KR20230063871A - Resin composition - Google Patents

Abstract

The present invention relates to a resin composition including: compounds including a biphenyl skeleton, a propenyl group and a phenolic hydroxyl group; an epoxy resin; active ester compounds; and an inorganic filler. According to the present invention, a cured product having excellent crack resistance and high adhesion to a conductor layer after a HAST test can be obtained.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition.

As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked and stacked is known. In the manufacturing method by a build-up method, generally, an insulating layer is formed of the hardened|cured material which hardened the resin composition (patent document 1).

Japanese Unexamined Patent Publication No. 2020-23714

The cured material contained in the insulating layer is required to have a low dielectric loss tangent. As one of the methods for obtaining a cured product having a low dielectric loss tangent, blending of an active ester compound and an inorganic filler with a resin composition is exemplified. However, when a resin composition containing an active ester compound and an inorganic filler is used, the smear removability of the insulating layer may decrease or cracks may easily occur in the insulating layer after the roughening treatment. Here, "smear removability" refers to a property that can easily remove smear as a resin residue.

In addition, the insulating layer using a resin composition in which an active ester compound and an inorganic filler were blended tended to have poor adhesion to the conductor layer after a high-accelerated life test (HAST test) in a high-temperature, high-humidity environment. In order to obtain an insulating layer capable of maintaining adhesion over a long period of time, development of a resin composition capable of enhancing adhesion after the HAST test described above is required.

The present invention was devised in view of the above problems, and a resin composition capable of obtaining a cured product having a low dielectric loss tangent, excellent smear removability and crack resistance, and high adhesion to the conductor layer after the HAST test; cured products of the resin composition; sheet-like laminated materials containing the resin composition; a resin sheet having a resin composition layer formed of the resin composition; a printed wiring board provided with an insulating layer containing a cured product of the resin composition; and a semiconductor device including the printed wiring board; It aims to provide

The present inventors intensively studied in order to solve the above problems. As a result, the inventors of the present invention (A) a compound containing a biphenyl skeleton, a propenyl group and a phenolic hydroxyl group, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler, a resin composition comprising This discovered that said subject could be solved, and completed this invention.

That is, the present invention includes the following.

[1] (A) a compound containing a biphenyl skeleton, a propenyl group and a phenolic hydroxyl group;

(B) an epoxy resin;

(C) an active ester compound, and

(D) An inorganic filler, A resin composition containing.

[2] When the non-volatile component in the resin composition is 100% by mass, (D) the content of the inorganic filler is 60% by mass or more, and (C) the content of the active ester compound is 10% by mass or more, in [1] The resin composition described.

[3] (A) The resin composition according to [1] or [2], wherein the compound containing a biphenyl skeleton, a propenyl group, and a phenolic hydroxyl group contains a group represented by the following formula (A1).

(In formula (A1), R each independently represents a monovalent hydrocarbon group; n represents an integer of 0 or more and 3 or less; * represents a bond.)

[4] (A) The resin composition according to any one of [1] to [3], wherein the compound containing a biphenyl skeleton, a propenyl group, and a phenolic hydroxyl group is represented by the following formula (A2).

(In formula (A2),

R ¹ each independently represents a monovalent hydrocarbon group;

R ² each independently represents a divalent aliphatic hydrocarbon group;

X each independently represents a halogen atom or a monovalent hydrocarbon group;

p each independently represents an integer of 0 or more and 3 or less;

q represents 0 or 1;

r represents an integer of 0 or more and 4 or less each independently.)

[5] The resin composition according to any one of [1] to [4], containing at least one (E) curing agent selected from the group consisting of a phenol-based curing agent and a carbodiimide-based curing agent.

[6] (F) The resin composition according to any one of [1] to [5], containing a curing accelerator.

[7] (G) The resin composition according to any one of [1] to [6], including a thermoplastic resin.

[8] The resin composition according to any one of [1] to [7], for forming an insulating layer.

[9] A cured product of the resin composition according to any one of [1] to [8].

[10] A sheet-like laminated material containing the resin composition according to any one of [1] to [8].

[11] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [8] on the support.

[12] A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of [1] to [8].

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

According to the present invention, a resin composition capable of obtaining a cured product having a low dielectric loss tangent, excellent smear removability and crack resistance, and high adhesion to the conductor layer after the HAST test; cured products of the resin composition; sheet-like laminated materials containing the resin composition; a resin sheet having a resin composition layer formed of the resin composition; a printed wiring board provided with an insulating layer containing a cured product of the resin composition; and a semiconductor device including the printed wiring board; can provide.

Hereinafter, embodiments and examples of the present invention are shown and described. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with arbitrary changes within a range not departing from the scope of the claims and their equivalents.

In the following description, the term "(meth)acrylic acid ester" includes acrylic acid esters, methacrylic acid esters, and combinations thereof unless otherwise specified. In addition, in the following description, the term "(meth)acrylate" includes acrylates, methacrylates, and combinations thereof unless otherwise indicated.

[One. Overview of Resin Composition]

A resin composition according to an embodiment of the present invention comprises (A) a compound containing a biphenyl skeleton, a propenyl group and a phenolic hydroxyl group, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler. , including in combination. In the following description, unless otherwise indicated, a "propenyl group" refers to a "1-propenyl group", and thus represents CH ₃ -CH=CH-. In the following description, "(A) a compound containing a biphenyl skeleton, a propenyl group and a phenolic hydroxyl group" may be referred to as "(A) specific propenylphenol compound". According to this resin composition, a cured product having a low dielectric loss tangent, excellent smear removability and crack resistance, and high adhesion to the conductor layer after the HAST test can be obtained. In addition, this cured product is usually excellent in adhesion to the conductor layer not only after the HAST test but also before the HAST test. This hardened|cured material can be used suitably as a material of the insulating layer of a printed wiring board, for example.

The present inventors estimate as follows a system from which the cured product of the resin composition according to the present embodiment can obtain the above-excellent advantages. However, the technical scope of the present invention is not limited by the system described below.

A cured product of a conventional resin composition containing an epoxy resin, an active ester compound, and an inorganic filler usually has a low dielectric loss tangent. However, generally, the cured product of the resin composition tends to be inferior in smear removability, crack resistance, and adhesion to the conductor layer after the HAST test.

Generally, when an epoxy resin and an active ester compound react, an ester bond is formed. This ester bond is prone to hydrolysis. Therefore, in the cured product of the conventional resin composition, the ester bond is cut by the HAST test, and the mechanical strength of the cured product tends to decrease. Therefore, peeling accompanying resin destruction tends to occur, and therefore the adhesion after the HAST test tends to be low.

In contrast, in (A) the specific propenylphenol compound contained in the resin composition according to the present embodiment, the ethylenically unsaturated bond contained in the propenyl group causes radical polymerization, and (A) the molecules of the specific propenylphenol compound can be combined. Since the bond formed in this way is not easily hydrolyzed, a decrease in the mechanical strength of the cured product by the HAST test can be suppressed. Therefore, the adhesiveness after the HAST test can be improved.

In addition, usually, not all of the propenyl groups of the specific propenylphenol compound (A) cause polymerization, and some of them may remain without polymerization. This remaining propenyl group is easily oxidized during the roughening treatment. Therefore, since it is possible to effectively remove smear as a resin residue by the oxidation described above during the roughening treatment, smear removability can be improved.

Further, (A) in the specific propenylphenol compound, the hydroxyl group bonded to the aromatic ring (phenolic hydroxyl group) may react with the epoxy group of the (B) epoxy resin. Therefore, during curing of the resin composition, not only the molecules of (A) specific propenylphenol compound are bonded to each other by radical polymerization as described above, but also by the reaction between the phenolic hydroxyl group and the epoxy group (A) specific propenylphenol The compound and (B) epoxy resin may be combined. Therefore, since bonding points between molecules can be increased, the mechanical strength of the cured product can be increased. Further, (A) Since the biphenyl skeleton contained in the specific propenylphenol compound is a rigid structure, the rigidity of the cured product can be increased by the biphenyl skeleton. In addition, since the methyl group at the terminal of the propenyl group becomes steric hindrance and free volume is formed between the molecular chains, the flexibility of the molecules is improved and the toughness of the cured product can be increased. Therefore, since the resistance to stress of the cured product can be improved, it is possible to increase the crack resistance.

As described above, when the specific propenylphenol compound (A) and the epoxy resin (B) are bonded, a polar group such as a hydroxyl group may be formed at the bonded portion. On the other hand, however, polar groups do not normally occur in (A) bonding between molecules of a specific propenylphenol compound and bonding between (B) an epoxy resin and (C) an active ester compound. Therefore, the degree of increase in the polarity of the cured product that can occur by using the (A) specific propenylphenol compound is small. Therefore, since the amount of polar groups is small as a whole, the cured product of the resin composition according to the present embodiment improves smear removability, crack resistance, and adhesion to the conductor layer after the HAST test as described above, A small dielectric loss tangent can be achieved.

In addition, as described above, since destruction of the cured product can be suppressed by increasing the rigidity and toughness of the cured product, in the present embodiment, peeling of the conductor layer accompanying destruction of the cured product is prevented not only after the HAST test but also before the HAST test. can be suppressed Therefore, usually, the adhesiveness of the hardened|cured material before a HAST test and a conductor layer can be made high.

[2. (A) A compound containing a biphenyl skeleton, a propenyl group and a phenolic hydroxyl group]

The resin composition according to the present embodiment includes (A) a compound containing a biphenyl skeleton, a propenyl group and a phenolic hydroxyl group (ie, (A) specific propenylphenol compound) as component (A).

(A) A specific propenylphenol compound contains a phenolic hydroxyl group as a hydroxyl group bonded to an aromatic ring in its molecule. This phenolic hydroxyl group can usually react with the epoxy group contained in the (B) epoxy resin during curing of the resin composition. (A) The number of phenolic hydroxyl groups contained in the specific propenylphenol compound may be one or two or more. (A) The specific number of phenolic hydroxyl groups contained in the molecule of the specific propenylphenol compound is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 4 or less, and particularly preferably 3 below

(A) A specific propenylphenol compound contains a propenyl group in its molecule. The carbon-carbon unsaturated bond (ethylenically unsaturated bond) contained in the propenyl group may normally undergo a radical polymerization reaction during curing of the resin composition. (A) The number of propenyl groups contained in the specific propenylphenol compound may be 1 or 2 or more. (A) The specific number of propenyl groups contained in the molecule of the specific propenylphenol compound is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less. am. It is preferable to couple|bond with the aromatic ring which a propenyl group contains (A) specific propenyl phenol compound.

An aromatic ring represents a ring according to Hückel's rule in which the number of electrons contained in the cyclic π electron system is 4p+2 (p is a natural number). The aromatic ring may be an aromatic carbocycle containing only carbon atoms as ring-constituting atoms, and an aromatic heterocycle having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom in addition to a carbon atom as a ring-constituting atom. (A) The aromatic ring contained in the specific propenylphenol compound may be any of an aromatic carbocyclic ring and an aromatic heterocyclic ring, or both may be used, but an aromatic carbocyclic ring is preferable. Further, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 6- to 14-membered aromatic ring, still more preferably a 6- to 10-membered aromatic ring. Preferable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

(A) A substituent may be bonded to the aromatic ring contained in the specific propenylphenol compound. Although it does not specifically limit as a substituent, For example, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; monovalent hydrocarbon groups such as an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group (an alkyl group substituted with an aryl group), and an alkyl-aryl group (an aryl group substituted with an alkyl group); and the like.

The alkyl group represents a straight-chain, branched-chain and/or cyclic monovalent aliphatic saturated hydrocarbon group. The number of carbon atoms in the alkyl group is preferably 1 to 14, more preferably 1 to 10, and particularly preferably 1 to 6. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, A decyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, etc. are mentioned.

The alkenyl group represents a straight-chain, branched-chain and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The number of carbon atoms in the alkenyl group is preferably 2 to 14, more preferably 2 to 10, and particularly preferably 2 to 6. Examples of the alkenyl group include a vinyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, and a cyclohexenyl group.

An aryl group represents a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbocyclic ring. The number of carbon atoms in the aryl group is preferably 6 to 14, more preferably 6 to 10. As an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group etc. are mentioned, for example.

(A) In the specific propenylphenol compound, it is preferable that the phenolic hydroxyl group and the propenyl group are bonded to the same aromatic ring. Moreover, it is especially preferable that the (A) specific propenylphenol compound contains a group represented by the following formula (A1).

(In formula (A1), R each independently represents a monovalent hydrocarbon group; n represents an integer of 0 or more and 3 or less; * represents a bond.)

In the formula (A1), R each independently represents a monovalent hydrocarbon group. As a monovalent hydrocarbon group, what was mentioned above as a substituent which may be couple|bonded with the aromatic ring contained in (A) specific propenylphenol compound is mentioned, for example. Especially, an alkyl group is preferable, and an alkyl group of 1 to 6 carbon atoms is more preferable.

In Formula (A1), n represents an integer of 0 or more and 3 or less, and is preferably 0.

(A) A specific propenylphenol compound has a biphenyl skeleton in its molecule. (A) The number of biphenyl skeletons included in the molecule of the specific propenylphenol compound may be 1 or 2 or more. (A) As described above, a substituent may be bonded to the benzene ring contained in the biphenyl skeleton of the specific propenylphenol compound. Moreover, a phenolic hydroxyl group and a propenyl group may be bonded to the benzene ring contained in the biphenyl skeleton.

As a preferable (A) specific propenylphenol compound, the compound represented by the following formula (A2) is mentioned, for example.

(In formula (A2), R ¹ each independently represents a monovalent hydrocarbon group; R ² each independently represents a divalent aliphatic hydrocarbon group; X each independently represents a halogen atom or a monovalent hydrocarbon group; represents a group; p each independently represents an integer of 0 or more and 3 or less; q represents 0 or 1; r each independently represents an integer of 0 or more and 4 or less.)

In the formula (A2), R ¹ each independently represents the same as R in the formula (A1).

In Formula (A2), R ² each independently represents a divalent aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be linear or branched, and may contain a cyclic structure. Further, the divalent aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group. The number of carbon atoms in the divalent aliphatic hydrocarbon group is usually 1 or more, preferably 12 or less, more preferably 6 or less, still more preferably 4 or less, and particularly preferably 2 or less. As an example of a preferable divalent hydrocarbon group, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group are mentioned.

In Formula (A2), X each independently represents a halogen atom or a monovalent hydrocarbon group. Examples of the halogen atom and the monovalent hydrocarbon group include those described as the substituent which may be bonded to the aromatic ring contained in (A) the specific propenylphenol compound.

In the formula (A2), p each independently represents the same as n in the formula (A1).

In Formula (A2), q represents 0 or 1.

In the formula (A2), r each independently represents an integer of 0 or more and 4 or less, and is preferably 0.

(A) As a specific propenylphenol compound, the compound represented by the following formula (A3) - (A4) is mentioned, for example. In the formula (A4), m represents a positive number, usually represents a number of 0<m≤1, and preferably represents 1. The compound represented by Formula (A4) can be obtained as "SBA02A" by Gunei Chemical Co., Ltd.

(A) A specific propenylphenol compound may be used individually by 1 type, and may be used in combination of 2 or more types.

(A) The hydroxyl equivalent of the specific propenylphenol compound is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. to 400 g/eq., more preferably 100 g/eq. to 300 g/eq. A hydroxyl group equivalent shows the mass of (A) specific propenylphenol compound per 1 equivalent of phenolic hydroxyl groups.

(B) When the number of epoxy groups of the epoxy resin is 1, (A) the number of phenolic hydroxyl groups of the specific propenylphenol compound is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, It is preferably 3.0 or less, more preferably 2.0 or less, and particularly preferably 1.0 or less. "The number of phenolic hydroxyl groups of (A) specific propenylphenol compound" means the total value obtained by dividing the mass of the non-volatile component of (A) specific propenylphenol compound present in the resin composition by the hydroxyl equivalent. . In addition, "the number of epoxy groups of (B) epoxy resin" shows the value which summed all the values obtained by dividing the mass of the non-volatile component of the (B) epoxy resin present in the resin composition by the epoxy equivalent.

The mass ratio W _A /W B of the mass W A of the specific propenylphenol compound ₍ A) in the resin composition and the mass W _B of the (B) epoxy resin is preferably _0.01 or more, more preferably 0.05 or more, still more preferably It is preferably 0.10 or more, particularly preferably 0.15 or more, preferably 1.0 or less, more preferably 0.7 or less, still more preferably 0.5 or less, and particularly preferably 0.3 or less. When the mass ratio W _A /W _B is within the above range, the dielectric loss tangent of the cured product of the resin composition, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test can be effectively improved, and usually , the adhesion before the HAST test can also be made good.

The mass ratio W _A /W _C of the mass W A of the specific propenylphenol compound (A) in the resin composition and the mass W _C of the (C) active ester compound is preferably _0.01 or more, more preferably 0.02 or more. It is preferably 0.03 or more, particularly preferably 0.05 or more, preferably 1.0 or less, more preferably 0.5 or less, still more preferably 0.3 or less, and particularly preferably 0.1 or less. When the mass ratio W _A /W _C is within the above range, the dielectric loss tangent of the cured product of the resin composition, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test can be effectively improved, and usually , the adhesion before the HAST test can also be made good.

Mass ratio W A /(W B + W _C ) of the mass W _A of ( _A ) specific propenylphenol compound in the resin composition and the total mass W _B + W _C of ( _B ) epoxy resin and (C) active ester compound is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, particularly preferably 0.04 or more, preferably 0.8 or less, more preferably 0.5 or less, still more preferably 0.3 or less, Especially preferably, it is 0.1 or less. When the mass ratio W _A / (W _B + W _C ) is within the above range, the dielectric loss tangent, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test of the cured product of the resin composition can be effectively improved. There is, and usually, the adhesion before the HAST test can also be made good.

The mass ratio W _A /W _D of the mass W A of the specific propenylphenol compound (A) in the resin composition and the mass W _D of the inorganic filler (D) is preferably _0.001 or more, more preferably 0.005 or more, and furthermore It is preferably 0.010 or more, particularly preferably 0.015 or more, preferably 0.10 or less, more preferably 0.07 or less, still more preferably 0.05 or less, and particularly preferably 0.03 or less. When the mass ratio W _A /W _D is within the above range, the dielectric loss tangent of the cured product of the resin composition, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test can be effectively improved, and usually , the adhesion before the HAST test can also be made good.

The content of the (A) specific propenylphenol compound in the resin composition is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, and particularly preferably 0.10% by mass or more, when the non-volatile component of the resin composition is 100% by mass. It is 0.5 mass % or more, Preferably it is 10 mass % or less, More preferably, it is 5 mass % or less, Especially preferably, it is 3 mass % or less. (A) When the content of the specific propenylphenol compound is within the above range, the dielectric loss tangent, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test of the cured product of the resin composition can be effectively improved, Also, usually, the adhesion before the HAST test can be made good.

The content of the (A) specific propenylphenol compound in the resin composition is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, and particularly preferably 1.0% by mass, when the resin component of the resin composition is 100% by mass. It is mass % or more, Preferably it is 50 mass % or less, More preferably, it is 30 mass % or less, Especially preferably, it is 10 mass % or less. The resin component of a resin composition means the component except (D) inorganic filler among the non-volatile components of a resin composition. (A) When the content of the specific propenylphenol compound is within the above range, the dielectric loss tangent, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test of the cured product of the resin composition can be effectively improved, Also, usually, the adhesion before the HAST test can be made good.

[3. (B) Epoxy Resin]

The resin composition according to the present embodiment contains (B) an epoxy resin as component (B). (B) The epoxy resin may be a curable resin having an epoxy group. The (B) epoxy resin does not include those corresponding to the component (A) described above.

(B) As the epoxy resin, 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, tris Phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin , glycidyl ester type epoxy resins, cresol novolak type epoxy resins, phenolaralkyl type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, Spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimide A Dean type epoxy resin etc. are mentioned. (B) An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) It is preferable that the epoxy resin contains the epoxy resin containing an aromatic structure from a viewpoint of obtaining hardened|cured material excellent in heat resistance. An aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles. Examples of the epoxy resin containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin. , naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, glycol having an aromatic structure Cydylamine type epoxy resin, glycidyl ester type epoxy resin having an aromatic structure, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, epoxy having a butadiene structure having an aromatic structure Resin, alicyclic epoxy resin having an aromatic structure, heterocyclic epoxy resin, spiro ring-containing epoxy resin having an aromatic structure, cyclohexane dimethanol type epoxy resin having an aromatic structure, naphthylene ether type epoxy resin, trimethyl having an aromatic structure All-type epoxy resins, tetraphenylethane-type epoxy resins having an aromatic structure, and the like are exemplified.

It is preferable that a resin composition contains the epoxy resin which has 2 or more epoxy groups in 1 molecule as (B) epoxy resin. (B) The ratio of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile component of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably is 70% by mass or more.

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

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

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

As a specific example of a liquid epoxy resin, "HP4032" by DIC Corporation, "HP4032D", "HP4032SS" (naphthalene type epoxy resin); "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F type) manufactured by Mitsubishi Chemical Corporation epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" by Mitsubishi Chemical Corporation, "630LSD", "604" (glycidylamine type|mold epoxy resin); "ED-523T" by ADEKA (a glycerol-type epoxy resin); "EP-3950L" by ADEKA, "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" by ADEKA (dicyclopentadiene type epoxy resin); "ZX1059" (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon-tsu Chemical & Material Chemical Co., Ltd.; "EX-721" by Nagase ChemteX Co., Ltd. (glycidyl ester type epoxy resin); "Celoxide 2021P" by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton); "PB-3600" by Daicel Co., Ltd., "JP-100" by Nippon Soda Co., Ltd., "JP-200" (epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon-Stetsu Chemical & Materials, etc. are exemplified. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As a solid-state epoxy resin, the solid-state epoxy resin which has 3 or more epoxy groups in 1 molecule is preferable, and the aromatic solid-state epoxy resin which has 3 or more epoxy groups in 1 molecule is more preferable.

Examples of solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol novolac-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, and trisphenol-type epoxy resins. , naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol A phthalimidine type epoxy resin is preferable.

As a specific example of a solid-state epoxy resin, "HP4032H" by DIC Corporation (naphthalene-type epoxy resin); "HP-4700" by DIC Corporation, "HP-4710" (naphthalene type tetrafunctional epoxy resin); "N-690" by DIC Corporation (cresol novolak-type epoxy resin); "N-695" by DIC Corporation (cresol novolak-type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC; Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", and "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel & Materials Co., Ltd.; "ESN485" (naphthol type epoxy resin) manufactured by Nippon-tsu Chemical &Materials; "ESN375" (dihydroxy naphthalene type epoxy resin) by the Nippon Steel & Materials company; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical Corporation "YX8800" (anthracene-type epoxy resin); Mitsubishi Chemical Corporation "YX7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; Mitsubishi Chemical Corporation "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin); "jER1010" (bisphenol A type epoxy resin) by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "jER1031S" (tetraphenylethane type epoxy resin); "WHR991S" (phenolphthalimidine type epoxy resin) by Nippon Kayaku Co., Ltd., etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) As the epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10 :1 to 1:10, particularly preferably 7:1 to 1:7.

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

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

The content of the (B) epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 4% by mass, when the non-volatile component in the resin composition is 100% by mass. or more, preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. (B) When the content of the epoxy resin is within the above range, the dielectric loss tangent of the cured product of the resin composition, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test can be effectively improved, and usually , the adhesion before the HAST test can also be made good.

The content of the (B) epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more, when the resin component in the resin composition is 100% by mass. and is preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less. (B) When the content of the epoxy resin is within the above range, the dielectric loss tangent of the cured product of the resin composition, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test can be effectively improved, and usually , the adhesion before the HAST test can also be made good.

[4. (C) active ester compound]

The resin composition according to the present embodiment contains (C) an active ester compound as component (C). In this (C) active ester compound, those corresponding to the components (A) to (B) described above are not included. (C) The active ester compound may have a function as an epoxy resin curing agent that reacts with the (B) epoxy resin to cure the resin composition. (C) An active ester compound may be used individually by 1 type, and may be used in combination of 2 or more types.

(C) As the active ester compound, generally two or more ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are used in one molecule. A compound having is preferably used. It is preferable that the said active ester compound is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester compound obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. are mentioned. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensation of two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, as the (C) active ester compound, a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, benzoyl of phenol novolac Active ester compounds containing a cargo are preferred, and among these, at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

(C) Examples of commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L" and "EXB" as active ester compounds containing a dicyclopentadiene type diphenol structure. -8000L-65M”, “EXB-8000L-65TM”, “HPC-8000L-65TM”, “HPC-8000”, “HPC-8000-65T”, “HPC-8000H”, “HPC-8000H-65TM” ( manufactured by DIC); "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK" as active ester compounds containing a naphthalene structure , "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); As a phosphorus containing active ester compound, "EXB9401" (made by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is an acetylated product of phenol novolac; "YLH1026", "YLH1030", "YLH1048" (made by Mitsubishi Chemical Corporation) as active ester compounds which are benzoyl compounds of phenol novolac; "PC1300-02-65MA" (made by Air Water) etc. are mentioned as an active ester compound containing a styryl group and a naphthalene structure.

(C) The active ester group equivalent of the active ester compound is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. to 400 g/eq., more preferably 100 g/eq. to 300 g/eq. The active ester group equivalent represents the mass of the active ester compound per 1 equivalent of the active ester group.

(B) When the number of epoxy groups of the epoxy resin is 1, the number of active ester groups of the (C) active ester compound is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and preferably 8.0 or less, more preferably 6.0 or less, and particularly preferably 4.0 or less. "(C) The number of active ester groups of the active ester compound" represents a value obtained by dividing the mass of the non-volatile component of the (C) active ester compound present in the resin composition by the active ester group equivalent and adding up all the values.

The content of the (C) active ester compound in the resin composition is usually 10% by mass or more, preferably 11% by mass or more, more preferably 12% by mass or more, when the non-volatile component in the resin composition is 100% by mass, It is more preferably 13% by mass or more, particularly preferably 14% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less. (C) When the amount of the active ester compound is within the above range, the dielectric loss tangent of the cured product of the resin composition, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test can be effectively improved. Silver can also make the adhesiveness before a HAST test favorable.

The content of the (C) active ester compound in the resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass, when the resin component in the resin composition is 100% by mass. or more, preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. (C) When the amount of the active ester compound is within the above range, it is possible to effectively improve the dielectric loss tangent, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test of the cured product of the resin composition. Silver can also make the adhesiveness before a HAST test favorable.

[5. (D) inorganic filler]

The resin composition according to the present embodiment includes (D) an inorganic filler as component (D). (D) An inorganic filler is usually contained in a resin composition in the form of particles.

(D) As a material of an inorganic filler, an inorganic compound is used. (D) Materials of the inorganic filler include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, hydroxide Aluminum, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, Zirconate barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, etc. are mentioned.

Moreover, you may use an inorganic composite oxide as a material of (D) inorganic filler. The inorganic composite oxide refers to an oxide containing two or more types of atoms selected from the group consisting of metal atoms and semimetal atoms. As such an inorganic composite oxide, an oxide containing a combination of silicon and one or more types of atoms selected from the group consisting of metal atoms and semimetal atoms other than silicon is preferable. Examples of metal atoms combined with silicon include aluminum, lead, nickel, cobalt, copper, zinc, zirconium, iron, lithium, magnesium, barium, potassium, calcium, titanium, boron, sodium, etc. Among them, aluminum particularly preferred. Therefore, as the inorganic composite oxide, an oxide containing silicon and aluminum is preferable, and an aluminosilicate is particularly preferable.

Among the materials for the inorganic filler (D), silica, alumina and aluminosilicate are suitable, and silica is particularly suitable. As silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica etc. are mentioned, for example. Moreover, as a silica, spherical silica is preferable. (D) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

(D) The inorganic filler can be classified into a hollow inorganic filler having pores therein and a solid inorganic filler having no pores therein. (D) As the inorganic filler, only a hollow inorganic filler may be used, only a solid inorganic filler may be used, or a hollow inorganic filler and a solid inorganic filler may be used in combination. When using a hollow inorganic filler, normally, the dielectric constant of the hardened|cured material of a resin composition can be made low.

Since the hollow inorganic filler has pores, it usually has a larger porosity than 0 volume%. From the viewpoint of lowering the dielectric constant of the insulating layer containing the cured product of the resin composition, the hollow inorganic filler has a porosity of preferably 10% by volume or more, more preferably 20% by volume or more, and particularly preferably 30% by volume. more than % From the viewpoint of the mechanical strength of the cured product of the resin composition, the hollow inorganic filler has a porosity of preferably 95 vol% or less, more preferably 90 vol% or less, and particularly preferably 85 vol% or less.

The porosity P (volume%) of a particle is the volume-based ratio of the total volume of one or two or more vacancies present inside the particle to the total volume of the particle based on the outer surface of the particle (total volume of voids / particle is defined as the volume of This porosity P _is determined by the following _formula (X1 ) can be calculated by

The hollow inorganic filler may be manufactured by, for example, the method described in Japanese Patent No. 5940188 and Japanese Patent No. 5864299 or a method similar thereto.

(D) As a commercial item of an inorganic filler, it is "UFP-30" by Denka Chemical Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex; "UFP-30" by Denka Corporation; "Silent NSS-3N", "Silent NSS-4N", and "Silent NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Adomatex; "DAW-03" and "FB-105FD" manufactured by Denka; "MG-005" by Taiheyo Cement Co., Ltd., etc. are mentioned.

(D) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and preferably 10 μm or more, from the viewpoint of significantly obtaining the desired effect of the present invention. It is micrometer or less, More preferably, it is 5 micrometers or less, More preferably, it is 2 micrometers or less.

(D) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by preparing the particle size distribution of the inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution analyzer and taking the median diameter as the average particle size. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone were weighed into a vial bottle and dispersed by ultrasonic waves for 10 minutes can be used. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, using blue and red light source wavelengths, and measuring the volume-based particle size distribution of the inorganic filler by the flow cell method, and from the obtained particle size distribution, the median diameter As a result, the average particle diameter can be calculated. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba Seisakusho Co., Ltd. and the like.

(D) The specific surface area of the inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m 2 / g or more, from the viewpoint of significantly obtaining the desired effect of the present invention. Especially preferably, it is 3 m2/g or more, preferably 100 m2/g or less, more preferably 70 m2/g or less, still more preferably 50 m2/g or less, and particularly preferably 40 m2/g or less. . The specific surface area of the inorganic filler can be measured according to the BET method by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) and calculating the specific surface area using the BET multi-point method. can

(D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. A ring agent etc. are mentioned. A surface treatment agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

As a commercial item of a surface treatment agent, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane) Silane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Kogyo Co., Ltd. "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane couple) manufactured by Shin-Etsu Chemical Co., Ltd. ring agent), Shin-Etsu Chemical Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc. are mentioned.

The degree of surface treatment by the surface treatment agent is preferably within a specific 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, more preferably 0.2% by mass to 3% by mass of a surface treatment agent, It is more preferable that the surface is treated with a surface treatment agent of 0.3% by mass to 2% by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more, from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, 1.0 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable.

(D) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the surface-treated inorganic filler with a surface treatment agent, followed by ultrasonic cleaning at 25°C for 5 minutes. After removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. or the like can be used.

The content of the inorganic filler (D) in the resin composition is preferably 60% by mass or more, more preferably 62% by mass or more, and particularly preferably 65% by mass, when the non-volatile component in the resin composition is 100% by mass. or more, preferably 85% by mass or less, more preferably 80% by mass or less, and particularly preferably 75% by mass or less. (D) When the amount of the inorganic filler is within the above range, the dielectric loss tangent of the cured product of the resin composition, smear removability, crack resistance, and adhesion to the conductor layer after the HAST test can be effectively improved, and usually , the adhesion before the HAST test can also be made good.

[6. (E) optional curing agent]

The resin composition according to the present embodiment may further contain (E) an arbitrary curing agent as an optional component in combination with the components (A) to (D) described above. (E) arbitrary curing agents as this component (E) do not include those corresponding to the components (A) to (D) described above. (E) The optional curing agent may have a function as an epoxy resin curing agent that reacts with (B) an epoxy resin to cure the resin composition, similar to the above-described (A) specific propenylphenol compound and (C) active ester compound. there is. (E) Arbitrary hardener may be used individually by 1 type, and may be used in combination of 2 or more types.

(E) Optional curing agents include, for example, phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents. . Among them, it is preferable to use at least one type of curing agent selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents.

As the phenolic curing agent, a curing agent having one or more, preferably two or more hydroxyl groups (phenolic hydroxyl groups) bonded to an aromatic ring such as a benzene ring or naphthalene ring in one molecule can be used. From the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferable. Further, from the viewpoint of adhesiveness, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness. Specific examples of the phenolic curing agent include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Maywa Kasei, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd. ", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375" manufactured by Nittetsu Chemical & Materials Co., Ltd. ", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD" manufactured by DIC -2090-60M” and the like.

As the carbodiimide-based curing agent, a curing agent having one or more, preferably two or more carbodiimide structures in one molecule can be used. Specific examples of the carbodiimide-based curing agent include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); Aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide) ; Poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide) , poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethyl polycarbodiimides such as aromatic polycarbodiimides such as xylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. Examples of commercially available carbodiimide-based curing agents include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K" and "Carbodilite" manufactured by Nisshinbo Chemical Co., Ltd. V-07” and “Carbodilite V-09”; "Stavaczol P", "Stavaczol P400", "Hycardil 510", etc. manufactured by Rhein Chemistry are mentioned.

As the acid anhydride-based curing agent, a curing agent having at least one acid anhydride group in one molecule can be used, and a curing agent having two or more acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, and trialkyltetrahydrophthalic anhydride. , dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride , Benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfotetracarboxylic dianhydride, 1,3,3a ,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis( and polymeric acid anhydrides such as anhydrotrimellitate) and styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid. Examples of commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA" and "OSA" manufactured by Shinnippon Rica Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; Hitachi Chemical Co., Ltd. "HN-2200", "HN-5500"; "EF-30", "EF-40", "EF-60", "EF-80" etc. by the Clay Valley company are mentioned.

As the amine-based curing agent, a curing agent having one or more, preferably two or more amino groups in one molecule can be used. Examples of the amine-based curing agent include aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines, and among these, aromatic amines are preferable. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'- Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diamino ratio Phenyl, 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. As a commercial item of an amine type hardening|curing agent, it is "SEIKACURE-S" by a Seika company, for example; "KAYABOND C-200S", "KAYABOND C-100", "Kaya Hard A-A", "Kaya Hard A-B", "Kaya Hard A-S" manufactured by Nippon Kayaku Co., Ltd.; "Epicure W" by Mitsubishi Chemical Corporation; "DTDA" by Sumitomo Seika Co., Ltd., etc. are mentioned.

As a specific example of a benzoxazine system hardening|curing agent, "JBZ-OP100D" by the JFE Chemical company, "ODA-BOZ"; "HFB2006M" by Showa Kobunshi Co., Ltd.; "P-d" and "F-a" manufactured by Shikoku Kasei Kogyo Co., Ltd., etc. are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylencyanate)), and 4,4'-methylenebis(2,6). -Dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4 -Cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4- Bifunctional cyanate resins such as cyanatephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolaks and cresol novolacs, etc., these cyanate resins are partially triazinated A prepolymer etc. are mentioned. As specific examples of the cyanate ester curing agent, "PT30" and "PT60" (all phenol novolak type polyfunctional cyanate ester resins) manufactured by Lonza Japan, "BA230", "BA230S75" (part of bisphenol Adicyanate) or a prepolymer in which all triazine was formed to form a trimer), and the like.

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

(E) The reactive equivalent of the optional curing agent is preferably 50 g/eq. to 3000 g/eq., more preferably 100 g/eq. to 1000 g/eq., more preferably 100 g/eq. to 500 g/eq., particularly preferably 100 g/eq. to 300 g/eq. The reactor equivalent represents the mass of the curing agent per 1 equivalent of the reactor.

(B) When the number of epoxy groups of the epoxy resin is 1, (E) the number of reactive groups of any curing agent may be 0 or may be greater than 0, preferably 0.01 or more, more preferably 0.10 or more, particularly preferably is 0.15 or more, preferably 2.0 or less, more preferably 1.0 or less, and particularly preferably 0.5 or less. "The number of reactors of (E) arbitrary curing agent" represents a value obtained by dividing the mass of non-volatile components of (E) arbitrary curing agent present in the resin composition by the reactor equivalent and summing all the values.

(B) When the number of epoxy groups of the epoxy resin is 1, (A) the number of phenolic hydroxyl groups of the specific propenylphenol compound, (C) the number of active ester groups of the active ester compound, and (E) the total number of reactive groups of any curing agent The number is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.0 or more, preferably 6.0 or less, more preferably 5.0 or less, and particularly preferably 4.0 or less.

When the non-volatile component in the resin composition is 100% by mass, the content of the optional curing agent (E) in the resin composition may be 0% by mass or greater than 0% by mass, preferably 0.01% by mass or more, more preferably It is preferably 0.1% by mass or more, particularly preferably 1.0% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

When the resin component in the resin composition is 100% by mass, the content of the optional curing agent (E) in the resin composition may be 0% by mass or may be greater than 0% by mass, preferably 0.1% by mass or more, more preferably is 1.0% by mass or more, particularly preferably 5.0% by mass or more, preferably 50% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.

[7. (F) curing accelerator]

The resin composition according to the present embodiment may further contain (F) a curing accelerator as an optional component in combination with the components (A) to (E) described above. The (F) hardening accelerator as this component (F) does not include those corresponding to the components (A) to (E) described above. (F) The curing accelerator has a function as a curing catalyst that promotes curing of the (B) epoxy resin.

(F) Examples of the curing accelerator include phosphorus curing accelerators, urea curing accelerators, guanidine curing accelerators, imidazole curing accelerators, metal curing accelerators, and amine curing accelerators. Among them, an imidazole-based curing accelerator is preferable. (F) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

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

Examples of the urea-based curing accelerator include 1,1-dimethylurea; Aliphatic dimethyl urea, such as 1,1,3-trimethyl urea, 3-ethyl-1,1-dimethyl urea, 3-cyclohexyl-1,1-dimethyl urea, and 3-cyclooctyl-1,1-dimethyl urea; 3-phenyl-1,1-dimethyl urea, 3-(4-chlorophenyl)-1,1-dimethyl urea, 3-(3,4-dichlorophenyl)-1,1-dimethyl urea, 3-(3- Chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4 -Dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4 -Nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]- 1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea ), and aromatic dimethylurea such as N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea].

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimida Zolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-unde Silimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s -triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid Adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzimidazolium chloride, 2-methylimidazolin, imidazole compounds such as 2-phenylimidazolin, imidazole compounds and epoxy resins The adduct form of Examples of commercially available imidazole curing accelerators include "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" by the Mitsubishi Chemical Corporation etc. are mentioned.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex 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. organic iron complexes such as organic zinc complexes and iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic 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, 1, 8-diazabicyclo(5,4,0)-undecene etc. are mentioned. As an amine-type hardening accelerator, you may use a commercial item, for example, "MY-25" by Ajinomoto Fine Techno Co., Ltd. etc. are mentioned.

The content of the curing accelerator (F) in the resin composition, when the non-volatile component in the resin composition is 100% by mass, may be 0% by mass or may be larger than 0% by mass, preferably 0.01% by mass or more, more preferably is 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, and particularly preferably 0.1% by mass or less.

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

[8. (G) thermoplastic resin]

The resin composition according to the present embodiment may further contain (G) a thermoplastic resin as an optional component in combination with the components (A) to (F) described above. The thermoplastic resin (G) as the component (G) does not include those corresponding to the components (A) to (F) described above.

(G) Examples of the thermoplastic resin include phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, Polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. are mentioned. (G) A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, and naphthalene. and phenoxy resins having at least one type of skeleton selected from the group consisting of skeletons, anthracene skeletons, adamantane skeletons, terpene skeletons, and trimethylcyclohexane skeletons. Any functional group, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin. As a specific example of a phenoxy resin, "1256" and "4250" by the Mitsubishi Chemical Corporation (both are bisphenol A frame|skeleton containing phenoxy resins); “YX8100” (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical; "YX6954" (bisphenol acetophenone frame|skeleton containing phenoxy resin) by the Mitsubishi Chemical company; "FX280" and "FX293" manufactured by Nippon Steel Sumikin Chemical Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Mitsubishi Chemical; etc. can be mentioned.

As a specific example of polyimide resin, "SLK-6100" by Shin-Etsu Chemical Co., Ltd., "Ricacoat SN20" and "Ricacoat PN20" by Shin-Nippon Rica Co., Ltd., etc. are mentioned.

As polyvinyl acetal resin, polyvinyl formal resin and polyvinyl butyral resin are mentioned, for example, and polyvinyl butyral resin is preferable. As specific examples of the polyvinyl acetal resin, "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Denki Chemical Co., Ltd. ; Srek BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series manufactured by Sekisui Kagakuko Co., Ltd.; etc. can be mentioned.

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

Examples of the polybutadiene resin include hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing polybutadiene resin, phenolic hydroxyl group-containing polybutadiene resin, carboxyl group-containing polybutadiene resin, acid anhydride group-containing polybutadiene resin, and epoxy group-containing polybutadiene. resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins.

As a specific example of the polyamide-imide resin, "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd. are exemplified. Specific examples of the polyamide-imide resin include further modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Co., Ltd.

As a specific example of polyether sulfone resin, "PES5003P" by Sumitomo Chemical Co., Ltd., etc. are mentioned.

As a specific example of polysulfone resin, polysulfone "P1700" by the Solvay Advanced Polymers company, "P3500", etc. are mentioned.

As a specific example of polyphenylene ether resin, "NORYL SA90" by SABIC etc. is mentioned. As a specific example of polyetherimide resin, "Ultem" by GE Corporation etc. are mentioned.

Examples of the polycarbonate resin include hydroxyl group-containing carbonate resin, phenolic hydroxyl group-containing carbonate resin, carboxyl group-containing carbonate resin, acid anhydride group-containing carbonate resin, isocyanate group-containing carbonate resin, and urethane group-containing carbonate resin. there is. As a specific example of the polycarbonate resin, "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" manufactured by Asahi Kasei Chemicals, Inc., "T6001" (polycarbonate diol), "C-1090" manufactured by Kuraray, "C-2090" ”, “C-3090” (polycarbonate diol), and the like. As a specific example of polyether ether ketone resin, "Smiproy K" by Sumitomo Chemical Co., Ltd., etc. are mentioned.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl. A terephthalate resin etc. are mentioned.

(G) The weight average molecular weight (MW) of the thermoplastic resin is preferably greater than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more It is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

The content of the (G) thermoplastic resin in the resin composition may be 0 mass% or greater than 0 mass%, preferably 0.01 mass% or more, more preferably 0.01 mass% or more, when the non-volatile component in the resin composition is 100 mass%. is 0.10% by mass or more, particularly preferably 0.20% by mass or more, preferably 5.0% by mass or less, more preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less.

The content of the (G) thermoplastic resin in the resin composition, when the resin component in the resin composition is 100% by mass, may be 0% by mass or may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 0.50% by mass or more, preferably 10% by mass or less, more preferably 5.0% by mass or less, and particularly preferably 3.0% by mass or less.

[9. (H) radically polymerizable compound]

The resin composition according to the present embodiment may further contain (H) an arbitrary radical polymerizable compound as an optional component in combination with the components (A) to (G) described above. The (H) radically polymerizable compound as this (H) component does not include those corresponding to the components (A) to (G) described above. (H) A radically polymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more types.

(H) The radically polymerizable compound may have an ethylenically unsaturated bond. (H) Radical polymerizable compounds, for example, unsaturated hydrocarbon groups such as allyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, p-vinylphenyl group, m-vinylphenyl group, o-vinylphenyl group; α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, and maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl group); You may have a radical polymerizable group, such as. (H) It is preferable that the radically polymerizable compound has two or more radically polymerizable groups.

(H) As a radically polymerizable compound, a (meth)acrylic radically polymerizable compound, a styrenic radically polymerizable compound, an allyl radically polymerizable compound, a maleimide radically polymerizable compound, etc. are mentioned, for example.

The (meth)acrylic radically polymerizable compound is, for example, a compound having one or more, preferably two or more acryloyl groups and/or methacryloyl groups. Examples of the (meth)acrylic radical polymerizable compound include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, and tricyclodecanedi. Methanoldi(meth)acrylate, neopentylglycoldi(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,8-octanedioldi (meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethanetri(meth)acrylate low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylic acid ester compounds such as lactate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; Dioxane glycoldi(meth)acrylate, 3,6-dioxa-1,8-octanedioldi(meth)acrylate, 3,6,9-trioxaundecane-1,11-dioldi(meth) Acrylates, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, ethoxylated bisphenol A di ( ether-containing (meth)acrylic acid ester compounds of low molecular weight (molecular weight less than 1000) such as meth)acrylate and propoxylated bisphenol A di(meth)acrylate; Tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester compounds such as; High molecular weight (molecular weight 1000 or more) acrylic acid ester compounds, such as (meth)acrylic modified polyphenylene ether resin, etc. are mentioned. As a commercial item of a (meth)acrylic-type radically polymerizable compound, "A-DOG" (dioxane glycol diacrylate) by Shin Nakamura Chemical Co., Ltd. and "DCP-A" by Kyoeisha Chemical Co., Ltd. make, for example. (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate), Nippon Kayaku Co., Ltd. "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), “KAYARAD R-604” (dioxane glycol diacrylate), “SA9000” and “SA9000-111” (methacryl-modified polyphenylene ether) manufactured by SABIC Innovative Plastics, Inc., and the like are exemplified.

The styrenic radically polymerizable compound is, for example, a compound having at least one, preferably two or more vinyl groups bonded directly to aromatic carbon atoms. Examples of the styrenic radical polymerizable compound include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, low molecular weight (molecular weight less than 1000) styrenic compounds such as 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; and high molecular weight (molecular weight of 1000 or more) styrenic compounds such as vinylbenzyl-modified polyphenylene ether resin and styrene-divinylbenzene copolymer. Examples of commercially available styrenic radical polymerizable compounds include "ODV-XET (X03)", "ODV-XET (X04)" and "ODV-XET (X05)" (styrene -Divinylbenzene copolymer), "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

The allyl radical polymerizable compound is, for example, a compound having one or more, preferably two or more allyl groups. Examples of the allyl radical polymerizable compound include diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylic acid, and 2,3-naphthalene. aromatic carboxylic acid allyl ester compounds such as diallyl carboxylic acid; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl etherbenzene; Allylsilane compounds, such as diallyldiphenylsilane, etc. are mentioned. As a commercial item of an allyl type radically polymerizable compound, "TAIC" (1,3,5- triallyl isocyanurate) by Nippon Kasei Co., Ltd., "DAD" by Nisshoku Techno Fine Chemical Co., Ltd. (Dipen acid diallyl), "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., trade name "DAND" (2,3-naphthalenecarboxylic acid diallyl) manufactured by Nippon Zoryu Chemical Industry Co., Ltd., Shikoku Kasei Kogyo Chemical Manufactured "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane), manufactured by Nippon Kayaku Co., Ltd. "RE- 810NM” (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane), “DA-MGIC” manufactured by Shikoku Chemical Co., Ltd. (1,3-diallyl-5-glycidyl isocyanurate) and the like.

The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. As a commercial item of a maleimide system radical polymerizable compound, "SLK-2600" by Shin-Etsu Chemical Co., Ltd., "BMI-1500" by Designer Molecules, "BMI-1700", "BMI-3000J", for example. ", "BMI-689", "BMI-2500" (dimerdiamine structure-containing maleimide compound), "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules, Inc., "MIR-5000" manufactured by Nippon Kayaku Co., Ltd. -60T", "MIR-3000-70MT" (biphenylaralkyl type maleimide compound), "BMI-70" and "BMI-80" manufactured by Kei Kasei Co., Ltd., "BMI-2300" manufactured by Yamato Chemical Co., Ltd. "BMI-TMH" etc. are mentioned. Further, as the maleimide-based radically polymerizable compound, a maleimide resin (a maleimide compound containing an indan ring skeleton) disclosed in Publication Publication No. 2020-500211 of the Invention Association may be used.

(H) The ethylenically unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g/eq. to 3000 g/eq., more preferably 50 g/eq. to 2500 g/eq., more preferably 70 g/eq. to 2000 g/eq., particularly preferably 90 g/eq. to 1500 g/eq. The ethylenically unsaturated bond equivalent represents the mass of the radically polymerizable compound per equivalent of ethylenically unsaturated bond.

(H) The weight average molecular weight (MW) of the radically polymerizable compound is preferably 40000 or less, more preferably 10000 or less, even more preferably 5000 or less, and particularly preferably 3000 or less. The lower limit is not particularly limited, but can be, for example, 150 or more.

The mass ratio W _H /W A of the mass W A of the specific propenylphenol compound (A) in the resin composition and the mass W _H of the (H) _radical polymerizable compound may be ₀ , may be greater than 0, and is preferably 0.01. or more, more preferably 0.10 or more, particularly preferably 0.50 or more, preferably 5.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less.

The content of the (H) radically polymerizable compound in the resin composition may be 0% by mass or greater than 0% by mass, preferably 0.01% by mass or more, when the non-volatile component in the resin composition is 100% by mass. It is preferably 0.10% by mass or more, particularly preferably 0.50% by mass or more, preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and particularly preferably 2.0% by mass or less.

The content of the (H) radically polymerizable compound in the resin composition, when the resin component in the resin composition is 100% by mass, may be 0% by mass, may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably It is preferably 0.10% by mass or more, particularly preferably 1.0% by mass or more, preferably 20% by mass or less, more preferably 10.0% by mass or less, and particularly preferably 5.0% by mass or less.

[10. (I) optional additives]

The resin composition according to the present embodiment may further contain (I) optional additives as optional non-volatile components in combination with the components (A) to (H) described above. (I) Optional additives include, for example, radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, and silicone resins; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenolic antioxidants; optical whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (eg, phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red), nitrogen-based flame retardants (eg, melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (eg, antimony trioxide); dispersants such as phosphoric acid ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid-anhydride-based stabilizers; (I) Arbitrary additives may be used individually by 1 type, and may be used in combination of 2 or more type.

[11. (J) Solvent]

The resin composition according to the present embodiment may further contain (J) a solvent as an optional volatile component in combination with non-volatile components such as components (A) to (I) described above. (J) As a solvent, an organic solvent is usually used. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide-based solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (J) A solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

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

[12. Manufacturing method of resin composition]

The resin composition according to the present embodiment can be produced, for example, by mixing the components described above. Some or all of the components described above may be mixed simultaneously or sequentially. In the process of mixing each component, the temperature may be set appropriately, so you may heat and/or cool temporarily or continuously. In addition, in the process of mixing each component, you may perform stirring or shaking.

[13. Physical properties of resin composition]

The resin composition according to the present embodiment can obtain a cured product having excellent smear removability. For example, when the smear removability is evaluated under the conditions described in the section [Evaluation method of smear removability and arithmetic average roughness (Ra)] of the examples described later, the maximum smear extending from the wall surface of the bottom portion of the via hole The smear length can be made less than 5 micrometers. Generally, the shorter the maximum smear length, the better the smear removability.

With the resin composition according to the present embodiment, a cured product having excellent crack resistance can be obtained. For example, when crack resistance is evaluated under the conditions described in the section of [Method for Evaluating Crack Resistance] in Examples described later, the yield can be set to 40% or more. It shows that crack resistance is so excellent that the value of this yield is large.

The resin composition according to the present embodiment can obtain a cured product having excellent adhesion to the conductor layer after the HAST test. For example, when a layer of a resin composition is formed on metal foil and cured to form a cured product, high adhesion between the metal foil and the cured product can be obtained after the HAST test. For a specific example, when the copper foil peel strength after the HAST test is measured under the conditions described in the section of [Method for evaluating adhesion of the conductor layer] in Examples to be described later, the copper foil peel strength can be increased. Said copper foil peeling strength shows the magnitude|size of the force required to remove copper foil as a conductor layer from the hardened|cured material of a resin composition, and this copper foil peeling strength shows excellent adhesiveness, so that this copper foil peeling strength is large. The copper foil peel strength after the above HAST test is preferably 0.40 kgf/cm or more, more preferably 0.50 kgf/cm or more, and particularly preferably 0.55 kgf/cm or more.

With the resin composition according to the present embodiment, a cured product having a low dielectric loss tangent can be obtained. For example, a low dielectric loss tangent can be obtained when the dielectric loss tangent of a cured product is measured under the conditions described in the section of [Dielectric Characteristics Measurement Method] of Examples described later. The dielectric loss tangent of the cured product is preferably 0.0032 or less, more preferably 0.0030 or less, and particularly preferably 0.0028 or less.

The resin composition according to the present embodiment can usually obtain a cured product having excellent adhesion to the conductor layer not only after the HAST test but also before the HAST test. For example, when a layer of a resin composition is formed on metal foil and cured to form a cured product, high adhesion between the metal foil and the cured product can be obtained before the HAST test. For a specific example, when the copper foil peel strength before the HAST test is measured under the conditions described in the section of [Method for evaluating adhesion of the conductor layer] in Examples to be described later, the copper foil peel strength can be increased. The copper foil peel strength before the above HAST test is preferably 0.50 kgf/cm or more, more preferably 0.60 kgf/cm or more, and particularly preferably 0.65 kgf/cm or more.

As described above, the resin composition according to the present embodiment can obtain a cured product having excellent adhesion to the conductor layer. Therefore, usually, a cured product of a resin composition can obtain a cured product having excellent adhesion to a conductor layer formed by plating (coating adhesion) as well as adhesion to the metal foil described above. That is, when a conductor layer is formed on the cured product of the resin composition by plating, high adhesion between the conductor layer and the cured product can be obtained. For example, when the plating peel strength is measured under the conditions described in the section of [Method for measuring plating adhesion (plating peel strength)] in Examples described later, the plating peel strength can be increased. The above plating peel strength indicates the magnitude of the force required to remove the conductor layer formed by plating on the cured product of the resin composition, and the greater the plating peel strength, the better the plating adhesion. The above plating peel strength is preferably 0.20 kgf/cm or more, more preferably 0.30 kgf/cm or more, and particularly preferably 0.35 kgf/cm or more.

The hardened|cured material of the resin composition concerning this embodiment can have a small surface roughness normally, when a roughening process is performed. For example, when the arithmetic mean roughness Ra of the cured product after roughening treatment is measured under the conditions described in the section [Evaluation method of smear removability and arithmetic mean roughness (Ra)] of Examples described later, a small arithmetic mean roughness Ra can be obtained. The above arithmetic average roughness Ra is preferably 150 nm or less, more preferably 100 nm or less, and particularly preferably 80 nm or less. The lower limit is not particularly limited, and may be 30 nm or more, 40 nm or more, and the like.

The resin composition according to the present embodiment can usually obtain a cured product having a low dielectric constant. For example, when the relative permittivity of a cured product is measured under the conditions described in the section of [Method of measuring dielectric properties] in Examples to be described later, a low relative permittivity can be obtained. The dielectric constant of the cured product is preferably 4.0 or less, more preferably 3.8 or less, and particularly preferably 3.5 or less.

[14. Use of Resin Composition]

The resin composition according to the present embodiment can be used as a resin composition for insulating applications, and can be particularly suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer). For example, the resin composition according to the present embodiment can be used as a resin composition for forming an insulating layer of a printed wiring board, and can be suitably used as a resin composition for forming an interlayer insulating layer (resin composition for interlayer insulating use). can

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

(1) a step of laminating a temporarily fixed film on a base material;

(2) a step of temporarily fixing a semiconductor chip on a temporarily fixing film;

(3) forming a sealing layer on the semiconductor chip;

(4) a step of peeling the substrate and temporarily fixed film from the semiconductor chip;

(5) a step of forming a redistribution layer as an insulating layer on the surface of the substrate and temporarily fixed film of the semiconductor chip, and

(6) Step of forming a redistribution layer as a conductor layer on the rewiring formation layer

In addition, the resin composition according to the present embodiment is, for example, a resin sheet, a sheet-like laminated material such as prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, a resin for embedding parts, and the like. It can be used in a wide range of applications for which the composition is used.

[15. Sheet-like laminated material]

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

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

In one embodiment, a resin sheet includes a support and a resin composition layer provided on the support. The resin composition layer is formed of the resin composition according to the present embodiment. 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 40 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. . The lower limit of the thickness of the resin composition layer is not particularly limited, but may be 5 μm or more, 10 μm or more, and the like.

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

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

When using metal foil as a support body, as a metal foil, copper foil, aluminum foil, etc. are mentioned, for example, and copper foil is preferable. As the copper foil, foil made of a single metal of copper may be used, or foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good night.

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

As a support body, you may use the support body with a release layer which has a release layer on the surface to which it joins with a resin composition layer. As a mold release agent used for the mold release layer of the support body with a mold release layer, 1 or more types of mold release agents chosen from the group which consists of alkyd resins, polyolefin resins, urethane resins, and silicone resins are mentioned, for example. The support with the release layer may use a commercial item, for example, "SK-1", "AL-5", "AL-5", "AL- 7", "Lumira T60" manufactured by Tore, Inc., "Purex" manufactured by Teijin, and "Uni-Peel" manufactured by Unitica, etc. are exemplified.

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

In one embodiment, the resin sheet may further include an arbitrary layer as needed. As such an optional layer, for example, a protective film or the like provided on the surface of the resin composition layer not bonded to the support (ie, the surface on the opposite side to the support) according to the support is exemplified. 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 to the surface of the resin composition layer and scratches can be suppressed.

The resin sheet is, for example, a liquid (varnish) resin composition as it is or prepared by dissolving the resin composition in a solvent to prepare a liquid (varnish) resin composition, and applying this onto a support using a die coater or the like And, it can be prepared by further drying to form a resin composition layer.

As a solvent, the thing similar to the solvent demonstrated as a component of a resin composition is mentioned. A solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying may be performed by methods such as heating and hot air spraying. Drying conditions are not particularly limited, but drying is performed 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. Depending on the boiling point of the solvent in the resin composition, for example, when using a resin composition containing 30% by mass to 60% by mass of the solvent, drying the resin composition layer at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes can form

The resin sheet can be wound up in a roll shape and stored. When a resin sheet has a protective film, it becomes usable normally by peeling off a protective film.

In one embodiment, a prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition according to the present embodiment.

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

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

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

The sheet-like laminate material can be suitably used for forming the insulating layer of a printed wiring board (for the insulating layer of the printed wiring board), and is more suitable for forming the interlayer insulating layer of the printed wiring board (for the interlayer insulating layer of the printed wiring board). can be used

[16. 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 according to the present embodiment. This printed wiring board can be manufactured by the method including the process of following (I) and (II) using the above-mentioned resin sheet, for example.

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

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

The "inner layer substrate" used in step (I) is a member to be a substrate of a printed wiring board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene An ether substrate etc. are mentioned. In addition, the board|substrate may have a conductor layer on one side or both sides thereof, and this conductor layer may be patterned. An inner layer board in which a conductor layer (circuit) is formed on one or both sides of the board is sometimes referred to as an "inner layer circuit board". In addition, when manufacturing a printed wiring board, an intermediate product in which an insulating layer and/or a conductor layer should be further formed is also included in the above "inner layer substrate". In the case where the printed wiring board is a component-embedded circuit board, an inner-layer board having components embedded may be used.

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support body side. Examples of the member for heat-pressing the resin sheet to the inner-layer substrate (hereinafter also referred to as “heat-bonding member”) include a heated metal plate (such as a SUS head plate) or a metal roll (SUS roll). On the other hand, it is preferable not to directly press the hot-compression member to the resin sheet, but to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the irregularities on the surface of the inner layer substrate.

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

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

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

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

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

For example, the thermal curing conditions of the resin composition layer vary depending on the type of resin composition, etc., but in one embodiment, the curing temperature is preferably 120 ° C to 240 ° C, more preferably 150 ° C to 220 ° C, More preferably, it is 170 degreeC - 210 degreeC. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, 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 thermally curing the resin composition layer, the resin composition layer is heated 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, You may preheat preferably for 5 minutes to 150 minutes, more preferably for 15 minutes to 120 minutes, and even more preferably for 15 minutes to 100 minutes.

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

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

Step (III) is a step of perforating the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) depends on the composition of the resin composition used for forming the insulating layer, and may be performed using, for example, a drill, laser, plasma, or the like. The size and shape of the hole may be appropriately determined according to 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). Therefore, the above-mentioned roughening process is sometimes called "desmear process". The procedures and conditions of the roughening treatment are not particularly limited, and known procedures and conditions normally used when forming the insulating layer of a printed wiring board are employable. For example, the insulation layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralization liquid in this order.

As a swelling liquid used for a roughening process, an alkali solution, surfactant solution, etc. are mentioned, for example, Preferably it is an alkali solution. As the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As a swelling liquid marketed, "Swelling Deep Securiganth P" by Atotech Japan, "Swelling Deep Securiganth SBU", etc. are mentioned, for example. The swelling treatment by the swelling solution can be performed by, for example, immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

As an oxidizing agent used for a roughening process, the alkaline permanganate solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned, for example. 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. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As an oxidizing agent marketed, alkaline performance manganic acid solutions, such as "Concentrate Compact CP" by Atotech Japan and "Dosing Solution Securiganth P", are mentioned, for example.

As a neutralization liquid used for a roughening process, an acidic aqueous solution is preferable, and as a commercial item, "Reduction Solution Securigant P" by Atotech Japan Co., Ltd. is mentioned, for example. The treatment with the neutralization liquid can be performed by immersing the treated surface subjected to the roughening treatment by the oxidizing agent in the neutralization liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the standpoint of workability and the like, a method of immersing the object subjected to the roughening treatment with an oxidizing agent in a neutralization solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

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

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

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method. From the viewpoint of the simplicity of production, the semi-additive method is preferred. Hereinafter, an example in which the conductor layer is formed by a semi-additive method is shown.

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

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

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

[17. semiconductor device]

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

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

[ Example ]

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

[Synthesis Example 1. Synthesis of Compound 1]

410 g of methanol, 48.0 g of sodium hydroxide, and 205.0 g of biphenol were injected into a reaction vessel with a net weight of 1 L equipped with a thermometer, stirrer and cooling tube, and 91.8 g of allyl bromide was added dropwise over 3 hours at 40 ° C. while paying attention to heat generation. did Thereafter, the temperature was raised to a temperature at which methanol refluxed (about 60° C.), and an allyl etherification reaction was performed for 4 hours. Then, after removing the salt by washing with water, the temperature was raised to 180°C, and a transfer reaction was performed for 10 hours. After the transfer reaction, the temperature was lowered to 100°C, 205.0 g of butanol was added to dissolve the resin, and 70.5 g of potassium hydroxide was further added, followed by a propenylation reaction at 115°C for 6 hours. Then, it was washed with water and concentrated to obtain "Compound 1" (propenyl form of biphenol, hydroxyl equivalent 133 g/eq.) represented by the formula (A3).

[Example 1]

Biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) 8 parts and a naphthalene type epoxy resin (“HP-4032-SS” manufactured by DIC Corporation, 1,6-bis(glycidyl) 2 parts of oxy)naphthalene, epoxy equivalent of about 145 g/eq.) were heated and dissolved in 15 parts of solvent naphtha while stirring. This was cooled to room temperature, and the dissolving composition of the epoxy resin was prepared.

To the dissolving composition of this epoxy resin, 2 parts of "Compound 1" prepared in Synthesis Example 1, an active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, active ester group equivalent of about 220 g/eq., non-volatile component ratio 62 mass% toluene solution) 40 parts, spherical silica surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C2" manufactured by Adomatex, solid inorganic filler, average particle diameter 0.5 µm, specific surface area 5.8 m/g) 100 parts, carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216 g/eq., toluene solution with non-volatile component ratio of 50%) 5 parts 0.1 part of an imidazole-based curing accelerator (“1B2PZ” manufactured by Shikoku Chemical Co., Ltd., 1-benzyl-2-phenylimidazole), and a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 30% by mass of non-volatile matter) 2 parts of a 1:1 solution of MEK and cyclohexanone) were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin composition.

[Example 2]

Instead of 2 parts of Compound 1, 1 part of Compound 1 and a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC Corporation, active group equivalent of about 151 g/eq., 2-method with a non-volatile component ratio of 50%) Toxypropanol solution) was used in combination with 1 part.

In addition, instead of 40 parts of the active ester compound (“HPC-8150-62T” manufactured by DIC, active ester group equivalent of about 220 g/eq., toluene solution with a non-volatile component ratio of 62% by mass), an active ester compound (manufactured by DIC "HPC-8000-65T", an active ester group equivalent of about 223 g/eq., a toluene solution with a non-volatile content of 65%) 40 parts were used.

A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 3]

Biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) 8 parts and a naphthalene type epoxy resin (“HP-4032-SS” manufactured by DIC Corporation, 1,6-bis(glycidyl) Instead of the combination of 2 parts of oxy)naphthalene and epoxy equivalent of about 145 g/eq.), 10 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) were used.

Also, the amount of Compound 1 was changed from 2 parts to 4 parts.

Further, spherical silica ("SO-C2" manufactured by Adomatex, average particle diameter 0.5 µm, specific surface area 5.8 m/g) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) The amount was changed from 100 parts to 120 parts.

A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 4]

Instead of 2 parts of Compound 1, 2 parts of a biphenyl type phenolic curing agent ("SBA02A" manufactured by Gun-A Chemical Co., Ltd., hydroxyl equivalent of about 222 g/eq.) was used.

In addition, 8 parts of a biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) and a naphthalene type epoxy resin (“HP-4032-SS” manufactured by DIC Corporation, 1,6-bis(glyc) Cydyloxy) naphthalene, epoxy equivalent of about 145 g/eq.) Instead of a combination of 2 parts, a naphthalene type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, 1,6-bis (glycidyloxy) naphthalene, epoxy Equivalent weight of about 145 g/eq.) 10 parts were used.

A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 5]

To the resin composition, 2 parts of a biphenylaralkyl novolak-type maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a mixed solution of MEK/toluene with a non-volatile content of 70%) was added. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 6]

To the resin composition, 2 parts of maleimide compound A (a solution with a non-volatile component ratio of 62%) synthesized by the method described in Synthesis Example 1 of Publication Publication No. 2020-500211 of the Korean Invention Association was added. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 7]

To the resin composition, 2 parts of dicyclopentadiene type acrylate (“DCP-A” manufactured by Kyoei Chemical Co., Ltd.) was further added. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 8]

Two parts of methacryl-modified polyphenylene ether ("SA9000-111" by SABIC Innovative Plastics) were further added to the resin composition. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 9]

To the resin composition, 2 parts of vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content of 65%) was added to the resin composition. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 10]

The amount of spherical silica ("SO-C2" manufactured by Adomatex, average particle diameter 0.5 µm, specific surface area 5.8 m/g) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) Changed from 100 copies to 70 copies.

In addition, 7 parts of hollow aluminosilicate particles ("MG-005" manufactured by Taiheyo Cement Co., Ltd., hollow inorganic filler, average particle diameter of 1.6 µm, porosity of 80% by volume) were added to the resin composition.

A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 1]

Instead of 2 parts of Compound 1, 2 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, active group equivalent of about 151 g/eq., 2-methoxypropanol solution with a non-volatile content of 50%) used A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 2]

Instead of 2 parts of Compound 1, 2 parts of biphenol (“Biphenol” manufactured by Honshu Kagaku Kogyo Co., Ltd.) was used.

In addition, instead of 40 parts of the active ester compound (“HPC-8150-62T” manufactured by DIC, active ester group equivalent of about 220 g/eq., toluene solution with a non-volatile component ratio of 62% by mass), an active ester compound (manufactured by DIC "HPC-8000-65T", an active ester group equivalent of about 223 g/eq., a toluene solution with a non-volatile content of 65%) 40 parts were used.

A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 3]

Instead of 2 parts of Compound 1, 2 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, active group equivalent of about 151 g/eq., 2-methoxypropanol solution with a non-volatile content of 50%) used

In addition, 8 parts of a biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) and a naphthalene type epoxy resin (“HP-4032-SS” manufactured by DIC Corporation, 1,6-bis(glyc) 10 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) was used instead of the combination of 2 parts of cydyloxy) naphthalene and epoxy equivalent of about 145 g/eq.).

Further, spherical silica ("SO-C2" manufactured by Adomatex, average particle diameter 0.5 µm, specific surface area 5.8 m/g) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) The amount was changed from 100 parts to 120 parts.

A resin composition was prepared in the same manner as in Comparative Example 1 except for the above matters.

[Comparative Example 4]

Instead of 2 parts of Compound 1, 2 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, active group equivalent of about 151 g/eq., 2-methoxypropanol solution with a non-volatile content of 50%) used

In addition, 8 parts of a biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) and a naphthalene type epoxy resin (“HP-4032-SS” manufactured by DIC Corporation, 1,6-bis(glyc) 10 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) was used instead of the combination of 2 parts of cydyloxy) naphthalene and epoxy equivalent of about 145 g/eq.).

In addition, the amount of the active ester compound ("HPC-8150-62T" manufactured by DIC, active ester group equivalent of about 220 g/eq., toluene solution with a non-volatile component ratio of 62% by mass) was changed from 40 parts to 10 parts.

Further, spherical silica ("SO-C2" manufactured by Adomatex, average particle diameter 0.5 µm, specific surface area 5.8 m/g) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) The amount was changed from 100 parts to 50 parts.

A resin composition was prepared in the same manner as in Comparative Example 1 except for the above matters.

[Comparative Example 5]

Instead of 2 parts of Compound 1, 2 parts of allyl group-containing bisphenol ("2,2'-bis(3-allyl-4-hydroxyphenyl)methane" manufactured by Mitsui Chemicals Fine Co., Ltd.) were used.

In addition, instead of 40 parts of the active ester compound (“HPC-8150-62T” manufactured by DIC, active ester group equivalent of about 220 g/eq., toluene solution with a non-volatile component ratio of 62% by mass), an active ester compound (manufactured by DIC "HPC-8000-65T", an active ester group equivalent of about 223 g/eq., a toluene solution with a non-volatile content of 65%) 40 parts were used.

A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 6]

Instead of 2 parts of Compound 1, 2 parts of allyl group-containing bisphenol ("bisphenol A diallyl ether" by Osaka Soda Co., Ltd.) was used.

In addition, instead of 40 parts of the active ester compound (“HPC-8150-62T” manufactured by DIC, active ester group equivalent of about 220 g/eq., toluene solution with a non-volatile component ratio of 62% by mass), an active ester compound (manufactured by DIC "HPC-8000-65T", an active ester group equivalent of about 223 g/eq., a toluene solution with a non-volatile content of 65%) 40 parts were used.

A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Production of Resin Sheet]

As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec, 38 μm in thickness) provided with a release layer was prepared. On the release layer of this support body, the resin composition obtained in Examples and Comparative Examples was uniformly applied so that the thickness of the resin composition layer after drying was 40 µm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet comprising a support and a resin composition layer.

[Evaluation method of smear removability and arithmetic mean roughness (Ra)]

<Production of evaluation board A>

(1) Under-treatment of the embedded substrate:

As the inner layer substrate, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness of 18 μm, substrate thickness of 0.8 mm, manufactured by Panasonic Corporation “R1515A”) having copper foil on the surface was prepared. The copper foil on the surface of this inner-layer substrate was etched with a copper etching amount of 1 μm using a microetching agent ("CZ8101" manufactured by Mack Corporation), and a roughening treatment was performed. After that, drying was performed at 190°C for 30 minutes.

(2) Lamination and Curing of Resin Sheets:

The resin sheets obtained in the above-described Examples and Comparative Examples are bonded to the inner layer substrate by using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials), The inner layer was laminated on both sides of the substrate. This lamination was carried out by reducing the pressure for 30 seconds and setting the atmospheric pressure to 13 hPa or less, and then press-bonding at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds.

Then, the laminated resin sheet was hot-pressed and smoothed under atmospheric pressure at 100°C and a pressure of 0.5 MPa for 60 seconds. Further, this was put into an oven at 130°C and heated for 30 minutes, then transferred to an oven at 170°C and heated for 30 minutes. The resin composition layer was thermally cured by this heating, and an insulating layer as a cured product layer made of a cured product of the resin composition was obtained.

(3) formation of via holes:

Using a CO ₂ laser processing machine ("LK-2K212/2C" manufactured by Via Mechanics Co., Ltd.), the insulating layer was processed under the conditions of a pulse width of 3 μsec at a frequency of 2000 Hz, an output of 0.95 W, and the number of shots 3, and penetrating the insulating layer. A via hole was formed. The top diameter (diameter) of the via hole on the surface of the insulating layer was 50 µm, and the diameter of the via hole on the bottom surface of the insulating layer was 40 µm. After that, the support was peeled off to obtain an intermediate substrate having a layer configuration of insulating layer/inner layer substrate/insulating layer.

(4) harmonization treatment:

A roughening treatment was performed on the insulating layer of the intermediate substrate. Specifically, the intermediate substrate was immersed in Swelling Deep Securigant P, which is a swelling liquid, manufactured by Atotech Japan, at 60°C for 10 minutes. Next, it was immersed at 80 degreeC for 20 minutes in the crude liquid Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) manufactured by Atotech Japan. Finally, it was immersed in reduction solution Securigant P manufactured by Atotech Japan, which is a neutralization solution, at 40°C for 5 minutes. The obtained board|substrate was called evaluation board|substrate A.

<Evaluation of smear removability>

The periphery of the bottom of the via hole of the evaluation substrate A was observed with a scanning electron microscope (SEM). From the image obtained by observation, the maximum smear length of the smear extending from the wall surface at the bottom of the via hole was measured and evaluated according to the following criteria.

"○": The maximum smear length is less than 5 µm.

"x": The maximum smear length is 5 µm or more.

<Measurement of arithmetic mean roughness (Ra)>

The arithmetic average roughness Ra of the surface of the insulating layer of the evaluation substrate A was measured using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by Vico Instruments) in VSI mode with a 50x lens, and the measurement range was set to 121 μm × 92 μm. measured. The measurement was performed at 10 randomly selected points, and the average value was calculated and shown in a table to be described later.

[Method for Measuring Plating Adhesion (Plating Peel Strength)]

<Production of evaluation board B>

The evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. After heating and annealing at 150 degreeC for 30 minutes, an etching resist was formed, and copper sulfate electrolytic plating was performed after pattern formation by etching, and the conductor layer of the thickness of 30 micrometers was formed. Next, an annealing treatment was performed at 200°C for 60 minutes, and the obtained substrate was referred to as evaluation substrate B.

<Measurement of peel strength (peel strength) of plated conductor layer>

An incision enclosing a portion with a width of 10 mm and a length of 150 mm was placed in a portion of the plated conductor layer of the evaluation substrate B that did not contain a via hole. One end of this part was peeled off and held with a tool of a tensile tester (Autocom type tester "AC-50C-SL" manufactured by TSE Co., Ltd.). The load [kgf/cm] when 100 mm was pulled out at room temperature (25°C) at a speed of 50 mm/min in the vertical direction was measured as the plating peel strength.

[Method of measuring dielectric properties]

The resin sheet obtained in each Example and each Comparative Example was thermally cured at 190°C for 90 minutes, and the support was peeled off to obtain a sheet-like cured product. The cured product was cut to obtain a test piece having a width of 2 mm and a length of 80 mm. For this test piece, using a cavity resonator perturbation method permittivity measuring device "CP521" manufactured by Kanto Oyo Denshi Kaihatsu Co., Ltd. and a network analyzer "E8362B" manufactured by Agilent Technologies Co., Ltd., at a frequency of 5.8 GHz measured by the cavity resonance method, the dielectric loss tangent ( tan δ) and relative permittivity were measured. Measurements were made on the two test pieces, and an average value was calculated.

[Method for Evaluating Adhesion of Conductive Layer]

Copper foil was used as the conductor layer, and copper foil peel strength was measured as an index of adhesiveness in the following procedure.

<Production of evaluation board>

(1) Underside treatment of copper foil:

The glossy surface of the electrolytic copper foil (“3EC-III” manufactured by Mitsui Kinzokukozan Co., Ltd., thickness 35 μm) is 1 μm etched with a microetching solution (“CZ8101” manufactured by Mack Corporation), and the copper surface is roughened, and then Antirust treatment (CL8300) was performed. In this way, the copper foil whose surface is etched with the above microetching agent may be referred to as "CZ copper foil" hereinafter. Thus, a CZ copper foil having a treated surface was obtained.

(2) Preparation of the inner layer substrate:

A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) having copper foil on the surface and having an inner layer circuit was prepared. Both surfaces of this glass-cloth base epoxy resin double-sided copper-clad laminate were etched to a thickness of 1 μm with a microetching liquid ("CZ8101" manufactured by Mack Corporation), and the copper surface was roughened. Further, heat treatment was performed in an oven at 130°C for 30 minutes to obtain an inner layer substrate.

(3) lamination of resin composition layers:

The resin sheets prepared in Examples and Comparative Examples were laminated on both sides of the inner layer substrate. This lamination was performed using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials) so that the resin composition layer was in contact with the inner layer substrate. In addition, after reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, the above lamination was performed by pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed on the laminated resin sheet at 100°C and a pressure of 0.5 MPa for 60 seconds. After that, the support was peeled off to expose the resin composition layer.

(4) Lamination of copper foil and curing of resin composition layer:

On the exposed resin composition layer, the treated surface of the CZ copper foil was laminated under the same conditions as in the above "(3) lamination of the resin composition layer". Then, the resin composition layer was cured under curing conditions of 200° C. for 90 minutes to form a cured product (insulating layer). Thus, an evaluation substrate C in which CZ copper foils were laminated on both sides of the insulating layer was obtained. This evaluation board|substrate C had the layer structure of CZ copper foil/insulation layer/inner layer substrate/insulation layer/CZ copper foil.

<Measurement of copper foil peel strength before HAST test>

Evaluation board C was cut into small pieces of 150 mm x 30 mm. In the CZ copper foil portion of the small piece, an incision enclosing a portion having a width of 10 mm and a length of 100 mm was made using a cutter. One end of this part was peeled off, and it was picked up with the clamping tool of the tensile tester. The load [kgf/cm] when pulling in the vertical direction at a speed of 50 mm/min at room temperature (room temperature) and peeling off 35 mm was measured as the copper foil peel strength. The value of the load obtained as a result of this measurement is referred to as "copper foil peel strength before HAST test". For the measurement, a tensile tester (Autocom Universal Tester "AC-50C-SL" manufactured by TSE Co., Ltd.) was used. The measurement was performed based on Japanese Industrial Standards JIS C6481.

<Measurement of copper foil peel strength after HAST test>

The evaluation board C was subjected to an accelerated environmental test (HAST test) for 100 hours under high temperature and high humidity conditions of 130°C and 85% RH using a highly accelerated life test apparatus ("PM422" manufactured by Kusumoto Kasei Co., Ltd.). Thereafter, using the evaluation substrate C after the HAST test, the copper foil peel strength was measured in the same manner as in the above "<measurement of copper foil peel strength before HAST test>". That is, when the evaluation board after the HAST test is cut into small pieces, an incision is made in the CZ copper foil portion, and one end of the portion surrounded by the incision is pulled vertically at room temperature (room temperature) at a speed of 50 mm/min to remove 35 mm. The load [kgf/cm] was measured as copper foil peel strength. The value of the load obtained as a result of this measurement is referred to as "copper foil peel strength after HAST test". The measurement was performed based on Japanese Industrial Standards JIS C6481.

[Evaluation method of crack resistance]

<Laminate of resin sheet>

Inner-layer board having circuit conductors (copper) formed in a wiring pattern of L/S = 8 μm/8 μm on both sides ("MCL-E700G" manufactured by Hitachi Kasei Co., Ltd., conductor layer thickness 35 μm, total thickness 0.4 mm, residual fluid rate) 40%) was prepared. Resin sheets were laminated on both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. This lamination was performed using a vacuum pressurized laminator (“MVLP-500” manufactured by Meiki Sesakusho Co., Ltd.), vacuum suction at a temperature of 120° C. for 30 seconds, and then from above the support under conditions of a temperature of 120° C. and a pressure of 7.0 kg/cm 2 . , It was carried out by pressing for 30 seconds through heat-resistant rubber. Next, under atmospheric pressure, using a SUS head plate, press was performed for 60 seconds under conditions of a temperature of 120°C and a pressure of 5.5 kg/cm 2 .

<Heat Curing of Resin Composition Layer>

The resin composition layer was thermally cured by heating at 130°C for 30 minutes and then heating at 170°C for 30 minutes to obtain an insulating layer as a cured product layer composed of a cured product of the resin composition. Then, the support was peeled off to obtain a sample substrate having a layer configuration of insulating layer/inner layer substrate/insulating layer.

<harmony processing>

A roughening treatment was performed on the insulating layer of the sample substrate. Specifically, the sample substrate was immersed at 60°C for 10 minutes in Swelling Deep Securigant P manufactured by Atotech Japan, which is a swelling liquid. Next, it was immersed for 20 minutes at 80 degreeC in Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) manufactured by Atotech Japan, which is a crude liquid. Finally, it was immersed in reduction solution Securigant P manufactured by Atotech Japan, which is a neutralization solution, at 40°C for 5 minutes.

<Evaluation of crack>

Among the surfaces of the insulating layer after the roughening treatment, the portion on the L/S pattern of the inner layer substrate was observed. According to the pattern shape of 100 inner layer substrates, it was checked whether cracks (cracks) were occurring on the surface, and the ratio of the number of parts on the pattern where cracks did not occur was counted. This ratio was calculated as "yield". In addition, the calculated yield was scored according to the following criteria.

1 point: 0% or more and less than 20%.

2 points: 20% or more and less than 40%.

3 points: 40% or more and less than 60%.

4 points: 60% or more and less than 80%.

5 points: 80% or higher.

Three points or more were evaluated as "○", and two points or less were evaluated as "x".

[result]

The results of the above examples and comparative examples are shown in the tables below. In the table below, the meaning of the abbreviation is as follows.

BAHPM: 2,2'-bis(3-allyl-4-hydroxyphenyl)methane.

Hollow Particles: Hollow aluminosilicate particles.

Copper foil adhesion before HAST: Copper foil peel strength before HAST test.

Copper foil adhesion after HAST: Copper foil peel strength after HAST test.

Claims (13)

(A) a compound containing a biphenyl skeleton, a propenyl group and a phenolic hydroxyl group;
(B) an epoxy resin;
(C) an active ester compound, and
(D) An inorganic filler, A resin composition containing. The resin according to claim 1, wherein the content of the inorganic filler (D) is 60% by mass or more, and the content of the active ester compound (C) is 10% by mass or more, when the non-volatile component in the resin composition is 100% by mass. composition. The resin composition according to claim 1, wherein (A) the compound containing a biphenyl skeleton, a propenyl group and a phenolic hydroxyl group contains a group represented by the following formula (A1).

(In formula (A1), R each independently represents a monovalent hydrocarbon group; n represents an integer of 0 or more and 3 or less; * represents a bond.) The resin composition according to claim 1, wherein (A) the compound containing a biphenyl skeleton, a propenyl group and a phenolic hydroxyl group is represented by the following formula (A2).

(In formula (A2),
R ¹ each independently represents a monovalent hydrocarbon group;
R ² each independently represents a divalent aliphatic hydrocarbon group;
X each independently represents a halogen atom or a monovalent hydrocarbon group;
p each independently represents an integer of 0 or more and 3 or less;
q represents 0 or 1;
r represents an integer of 0 or more and 4 or less each independently.) The resin composition according to claim 1, comprising at least one (E) curing agent selected from the group consisting of a phenol-based curing agent and a carbodiimide-based curing agent. The resin composition according to claim 1, comprising (F) a curing accelerator. The resin composition according to claim 1, comprising (G) a thermoplastic resin. The resin composition according to claim 1, which is for forming an insulating layer. A cured product of the resin composition according to any one of claims 1 to 8. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 8. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 8 on the support. A printed wiring board provided with an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 8. A semiconductor device comprising the printed wiring board according to claim 12.