roughening treatment to obtain a roughened substrate a. Specifically, the evaluation board was immersed in a swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous sodium hydroxide solution containing diethylene glycol monobutyl ether) at 60°C for 10 minutes, and then immersed in an oxidizing agent (Atotech Japan Co., Ltd.) for 10 minutes. ``Concentrate Compact CP'' manufactured by Atotech Japan, an aqueous solution with a concentration of potassium permanganate of approximately 6% by mass and a concentration of sodium hydroxide of approximately 4% by mass) at 80°C for 20 minutes, and then a neutralizing solution (manufactured by Atotech Japan) Reduction Solution Securigant P" (hydroxylamine sulfate aqueous solution) was immersed at 40°C for 5 minutes. Thereafter, it was dried at 80° C. for 15 minutes to obtain a roughened substrate a. A conductor layer was formed on the roughened surface of the insulating layer of this roughened substrate a according to a semi-additive method. That is, a conductor layer was formed by performing a plating process (copper plating process using a chemical solution manufactured by Atotech Japan) including steps 1 to 6 below.

1. Alkaline cleaning (cleaning of the surface of the insulating layer and charge adjustment)
The surface of the insulating layer was cleaned at 60° C. for 5 minutes using an alkaline solution “Cleaning Cleaner Securiganth 902”.

2. Soft etching (cleaning)
The insulating layer was treated at 30° C. for 1 minute using a sulfuric acid acidic sodium peroxodisulfate aqueous solution.

3. Pre-dip (adjustment of charge on the surface of the insulating layer for Pd application)
The insulating layer was treated with a surface charge control agent "Pre. Dip Neoganth B" at room temperature for 1 minute.

4. Addition of activator (application of Pd to the surface of the insulating layer)
The insulating layer was treated at 35° C. for 5 minutes using a palladium catalyst “Activator Neoganth 834”.

5. Reduction (reducing Pd applied to the insulating layer)
The surface of the insulating layer was treated at 30° C. for 5 minutes using a reducing agent (a mixed solution of “Reducer Neoganth WA” and “Reducer Accelerator 810 mod.”).

6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
Basic Solution Printganth MSK-DK (product name), Copper solution Printganth MSK (product name), Stabilizer Printganth MSK-DK (product name), and Reducer Cu (product name) ) to form an insulating layer. The surface was treated at 35° C. for 30 minutes to form an electroless copper plating layer with a thickness of 1 μm. Thereafter, copper sulfate electrolytic plating was performed using a chemical solution manufactured by Atotech Japan Co., Ltd. to form a conductor layer with a thickness of 25 μm, and annealing treatment was performed at 190° C. for 60 minutes.

A peel test of the conductor layer was conducted in accordance with Japanese Industrial Standards (JIS C6481). Specifically, a cut was made in the conductor layer formed on the insulating layer to surround a rectangular portion with a width of 10 mm and a length of 100 mm. One end of this rectangular part was peeled off and grabbed with a grip. The rectangular portion was peeled off in the vertical direction at a rate of 50 mm/min at room temperature, and the load (kgf/cm) when 35 mm was peeled off was measured as the peel strength (copper plating peel strength). A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement. A peel strength of less than 0.3 kgf/cm was rated "x", and a peel strength of 0.3 kgf/cm or more was rated "○".

<Evaluation of crack resistance>
In accordance with JIS K 5600-5-6, incisions were made in a checkerboard pattern in the insulating layer of the roughened substrate a manufactured using the same method as described in <Evaluation of adhesion>, and the presence or absence of cracks in the insulating layer was examined using an optical microscope. It was observed and evaluated. Specifically, incisions were made in the insulating layer of the roughened substrate a in a grid pattern at 1 mm intervals to form a total of 100 cured pieces, 10 in the vertical direction and 10 in the horizontal direction. Here, the term "cured piece" refers to each part of the insulating layer divided by cuts. These 100 cured pieces were observed with an optical microscope, and the number of cured pieces with cracks was counted. Crack resistance was evaluated using the following evaluation criteria based on the ratio of the number of cured pieces with cracks to the total number of 100 cured pieces.

Evaluation criteria "○": Almost no cracks in the insulation layer (the ratio of the number of cured pieces with cracks is less than 5%)
"△": There are slight cracks in the insulating layer (the ratio of the number of cured pieces with cracks is 5% or more and less than 15%)
"×": There are many cracks in the insulation layer (the ratio of the number of cured pieces with cracks is 15% or more)

<Results>
The results of the above-mentioned Examples and Comparative Examples are shown in the table below.

Claims (14)

(A) A compound containing a secondary carbon atom, an oxygen atom bonded to the secondary carbon atom with a single bond, and an aliphatic unsaturated bond, and
(B) A resin composition comprising a radically polymerizable resin that does not contain an oxygen atom bonded to a secondary carbon atom through a single bond and contains an aliphatic unsaturated bond. The resin composition according to claim 1, wherein the component (A) contains a compound represented by the following formula (A-1).

(In formula (A-1),
R ⁰ represents a hydrogen atom or a monovalent organic group,
R ¹ each independently represents a divalent hydrocarbon group which may have a substituent,
R ² each independently represents a divalent hydrocarbon group which may have a substituent,
R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent,
R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent,
R ⁵ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent,
n each independently represents an integer of 0 or more and 6 or less. ) The resin composition according to claim 1, wherein component (B) contains a maleimide resin. (C) The resin composition according to claim 1, comprising an epoxy resin. (D) The resin composition according to claim 1, comprising a curing agent. (E) The resin composition according to claim 1, comprising an inorganic filler. The resin composition according to claim 6, wherein the amount of the inorganic filler (E) is 50% by mass or more based on 100% by mass of nonvolatile components in the resin composition. (F) The resin composition according to claim 1, comprising a thermoplastic resin. The resin composition according to claim 1, which is used for forming an insulating layer. A cured product of the resin composition according to any one of claims 1 to 9. A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 9. comprising a support and a resin composition layer formed on the support,
A resin sheet, wherein the resin composition layer contains the resin composition according to any one of claims 1 to 9. A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor device comprising the printed wiring board according to claim 13.

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