JP2022122748A - resin composition - Google Patents

Abstract

To provide a resin composition capable of reducing occurrence of crack after desmear treatment and also capable of obtaining a cured matter whose dissipation factor (Df) is reduced.SOLUTION: A resin composition contains (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) an epoxy resin and (C) an active ester compound.SELECTED DRAWING: None

Description

The present invention relates to resin compositions containing epoxy resins. Furthermore, it relates to a cured product, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

2. Description of the Related Art As a technique for manufacturing printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition.

Printed wiring boards are generally exposed to a wide range of temperature environments, from low temperature environments such as room temperature to high temperature environments such as reflow. , cracks are generated by the distortion. Further, in recent years, there has been a demand for further improvement in dielectric properties such as dielectric loss tangent of insulating layers.

A compound having a terminal carbon-carbon double bond and a cyclopentadiene ring has been known so far (Patent Document 1).

U.S. Pat. No. 9,902,695

If an active ester compound is used as the curing agent for the epoxy resin composition used to form the insulating layer, instead of the general phenolic curing agent, the dielectric loss tangent can be kept lower, but cracks may occur after the desmear treatment. tend to occur more easily.

An object of the present invention is to provide a resin composition capable of suppressing the occurrence of cracks after desmear treatment and obtaining a cured product with a low dielectric loss tangent (Df).

In order to achieve the object of the present invention, the present inventors have made intensive studies and found that (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) an epoxy resin, and (C) an active ester compound. Surprisingly, by using a resin composition containing, it was found that it is possible to suppress the occurrence of cracks after desmear treatment and to obtain a cured product with a low dielectric loss tangent (Df), and completed the present invention. I came to let you.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) an epoxy resin, and (C) an active ester compound.
[2] Component (A) has the formula (A1):

[In the formula,
each R independently represents a substituent, and at least one R is a group having a terminal carbon-carbon double bond;
X each independently represents an organic group,
a is each independently 0, 1, 2, 3, or 4, and the sum of n+1 a's is 1 or more,
n represents 0 or an integer of 1 or more. ]
The resin composition according to [1] above, comprising a compound represented by:
[3] Component (A) has the formula (A2):

[In the formula,
R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group,
R ⁴ each independently represents a substituent,
X ¹ each independently represents a hydrocarbon group,
Y each independently represents a single bond, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO- or -OCO- ,
Z represents a single bond or an arylene group optionally substituted with an alkyl group,
b each independently represents 0, 1, 2, or 3;
n represents 0 or an integer of 1 or more,
m each independently represents 0, 1, 2, or 3; ]
The resin composition according to the above [1] or [2], comprising a compound represented by
[4] The resin composition according to [2] or [3] above, wherein n is 0.
[5] The resin composition according to any one of [1] to [4] above, wherein the content of component (A) is 20% by mass or less when the non-volatile component in the resin composition is 100% by mass. thing.
[6] The content of component (A) is 0.5% by mass or more when the non-volatile component in the resin composition is 100% by mass. Resin composition.
[7] The mass ratio of component (A) to component (B) (component (A)/component (B)) according to any one of [1] to [6] above, wherein the mass ratio is 0.05 to 3. Resin composition.
[8] The mass ratio of component (A) to component (C) (component (A)/component (C)) according to any one of [1] to [7] above, wherein the mass ratio is 0.05 to 3. Resin composition.
[9] The resin composition according to any one of [1] to [8] above, further comprising (D) an inorganic filler.
[10] The resin composition according to [9] above, wherein the component (D) is silica.
[11] The resin composition according to [9] or [10] above, wherein the content of component (D) is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[12] The resin according to any one of [1] to [11] above, wherein the cured product of the resin composition has a dielectric loss tangent (Df) of 0.0032 or less when measured at 5.8 GHz and 23°C. Composition.
[13] Any one of the above [1] to [12], wherein the cured product of the resin composition has a dielectric constant (Dk) of 3.5 or less when measured at 5.8 GHz and 23°C. Resin composition.
[14] A cured product of the resin composition described in any one of [1] to [13] above.
[15] A sheet-like laminate material containing the resin composition according to any one of [1] to [13] above.
[16] A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [13] provided on the support.
[17] A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [13] above.
[18] A semiconductor device including the printed wiring board according to [17] above.

According to the resin composition of the present invention, the occurrence of cracks after desmear treatment can be suppressed, and a cured product with a low dielectric loss tangent (Df) can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

<Resin composition>
The resin composition of the present invention contains (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, the occurrence of cracks after desmear treatment can be suppressed, and a cured product with a low dielectric loss tangent (Df) can be obtained.

The resin composition of the present invention further contains optional components in addition to (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) an epoxy resin, and (C) an active ester compound. good too. Examples of optional components include (D) an inorganic filler, (E) a radically polymerizable compound, (F) a curing accelerator, (G) other additives, and (H) an organic solvent.

Each component contained in the resin composition will be described in detail below.

<(A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring>
The resin composition of the present invention contains (A) a compound having a terminal carbon-carbon double bond (CH ₂ =C<) and a cyclopentadiene ring (hereinafter sometimes referred to as "cyclopentadiene compound") as a non-volatile component. (A) The cyclopentadiene compound is a compound having a cyclopentadiene ring to which a group having a terminal carbon-carbon double bond is bonded. (A) The cyclopentadiene compound has a group having one or more (preferably one in one embodiment) terminal carbon-carbon double bonds in one molecule. (A) The cyclopentadiene compound has one or more (in one embodiment, preferably one or two, more preferably one) cyclopentadiene rings in one molecule.

(A) The cyclopentadiene compound, in one embodiment, preferably has the formula (A1):

[In the formula,
each R independently represents a substituent, and at least one R is a group having a terminal carbon-carbon double bond;
X each independently represents an organic group,
a is each independently 0, 1, 2, 3, or 4, and the sum of n+1 a's is 1 or more,
n represents 0 or an integer of 1 or more. ]
Including the compound represented by.

Each R independently represents a substituent, and at least one R is a group having a terminal carbon-carbon double bond.

As used herein, the term "group having a terminal carbon-carbon double bond" is not particularly limited, but in one embodiment, for example, a carbon atom having one or more terminal carbon-carbon double bonds, an oxygen atom , a nitrogen atom, and a sulfur atom. , may contain a branched chain structure and/or a cyclic structure, and may be a group containing no aromatic ring or a group containing an aromatic ring, but in one embodiment, it is a group containing an aromatic ring preferable.

An aromatic ring means a ring conforming to Hückel's rule in which the number of electrons contained in the π-electron system on the ring is 4p+2 (p is a natural number). The aromatic ring is an aromatic carbocyclic ring having only carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring 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. However, in one embodiment, aromatic carbocycles are preferred. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 6- to 14-membered aromatic ring, and even more preferably a 6- to 10-membered aromatic ring. Preferable specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like, more preferably benzene ring or naphthalene ring, particularly preferably benzene ring.

The "group having a terminal carbon-carbon double bond" preferably has the formula (a1):

[In the formula,
R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group,
Y each independently represents a single bond, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO- or -OCO- ,
Z represents a single bond or an arylene group optionally substituted with an alkyl group,
m represents 0, 1, 2, or 3,
* indicates the binding site. ]
is a group represented by the formula (a2):

[In the formula,
each R ⁵ independently represents an alkyl group,
c represents 0, 1, or 2,
* indicates the binding site,
Other symbols are as described above. ]
is a group represented by

R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, and in one embodiment, preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.

Alkyl (group) means a linear, branched and/or cyclic monovalent saturated aliphatic hydrocarbon group. Unless otherwise specified, the alkyl (group) is preferably an alkyl (group) having 1 to 14 carbon atoms, more preferably an alkyl (group) having 1 to 10 carbon atoms, an alkyl (group) having 1 to 6 carbon atoms ( group) is more preferred. Alkyl (group) includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl decyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,2,4-trimethylcyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group and the like.

R ³ represents a hydrogen atom or an alkyl group, and in one embodiment, preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.

Y each independently represents a single bond, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO- or -OCO- , in one embodiment, is preferably a single bond or -O-, particularly preferably a single bond.

Z represents a single bond or an arylene group optionally substituted with an alkyl group. In one embodiment, it is preferably an arylene group optionally substituted with an alkyl group, more preferably an alkyl group. It is an optionally substituted phenylene group (1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group), particularly preferably (unsubstituted) phenylene group.

Arylene (group) means a divalent aromatic hydrocarbon group formed by removing two hydrogen atoms from an aromatic carbocyclic ring. Arylene (group) is preferably arylene (group) having 6 to 14 carbon atoms, more preferably arylene (group) having 6 to 10 carbon atoms, unless otherwise specified. Arylene (group) includes, for example, phenylene group (1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group), naphthylene group (1,2-naphthylene group, 1,3-naphthylene group , 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 1,8-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group) etc.

m represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 1 in one embodiment. Each R ⁵ independently represents an alkyl group, and in one embodiment, preferably a methyl group. c represents 0, 1 or 2, preferably 0 or 1, particularly preferably 0, in one embodiment.

As used herein, the term "substituent" is not particularly limited, but in one embodiment, for example, one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (eg, 1 to 100 (preferably 1 to 50, particularly preferably 1 to 20) skeletal atoms, which may contain a linear, branched and/or cyclic structure and does not contain an aromatic ring. It may be a group or a group containing an aromatic ring. In addition to alkyl groups, aryl groups, aryl-alkyl groups (alkyl groups substituted with aryl groups), alkyl-aryl groups (aryl groups substituted with alkyl groups), alkyl-oxy groups, aryl- monovalent substituents such as an oxy group, an alkyl-carbonyl group, an aryl-carbonyl group, an alkyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, and an aryl-carbonyl-oxy group; .

Aryl (group) means a monovalent aromatic hydrocarbon group having one hydrogen atom removed from an aromatic carbocyclic ring. The aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms, particularly preferably an aryl (group) having 6 to 10 carbon atoms, unless otherwise specified. Aryl (group) includes, for example, phenyl group, 1-naphthyl group, 2-naphthyl group and the like.

Each X independently represents an organic group, and in one embodiment, preferably represents a hydrocarbon group, more preferably represents an alkylene group.

As used herein, the term “organic group” is not particularly limited, but in one embodiment, for example, one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (eg, 1 to 100 (preferably 1 to 50, particularly preferably 1 to 20) skeletal atoms, which may contain a straight-chain structure, a branched-chain structure and/or a cyclic structure, and does not contain an aromatic ring. It may be a group or a group containing an aromatic ring.

As used herein, the term "hydrocarbon group" refers to an organic group in which only one or more (eg, 1 to 100, preferably 1 to 50, particularly preferably 1 to 20) carbon atoms are used as skeleton atoms. It is a divalent group that has a linear structure, a branched chain structure and/or a cyclic structure, and may be a group that does not contain an aromatic ring or a group that contains an aromatic ring. Examples of the "hydrocarbon group" include an alkylene group, an arylene group, an alkylene-arylene group, an arylene-arylene group, an arylene-alkylene-arylene group, an alkylene-arylene-alkylene group, an alkylene-arylene-arylene-alkylene group, and the like. mentioned.

Alkylene (group) refers to a linear, branched and/or cyclic divalent aliphatic saturated hydrocarbon group. Alkylene (group), unless otherwise specified, is preferably an alkylene (group) having 1 to 14 carbon atoms, more preferably an alkylene (group) having 1 to 10 carbon atoms, still more preferably a carbon atom It is an alkylene (group) of numbers 1 to 6. Examples of alkylene (group) include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched chain alkylene groups such as an ethylidene group, a propylidene group, an isopropylidene group, an ethylmethylmethylene group, and a diethylmethylene group;

Each a independently represents 0, 1, 2, 3, or 4, and the sum of n+1 a's is 1 or more. a each independently represents preferably 1, 2, 3 or 4, more preferably 1, 2 or 3, still more preferably 1 or 2 in one embodiment . n represents 0 or an integer of 1 or more, and in one embodiment, is preferably 0, or 1 to 100, more preferably 0, or 1 to 10, still more preferably 0, 1 , or 2, particularly preferably 0.

(A) The cyclopentadiene compound, in one embodiment, more preferably has the formula (A2):

[In the formula,
R ⁴ each independently represents a substituent,
X ¹ each independently represents a hydrocarbon group,
b each independently represents 0, 1, 2, or 3;
Other symbols are as described above. ]
Including the compound represented by.

Each R ⁴ independently represents a substituent, and in one embodiment, preferably a group represented by formula (a1), an alkyl group, or an aryl group, more preferably represented by formula (a1) It is a group represented. Each X ¹ independently represents a hydrocarbon group, and in one embodiment, preferably an alkylene group. b each independently represents 0, 1, 2, or 3, and in one embodiment, is preferably 0, 1, or 2, more preferably 0, or 1, and particularly preferably , 0.

(A) The cyclopentadiene compound, in one embodiment, more preferably has the formula (A3):

[In the formula, each symbol is as described above. ]
Including the compound represented by.

Specific examples of the cyclopentadiene compound (A) include formulas (A-1) to (A-12):

[Wherein, n ⁰ represents an integer of 2 or more (preferably 2 to 100, more preferably 2 to 10), n ¹ and n ² are each independently 1 or more (preferably 1 to 50, More preferably, it represents an integer of 1 to 5). ]
and in one embodiment, the compound represented by formula (A-2) is particularly preferred.

(A) The molecular weight of the cyclopentadiene compound is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 1,000 or less, and particularly preferably 500 or less. The lower limit can be, for example, 100 or more.

(A) Examples of commercially available cyclopentadiene compounds include "SLK-250" manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The content of (A) the cyclopentadiene compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably It is 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 6% by mass or less. The lower limit of the content of (A) the cyclopentadiene compound in the resin composition is not particularly limited, but is preferably 0.1% by mass or more when the non-volatile component in the resin composition is 100% by mass. , more preferably 0.5% by mass or more, still more preferably 1% by mass or more, even more preferably 2% by mass or more, and particularly preferably 3% by mass or more.

<(B) Epoxy resin>
The resin composition of the present invention contains (B) an epoxy resin as a non-volatile component. (B) Epoxy resin is a curable resin having an epoxy group.

(B) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxy resins. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, Cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, isocyanurate-type epoxy resin, phenolphthalimidine-type epoxy resin, phenolphthalein type epoxy resin and the like. (B) Epoxy resins may be used singly or in combination of two or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (B) the epoxy resin. (B) The ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and 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”). ). As the epoxy resin, the resin composition of the present invention may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. You can stay. The resin composition of the present invention preferably contains a solid epoxy resin as the epoxy resin.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

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

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation; ", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirrol type epoxy resin) manufactured by ADEKA; "EP-3950L" manufactured by ADEKA; "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; Bisphenol F type epoxy resin mixture); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); Daicel "PB-3600" manufactured by Nippon Soda Co., Ltd., "JP-100" and "JP-200" (epoxy resins having a butadiene structure); 1,4-glycidylcyclohexane type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalate A mijin-type epoxy resin and a phenolphthalein-type epoxy resin are preferred.

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

(B) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ~5,000g/eq. , more preferably 60 g/eq. ~2,000 g/eq. , more preferably 70 g/eq. ~1,000g/eq. , even more preferably 80 g/eq. ~500 g/eq. is. Epoxy equivalent weight is the mass of resin per 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 polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of the (B) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass. % by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 12% by mass or less. The lower limit of the content of the (B) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, It is more preferably 0.5% by mass or more, still more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

The mass ratio of the (A) cyclopentadiene compound to the (B) epoxy resin in the resin composition ((A) component/(B) component) is not particularly limited, but is preferably 0.01 or more, or more. It is preferably 0.05 or more, particularly preferably 0.1 or more. The upper limit of the mass ratio of (A) cyclopentadiene compound to (B) epoxy resin in the resin composition ((A) component/(B) component) is not particularly limited, but is preferably 5 or less, or more. It is preferably 3 or less, particularly preferably 1 or less.

<(C) Active ester compound>
The resin composition of the present invention contains (C) an active ester compound as a non-volatile component. (C) The active ester compound may be used singly or in combination of two or more at any ratio. (C) The active ester compound can function as an epoxy resin curing agent that reacts with (B) the epoxy resin to cure it.

(C) The active ester compound generally contains two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. is preferably used. The active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, the (C) active ester compound includes 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, and a benzoylated product of phenol novolak. Active ester compounds are preferred, among which at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred, and dicyclopentadiene-type active ester compounds are even more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

(C) Commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", and "EXB-8000L-65M" as active ester compounds containing a dicyclopentadiene type diphenol structure. ”, “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); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester compound, acetylated phenol novolac "DC808" (Mitsubishi Chemical Co., Ltd.) as an active ester compound, "YLH1026", "YLH1030", and "YLH1048" (Mitsubishi Chemical Co., Ltd.) as active ester compounds that are benzoyl compounds of phenol novolak, a styryl group and a naphthalene structure "PC1300-02-65MA" (manufactured by Air Water) and the like are examples of active ester compounds containing.

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

The content of (C) the active ester compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.1% by mass or more,
It is more preferably 1% by mass or more, still more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably 12% by mass or more. The upper limit of the content of (C) the active ester compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, or more. It is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

The mass ratio of the (A) cyclopentadiene compound to the (C) active ester compound in the resin composition ((A) component/(C) component) is not particularly limited, but is preferably 0.01 or more. More preferably 0.05 or more, particularly preferably 0.1 or more. The upper limit of the mass ratio ((A) component/(C) component) of the (A) cyclopentadiene compound to the (C) active ester compound in the resin composition is not particularly limited, but is preferably 5 or less. It is more preferably 3 or less, particularly preferably 1 or less.

<(D) Inorganic filler>
The resin composition of the present invention may contain (D) an inorganic filler as an optional non-volatile component. (D) The inorganic filler is contained in the resin composition in the form of particles.

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

(D) Commercially available inorganic fillers include, for example, “UFP-30” manufactured by Denka Kagaku Kogyo; “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; 5N”; “SC2500SQ”, “SO-C4”, “SO-C2” and “SO-C1” manufactured by Admatechs; “DAW-03” and “FB-105FD” manufactured by Denka.

The average particle size of the inorganic filler (D) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.001 μm or less. 7 μm or less. (D) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0 .2 μm or more. (D) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(D) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, still more preferably 1 m ² /g or more, Particularly preferably, it is 3 m ² /g or more. Although the upper limit of the specific surface area of the inorganic filler (D) is not particularly limited, it is preferably 100 m ² /g or less, more preferably 70 m ² /g or less, even more preferably 50 m ² /g or less, and particularly preferably is 40 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. obtained by

(D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate compounds. A coupling agent etc. are mentioned. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in combination.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM- 7103” (3,3,3-trifluoropropyltrimethoxysilane).

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, and is surface-treated with 0.2% to 3% by mass. more preferably 0.3 mass % to 2 mass % of the surface treatment.

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

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

The content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 90% by mass or less, more preferably It may be 85% by mass or less, more preferably 80% by mass or less, and particularly preferably 75% by mass or less. The lower limit of the content of the inorganic filler (D) in the resin composition is not particularly limited. % by mass or more, may be 10% by mass or more, preferably 20% by mass or more, 30% by mass or more, more preferably 40% by mass or more, 50% by mass or more, further preferably 50% by mass or more, 55% by mass or more, Even more preferably 60% by mass or more and 65% by mass or more, particularly preferably 68% by mass or more and 70% by mass or more.

The mass ratio of the (A) cyclopentadiene compound to the (D) inorganic filler in the resin composition ((A) component/(D) component) is not particularly limited, but is preferably 0.005 or more. More preferably 0.01 or more, particularly preferably 0.05 or more. The upper limit of the mass ratio ((A) component/(D) component) of the (A) cyclopentadiene compound to the (D) inorganic filler in the resin composition is not particularly limited, but is preferably 1 or less. It is more preferably 0.5 or less, particularly preferably 0.1 or less.

<(E) Radically polymerizable compound>
The resin composition of the present invention may contain (E) a radically polymerizable compound as an optional non-volatile component. The (E) radically polymerizable compound described here is a component that does not correspond to the (A) cyclopentadiene compound. (E) Radically polymerizable compounds may be used singly or in combination of two or more.

(E) The radically polymerizable compound is, in one embodiment, a radically polymerizable compound having an ethylenically unsaturated bond. (E) The radically polymerizable compound is not particularly limited, but for example, allyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, 2-vinylphenyl group, 3-vinylphenyl group, 4-vinyl Unsaturated hydrocarbon groups such as phenyl group; α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) can have a radically polymerizable group such as (E) The radically polymerizable compound preferably has two or more radically polymerizable groups.

(E) Radically polymerizable compound, in the first embodiment, preferably contains a thermoplastic resin having a vinylphenyl group and/or a (meth)acryloyl group. A (meth)acryloyl group means an acryloyl group or a methacryloyl group. Vinylphenyl groups include 2-vinylphenyl groups, 3-vinylphenyl groups, 4-vinylphenyl groups, and those in which these aromatic carbon atoms are further substituted with one or more alkyl groups. It is preferable to have two or more vinylphenyl groups and/or (meth)acryloyl groups in one molecule. Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polystyrene resins, polyethylene resins, polypropylene resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, and polyphenylene ether resins. , polyether ether ketone resins, polyester resins, etc., and (E) radically polymerizable compounds include modified resins having vinylphenyl groups and/or (meth)acryloyl groups of these resins in this embodiment.

(E) In the first embodiment, the radically polymerizable compound is more preferably a modified polyphenylene ether resin having a vinylphenyl group and/or (meth)acryloyl group (hereinafter referred to as "modified polyphenylene ether resin"), and a vinyl It includes resins selected from modified polystyrene resins having phenyl groups and/or (meth)acryloyl groups (hereinafter referred to as "modified polystyrene resins").

Preferred examples of modified polyphenylene ether resins include the formula (E-1):

[wherein R ¹¹ and R ¹² each independently represent an alkyl group; R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl R ³¹ and R ³² each independently represent a vinylphenyl group or (meth)acryloyl group; Y ¹ is a single bond, —C(R ^y ) ₂ —, —O—, —CO -, -S-, -SO-, or -SO ₂ -; R ^y each independently represents a hydrogen atom or an alkyl group; Y ² represents a single bond or an alkylene group; represents 0 or 1; q and r each independently represents an integer of 1 or more. ]
Including the resin represented by. The q unit and the r unit may be the same or different for each unit.

R ¹¹ and R ¹² each independently represent an alkyl group, and in one embodiment, preferably a methyl group. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group, and in one embodiment, preferably a hydrogen atom. R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group, and in one embodiment, preferably a hydrogen atom or a methyl group, more preferably a methyl group. R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group, and in one embodiment, preferably a hydrogen atom or a methyl group.

R ³¹ and R ³² each independently represent a vinylphenyl group or a (meth)acryloyl group, and Y ² represents a single bond or an alkylene group. In one embodiment, preferably R ³¹ and R ³² are a vinylphenyl group and Y ² is an alkylene group (particularly preferably a methylene group), or R ³¹ and R ³² are (meth) is an acryloyl group and Y ² is a single bond.

Y ¹ represents a single bond, —C(R ^y ) ₂ —, —O—, —CO—, —S—, —SO—, or —SO ₂ —, and in one embodiment, preferably a single bond , —C(R ^y ) ₂ —, or —O—. Each R ^y independently represents a hydrogen atom or an alkyl group, and in one embodiment, preferably represents a hydrogen atom or a methyl group. p represents 0 or 1, and is preferably 1 in one embodiment. q and r each independently represent an integer of 1 or more, and in one embodiment, preferably an integer of 1-200, more preferably an integer of 1-100.

Examples of commercially available modified polyphenylene ether resins include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Company; "SA9000" manufactured by SABIC Innovative Plastics. , “SA9000-111” (methacrylic-modified polyphenylene ether resin) and the like.

Preferred examples of modified polystyrene resins include the formula (E-2a):

[In the formula, R ⁴¹ , R ⁴² and R ⁴³ each independently represent a hydrogen atom or an alkyl group; R ⁴⁴ each independently represents an alkyl group; s is an integer of 0 to 3; show. ]
and a repeating unit represented by the formula (E-2b):

[wherein R ⁵¹ , R ⁵² and R ⁵³ each independently represent a hydrogen atom or an alkyl group; R ⁵⁴ each independently represents an alkyl group; t is an integer of 0 to 3; show. ]
is a resin having a repeating unit represented by The repeating units of the formula (E-2a) and the repeating units of the formula (E-2b) contained in one molecule of the modified polystyrene resin may be the same or different for each unit.

R ⁴¹ , R ⁴² , R ⁴³ , R ⁵¹ , R ⁵² and R ⁵³ each independently represent a hydrogen atom or an alkyl group, and in one embodiment are preferably a hydrogen atom or a methyl group, more preferably is a hydrogen atom. R ⁴⁴ and R ⁵⁴ each independently represent an alkyl group, and in one embodiment, preferably an ethyl group or a methyl group. s represents an integer of 0 to 3, preferably 0 or 1, more preferably 0 in one embodiment. t represents an integer from 0 to 3, preferably 0 or 1 in one embodiment.

The molar content of the repeating unit of the formula (E-2a) is 8 mol% to 54 mol when the total of the repeating unit of the formula (E-2a) and the repeating unit of the formula (E-2b) is 100 mol%. %.

Examples of commercially available modified polystyrene resins include "ODV-XET (X03)", "ODV-XET (X04)", and "ODV-XET (X05)" (styrene-divinylbenzene copolymer) and the like.

(E) In the second embodiment, the radically polymerizable compound preferably has the formula (E-3):

[wherein R ⁶ each independently represents a hydrogen atom or an alkyl group; ring A, ring B and ring C each independently represent an aromatic ring optionally having a substituent; each Z ¹ is independently a single bond, -C(R ^z ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO; -; R ^z each independently represents a hydrogen atom or an alkyl group; x represents an integer of 1 or more; y each independently represents 0 or 1; independently indicates 0, 1, 2 or 3; ]
Including the maleimide compound represented by. The x unit and z unit may be the same or different for each unit. The maleimide compound in the second embodiment may be used singly or in combination of two or more at any ratio.

Each ^R6 independently represents a hydrogen atom or an alkyl group, and in one embodiment, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. Ring A, ring B and ring C each independently represent an optionally substituted aromatic ring, and in one embodiment, preferably a benzene ring optionally having a substituent. , more preferably a benzene ring optionally substituted with a group selected from an alkyl group and an aryl group, and particularly preferably a (unsubstituted) benzene ring.

Z ¹ is each independently a single bond, -C(R ^z ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO- and in one embodiment is preferably a single bond, —C(R ^z ) ₂ — or —O—, more preferably a single bond or —C(R ^z ) ₂ —, especially A single bond is preferred. Each R ^z independently represents a hydrogen atom or an alkyl group, and in one embodiment, preferably represents a hydrogen atom or a methyl group.

x represents an integer of 1 or more, preferably an integer of 1-10. y each independently represents 0 or 1, preferably 1; z each independently represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, particularly preferably 1;

Commercially available products of (E) the radical polymerizable compound in the second embodiment include, for example, “MIR-3000-70MT” and “MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.

(E) In the third embodiment, the radically polymerizable compound preferably has the formula (E-4):

[wherein R ⁷ each independently represents an alkyl group; ring D and ring E each independently represents an aromatic ring which may have a substituent; u represents one or more Indicates an integer. ]
Including the maleimide compound represented by. The u units may be the same or different for each unit. The maleimide compound in the third embodiment may be used singly or in combination of two or more at any ratio.

Each R ⁷ independently represents an alkyl group, and in one embodiment, preferably a methyl group. Ring D each independently represents an optionally substituted aromatic ring, and in one embodiment, is preferably an optionally substituted benzene ring, more preferably alkyl A benzene ring optionally substituted with a group selected from groups, more preferably a benzene ring substituted with a group selected from alkyl groups. Each ring E independently represents an optionally substituted aromatic ring, and in one embodiment, is preferably an optionally substituted benzene ring, more preferably alkyl It is a benzene ring optionally substituted with a group selected from groups, more preferably a (unsubstituted) benzene ring. u represents an integer of 1 or more, preferably an integer of 1-20.

(E) the radically polymerizable compound in the third embodiment can be produced, for example, by using the method described in Japan Institute of Invention and Innovation No. 2020-500211 or a method based thereon.

(E) The radically polymerizable compound includes a suitable thermoplastic resin contained in the first embodiment, a suitable maleimide compound contained in the second embodiment, and a suitable maleimide compound contained in the third embodiment. , may be contained singly, but two or more of these may be contained in combination at an arbitrary ratio.

(E) The radically polymerizable group equivalent of the radically polymerizable compound is preferably 250 g/eq. ~2500 g/eq. , more preferably 300 g/eq. ~1500 g/eq. is. (E) The radically polymerizable group equivalent of the radically polymerizable compound represents the mass of the resin per equivalent of the radically polymerizable group.

(E) The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 500 to 40,000, more preferably 500 to 10,000, and particularly preferably 500 to 7,000. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of (E) the radically polymerizable compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably is 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of (E) the radical polymerizable compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, It is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and particularly preferably 2% by mass or more.

<(F) Curing accelerator>
The resin composition of the present invention may contain (F) a curing accelerator as an optional non-volatile component. The (F) curing accelerator functions as a curing catalyst that accelerates the curing of the (B) epoxy resin.

Examples of curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among them, imidazole-based curing accelerators are preferable from the viewpoint of improving crosslinkability. (F) The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 -methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; 2-butenyl)phosphine, aliphatic phosphines such as tricyclohexylphosphine; -tolylphosphine, tri-m-tolylphosphine, tri-p-tolyl Phosphine, 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) Aromatic phosphines such as butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether, and the like can be mentioned.

Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] etc.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins.

As the imidazole-based curing accelerator, a commercially available product may be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Kasei Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation. etc.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo (5,4,0)-undecene and the like.

As the amine-based curing accelerator, a commercially available product may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.

The content of the (F) curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably It is 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less. The lower limit of the content of (F) the curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0 It can be 0.001 wt% or more, 0.01 wt% or more, 0.1 wt% or more, and the like.

<(G) Other Additives>
The resin composition of the present invention may further contain optional additives as non-volatile components. Examples of such additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, Thermosetting resins other than epoxy resins such as unsaturated polyester resins, phenolic resins, melamine resins, silicone resins; phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents epoxy resin curing agents other than active ester compounds such as agents, cyanate ester curing agents, and thiol curing agents; phosphorus curing accelerators, urea curing accelerators, guanidine curing accelerators, imidazole curing accelerators, metals Curing accelerators such as system curing accelerators and amine curing accelerators; phenoxy resin, polyvinyl acetal resin, polyolefin resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon Coloring agents such as 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 antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; UV absorbers such as benzotriazole UV absorbers; adhesion improvers such as urea silane; triazole adhesion imparting agents , tetrazole-based adhesion-imparting agents, triazine-based adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; fluorine-based surfactants, silicones surfactants such as surfactants; Flame retardants such as retardants (for example, antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anions dispersing agents such as cationic dispersing agents; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic acid anhydrides stabilizers such as system stabilizers; (G) Other additives may be used singly or in combination of two or more at any ratio. (G) The content of other additives can be appropriately set by those skilled in the art.

<(H) Organic solvent>
The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile components described above. As the (H) organic solvent, a known one can be used as appropriate, and the type thereof is not particularly limited. Examples of (H) organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester-based solvents such as butyrolactone; Ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol Solvent; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, 2-hydroxyiso ester alcohol solvents such as methyl butyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide , N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide solvents; dimethyl sulfoxide and other sulfoxide solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane, etc. and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene. (H) The organic solvent may be used singly or in combination of two or more at any ratio.

In one embodiment, the content of the (H) organic solvent is not particularly limited, but when all components in the resin composition are 100% by mass, for example, 60% by mass or less, 40% by mass or less , 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, and the like.

<Method for producing resin composition>
The resin composition of the present invention, for example, in any preparation container (A) cyclopentadiene compound, (B) epoxy resin, (C) active ester compound, optionally (D) inorganic filler, optionally (E) a radically polymerizable compound, optionally (F) a curing accelerator, optionally (G) other additives, and optionally (H) an organic solvent, in any order and/or It can be produced by adding a part or all of them at the same time and mixing. Also, during the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or over time. In addition, during or after the addition and mixing, the resin composition may be stirred or shaken using a stirring or shaking device such as a mixer to uniformly disperse. Moreover, simultaneously with stirring or shaking, defoaming may be performed under low pressure conditions such as vacuum.

<Characteristics of resin composition>
The resin composition of the present invention contains (A) a cyclopentadiene compound, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, the occurrence of cracks after desmear treatment can be suppressed, and a cured product with a low dielectric loss tangent (Df) can be obtained.

The cured product of the resin composition of the present invention can suppress the occurrence of cracks after desmear treatment. Therefore, in one embodiment, after fabricating and desmearing a circuit board as in Test Example 2 below, when 100 copper pad portions of the circuit board are observed, the number of cracks may be preferably 10 or less.

A cured product of the resin composition of the present invention may have a feature of low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 0.0200 or less and 0.0100 or less. , more preferably 0.0090 or less, 0.0080 or less, 0.0070 or less, more preferably 0.0060 or less, 0.0050 or less, 0.0040 or less, particularly preferably 0.0035 or less, 0.0032 or less, It can be 0.0030 or less.

In one embodiment, the cured product of the resin composition of the present invention may be characterized by a low dielectric constant (Dk). Therefore, in one embodiment, the dielectric constant (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 6.0 or less, more preferably It can be 5.0 or less, more preferably 4.0 or less, still more preferably 3.5 or less, and particularly preferably 3.3 or less.

<Application of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulation, particularly as a resin composition for forming an insulation layer. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition). Moreover, in the printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention also includes resin sheets, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, and the like. It can be used in a wide range of applications.

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is used as an insulating layer for forming a rewiring layer. (a resin composition for forming a rewiring layer) and a resin composition for sealing a semiconductor chip (a resin composition for semiconductor chip sealing). A rewiring layer may be further formed on the encapsulation layer when the semiconductor chip package is manufactured.
(1) a step of laminating a temporary fixing film on a substrate;
(2) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the base material and the temporary fixing film from the semiconductor chip;
(5) forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed; and (6) forming a rewiring layer as a conductor layer on the rewiring layer. forming process

Moreover, since the resin composition of the present invention provides an insulating layer having good part-embedding properties, it can be suitably used when the printed wiring board is a component-embedded circuit board.

<Sheet-like laminated material>
Although the resin composition of the present invention can be applied in the form of a varnish, it is industrially preferably used in the form of a sheet-like laminated material containing the resin composition.

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

In one embodiment, the resin sheet comprises a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less, more It is preferably 40 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 5 μm or more, 10 μm or more, or the like.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain any layer as necessary. Examples of such an optional layer include a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

The resin sheet is produced by, for example, using a liquid resin composition as it is or preparing a resin varnish by dissolving the resin composition in an organic solvent, coating it on a support using a die coater or the like, and drying it. It can be produced by forming a resin composition layer.

Examples of the organic solvent include the same organic solvents as those described as components of the resin composition. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of the organic solvent, the temperature is 50° C. to 150° C. for 3 minutes to 10 minutes. A resin composition layer can be formed by drying for minutes.

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

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

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

A prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

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

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

<Printed wiring board>
The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

A printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate (II) Curing (for example, thermosetting) the resin composition layer to form an insulating layer process

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

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven 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 thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination can be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

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

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

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

For example, the thermosetting conditions for 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., and even more preferably 150° C. to 220° C. is between 170°C and 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50° C. to 120° C., preferably 60° C. to 115° C., more preferably 70° C. to 110° C. for 5 minutes or more, It may be preheated for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes.

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

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

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

Step (IV) is a step of roughening the insulating layer. Smear is usually also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used for forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.

The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned.

The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

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

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

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 kinds of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

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

In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Then, step (II) is performed to form an insulating layer. After that, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.

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

<Semiconductor device>
A semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

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

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples. The invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Unless otherwise specified, temperature conditions and pressure conditions are room temperature (23° C.) and atmospheric pressure (1 atm), respectively.

<Example 1>
Naphthol aralkyl skeleton epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 330 g / eq.) 10 parts, active ester curing agent ("HPC-8150-62T" manufactured by DIC, non-volatile component 62 mass % toluene solution, active ester group equivalent weight 234 g / eq.) 22.6 parts, cyclopentadiene compound (manufactured by Shin-Etsu Chemical Co., Ltd. "SLK-250") 5 parts, inorganic filler (amine-based alkoxysilane compound (Shin-Etsu Chemical 70 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5 μm, specific surface area 5.8 m ² /g)) surface-treated with "KBM573" manufactured by Co., Ltd.), curing accelerator (Shikoku A resin composition (resin varnish) was prepared by mixing 1 part of "1B2PZ" manufactured by Kasei Kogyo Co., Ltd., 10 parts of MEK, and 10 parts of toluene, and uniformly dispersing the mixture using a high-speed rotating mixer.

<Example 2>
The amount of naphthol aralkyl skeleton epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 330 g / eq.) was changed from 10 parts to 9 parts, and an active ester curing agent (“HPC -8150-62T”, a toluene solution of 62% by mass of non-volatile components, an active ester group equivalent of 234 g / eq. A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 4.3 parts of "3000-70 MT", a toluene/MEK mixed solution with a non-volatile content of 70%) was further added.

<Example 3>
A maleimide compound A (Mw/Mn=1.81, u′=1.81, u′=1.81, synthesized by the method described in Synthesis Example 1 of Institute of Invention and Innovation Public Technical Report No. 2020-500211, represented by the following formula (1). 47 (mainly 1, 2 or 3)) MEK solutions (non-volatile components 70% by weight) were prepared.

The amount of naphthol aralkyl skeleton epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 330 g / eq.) was changed from 10 parts to 9 parts, and an active ester curing agent (“HPC -8150-62T", a toluene solution of 62% by mass of non-volatile components, an active ester group equivalent of 234 g/eq. ) to prepare a resin composition (resin varnish) in the same manner as in Example 1, except that 4.3 parts of

<Example 4>
The amount of naphthol aralkyl skeleton epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 330 g / eq.) was changed from 10 parts to 9 parts, and an active ester curing agent (“HPC -8150-62T", a toluene solution of 62% by mass of non-volatile components, an active ester group equivalent of 234 g / eq.) The amount used was changed from 22.6 parts to 21 parts, and a styryl-modified polyphenylene ether resin A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 4.6 parts of "OPE-2St-1200" (a toluene mixed solution with a non-volatile content of 65%) was further added.

<Example 5>
The amount of naphthol aralkyl skeleton epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 330 g / eq.) was changed from 10 parts to 9 parts, and an active ester curing agent (“HPC -8150-62T", a toluene solution of 62% by mass of non-volatile components, an active ester group equivalent of 234 g / eq.) The amount used was changed from 22.6 parts to 21 parts, and an olefin compound (manufactured by Nippon Steel Chemical & Material Co., Ltd. " A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 4.6 parts of ODV-XET-X04, a toluene mixed solution with a non-volatile content of 65%, was further added.

<Example 6>
The amount of naphthol aralkyl skeleton epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 330 g / eq.) was changed from 10 parts to 9 parts, and an active ester curing agent (“HPC -8150-62T", a toluene solution of 62% by mass of non-volatile components, an active ester group equivalent of 234 g/eq.) was changed from 22.6 parts to 21 parts, and a terminal methacrylic modified polyphenylene ether resin A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 3 parts of SA9000-111”) was further added.

<Comparative Example 1>
Spherical silica (manufactured by Admatechs Co., Ltd.) surface-treated with an inorganic filler (amine-based alkoxysilane compound (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573") without using a cyclopentadiene compound (manufactured by Shin-Etsu Chemical Co., Ltd. "SLK-250") , “SO-C2”, average particle size 0.5 μm, specific surface area 5.8 m ² /g))) was changed from 70 parts to 53 parts, except that the amount used was changed from 70 parts to 53 parts. (resin varnish) was prepared.

<Comparative Example 2>
Active ester curing agent (DIC Corporation "HPC-8150-62T", toluene solution of 62% by mass of non-volatile components, active ester group equivalent weight 234 g / eq.) is not used, instead, a phenol-based curing agent curing agent (DIC Corporation "LA7054", MEK solution with a non-volatile content of 60%) was added, and 5 parts of spherical silica surface-treated with an inorganic filler (amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ^The resin composition ( resin varnish) was prepared.

<Test Example 1: Measurement of Dielectric Properties>
As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared. On the release layer of this support, the resin compositions prepared in Examples and Comparative Examples were 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 prepare a resin sheet including a support and a resin composition layer having a thickness of 40 μm.

The prepared resin sheet containing a resin composition layer having a thickness of 40 μm was heated at 190° C. for 90 minutes to thermally cure the resin composition layer. After that, the support was peeled off to obtain a cured product of the resin composition. This cured product was cut into test pieces having a width of 2 mm and a length of 80 mm. The dielectric constant (Dk) and dielectric loss tangent (Df) of the test piece were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by cavity resonance perturbation method using Agilent Technologies' HP8362B. Measurements were made on three specimens.

<Test Example 2: Evaluation of cracks after desmearing>
As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared. On the release layer of this support, the resin compositions prepared in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 25 μm. Thereafter, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 2.5 minutes to prepare a resin sheet including a support and a resin composition layer having a thickness of 25 μm.

A core material (Hitachi Chemical Co., Ltd.) was prepared by forming circular copper pads (thickness of copper: 35 μm) with a diameter of 350 μm in a lattice pattern at intervals of 400 μm so that the resin sheet containing the prepared resin composition layer with a thickness of 25 μm was 60%. Kogyo Co., Ltd. "E705GR", thickness 400 μm) on both sides using a batch type vacuum pressure laminator (Nikko Materials Co., Ltd. 2-stage build-up laminator "CVP700"), the resin composition layer and the inner layer substrate Both sides of the inner layer substrate were laminated so as to be bonded. This lamination was carried out by pressure bonding for 30 seconds at a temperature of 100° C. and a pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds. This was placed in an oven at 130° C. and heated for 30 minutes, then transferred to an oven at 170° C. and heated for 30 minutes. Further, the support layer was peeled off, and the resulting circuit board was immersed in a swelling liquid, Swelling Dip Securigant P (Atotech Japan Co., Ltd.), at 60° C. for 10 minutes. Next, it was immersed in a roughening solution, Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) available from Atotech Japan Co., Ltd., at 80° C. for 30 minutes. Finally, it was immersed for 5 minutes at 40° C. in Reduction Solution Securigant P available from Atotech Japan Co., Ltd., which is a neutralizing solution. After the roughening treatment, 100 copper pad portions of the circuit board were observed to confirm the presence or absence of cracks in the resin composition layer. If the number of cracks was 10 or less, it was evaluated as "O", and if it was more than 10, it was evaluated as "X".

Table 1 below shows the contents of non-volatile components in the resin compositions of Examples and Comparative Examples, and the measurement results and evaluation results of Test Examples.

As shown in Table 1, in Comparative Example 1 that does not use a cyclopentadiene compound, cracks tend to occur easily, while in Comparative Example 2 that uses a cyclopentadiene compound and does not use an active ester compound, cracks are suppressed. However, the dielectric loss tangent is a high value. In contrast, these problems can be overcome when a resin composition containing (A) a cyclopentadiene compound, (B) an epoxy resin, and (C) an active ester compound is used.

Claims (18)

A resin composition comprising (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) an epoxy resin, and (C) an active ester compound. The component (A) has the formula (A1):

[In the formula,
each R independently represents a substituent, and at least one R is a group having a terminal carbon-carbon double bond;
X each independently represents an organic group,
a is each independently 0, 1, 2, 3, or 4, and the sum of n+1 a's is 1 or more,
n represents 0 or an integer of 1 or more. ]
The resin composition according to claim 1, comprising a compound represented by. (A) component is the formula (A2):

[In the formula,
R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group,
R ⁴ each independently represents a substituent,
X ¹ each independently represents a hydrocarbon group,
Y each independently represents a single bond, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO- or -OCO- ,
Z represents a single bond or an arylene group optionally substituted with an alkyl group,
b each independently represents 0, 1, 2, or 3;
n represents 0 or an integer of 1 or more,
m each independently represents 0, 1, 2, or 3; ]
The resin composition according to claim 1 or 2, comprising a compound represented by. 4. The resin composition according to claim 2 or 3, wherein n is 0. The resin composition according to any one of claims 1 to 4, wherein the content of component (A) is 20% by mass or less when the non-volatile components in the resin composition are 100% by mass. The resin composition according to any one of claims 1 to 5, wherein the content of component (A) is 0.5% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 6, wherein the mass ratio of component (A) to component (B) (component (A)/component (B)) is 0.05 to 3. The resin composition according to any one of claims 1 to 7, wherein the mass ratio of component (A) to component (C) (component (A)/component (C)) is 0.05 to 3. (D) The resin composition according to any one of claims 1 to 8, further comprising an inorganic filler. 10. The resin composition according to claim 9, wherein component (D) is silica. 11. The resin composition according to claim 9 or 10, wherein the content of component (D) is 40% by mass or more based on 100% by mass of non-volatile components in the resin composition. The resin composition according to any one of claims 1 to 11, wherein the cured product of the resin composition has a dielectric loss tangent (Df) of 0.0032 or less when measured at 5.8 GHz and 23°C. The resin composition according to any one of claims 1 to 12, wherein the cured product of the resin composition has a dielectric constant (Dk) of 3.5 or less when measured at 5.8 GHz and 23°C. A cured product of the resin composition according to any one of claims 1 to 13. A sheet-like laminate material containing the resin composition according to any one of claims 1 to 13. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 13 provided on the support. A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 13. A semiconductor device comprising the printed wiring board according to claim 17 .