WO2023048170A1

WO2023048170A1 - Thermosetting resin composition

Info

Publication number: WO2023048170A1
Application number: PCT/JP2022/035128
Authority: WO
Inventors: 遼平早坂; 壮宮田; 幹広樫尾
Original assignee: リンテック株式会社
Priority date: 2021-09-24
Filing date: 2022-09-21
Publication date: 2023-03-30

Abstract

The present invention relates to a thermosetting resin composition containing a multifunctional phenolic compound (A) obtained using oxidative polymerization to copolymerize a phenolic compound (a1) having an unsaturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon (a2), an epoxy resin (B), and a curing accelerator (C), wherein: the storage modulus E'(23°C) at 23°C of a cured product of the thermosetting resin composition is 20-2,500 MPa; and a ratio [E'(23°C)/E'(Tg+50°C)] of the storage modulus E'(23°C) to the storage modulus E'(Tg+50°C) at the glass transition temperature + 50°C of the cured product of the thermosetting resin composition is 1-50.

Description

Thermosetting resin composition

The present invention relates to thermosetting resin compositions.

Conventionally, a thermosetting resin composition containing an epoxy resin and a phenolic resin as its curing agent yields a cured product that is excellent in heat resistance, electrical insulation, adhesion and the like. It is used in various fields such as wiring boards, paints, and adhesives.

In recent years, electronic components have become smaller, thinner, and finer, and along with this, thermosetting resin compositions used in electronic components are required to have higher reliability than ever before. In particular, in miniaturized circuits, the contact area between a conductor layer such as copper foil and an insulating layer becomes smaller, so adhesion with the conductor layer (hereinafter also referred to as "conductor adhesion") is required more than before. be done.

For example, Patent Document 1 describes epoxy resin (1-A) and phenol resin (1 -B), an active ester compound (1-C), and a rosin resin (1-D), and the content of the resin component (1) in the non-volatile components of the curable resin composition ( %) is M ₁ and the content (% by mass) of the rosin resin (1-D) is M _D , M _D /M ₁ is 0.001 to 0.05. A curable resin composition is disclosed.

JP 2020-145242 A

The technique of Patent Document 1 aims to improve conductor adhesiveness by blending a rosin-based resin as an adhesion imparting agent. However, if an adhesion imparting agent such as a rosin-based resin is added in a large amount, problems such as bleed-out may occur. Therefore, in order to achieve further improvement in conductor adhesion, there is a demand for a technique for improving the conductor adhesion of cured products themselves formed from epoxy resins and phenol resins.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a thermosetting resin composition having excellent conductor adhesion.

The present inventors have solved the above problems with a thermosetting resin composition containing a specific polyfunctional phenol compound, an epoxy resin and a curing accelerator, and having a storage elastic modulus E' of the cured product satisfying specific requirements. We have found that it is possible, and have completed the present invention.

That is, the present invention relates to the following [1] to [13].
[1] (A) (a1) a polyfunctional phenol compound obtained by copolymerizing a phenol compound having an unsaturated aliphatic hydrocarbon group and (a2) an unsaturated aliphatic hydrocarbon by oxidative polymerization;
(B) an epoxy resin;
(C) a thermosetting resin composition containing a curing accelerator,
The cured product of the thermosetting resin composition has a storage elastic modulus E' (23°C) at 23°C of 20 to 2,500 MPa,
The ratio of the storage elastic modulus E ' (23 ° C.) to the storage elastic modulus E ' (Tg + 50 ° C.) at the glass transition temperature + 50 ° C. of the cured product of the thermosetting resin composition [E ' (23 ° C.) / E '(Tg+50°C)] is 1 to 50, a thermosetting resin composition.
[2] The above-mentioned [1], wherein the (a1) phenolic compound having an unsaturated aliphatic hydrocarbon group is one or more selected from compounds represented by the following general formula (A-1): A thermosetting resin composition.

(wherein R is an unsaturated aliphatic hydrocarbon group containing 1 to 3 aliphatic unsaturated bonds, X ¹ is a hydrogen atom or a hydroxy group, and X ² is a hydrogen atom or a 5 is an alkyl group, and X ³ is a hydrogen atom, a hydroxy group or a carboxy group.)
[3] The (a1) phenol compound having an unsaturated aliphatic hydrocarbon group is a compound in which in the general formula (A-1), X ¹ , X ² and X ³ are all hydrogen atoms, % or more, the thermosetting resin composition according to the above [2].
[4] The above-mentioned [1] to [3], wherein the (a1) phenolic compound having an unsaturated aliphatic hydrocarbon group has an unsaturated aliphatic hydrocarbon group having 8 to 30 carbon atoms. A thermosetting resin composition.
[5] The thermosetting resin composition according to any one of [1] to [4] above, wherein (a2) the unsaturated aliphatic hydrocarbon has 10 to 40 carbon atoms.
[6] The thermosetting resin composition according to any one of [1] to [5] above, wherein the unsaturated aliphatic hydrocarbon (a2) contains 3 to 9 aliphatic unsaturated bonds.
[7] The thermosetting resin composition according to any one of [1] to [6] above, wherein the (a2) unsaturated aliphatic hydrocarbon is squalene.
[8] The thermosetting resin composition according to any one of [1] to [7] above, wherein the (a1) phenolic compound having an unsaturated aliphatic hydrocarbon group is a biomass-derived compound.
[9] The thermosetting resin composition according to any one of [1] to [8] above, wherein the (a2) unsaturated aliphatic hydrocarbon is a biomass-derived compound.
[10] The thermosetting resin composition according to any one of [1] to [9] above, wherein the weight average molecular weight (Mw) of component (A) is 8,000 to 200,000.
[11] When performing the oxidative polymerization, the (a1) blending amount (W _A ) of the phenol compound having an unsaturated aliphatic hydrocarbon group and the (a2) blending amount (W The thermosetting resin composition according to any one of the above [1] to [10], wherein the ratio [W _A /W _B ] to _B ) is 0.1 to 20 in terms of molar ratio.
[12] The thermosetting resin composition according to any one of [1] to [11] above, wherein the cured product has a glass transition temperature of 5 to 60°C.
[13] The thermosetting resin composition according to any one of [1] to [12] above, wherein the cured product has a breaking elongation of 15 to 200%.

According to the present invention, it is possible to provide a thermosetting resin composition with excellent conductor adhesion.

In the present specification, the number average molecular weight (Mn) and the mass average molecular weight (Mw) are values converted to standard polystyrene measured by gel permeation chromatography (GPC), specifically described in Examples. It is a value measured based on the method.

In this specification, the lower and upper limits described stepwise for preferable numerical ranges (for example, ranges of contents, etc.) can be independently combined. For example, from the statement "preferably 10 to 90, more preferably 30 to 60", combining "preferred lower limit (10)" and "more preferred upper limit (60)" to "10 to 60" can also

As used herein, "biomass" means a renewable organic resource derived from living organisms, excluding fossil resources.

As used herein, the term "solid content" refers to the components contained in the target composition, excluding diluent solvents such as water and organic solvents.

The mechanism of action described in this specification is speculation, and does not limit the mechanism of the effects of the present invention.

[Thermosetting resin composition]
The thermosetting resin composition of this embodiment is
(A) A polyfunctional phenol compound (hereinafter referred to as "(A) (Also referred to as "polyfunctional phenol compound"),
(B) an epoxy resin;
(C) a thermosetting resin composition containing a curing accelerator,
The cured product of the thermosetting resin composition has a storage elastic modulus E' (23°C) at 23°C of 20 to 2,500 MPa,
The ratio of the storage elastic modulus E ' (23 ° C.) to the storage elastic modulus E ' (Tg + 50 ° C.) at the glass transition temperature + 50 ° C. of the cured product of the thermosetting resin composition [E ' (23 ° C.) / E '(Tg+50°C)] is 1 to 50, the thermosetting resin composition.

The reason why the thermosetting resin composition of the present embodiment is excellent in conductor adhesion is not clear, but (A) contains a unique branched structure possessed by a polyfunctional phenol compound, and has a storage elastic modulus E' at 23 ° C. (23 ° C. ) and the ratio of storage elastic modulus E′ [E′ (23° C.)/E′ (Tg+50° C.)] satisfies the above range. It is presumed that this is due to the fact that it has toughness, which makes it possible to follow deformation even though it has a crosslinked structure.
Each component contained in the thermosetting resin composition of the present embodiment will be described below.

<(A) Polyfunctional phenol compound>
(A) The polyfunctional phenol compound includes (a1) a phenol compound having an unsaturated aliphatic hydrocarbon group (hereinafter also simply referred to as "(a1) phenol compound"), (a2) an unsaturated aliphatic hydrocarbon, is a polyfunctional phenol compound obtained by copolymerizing by oxidative polymerization.
(A) A polyfunctional phenol compound may be used individually by 1 type, and may use 2 or more types together.

((a1) phenol compound)
(a1) The phenol compound is a raw material monomer for (A) the polyfunctional phenol compound and is a phenol compound having an unsaturated aliphatic hydrocarbon group.
(A) The polyfunctional phenol compound is obtained by reacting the unsaturated aliphatic hydrocarbon group of the (a1) phenol compound to increase the molecular weight. The reaction is presumed to occur, for example, by a known reaction mechanism proposed as a mechanism for oxidizing unsaturated fatty acids.

(a1) The phenolic compound usually comprises one benzene ring, one or more phenolic hydroxyl groups directly bonded to the benzene ring, and one or more unsaturated aliphatic hydrocarbon groups directly bonded to the benzene ring. and have

(a1) The number of phenolic hydroxyl groups possessed by the phenolic compound is preferably 1 to 3, more preferably 1 or 2, still more preferably 1, from the viewpoint of conductor adhesion.

(a1) The number of unsaturated aliphatic hydrocarbon groups possessed by the phenolic compound is preferably 1 to 3, more preferably 1 or 2, from the viewpoint of conductor adhesion and gelation suppression during oxidative polymerization. One is preferable.
(a1) The number of aliphatic unsaturated bonds contained in the unsaturated aliphatic hydrocarbon group of the phenol compound is preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 to 4, from the viewpoint of conductor adhesion. is 1 to 3.
(a1) The unsaturated aliphatic hydrocarbon group possessed by the phenolic compound may be linear or branched, but from the viewpoint of conductor adhesion, it is preferably linear. .

(a1) The number of carbon atoms in the unsaturated aliphatic hydrocarbon group of the phenol compound is preferably 8 to 30, more preferably 10 to 25, still more preferably 13 to 20, particularly preferably 15, from the viewpoint of conductor adhesion. ~17.

(a1) As the unsaturated aliphatic hydrocarbon group possessed by the phenol compound, unsaturated aliphatic hydrocarbon groups represented by the following formulas (R-1) to (R-14) are preferable.

(In the formula, * is a site directly bonded to the benzene ring.)

Among the above options, the unsaturated aliphatic hydrocarbon group is an unsaturated group represented by the above formula (R-1), the above formula (R-2), or the above formula (R-3) from the viewpoint of conductor adhesion. It is preferably an aliphatic hydrocarbon group.

(a1) The phenol compound is preferably one or more selected from compounds represented by the following general formula (A-1) from the viewpoint of conductor adhesion.

(wherein R is an unsaturated aliphatic hydrocarbon group containing 1 to 3 aliphatic unsaturated bonds, X ¹ is a hydrogen atom or a hydroxy group, and X ² is a hydrogen atom or a 5 is an alkyl group, and X ³ is a hydrogen atom, a hydroxy group or a carboxy group.)

A description of a preferred embodiment of the unsaturated aliphatic hydrocarbon group represented by R in the general formula (A-1) is as described above for the unsaturated aliphatic hydrocarbon group of (a1) the phenol compound. is.

X ¹ in the general formula (A-1) is a hydrogen atom or a hydroxy group, preferably a hydrogen atom from the viewpoint of availability.
X ² in the general formula (A-1) is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom from the viewpoint of availability. Examples of the alkyl group having 1 to 5 carbon atoms represented by X ² include methyl group, ethyl group, propyl group, butyl group and pentyl group. Among these, a methyl group is preferred.
X ³ in the general formula (A-1) is a hydrogen atom, a hydroxy group or a carboxy group, preferably a hydrogen atom from the viewpoint of availability.

(a1) The phenol compound is a compound in which X ¹ , X ² and X ³ are all hydrogen atoms in the above general formula (A-1), that is, the following general formula (A-2 ) preferably contains a compound represented by

(Wherein, R is the same as R in the above general formula (A-1).)

(a1) The content of the compound represented by the general formula (A-2) in the phenol compound is not particularly limited, but is preferably 90% by mass or more, more preferably 92% by mass or more, and still more preferably 94% by mass. % by mass or more. In addition, the content of the compound represented by the general formula (A-2) in (a1) the phenol compound is not particularly limited, but is preferably 99% by mass or less, more preferably 98% by mass or less, and still more preferably is 96% by mass or less.

(a1) The phenol compound is a compound in which X ¹ is a hydroxy group and both X ² and X ³ are hydrogen atoms in the above general formula (A-1), i.e., the following general formula ( It may contain a compound represented by A-3).

(Wherein, R is the same as R in the above general formula (A-1).)

(a1) The content of the compound represented by the general formula (A-3) in the phenol compound is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 4% by mass. % by mass or more. The content of the compound represented by the general formula (A-3) in (a1) the phenol compound is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably is 6% by mass or less.

(a1) The phenol compound is preferably a biomass-derived compound from the viewpoint of reducing environmental load.
Examples of biomass-derived (a1) phenolic compounds include cardanol, cardol, 2-methylcardol, and anacardic acid, which are phenolic compounds contained in CNSL extracted from cashew nut shells; Those contained in plant-derived phenolic compounds such as ol, thithiol, and laccol; The plant-derived phenol compound is preferably cardanol, cardol, 2-methylcardol, or anacardic acid, more preferably cardanol or cardol, and still more preferably cardanol, from the viewpoint of effective utilization of waste resources and easy availability.

Cardanol has a structure represented by the following formula (A-4), cardol has a structure represented by the following formula (A-5), 2-methylcardol has a structure represented by the following formula (A-6), and anacardic acid has a structure represented by the following formula (A-7). includes.

In each of the above formulas (A-4) to (A-7), R ¹ is represented by the above formula (R-1), (R-2), (R-3) or (RC) is a group. In the above formulas (R-1), (R-2), (R-3) or (R-C), * is a site directly bonded to the benzene ring.
Cardanol, cardol, 2-methylcardol and anacardic acid are each a compound having a group represented by formula (R-1) as R ¹ and a group represented by formula (R-2) as R ¹ a compound having a group represented by formula (R-3) as R ¹ , and a compound having a group represented by formula (R—C) as R ¹ .
Cardanol, cardol, 2-methylcardol and anacardic acid each usually contain a compound having a group represented by the formula (R-1) as R ¹ , although it varies depending on purification conditions and the like. 40 mol%, the content of the compound having the group represented by the formula (R- ² ) as R 1 is 10 to 25 mol%, and the content of the compound having the group represented by the formula (R-3) as R ¹ The amount is 40 to 60 mol %, and the content of the compound having the group represented by the formula (RC) as R ¹ is 1 to 5 mol %.

((a2) unsaturated aliphatic hydrocarbon)
(A) Polyfunctional phenol compound is obtained by copolymerizing (a1) phenol compound and (a2) unsaturated aliphatic hydrocarbon by oxidative polymerization. (a2) Copolymerization of the unsaturated aliphatic hydrocarbon tends to improve the flexibility, elongation at break, stress relaxation rate, conductor adhesion, etc. of the cured product.
(a2) The unsaturated aliphatic hydrocarbon is preferably a biomass-derived compound from the viewpoint of reducing the burden on the environment.
(a2) Unsaturated aliphatic hydrocarbons may be used alone or in combination of two or more.

(a2) The number of carbon atoms in the unsaturated aliphatic hydrocarbon is preferably 10 to 40, more preferably 15 to 37, from the viewpoint of improving the flexibility, breaking elongation, stress relaxation rate and conductor adhesion of the cured product. , more preferably 20-35, particularly preferably 25-32.

(a2) The number of aliphatic unsaturated bonds contained in the unsaturated aliphatic hydrocarbon is preferably 3 to 9, more preferably 4 to 8, still more preferably 5, from the viewpoint of reactivity and availability. ~7.

(a2) The unsaturated aliphatic hydrocarbon may be linear or may have a structure having a side chain, but preferably has a structure having a side chain.
(a2) The unsaturated aliphatic hydrocarbon may have a substituent other than the aliphatic hydrocarbon, but preferably has no substituent other than the aliphatic hydrocarbon. That is, (a2) the unsaturated aliphatic hydrocarbon is preferably a compound consisting only of carbon atoms and hydrogen atoms.

(a2) Examples of unsaturated aliphatic hydrocarbons include squalene, botryococcene, farnesene, and myrcene. Although they can be chemically synthesized, they are all contained in plants or animals, and can also be produced from plants or animals. Among these, squalene is preferable from the viewpoint of reactivity and availability. Squalene is represented by the following formula (B-1) and is a compound contained in plants or animals, and is extracted from, for example, shark liver oil, microorganisms, and the like.

[Blending ratio of (a1) phenolic compound and (a2) unsaturated aliphatic hydrocarbon]
The ratio [W _A /W _B ] of the blending amount (W _A ) of (a1) the phenolic compound and the blending amount (W _B ) of (a2) the unsaturated aliphatic hydrocarbon when performing oxidative polymerization is particularly Although not limited, the molar ratio is preferably 0.1 to 20, more preferably 0.1 to 20, from the viewpoint of improving the balance of mechanical strength, flexibility, elongation at break, stress relaxation rate, conductor adhesion, etc. of the cured product. 0.3 to 15, more preferably 0.7 to 12.

[(a1) Phenol Compound and (a2) Raw Material Monomers Other than Unsaturated Aliphatic Hydrocarbons]
(A) a polyfunctional phenol compound, together with (a1) a phenol compound and (a2) an unsaturated aliphatic hydrocarbon, oxidatively polymerizes other raw material monomers other than (a1) a phenol compound and (a2) an unsaturated aliphatic hydrocarbon. It may be obtained by oxidative polymerization of (a1) the phenol compound and (a2) the unsaturated aliphatic hydrocarbon alone. When other raw material monomers are used, the other raw material monomers are preferably biomass-derived compounds from the viewpoint of reducing environmental load.
(A) In the total amount of raw material monomers for the polyfunctional phenol compound, the total content of (a1) the phenol compound and (a2) the unsaturated aliphatic hydrocarbon is preferably 90 to 100% by mass, more preferably 92 to 100% by mass. %, more preferably 95 to 100 mass %.
(A) The content of the biomass-derived raw material in the raw material excluding oxygen of the polyfunctional phenol compound is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and still more preferably 98 to 100% by mass. .

[(A) Properties of polyfunctional phenol compound]
(A) The polyfunctional phenol compound is preferably solid at 23°C or has a viscosity at 23°C of more than 50,000 mPa·s.
In the present embodiment, the term “solid state” means a state of not having fluidity under an environment of 1 atmospheric pressure and 23°C. In the case of a compound having a melting point, the term "non-fluid state" means a state in which the temperature is below the melting point, and in the case of a compound without a melting point, it means a state in which the temperature is below the melting point. do.
Further, in the present embodiment, "the viscosity at 23 ° C. is more than 50,000 mPa s" means that the viscosity is measurable under an environment of 1 atm and 23 ° C., and the viscosity is It means a state of exceeding 50,000 mPa·s.

(A) Since the polyfunctional phenol compound is solid at 23° C., a thermosetting resin composition that is solid at room temperature can be formed. Thermosetting resin compositions that are solid at room temperature are easy to handle and can be applied to a wider variety of uses than ever before.
On the other hand, (A) the polyfunctional phenol compound has a viscosity of more than 50,000 mPa·s at 23° C., so that it can form a highly viscous thermosetting resin composition at room temperature. A thermosetting resin composition having a high viscosity at room temperature can suppress dripping and the like, and is therefore excellent in handleability as a liquid thermosetting resin composition.
(A) The viscosity of the polyfunctional phenol compound at 23°C can be measured according to JIS Z 8803 (2011).

As described above, (A) the polyfunctional phenol compound may be solid at 23°C and may have a viscosity of more than 50,000 mPa s at 23°C, but can be applied to a wider variety of uses. and is preferably solid at 23° C. from the viewpoint of being effective in reducing environmental load.
On the other hand, when (A) the polyfunctional phenol compound has a viscosity of more than 50,000 mPa s at 23 ° C., the viscosity of (A) the polyfunctional phenol compound at 23 ° C. is (A) thickened by the polyfunctional phenol compound From the viewpoint of enhancing the effect, it is preferably 60,000 mPa·s or more, more preferably 70,000 mPa·s or more, and still more preferably 100,000 mPa·s or more. The upper limit of the viscosity at 23° C. of (A) the polyfunctional phenol compound is not particularly limited, but may be, for example, 300,000 mPa·s or less, or 200,000 mPa·s or less.

[(A) Number average molecular weight (Mn) of polyfunctional phenol compound]
(A) The number average molecular weight (Mn) of the polyfunctional phenol compound is not particularly limited, but from the viewpoint of handleability, it is preferably 2,000 to 10,000, more preferably 2,500 to 8,000, and still more preferably is between 3,000 and 6,000.

[(A) Mass average molecular weight (Mw) of polyfunctional phenol compound]
(A) The mass average molecular weight (Mw) of the polyfunctional phenol compound is not particularly limited, but from the viewpoint of handleability, preferably 8,000 to 200,000, more preferably 15,000 to 150,000, and even more preferably is between 20,000 and 100,000, even more preferably between 30,000 and 50,000.

((A) Method for producing a polyfunctional phenol compound)
(A) A polyfunctional phenol compound can be produced by copolymerizing (a1) a phenol compound and (a2) an unsaturated aliphatic hydrocarbon by oxidation polymerization.

As a method of oxidative polymerization, a method of heating a raw material monomer containing (a1) a phenol compound and (a2) an unsaturated aliphatic hydrocarbon in the presence of an oxidizing agent while stirring is preferred.
The method of oxidative polymerization of (a1) the phenol compound and (a2) the unsaturated aliphatic hydrocarbon may be, for example, a bulk polymerization method or a solution polymerization method, depending on the state of these raw materials. .
(a1) The phenol compound and (a2) the unsaturated aliphatic hydrocarbon are usually liquid at the reaction temperature, and tend to be able to maintain good stirring efficiency even when the oxidation polymerization proceeds. , a bulk polymerization method is preferred.

Examples of organic solvents used for solution polymerization include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ether solvents such as tetrahydrofuran; Aromatic solvents such as toluene, xylene, and mesitylene; Nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Solvents containing sulfur atoms such as dimethyl sulfoxide; Examples thereof include ester solvents such as butyrolactone. Among these, nitrogen atom-containing solvents and sulfur atom-containing solvents are preferable, and dimethyl sulfoxide is more preferable, from the viewpoint of solubility in raw material monomers and products.

Examples of oxidizing agents include oxygen; hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, peracetic acid, perbenzoic acid and other peroxides; is mentioned. Among these, oxygen is preferable from the viewpoint of productivity.
Oxygen is preferably supplied as a gas containing oxygen. That is, (A) a method for producing a polyfunctional phenol compound is a method in which oxidative polymerization is performed by heating (a1) a phenol compound and (a2) an unsaturated aliphatic hydrocarbon while supplying a gas containing oxygen. Preferably.
The oxygen-containing gas may be oxygen gas itself, a mixed gas of oxygen and an inert gas such as nitrogen, or air. Air is preferable from the point of view.

The oxygen-containing gas may be, for example, purged into the reaction vessel, passed over the reaction solution, or bubbled into the reaction solution. Among these, the method of bubbling in the reaction solution is preferable from the viewpoint of reactivity.
The pressure during the oxidation polymerization may be pressurized or normal pressure.
Further, when performing the oxidation reaction, for example, a reaction catalyst such as a metal catalyst may be used, but a reaction catalyst may not be used.

The reaction temperature of the oxidative polymerization is not particularly limited, but is preferably 100 to 250° C., more preferably 120° C., from the viewpoint of facilitating adjustment of the properties of (A) the polyfunctional phenol compound while obtaining an appropriate reaction rate. to 210°C, more preferably 140 to 180°C.
The reaction time of the oxidative polymerization is not particularly limited, and the time for obtaining the polyfunctional phenol compound (A) having desired properties may be determined as appropriate. More preferably 30 to 60 hours, still more preferably 36 to 54 hours.

In the production method of the present embodiment, of the total amount of aliphatic unsaturated bonds contained in (a1) the phenol compound and (a2) unsaturated aliphatic hydrocarbon before oxidative polymerization, the aliphatic unsaturated bonds that disappear by oxidative polymerization Although the aliphatic unsaturated bond disappearance ratio, which represents the ratio of is not particularly limited, it is preferably 20 to 75%, more preferably 30 to 65%, and still more preferably 35 to 60%.
The aliphatic unsaturated bond disappearance rate can be measured by the method described in Examples.

(A) polyfunctional phenol compound obtained by completing oxidative polymerization may be purified by known methods such as distillation, reprecipitation, centrifugation, and washing, if necessary.

<(B) Epoxy resin>
(B) Epoxy resins include, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; novolac type epoxy resin such as phenol novolac type epoxy resin and cresol novolak type epoxy resin. Resin; epoxy resin having a dicyclopentadiene skeleton; epoxy resin having a biphenol skeleton; epoxy resin having an aralkyl skeleton; epoxy resin having a fluorene skeleton; Resin; glycidyl ester type epoxy resin; 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, epsilon-caprolactone-modified-3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate , alicyclic epoxy resins such as bis-(3,4-epoxycyclohexyl) adipate;
(B) Epoxy resins may be used alone or in combination of two or more.

(B) Epoxy resin may be appropriately selected from the above options according to the purpose, but from the viewpoint of reducing environmental load, biomass-derived epoxy resin is preferable, and plant-derived epoxy resin is more preferable.

In addition, (B) the epoxy resin is preferably an epoxy resin obtained by oxidative polymerization (hereinafter also referred to as “oxidatively polymerized epoxy resin”) from the viewpoint of reducing environmental load.
The oxidatively polymerized epoxy resin may be, for example, an epoxy resin obtained by oxidatively polymerizing a monomer having an epoxy group, or a phenolic resin obtained by oxidatively polymerizing a phenolic compound in which the phenolic hydroxyl group is glycidyl-etherified. There may be.
Examples of epoxy resins obtained by oxidatively polymerizing a monomer having an epoxy group include (a1) an epoxy resin obtained by oxidatively polymerizing an epoxidized monomer obtained by glycidyl-etherifying a phenolic hydroxyl group of a phenol compound (hereinafter referred to as "oxidation (Also referred to as "polymerized epoxy resin (EA)"), (a1) an epoxy resin obtained by oxidative polymerization of an epoxidized monomer obtained by glycidyl-etherifying a phenolic compound other than a phenolic compound, and oxidizing a monomer having an epoxy group other than glycidyl ether. Examples thereof include epoxy resins obtained by polymerization.
Examples of glycidyl-etherified phenolic hydroxyl groups of a phenol resin obtained by oxidative polymerization of a phenol compound include (a1) glycidyl-etherified phenolic hydroxyl groups of a polyfunctional phenol compound obtained by oxidative polymerization of a phenol compound; and (a1) an epoxy resin obtained by glycidyl-etherifying the phenolic hydroxyl group of a polyfunctional phenolic compound obtained by oxidative polymerization of a phenolic compound other than the phenolic compound.
Among these, the oxidatively polymerized epoxy resin (EA) is preferable as the oxidatively polymerized epoxy resin from the viewpoint of further reducing the environmental load.
Next, the oxidatively polymerized epoxy resin (EA) will be described.

[Oxidative polymerization epoxy resin (EA)]
The oxidatively polymerized epoxy resin (EA) is an epoxy resin obtained by oxidatively polymerizing an epoxidized monomer (a1) obtained by glycidyl-etherifying a phenolic hydroxyl group of a phenol compound.
(a1) As a method for glycidyl-etherifying a phenolic hydroxyl group of a phenolic compound, a known method can be applied. For example, (a1) a method of reacting a phenolic compound with epihalohydrin in the presence of a basic compound. is mentioned.
The reaction is preferably carried out in an organic solvent from the viewpoint of homogeneous progress of the reaction. Examples of the organic solvent include the same organic solvents as those exemplified in (A) the method for producing a polyfunctional phenol compound, and preferred embodiments are also the same.

Epihalohydrin includes, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, and the like. Among these, epichlorohydrin is preferable from the viewpoint of reactivity. The amount of epihalohydrin to be used is not particularly limited, but is preferably 1 to 6 mol, more preferably 1.5 to 5 mol, still more preferably 2 to 4 mol, per 1 mol of phenolic hydroxyl group.

Preferred examples of basic compounds include alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, and the like. Among these, alkali metal hydroxides are preferable from the viewpoint of reactivity. As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide are preferred, and potassium hydroxide is more preferred.
The amount of the basic compound to be used is not particularly limited, but is preferably 1.2 to 5 mol, more preferably 1.5 to 4 mol, still more preferably 1.8 to 3 mol, per 1 mol of epihalohydrin. .

(a1) It is preferable to allow the phenol compound and the basic compound to react before starting the reaction of the phenol compound and epihalohydrin. The reaction conditions are not particularly limited, and for example, the reaction may be carried out at 15 to 40° C. for 0.5 to 4 hours.
(a1) The reaction conditions of the phenol compound and epihalohydrin are not particularly limited, and the reaction may be carried out at 15 to 40° C. for 1 to 8 hours, for example.
The obtained reaction product may be purified by known methods such as distillation, reprecipitation, centrifugation, and washing, if necessary.

The method and conditions for oxidative polymerization of the resulting epoxidized monomer are the same as the oxidative polymerization in (A) the method for producing a polyfunctional phenol compound, and the preferred aspects thereof are also the same.

Although the mass average molecular weight (Mw) of the oxidatively polymerized epoxy resin (EA) is not particularly limited, it is preferably 6,000 to 300,000, more preferably 12,000 to 100,000, still more preferably 12,000 to 100,000, from the viewpoint of handleability. is between 18,000 and 30,000.

The oxidatively polymerized epoxy resin (EA) may be liquid or solid at 23°C, but is preferably liquid at 23°C from the viewpoint of ease of handling.

Although the mass ratio [(B) epoxy resin/(A) polyfunctional phenol compound] of (B) epoxy resin and (A) polyfunctional phenol compound in the thermosetting resin composition of the present embodiment is not particularly limited, , preferably 0.7 to 1.5, more preferably 0.8 to 1.3, still more preferably 0.9 to 1.2, from the viewpoint of suppressing characteristic fluctuations due to residual unreacted functional groups. .

The thermosetting resin composition of the present embodiment may contain a phenol-based curing agent other than (A) the polyfunctional phenol compound as (B) the epoxy resin curing agent. In that case, the blending ratio of the (B) epoxy resin and the phenol-based curing agent is the mass ratio of (B) the epoxy resin and (A) all the phenol-based curing agents containing the polyfunctional phenol compound [epoxy group/phenol functional hydroxyl group] is preferably within the above range.

<(C) Curing accelerator>
(C) Curing accelerators include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine and the like organic phosphines; phosphonium salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, tributyl(methyl)phosphonium dimethylphosphate; and the like.
(C) A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
Among these, phosphonium salts are preferred from the viewpoint of compatibility and reactivity, and tributyl(methyl)phosphonium dimethyl phosphate is more preferred.

The content of the (C) curing accelerator in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoint of storage stability and curability, (B) per 100 parts by mass of the epoxy resin, It is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and still more preferably 0.7 to 3 parts by mass.

<Other ingredients>
In addition to the above components, the thermosetting resin composition of the present embodiment includes, for example, resin components such as thermosetting resins and thermoplastic resins other than the above components; fillers such as inorganic fillers and organic fillers a coupling agent such as a silane coupling agent; a flame retardant; a thickener; a coloring agent; an antioxidant;
Each of these other components may be used alone or in combination of two or more.

The total content of components (A), (B) and (C) in the thermosetting resin composition of the present embodiment is not particularly limited, but the solid content of the thermosetting resin composition of the present embodiment It is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, still more preferably 50 to 100% by mass relative to the total amount (100% by mass).

<Method for producing thermosetting resin composition>
The thermosetting resin composition of this embodiment can be produced by mixing the components described above.
Mixing of each component may be, for example, a method of melt-kneading each component under heating using a heating kneader, a heating roll, etc., or a method of dissolving or dispersing each component in an organic solvent and mixing. may Examples of the organic solvent include the same organic solvents as exemplified in (A) the method for producing a polyfunctional phenol compound. When performing a method of dissolving or dispersing each component in an organic solvent and mixing, the amount of the organic solvent used is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and more preferably 20 to 60% by mass. The amount is preferably 30 to 50% by mass.
Conditions such as the order of mixing raw materials, mixing temperature, and mixing time are not particularly limited, and may be arbitrarily set according to the type of raw materials.
The form of the thermosetting resin composition of the present embodiment at 23° C. is not particularly limited, and may be solid or liquid. When the thermosetting resin composition of the present embodiment is liquid at 23° C., the thermosetting resin composition of the present embodiment may contain an organic solvent, or does not contain an organic solvent. may be
As the organic solvent, the same one as that used in the method of dissolving or dispersing and mixing the above components can be used, and the suitable usage amount is also the same.

The curing conditions of the thermosetting resin composition of the present embodiment are not particularly limited, and may be appropriately adjusted according to the types of components (A) to (C). .5 to 24 hours.

<Storage elastic modulus E' (23°C) of cured product at 23°C>
The cured product of the thermosetting resin composition of the present embodiment has a storage elastic modulus E' (23°C) at 23°C of 20 to 2,500 MPa, preferably 24 to 2,000 MPa, from the viewpoint of conductor adhesion. , more preferably 27 to 1,500 MPa, still more preferably 30 to 1,200 MPa.
The storage elastic modulus E' (23°C) of the cured product can be measured by the method described in Examples.

<Storage elastic modulus E' at glass transition temperature +50°C of cured product (Tg + 50°C)>
The cured product of the thermosetting resin composition of the present embodiment has a storage elastic modulus E' (Tg + 50 ° C.) at a glass transition temperature + 50 ° C., from the viewpoint of conductor adhesion and heat resistance, preferably 3 to 2,000 MPa, more It is preferably 5 to 1,500 MPa, more preferably 10 to 1,000 MPa, particularly preferably 15 to 500 MPa.
The storage elastic modulus E′ (Tg+50° C.) of the cured product can be measured by the method described in Examples.

<Ratio of storage elastic modulus E′ of cured product [E′ (23° C.)/E′ (Tg+50° C.)]>
Ratio of storage elastic modulus E ' (23 ° C.) to storage elastic modulus E ' (Tg + 50 ° C.) at the glass transition temperature + 50 ° C. of the cured product of the thermosetting resin composition of the present embodiment [E ' (23 ° C.) /E' (Tg + 50 ° C.)] is 1 to 50, preferably 1.2 to 20, more preferably 1.4 to 10, more preferably 1.5 to 1.5 from the viewpoint of conductor adhesion and heat resistance. 5.
The ratio [E'(23°C)/E'(Tg+50°C)] of the storage elastic modulus E' of the cured product can be measured by the method described in Examples.

The storage elastic modulus E′ (23° C.) of the cured product at 23° C., the storage elastic modulus E′ (Tg+50° C.) and the ratio [E′ (23° C.)/E′ (Tg+50° C.)] are, for example, (A) multi The number of carbon atoms in (a1) the phenol compound and (a2) unsaturated aliphatic hydrocarbon, the number of aliphatic unsaturated bonds, and the compounding ratio of these raw materials, which are raw materials of the functional phenol compound, can be adjusted.

<Glass transition temperature of cured product>
The glass transition temperature of the cured product of the thermosetting resin composition of the present embodiment is preferably 5 to 60°C, more preferably 10 to 50°C, and still more preferably 15 to 40°C from the viewpoint of conductor adhesion. be.
The glass transition temperature of the cured product can be measured by the method described in Examples.

<Breaking elongation of cured product>
The breaking elongation of the cured product of the thermosetting resin composition of the present embodiment is preferably 5 to 300%, more preferably 15 to 200%, and still more preferably 30 to 130% from the viewpoint of conductor adhesion. .
The breaking elongation of the cured product can be measured by the method described in Examples.

<Biomass degree of cured product>
The biomass degree of the cured product of the thermosetting resin composition of the present embodiment is preferably 20 to 98%, more preferably 30 to 96%, and still more preferably 40%, from the viewpoint of reducing environmental load and ease of production. ~94%.
The biomass degree of the cured product can be calculated by the method described in Examples.

<Application of thermosetting resin composition>
The field of application of the thermosetting resin composition of the present embodiment is not particularly limited, but the cured product of the thermosetting resin composition of the present embodiment has excellent conductor adhesion, so it can be Suitable for substrate applications. In addition, the cured product of the thermosetting resin composition of the present embodiment has excellent conductor adhesiveness, flexibility, breaking elongation and stress relaxation rate, so it is particularly suitable for flexible printed circuits (FPC). etc.

The present invention will be specifically described by the following examples, but the present invention is not limited to the following examples.

[Number average molecular weight (Mn), mass average molecular weight (Mw)]
The number average molecular weight (Mn) and mass average molecular weight (Mw) of the product are measured using a gel permeation chromatograph (manufactured by Tosoh Corporation, product name "HLC-8020") under the following conditions, and converted to standard polystyrene. Measured at
(Measurement condition)
・ Column: “TSK guard column SuperH-H”, “TSK gel SuperHM-H”, “TSK gel SuperHM-H”, “TSK gel SuperH2000” (both manufactured by Tosoh Corporation) are sequentially connected ・Column temperature: 40 ° C.
・Developing solvent: Tetrahydrofuran ・Injection volume: 20 μl
・Flow rate: 1.0 mL/min
・Detector: Differential refractometer

[ ¹ H-NMR measurement]
¹ H-NMR measurements in the analysis of starting materials and products were carried out under the following conditions.
Apparatus: manufactured by Bruker Biospin, trade name "AV-500"
¹ H-NMR resonance frequency: 500 MHz
Probe: 5 mmφ solution probe Deuterated solvent: Deuterated acetone Internal standard substance: TMS (tetramethylsilane)
Sample amount: 20-50mg
Measurement temperature: 25°C
Number of times of integration: 16 times <Method for preparing sample for ¹ H-NMR measurement>
A ¹ H-NMR measurement sample was prepared by dissolving a measurement sample in deuterated acetone containing TMS as an internal standard so that the concentration of the measurement sample was 3% by mass.

[Aliphatic Unsaturated Bond Disappearance Rate by Oxidative Polymerization]
The rate of disappearance of aliphatic unsaturation due to oxidative polymerization is determined by the total mole number (M _A1 ) of aliphatic unsaturated bonds contained in the raw material components, calculated by ¹ H-NMR, and the aliphatic unsaturation contained in the product. It was calculated by the following formula (1) from the total number of moles of binding (M _A2 ).
Aliphatic unsaturated bond disappearance rate (%) = 100 × (M _A1 -M _A2 )/M _A1 (1)

Production example 1
(Production of oxidized copolymer CNSL1)
As the plant-derived (a1) phenol compound, CNSL containing 95% by mass of cardanol and 5% by mass of cardol (hereinafter also referred to as “raw material CNSL”) was prepared. The composition of cardanol determined by ¹ H-NMR is shown in Table 1.

A total of 100 parts by mass of the above raw material CNSL at a blending ratio of 90 mol% and 10 mol% of squalene as the unsaturated aliphatic hydrocarbon (a2) was put into a glass reaction vessel and mixed. was used as the reaction solution. Then, while bubbling air into the reaction solution, the reaction solution was subjected to oxidative polymerization by bulk polymerization for 48 hours while stirring at 160° C. to obtain a reaction product before purification.
Next, the obtained reactant before purification was diluted with 300 parts by mass of acetone, and reprecipitated by dropping into 2,000 parts by mass of methanol under stirring at 23° C. at a rate of 20 parts by mass/minute. The resulting precipitate was washed with methanol three times and then dried in an evaporator at 40°C for 120 minutes to obtain (A) polyfunctional phenol compound oxidative copolymer CNSL1 that was solid at 23°C. .
The oxidized copolymer CNSL1 obtained above had a number average molecular weight (Mn) of 3,400 and a weight average molecular weight (Mw) of 32,600. Moreover, the aliphatic unsaturated bond disappearance rate by oxidative polymerization was 41%.

Production example 2
(Production of oxidized copolymer CNSL2)
Solid oxidative copolymer CNSL2 was obtained at 23°C in the same manner as in Example 1, except that the blending ratio of raw material CNSL was changed to 50 mol% and the blending ratio of squalene was changed to 50 mol%. rice field.
The oxidized copolymer CNSL2 obtained above had a number average molecular weight (Mn) of 5,000 and a weight average molecular weight (Mw) of 37,100. Moreover, the aliphatic unsaturated bond disappearance rate by oxidative polymerization was 55%.

As described above, (A) the polyfunctional phenol compound was a solid compound at 23°C.
Moreover, the rate of disappearance of aliphatic unsaturated bonds suggests that the aliphatic unsaturated bonds of the raw material CNSL and squalene are undergoing polymerization.

Production example 3
(Production of oxidative polymerization epoxidized CNSL)
100 parts by mass of the raw material CNSL, 44 parts by mass of potassium hydroxide and 55 parts by mass of dimethyl sulfoxide were charged into a glass reaction vessel and reacted for 120 minutes with stirring at 23 ° C., followed by 92.5 parts of epichlorohydrin. A part by mass was put into a reaction vessel and reacted for 240 minutes. After that, it was extracted three times with 500 parts by mass of hexane, and then washed three times with 500 parts by mass of saturated brine. Then, it was filtered through silica gel to obtain a liquid epoxidized monomer obtained by glycidyl-etherifying the phenolic hydroxyl groups contained in the raw material CNSL.
Next, the liquid epoxidized monomer obtained by the above reaction is used as a reaction solution for oxidative polymerization, and is oxidized by a bulk polymerization method for 24 hours with stirring at a temperature of 160° C. while bubbling air into the reaction solution. Polymerization was performed to obtain a reaction product before purification.
Next, the obtained reaction product before purification was diluted with 300 parts by mass of acetone, and reprecipitated by dropping into 2,000 parts by mass of methanol under stirring at 23° C. at a rate of 20 parts by mass/minute. The resulting precipitate was washed with methanol three times and then dried in an evaporator at 40°C for 120 minutes to obtain oxidatively polymerized epoxidized CNSL, which is an oxidatively polymerized epoxy resin (EA) liquid at 23°C. rice field.
The weight average molecular weight (Mw) of the oxidatively polymerized epoxidized CNSL was 22,000.

Examples 1 to 3, Comparative Example 1
(Manufacture of thermosetting resin composition)
A polyfunctional phenol compound shown in Table 2, (B) epoxy resin and (C) tributyl (methyl) phosphonium dimethyl phosphate as a curing accelerator, and toluene as an organic solvent are blended to give a solid content concentration of 40 mass. % of the thermosetting resin composition was prepared.
The compounding ratio of the polyfunctional phenol compound and the (B) epoxy resin is such that the mass ratio of the (B) epoxy resin to the polyfunctional phenol compound [(B) epoxy resin/polyfunctional phenol compound] is 1.0. ratio. The amount of the curing accelerator (C) to be blended was such that the content of the curing accelerator (C) was 1 part by mass with respect to 100 parts by mass of the epoxy resin (B).

Details of the materials used in Comparative Example 1 are as follows.
・Bisphenol type epoxy resin: 2,2-bis(4-glycidyloxyphenyl)propane ・Cresol novolac resin: manufactured by DIC Corporation, trade name “KA-1160”

(Production of cured product of thermosetting resin composition)
The solution of the thermosetting resin composition obtained above is applied to the process film 1 (manufactured by Lintec Corporation, product name “SP-PET382150”, polyethylene terephthalate film coated with silicone release agent, thickness 38 μm). On the treated surface, apply so that the thickness of the cured product obtained after drying and curing is 70 μm, dry at 80 ° C. for 3 minutes, process film 2 (manufactured by Lintec Corporation, product name “SP-PET381031” , and a polyethylene terephthalate film coated with a silicone-based release agent (thickness: 38 μm). Then, it was cured at 150° C. for 2 hours to obtain a cured product of the thermosetting resin composition sandwiched between two process films.

Comparative example 2
As a comparative adhesive, a general-purpose adhesive "Super X Hyper Wide" manufactured by Cemedine Co., Ltd. was prepared.

[Measurement of glass transition temperature and storage elastic modulus E′ of cured product]
Two process films were peeled off from the cured product obtained in each example, and a test piece was cut into a size of 5 mm×20 mm. This test piece was attached to a thermomechanical analyzer (manufactured by NETZSCH, trade name "DMA242E") at a distance between chucks of 15 mm, and while applying strain at a frequency of 10 Hz, the temperature was increased from -100 ° C. to 200 ° C. at a rate of 5 ° C./min. The temperature was raised to ° C., and the storage elastic modulus E' and tan δ were measured.
The temperature showing the peak of tan δ in the above measurement range is the glass transition temperature (Tg), the storage elastic modulus E' at 23 ° C. (23 ° C.), and the storage elastic modulus E' at a temperature 50 ° C. lower than Tg (Tg-50 ° C.) , and the storage modulus E′ (Tg+50° C.) at a temperature 50° C. higher than Tg. Table 2 shows the measurement results.

[Biomass degree of cured product]
The degree of biomass of the cured product is the mass ratio of the biomass-derived raw material used when producing the cured product to the total mass of the cured product, and was calculated by the following formula. Table 2 shows the measurement results.
Biomass degree of cured product (% by mass) = 100 × [mass of biomass-derived raw material (g)] / [total mass of cured product (g)]

[Measurement of stress relaxation rate of cured product]
The process film was peeled off from the cured product obtained in each example, and a test piece was cut into a size of 10 mm×70 mm. This test piece was attached to a tensile tester (manufactured by Shimadzu Corporation, trade name "Autograph AG-Xplus") at a distance between chucks of 50 mm, and the stress F when stretched 10% at 23 ° C. and a tensile speed of 200 mm / min. ₁ (N/m ² ) and stress F ₂ (N/m ² ) 100 seconds after the extension was stopped, the stress relaxation rate was obtained from the following equation. Table 2 shows the measurement results. However, since the cured product of Comparative Example 1 could not be stretched under the above conditions, the stress relaxation rate could not be measured.
Stress relaxation rate (%) = (F ₁ - F ₂ )/F ₁ × 100 (%)

[Measurement of breaking elongation of cured product]
The process film was peeled off from the cured product obtained in each example, and a test piece was cut into a size of 10 mm×70 mm. This test piece was attached to a tensile tester (manufactured by Shimadzu Corporation, trade name "Autograph AG-Xplus") at a distance between chucks of 50 mm, and the elongation at break was measured under the conditions of 23 ° C. and a tensile speed of 200 mm / min. degree was measured. Table 2 shows the measurement results.

[Measurement of copper foil peel strength of cured product]
(1) Evaluation sample preparation method of Examples 1 to 3 The solution of the thermosetting resin composition obtained in each example was applied to process film 1 (manufactured by Lintec Corporation, product name “SP-PET382150”, polyethylene terephthalate film with silicone Coated with a release agent, thickness 38 μm), coated so that the thickness of the cured product obtained after drying and curing is 70 μm, dried at 80 ° C. for 3 minutes, and then processed film 2 (manufactured by Lintec Corporation, product name “SP-PET381031”, polyethylene terephthalate film coated with a silicone release agent, thickness 38 μm) was laminated to obtain a sheet for peel strength measurement.
The process film 2 was removed from the resulting sheet, and it was laminated to a copper plate (manufactured by Yukou Co., Ltd., product name “C1220P”, thickness 400 μm), and a laminating device (manufactured by Nikko Materials Co., Ltd. “V-130”). , ultimate pressure: 2.0 hPa, temperature of 100° C., pressure of 0.5 MPa, pressure bonding time of 30 seconds).
After that, the process film 1 is removed, and a copper foil (manufactured by Yukou Shokai Co., Ltd., product name “C1100P”, size: long side 50 mm × short side 10 mm × thickness 150 μm) is used as a grip part of the chuck. 10 mm of the long side was left as a non-adhered region, and cured at 150° C. for 2 hours to obtain an evaluation sample for copper foil peel strength measurement.

(2) Evaluation sample preparation method of Comparative Example 1 The solution of the thermosetting resin composition of Comparative Example 1 was subjected to removal of the organic solvent by an evaporator, and a copper foil (manufactured by Yuko Co., Ltd., product name “C1100P”, Size: long side 50 mm x short side 10 mm x thickness 150 μm), leaving a long side 10 mm as a region where the copper foil that will be the grip part of the chuck is not adhered, and the thickness after curing is 70 μm. was applied to The area of the copper foil coated with the thermosetting resin composition is attached to a copper plate (manufactured by Yukou Shokai, product name “C1220P”, thickness 400 μm), and the copper foil is cured at 150 ° C. for 2 hours. It was used as an evaluation sample for peel strength measurement.

(3) Evaluation sample preparation method of Comparative Example 2 The adhesive for comparison of Comparative Example 2 was coated with a copper foil (manufactured by Yuko Shokai Co., Ltd., product name “C1100P”, size: long side 50 mm × short side 10 mm × thickness 150 μm ), leaving a long side of 10 mm as a non-adhered area of the copper foil that will be the gripping portion of the chuck. After that, the area of the copper foil coated with the adhesive for comparison is attached to a copper plate (manufactured by Yukou Shokai, product name “C1220P”, thickness 400 μm), and the copper foil is cured at 23 ° C. for 24 hours. It was used as an evaluation sample for peel strength measurement.

(4) Measurement method of copper foil peel strength The evaluation sample prepared above was attached to a tensile tester (manufactured by Shimadzu Corporation, trade name “Autograph AG-Xplus”), and the area where the copper foil was not adhered was measured. The peel strength of the copper foil was measured by holding it with a gripper and peeling it off in a 90° direction at a peeling speed of 50 mm/min. Table 2 shows the measurement results.

From Table 2, it can be seen that the thermosetting resin compositions of Examples 1 to 3 of the present embodiment have excellent copper foil peel strength. On the other hand, Comparative Example 1 using a polyfunctional phenol compound other than component (A) and Comparative Example 2 using a general-purpose adhesive had low copper foil peel strength.

Claims

(A) a polyfunctional phenol compound obtained by copolymerizing (a1) a phenol compound having an unsaturated aliphatic hydrocarbon group and (a2) an unsaturated aliphatic hydrocarbon by oxidative polymerization;
(B) an epoxy resin;
(C) a thermosetting resin composition containing a curing accelerator,
The cured product of the thermosetting resin composition has a storage elastic modulus E' (23°C) at 23°C of 20 to 2,500 MPa,
The ratio of the storage elastic modulus E ' (23 ° C.) to the storage elastic modulus E ' (Tg + 50 ° C.) at the glass transition temperature + 50 ° C. of the cured product of the thermosetting resin composition [E ' (23 ° C.) / E '(Tg+50°C)] is 1 to 50, a thermosetting resin composition.
The thermosetting resin according to claim 1, wherein the (a1) phenolic compound having an unsaturated aliphatic hydrocarbon group is one or more selected from compounds represented by the following general formula (A-1): Composition.

(wherein R is an unsaturated aliphatic hydrocarbon group containing 1 to 3 aliphatic unsaturated bonds, X 1 is a hydrogen atom or a hydroxy group, and X 2 is a hydrogen atom or a 5 is an alkyl group, and X 3 is a hydrogen atom, a hydroxy group or a carboxy group.)
The (a1) phenol compound having an unsaturated aliphatic hydrocarbon group contains 90% by mass or more of a compound in which X 1 , X 2 and X 3 are all hydrogen atoms in the general formula (A-1). The thermosetting resin composition according to claim 2, wherein
The thermosetting resin according to any one of claims 1 to 3, wherein the (a1) phenolic compound having an unsaturated aliphatic hydrocarbon group has an unsaturated aliphatic hydrocarbon group having 8 to 30 carbon atoms. Composition.
The thermosetting resin composition according to any one of claims 1 to 3, wherein (a2) the unsaturated aliphatic hydrocarbon has 10 to 40 carbon atoms.
The thermosetting resin composition according to any one of claims 1 to 3, wherein the (a2) unsaturated aliphatic hydrocarbon contains 3 to 9 aliphatic unsaturated bonds.
The thermosetting resin composition according to any one of claims 1 to 3, wherein the (a2) unsaturated aliphatic hydrocarbon is squalene.
The thermosetting resin composition according to any one of claims 1 to 3, wherein the (a1) phenolic compound having an unsaturated aliphatic hydrocarbon group is a biomass-derived compound.
The thermosetting resin composition according to any one of claims 1 to 3, wherein the (a2) unsaturated aliphatic hydrocarbon is a biomass-derived compound.
The thermosetting resin composition according to any one of claims 1 to 3, wherein the weight average molecular weight (Mw) of component (A) is 8,000 to 200,000.
When performing the oxidative polymerization, the blending amount (W A ) of the (a1) phenol compound having an unsaturated aliphatic hydrocarbon group and the blending amount (W B ) of the (a2) unsaturated aliphatic hydrocarbon The thermosetting resin composition according to any one of claims 1 to 3, wherein the ratio [W A /W B ] in terms of molar ratio is 0.1 to 20.
The thermosetting resin composition according to any one of claims 1 to 3, wherein the cured product has a glass transition temperature of 5 to 60°C.
The thermosetting resin composition according to any one of claims 1 to 3, wherein the cured product has a breaking elongation of 15 to 200%.