WO2023048164A1

WO2023048164A1 - Multifunctional phenolic compound and production method therefor

Info

Publication number: WO2023048164A1
Application number: PCT/JP2022/035111
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
Also published as: JPWO2023048164A1

Abstract

The present invention relates to: a multifunctional phenolic compound obtained by carrying out copolymerization, by means of oxidative polymerization, of a phenolic compound (A) that is derived from a plant and has a C15-17 unsaturated aliphatic hydrocarbon group, and a C10-40 unsaturated aliphatic hydrocarbon (B); and a production method for the multifunctional phenolic compound.

Description

Polyfunctional phenol compound and method for producing the same

The present invention relates to a polyfunctional phenol compound and a method for producing the same.

In recent years, due to concerns about global warming and depletion of fossil resources due to increased _CO2 emissions, there is a demand for effective use of non-edible biomass, which is a renewable resource and has a low environmental impact.
As a study to utilize non-edible biomass, for example, a study to use a plant-derived phenol compound as a raw material monomer for various resins is being conducted. Plant-derived phenolic compounds include, for example, vegetable oil extracted from cashew nut shells (hereinafter also referred to as "CNSL". CNSL is an abbreviation for Cashew Nut Shell Liquid), long-chain unsaturated compounds contained in lacquer, etc. A phenol compound having an aliphatic hydrocarbon group can be mentioned. In particular, a large amount of cashew nut shells are discarded as cashew nut by-products, and the establishment of a technology for effectively using them will greatly contribute to reducing the environmental load.

For example, Patent Document 1 discloses a polymer of a CNSL-derived allylcardanol (A) and a thiol compound (B) as a polymer whose dynamic viscoelasticity changes over time is suppressed, and has a disulfide bond. The ratio ^of the peak intensity [I (530)] at a Raman shift of 530 ^cm to the peak intensity [I (1450)] at a Raman shift of 1450 cm when irradiated with a laser beam of 532 nm [I (530) / I (1450)] is greater than or equal to 0.10.

JP 2021-011541 A

Resins synthesized from plant-derived phenol compounds (hereinafter also referred to as “plant-derived resins”) are being investigated for industrial use as, for example, adhesives, paints, various additives, and the like.
However, conventional plant-derived resins cannot be said to be applicable to a wide range of fields due to restrictions on production methods, molecular structures, physical properties, and the like. In order to meet the demand for the reduction of environmental load, which is expected to increase more and more in the future, it is desirable to develop a wide variety of plant-derived resins and apply them to a wide range of applications.

The present invention has been made in view of the above problems, and aims to provide a polyfunctional phenol compound with low environmental load and a method for producing the same.

The present inventors have found that the above problems can be solved by a polyfunctional phenol compound obtained by copolymerizing a plant-derived phenol compound and a specific unsaturated aliphatic hydrocarbon by oxidative polymerization, and have completed the present invention. reached.

That is, the present invention relates to the following [1] to [12].
[1] Oxidative polymerization of a phenol compound (A) derived from a plant and having an unsaturated aliphatic hydrocarbon group having 15 to 17 carbon atoms and an unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B) A polyfunctional phenol compound obtained by copolymerizing with.
[2] The polyfunctional phenol compound according to [1] above, wherein the phenol compound (A) is one or more selected from compounds represented by the following general formula (A-1).

(In the formula, R is an unsaturated aliphatic hydrocarbon group having 15 to 17 carbon atoms 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 an alkyl group having 1 to 5 carbon atoms, and X ³ is a hydrogen atom, a hydroxy group, or a carboxy group.)
[3] The above [2], wherein the phenol compound (A) 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). Polyfunctional phenol compound according to.
[4] The polyfunctional phenol compound according to any one of [1] to [3] above, which has a weight average molecular weight (Mw) of 8,000 to 200,000.
[5] The polyfunctional phenol compound according to any one of [1] to [4] above, wherein the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B) is a biomass-derived compound.
[6] The polyfunctional phenol according to any one of [1] to [5] above, wherein the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B) contains 3 to 9 aliphatic unsaturated bonds. Compound.
[7] The polyfunctional phenol compound according to any one of [1] to [6] above, wherein the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B) is squalene.
[8] The blending amount (W _A ) of the phenol compound (A) and the blending amount (W B ) of the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms ( _B ) when performing the oxidation polymerization. The polyfunctional phenol compound according to any one of [1] to [7] above, wherein the ratio [W _A /W _B ] in terms of molar ratio is 0.1 to 20.
[9] The polyfunctional phenol compound according to any one of [1] to [8] above, which is used as a curing agent for thermosetting resins.
[10] The polyfunctional phenol compound according to [9] above, wherein the thermosetting resin is an epoxy resin.
[11] A method for producing a polyfunctional phenol compound according to any one of [1] to [10] above, which is derived from the plant and has an unsaturated aliphatic hydrocarbon group with 15 to 17 carbon atoms. A method for producing a polyfunctional phenol compound, comprising copolymerizing the phenol compound (A) and the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B) by oxidative polymerization.
[12] The above [11], wherein the oxidative polymerization is performed by heating the phenol compound (A) and the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B) while supplying a gas containing oxygen. ] The manufacturing method of the polyfunctional phenol compound as described in ].

According to the present invention, it is possible to provide a polyfunctional phenol compound with low environmental load and a method for producing the same.

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 "active ingredient" refers to an ingredient excluding dilution solvents such as water and organic solvents among the ingredients contained in the target composition.　

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

[Polyfunctional phenol compound]
The polyfunctional phenol compound of the present embodiment is a phenol compound (A) derived from a plant and having an unsaturated aliphatic hydrocarbon group with 15 to 17 carbon atoms (hereinafter also simply referred to as "phenol compound (A)"). , a polyfunctional phenol compound obtained by copolymerizing an unsaturated aliphatic hydrocarbon (B) having 10 to 40 carbon atoms (hereinafter also simply referred to as "unsaturated aliphatic hydrocarbon (B)") by oxidative polymerization. be.

The polyfunctional phenol compound of the present embodiment uses a plant-derived phenol compound (A) as a raw material monomer, so it is a material that enables effective use of non-edible biomass and has a low environmental impact.

(Phenolic compound (A))
The phenol compound (A) is a raw material monomer for the polyfunctional phenol compound of the present embodiment, is derived from a plant, and contains an unsaturated aliphatic hydrocarbon group having 15 to 17 carbon atoms (hereinafter referred to as "long-chain unsaturated aliphatic It is a phenol compound having a hydrocarbon group (R).
The polyfunctional phenol compound of the present embodiment has a high molecular weight due to the reaction of the long-chain unsaturated aliphatic hydrocarbon group (R) of the phenol compound (A). The reaction is presumed to occur, for example, by a known reaction mechanism proposed as a mechanism for oxidizing unsaturated fatty acids.

The phenolic compound (A) generally comprises one benzene ring, one or more phenolic hydroxyl groups directly bonded to the benzene ring, and one or more long-chain unsaturated aliphatic hydrocarbons directly bonded to the benzene ring. and a hydrogen group (R).

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

The number of long-chain unsaturated aliphatic hydrocarbon groups (R) possessed by the phenolic compound (A) is preferably 1 to 3, more preferably 1, from the viewpoint of ease of availability and suppression of gelation during oxidative polymerization. or two, more preferably one.
The number of carbon atoms in the long-chain unsaturated aliphatic hydrocarbon group (R) of the phenol compound (A) is preferably 15 or 16, more preferably 15, from the viewpoint of availability.
The number of aliphatic unsaturated bonds contained in the long-chain unsaturated aliphatic hydrocarbon group (R) of the phenol compound (A) is preferably 1 to 5, more preferably 1 to 5, from the viewpoint of availability. 4, more preferably 1 to 3.
The long-chain unsaturated aliphatic hydrocarbon group (R) of the phenol compound (A) may be linear or branched. is preferably
Examples of the long-chain unsaturated aliphatic hydrocarbon group (R) possessed by the phenol compound (A) include unsaturated aliphatic hydrocarbon groups represented by the following formulas (R-1) to (R-14). be done.

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

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

From the viewpoint of availability, the phenol compound (A) is preferably one or more selected from compounds represented by the following general formula (A-1).

(In the formula, R is an unsaturated aliphatic hydrocarbon group having 15 to 17 carbon atoms 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 an alkyl group having 1 to 5 carbon atoms, and X ³ is a hydrogen atom, a hydroxy group, or a carboxy group.)

The unsaturated aliphatic hydrocarbon group having 15 to 17 carbon atoms containing 1 to 3 aliphatic unsaturated bonds represented by R in the general formula (A-1) is the long-chain unsaturated aliphatic hydrocarbon group described above. Among the hydrogen groups (R), it corresponds to those containing 1 to 3 aliphatic unsaturated bonds. Therefore, the number of carbon atoms in the group, the number of aliphatic unsaturated bonds, and preferred embodiments of specific examples are as described above for the long-chain unsaturated aliphatic hydrocarbon group (R).

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.

From the viewpoint of availability, the phenol compound (A) 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).)

The content of the compound represented by the general formula (A-2) in the phenol compound (A) 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 the phenol compound (A) 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.

From the viewpoint of availability, the phenol compound (A) is a compound represented by the general formula (A-1) in which X ¹ is a hydroxy group and both X ² and X ³ are hydrogen atoms, that is, 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).)

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

Examples of the phenolic compound (A) include cardanol, cardol, 2-methylcardol, and anacardic acid, which are phenolic compounds contained in CNSL extracted from cashew nut shells; urushiol, which is a phenolic compound contained in lacquer. , thithiol and laccol; and those contained in plant-derived phenolic compounds. As the plant-derived phenol compound, cardanol, cardol, 2-methylcardol, and anacardic acid are preferable, cardanol and cardol are more preferable, and cardanol is more preferable, from the viewpoint of effective utilization of waste resources and easy availability. More preferred.

Cardanol is represented by the following formula (A-4), cardol is represented by the following formula (A-5), 2-methylcardol is represented by the following formula (A-6), and anacardic acid is represented by the following formula (A-7). It contains structure.

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 group, a compound having a group represented by formula (R-3) as R ¹ , and a compound containing a group represented by formula (RC) as R ¹ .
Cardanol, cardol, 2-methylcardol and anacardic acid each generally contain a compound having a group represented by the formula (R- ¹ ) as R1, although this varies depending on the purification conditions and the like. 25 to 40 mol%, the content of the compound having the group represented by formula (R-2) as R ¹ is 10 to 25 mol%, and the compound having the group represented by formula (R-3) as R ¹ is 40 to 60 mol %, and the content of the compound having a group represented by the formula (RC) as R ¹ is 1 to 5 mol %.

(Unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B))
The polyfunctional phenol compound of the present embodiment uses, in addition to the phenol compound (A) as raw material monomers, an unsaturated aliphatic hydrocarbon (B) having 10 to 40 carbon atoms, and these are copolymerized by oxidative polymerization. It is a thing. By copolymerizing the unsaturated aliphatic hydrocarbon (B), when the polyfunctional phenol compound of the present embodiment is applied to a thermosetting resin composition, the flexibility of the cured product, the breaking elongation, the stress relaxation rate , adhesive strength, etc. tend to improve.
The unsaturated aliphatic hydrocarbon (B) is preferably a biomass-derived compound from the viewpoint of reducing the burden on the environment.
One of the unsaturated aliphatic hydrocarbons (B) may be used alone, or two or more thereof may be used.

The number of carbon atoms in the unsaturated aliphatic hydrocarbon (B) improves the flexibility, breaking elongation, stress relaxation rate and adhesive strength of the cured product of the thermosetting resin composition to which the polyfunctional phenol compound of the present embodiment is applied. It is 10 to 40, preferably 15 to 37, more preferably 20 to 35, still more preferably 25 to 32, from the viewpoint of increasing the

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

The unsaturated aliphatic hydrocarbon (B) may be linear or may have a structure having a side chain, but preferably has a structure having a side chain.
Although the unsaturated aliphatic hydrocarbon (B) may have substituents other than aliphatic hydrocarbons, it preferably does not have substituents other than aliphatic hydrocarbons. That is, the unsaturated aliphatic hydrocarbon (B) is preferably a compound consisting only of carbon atoms and hydrogen atoms.

Examples of unsaturated aliphatic hydrocarbons (B) 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 phenolic compound (A) and unsaturated aliphatic hydrocarbon (B))
The ratio [W _A /W _B ] of the blending amount (W _A ) of the phenolic compound (A) and the blending amount (W _B ) of the unsaturated aliphatic hydrocarbon (B) when performing oxidative polymerization is particularly Although not limited, the viewpoint of improving the balance of mechanical strength, flexibility, elongation at break, stress relaxation rate, adhesive strength, etc. of the cured product of the thermosetting resin composition to which the polyfunctional phenol compound of the present embodiment is applied Therefore, the molar ratio is preferably 0.1 to 20, more preferably 0.3 to 15, still more preferably 0.7 to 12.

(Raw material monomers other than phenol compound (A) and unsaturated aliphatic hydrocarbon (B))
The polyfunctional phenol compound of the present embodiment oxidizes other raw material monomers other than the phenol compound (A) and the unsaturated aliphatic hydrocarbon (B) together with the phenol compound (A) and the unsaturated aliphatic hydrocarbon (B). It may be obtained by polymerization, or may be obtained by oxidative polymerization of only the phenol compound (A) and the unsaturated aliphatic hydrocarbon (B). When other raw material monomers are used, the other raw material monomers are preferably biomass-derived compounds from the viewpoint of reducing environmental load.
In the total amount of raw material monomers for the polyfunctional phenol compound of the present embodiment, the total content of the phenol compound (A) and the unsaturated aliphatic hydrocarbon (B) is preferably 90 to 100 mass%, more preferably 92 to 100. % by mass, more preferably 95 to 100% by mass.
In the raw material excluding oxygen of the polyfunctional phenol compound of the present embodiment, the content of the biomass-derived raw material is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and still more preferably 98 to 100% by mass. be.

(Properties of polyfunctional phenol compound)
The polyfunctional phenol compound of the present embodiment is preferably solid at 23°C or has a viscosity of more than 50,000 mPa·s at 23°C.
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.

Because the polyfunctional phenol compound of the present embodiment is solid at 23 ° C., for example, when the polyfunctional phenol compound of the present embodiment is used as a main agent or curing agent of a thermosetting resin composition, it is solid at room temperature. A thermoset resin composition 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, since the polyfunctional phenol compound of the present embodiment has a viscosity of more than 50,000 mPa s at 23° C., for example, the polyfunctional phenol compound of the present embodiment is used as the main agent or curing agent of the thermosetting resin composition. can form a highly viscous thermosetting resin composition at room temperature. Thermosetting resin compositions with high viscosity at room temperature are useful for high-viscosity adhesives and the like that require suppression of dripping and the like. Moreover, the highly viscous polyfunctional phenol compound can also be used as a reactive thickener or the like.
The viscosity of the polyfunctional phenol compound at 23°C can be measured according to JIS Z 8803 (2011).

As described above, the polyfunctional phenol compound of the present embodiment 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. From the viewpoint of being possible and being effective in reducing the environmental load, it is preferably solid at 23°C.
On the other hand, when the polyfunctional phenol compound of the present embodiment has a viscosity of more than 50,000 mPa s at 23°C, the viscosity of the polyfunctional phenol compound of the present embodiment at 23°C is the same as that of the polyfunctional phenol compound of the present embodiment. From the viewpoint of enhancing the thickening effect of the viscosity, 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 the polyfunctional phenol compound of the present embodiment is not particularly limited, but may be, for example, 300,000 mPa·s or less, or 200,000 mPa·s or less.

(Number average molecular weight (Mn) of polyfunctional phenol compound)
The number average molecular weight (Mn) of the polyfunctional phenol compound of the present embodiment is not particularly limited, but from the viewpoint of handleability, preferably 2,000 to 10,000, more preferably 2,500 to 8,000, and further It is preferably 3,000 to 6,000.

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

(Application of polyfunctional phenol compound)
The polyfunctional phenol compound of the present embodiment is useful, for example, as a main agent of a thermosetting resin composition, a curing agent for a thermosetting resin, an additive for modifying the physical properties of a thermosetting resin composition, or the like. .
When using a polyfunctional phenol compound as a curing agent for a thermosetting resin, the thermosetting resin is preferably an epoxy resin.
The application field of the thermosetting resin composition using the polyfunctional phenol compound of the present embodiment is not particularly limited, but examples thereof include adhesives, electrical insulating materials, paints, civil engineering/building materials, and the like.
In particular, the cured product of the thermosetting resin composition using the polyfunctional phenol compound of the present embodiment is excellent in flexibility, elongation at break, stress relaxation rate and adhesive strength. It is suitable as a flexible adhesive for adhesion between bodies, adhesion of adherends to which stress is generated by thermal expansion and thermal contraction, and adhesion of adherends to which stress such as vibration and impact is likely to be applied.

[Method for producing polyfunctional phenol compound]
Next, a method for producing the polyfunctional phenol compound of the present embodiment will be described.
The method for producing a polyfunctional phenol compound of the present embodiment is a method for producing a polyfunctional phenol compound by copolymerizing a phenol compound (A) and an unsaturated aliphatic hydrocarbon (B) by oxidative polymerization.

As a method of oxidative polymerization, a method of heating raw material monomers containing a phenol compound (A) and an unsaturated aliphatic hydrocarbon (B) in the presence of an oxidizing agent while stirring is preferred.
The method of oxidative polymerization of the phenolic compound (A) and the unsaturated aliphatic hydrocarbon (B) may be, for example, a bulk polymerization method or a solution polymerization method, depending on the state of these raw materials. .
The phenolic compound (A) and the unsaturated aliphatic hydrocarbon (B) are usually liquid at the reaction temperature, and tend to be able to maintain good stirring efficiency even when the oxidative 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, 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, the method for producing a polyfunctional phenol compound of the present embodiment is a method of performing oxidative polymerization by heating a phenol compound (A) and an unsaturated aliphatic hydrocarbon (B) while supplying a gas containing oxygen. is 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 to 210° C., from the viewpoint of facilitating adjustment of the properties of the polyfunctional phenol compound while obtaining an appropriate reaction rate. , more preferably 140 to 180°C.
The reaction time of oxidative polymerization is not particularly limited, and the time for obtaining a polyfunctional phenol compound having desired properties may be appropriately determined. From the viewpoint of productivity, it is preferably 20 to 72 hours, more preferably 20 to 72 hours. 30 to 60 hours, more preferably 36 to 54 hours.

In the production method of the present embodiment, of the total amount of aliphatic unsaturated bonds contained in the phenol compound (A) and the unsaturated aliphatic hydrocarbon (B) 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.

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

[Thermosetting resin composition]
The present invention can also provide a thermosetting resin composition using the polyfunctional phenol compound of the present embodiment as a curing agent for epoxy resin.
A thermosetting resin composition containing an epoxy resin and the polyfunctional phenol compound of the present embodiment will be described below.

(Epoxy resin)
Examples of epoxy resins include 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 resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin; epoxy resins having a cyclopentadiene skeleton; epoxy resins having a biphenol skeleton; epoxy resins having an aralkyl skeleton; epoxy resins having a fluorene skeleton; glycidyl ether type epoxy resins such as epoxy resins having a naphthalene skeleton; Ester type epoxy resin; 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epsilon-caprolactone-modified-3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, bis- alicyclic epoxy resins such as (3,4-epoxycyclohexyl) adipate;
Epoxy resins may be used alone or in combination of two or more.

For example, the epoxy resin may be appropriately selected from the above options according to the purpose, but from the viewpoint of reducing the environmental load, biomass-derived epoxy resins are preferable, and plant-derived epoxy resins are more preferable.

Moreover, 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.
As the epoxy resin obtained by oxidative polymerization of a monomer having an epoxy group, for example, an epoxy resin obtained by oxidative polymerization of an epoxidized monomer obtained by glycidyl-etherifying the phenolic hydroxyl group of the phenol compound (A) (hereinafter referred to as "oxidation Polymerized epoxy resin (EA)"), an epoxy resin obtained by oxidative polymerization of an epoxidized monomer obtained by glycidyl-etherifying a phenolic compound other than the phenolic compound (A), and an oxidized 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 phenolic resin obtained by oxidative polymerization of a phenol compound include, for example, glycidyl-etherified phenolic hydroxyl groups of a polyfunctional phenol compound obtained by oxidative polymerization of the phenol compound (A). epoxy resin, and an epoxy resin obtained by glycidyl-etherifying the phenolic hydroxyl group of a polyfunctional phenol compound obtained by oxidative polymerization of a phenol compound other than the phenol compound (A).
Examples of phenolic compounds other than the phenolic compound (A) that can be used in oxidation polymerization include phenolic compounds having an unsaturated aliphatic hydrocarbon group other than the long-chain unsaturated aliphatic hydrocarbon group (R).
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 obtained by glycidyl-etherifying the phenolic hydroxyl group of the phenol compound (A).
As a method for glycidyl-etherifying the phenolic hydroxyl group of the phenolic compound (A), a known method can be applied, for example, a method of reacting the phenolic compound (A) 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 exemplified in 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. .

It is preferable to react the phenol compound (A) with a basic compound before starting the reaction between the phenol compound (A) 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.
The reaction conditions of the phenol compound (A) 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 the method for producing a polyfunctional phenol compound of the present embodiment, 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.

(Polyfunctional phenol compound)
In the thermosetting resin composition of the present embodiment, the polyfunctional phenol compound of the present embodiment is used as a curing agent for epoxy resin.
Polyfunctional phenol compounds may be used alone or in combination of two or more.

Although the mass ratio [epoxy resin/polyfunctional phenol compound] of the epoxy resin and the polyfunctional phenol compound in the thermosetting resin composition of the present embodiment is not particularly limited, it suppresses characteristic fluctuations due to residual unreacted functional groups. From the point of view that it is to

The thermosetting resin composition of the present embodiment may contain a phenol-based curing agent other than the polyfunctional phenol compound of the present embodiment as a curing agent for the epoxy resin. In that case, the compounding ratio of the epoxy resin and the phenolic curing agent is such that the mass ratio [epoxy group/phenolic hydroxyl group] of the epoxy resin and all the phenolic curing agents including the polyfunctional phenolic compound of the present embodiment is It is preferable to fall within the above range.

(Curing accelerator)
The thermosetting resin composition of the present embodiment preferably further contains a curing accelerator.
Curing accelerators include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl -imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine phosphonium salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, and tributyl(methyl)phosphonium dimethylphosphate; and the like.
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 curing accelerator in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoint of storage stability and curability, it is preferably 0.1 to 0.1 parts per 100 parts by mass of the epoxy resin. 10 parts by mass, more preferably 0.5 to 5 parts by mass, 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.

(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 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 such that the concentration of the active ingredient is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and further 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 type of resin and curing accelerator. It can be a 24 hour condition.

The application field of the thermosetting resin composition of the present embodiment will be explained in the same manner as the application field of the polyfunctional phenol compound of the present embodiment described above.

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 of polyfunctional phenol compound]
Example 1
(Production of oxidized copolymer CNSL1)
As a plant-derived phenolic compound (A), 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 raw materials CNSL and 10 mol% of squalene were put into a glass reaction vessel and mixed to obtain a 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 oxidized copolymer CNSL1, which is a polyfunctional phenol compound 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%.

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%.

Reference example 1
(Production of oxidative polymerization CNSL)
100 parts by mass of raw material CNSL and 200 parts by mass of dimethyl sulfoxide were put into a reaction vessel made of glass and mixed to obtain a reaction solution. Then, while bubbling air into the reaction liquid, the reaction liquid was oxidatively polymerized by a solution polymerization method for 24 hours while stirring at 160° C. to obtain a reaction product before purification. Thereafter, reprecipitation, washing and drying were carried out in the same manner as in Example 1 to obtain a solid oxidatively polymerized CNSL at 23°C.
The oxidatively polymerized CNSL obtained above had a number average molecular weight (Mn) of 5,300 and a weight average molecular weight (Mw) of 46,200. Also, the rate of loss of aliphatic unsaturated bonds by oxidative polymerization was 53%.

As described above, the polyfunctional phenol compound of the present embodiment 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 and evaluation of thermosetting resin composition]
Next, a thermosetting resin composition was produced using an epoxy resin as a thermosetting resin and the polyfunctional phenol compound obtained in each example as a curing agent for the epoxy resin.
As the plant-derived epoxy resin, oxidatively polymerized epoxidized CNSL, which is an oxidatively polymerized epoxy resin (EA), was synthesized according to Production Example 1 below.

Production example 1
(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 3-4, Reference Example 2, Comparative Example 1
(Manufacture of thermosetting resin composition)
The epoxy resin and phenol-based curing agent shown in Table 2, tributyl (methyl) phosphonium dimethyl phosphate as a curing accelerator, and toluene as an organic solvent are blended, and the solid content concentration is 40% by mass. A solution of the resin composition was prepared.
The compounding ratio of the epoxy resin and the phenolic curing agent was such that the mass ratio [epoxy resin/phenolic curing agent] of the epoxy resin and the phenolic curing agent was 1.0. In addition, the amount of the curing accelerator was set so that the content of the curing accelerator was 1 part by mass with respect to 100 parts by mass of the epoxy resin.

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 an adhesive for comparison of copper foil peel strength, 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 at a temperature 50 ° C. lower than Tg is the storage elastic modulus E 'of the glassy region, and the storage elastic modulus at a temperature 50 ° C. higher than Tg. was taken as the storage elastic modulus E' of the rubbery region. Table 2 shows the measurement results.

[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 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 copper foil peel strength of cured product]
(1) Method for preparing evaluation samples of Examples 3 to 4 and Reference Example 2 A solution of the thermosetting resin composition obtained in each example was coated with a process film 1 (manufactured by Lintec Corporation, product name “SP-PET382150”, polyethylene A terephthalate film coated with a silicone release agent (thickness: 38 μm) was coated on a release-treated surface so that the thickness of the cured product obtained after drying and curing was 70 μm, and dried at 80° C. for 3 minutes. After that, the release treated surface of process 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 form a sheet for peel strength measurement. Obtained.
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.

[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)]

From Table 2, it can be seen that the cured products obtained in Examples 3 and 4 using the polyfunctional phenol compound of the present embodiment as a phenolic curing agent had a storage elastic modulus E' equal to or greater than a certain level without melting even in the rubbery region. had From this, it can be seen that the polyfunctional phenol compound of the present embodiment functions as a curing agent for epoxy resins and is a material with low environmental load that can increase the degree of biomass.
In addition, the cured products obtained in Examples 3 and 4 have a lower glass transition temperature and a lower storage elastic modulus E' at 23°C than the cured product of Comparative Example 1 using a conventional phenolic curing agent. Nevertheless, the storage modulus E' of the rubbery region was higher than that of the cured product of Comparative Example 1. That is, the cured products obtained in Examples 3 and 4 have both flexibility and heat resistance at room temperature, and are useful, for example, as flexible adhesives.
In addition, the cured products obtained in Examples 3 and 4 had a lower storage elastic modulus E' at 23°C than the cured product of Reference Example 2 in which squalene was not used, and the elongation at break, stress relaxation rate and copper All of the foil peel strengths were improved, and the copper foil peel strength was higher than that of the general-purpose adhesive of Comparative Example 2.

Claims

Copolymerization of a phenol compound (A) derived from a plant and having an unsaturated aliphatic hydrocarbon group with 15 to 17 carbon atoms and an unsaturated aliphatic hydrocarbon group with 10 to 40 carbon atoms (B) by oxidative polymerization. A polyfunctional phenol compound comprising:
The polyfunctional phenol compound according to claim 1, wherein the phenol compound (A) is one or more selected from compounds represented by the following general formula (A-1).

(In the formula, R is an unsaturated aliphatic hydrocarbon group having 15 to 17 carbon atoms 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 an alkyl group having 1 to 5 carbon atoms, and X 3 is a hydrogen atom, a hydroxy group, or a carboxy group.)
3. The multi-layer according to claim 2, wherein the phenol compound (A) 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). Functional phenolic compound.
The polyfunctional phenol compound according to any one of claims 1 to 3, which has a mass average molecular weight (Mw) of 8,000 to 200,000.
The polyfunctional phenol compound according to any one of claims 1 to 3, wherein the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B) is a biomass-derived compound.
The polyfunctional phenol compound according to any one of claims 1 to 3, wherein the unsaturated aliphatic hydrocarbon (B) having 10 to 40 carbon atoms contains 3 to 9 aliphatic unsaturated bonds.
The polyfunctional phenol compound according to any one of claims 1 to 3, wherein the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B) is squalene.
The ratio of the blending amount (W A ) of the phenolic compound (A) to the blending amount (W B ) of the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms ( B ) when performing the oxidative polymerization [ 4. The polyfunctional phenol compound according to any one of claims 1 to 3, wherein W A /W B ] is in a molar ratio of 0.1 to 20.
The polyfunctional phenol compound according to any one of claims 1 to 3, which is used as a curing agent for thermosetting resins.
The polyfunctional phenol compound according to claim 9, wherein the thermosetting resin is an epoxy resin.
A method for producing a polyfunctional phenol compound according to any one of claims 1 to 3, wherein the phenol compound (A ) and the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B) are copolymerized by oxidative polymerization.
The oxidative polymerization according to claim 11, wherein the phenolic compound (A) and the unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms (B) are heated while supplying a gas containing oxygen. A method for producing a polyfunctional phenol compound.