KR20130059389A - Phenol resin and epoxy resin and manufacturing method for same - Google Patents

Abstract

(식 중, R¹은 (n+l)가의 다가 알코올 유도체를 나타내고, R²는 치환 또는 비치환 방향족환을 나타내고, R³은 CH₂, C₂H₄, C₃H₆, C₄H₈ 치환 또는 비치환 방향족환 중 어느 하나를 나타내고, m 및 n은 1 이상의 정수이며, l은 0 또는 1 이상의 정수를 나타냄)The present invention suppresses environmental load and provides a phenol resin or epoxy resin having good properties. In a phenol resin or an epoxy resin, the compound containing the structure represented by following General formula (1) is used as a raw material.

(Wherein R ¹ represents a (n + l) valent polyhydric alcohol derivative, R ² represents a substituted or unsubstituted aromatic ring, and R ³ represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ represents any of a substituted or unsubstituted aromatic ring, m and n are integers of 1 or more, and l represents 0 or an integer of 1 or more)

Description

Phenolic resin and epoxy resin, and the manufacturing method thereof {PHENOL RESIN AND EPOXY RESIN AND MANUFACTURING METHOD FOR SAME}

The present invention relates to phenol resins and epoxy resins, and methods for their preparation.

In recent years, consideration has been given to environmental considerations in phenol resins widely used as components of adhesives and coatings. For example, phenol resins with reduced free monomers and phenol resins that do not generate gas during molding have already been put on the market.

Moreover, in the epoxy resin widely used as a component of an adhesive agent or a coating material, environmental consideration is examined. For example, the thing which can collect | recover and reuse the mist generate | occur | produced in the spraying process which sprays resin and forms into a film, what is soluble in a chemical solvent, and what is water-based is already put into the market.

On the other hand, PET (Polyethylene Terephthalate) bottles are lightweight, have excellent transparency, gas barrier properties, and high strength. In addition, as the amount of use increases, the amount of waste increases, which is a social problem.

PET bottles are collected and recycled. However, when regenerating the PET resin, the molecular weight of the PET decreases due to hydrolysis of the ester bonds, resulting in a problem that the melt viscosity and the mechanical strength of the PET decrease. As a result, recycled PET resins are currently used mainly in the field of textiles and industrial materials.

Therefore, a new method of using recycled PET resin is being sought. For example, alkyd resin (refer patent document 1 etc.), polyester resin (refer patent document 2, etc.), photocurable urethane resin (refer patent document 3, etc.) produced | generated using the depolymerization reaction by glycols, etc., respectively, Use as a paint is examined.

Japanese Patent No. 3310661 (Patent Claims) Japanese Patent No. 3434409 (Patent Claims) Japanese Patent Laid-Open No. 2004-307779 (claims, examples)

Thus, in the conventional recycled PET resin, there exists a problem that a use is limited by the characteristic fall at the time of decomposition.

Therefore, an object of the present invention is to provide a phenol resin and an epoxy resin having favorable characteristics while suppressing environmental load in view of such a problem.

In order to solve such a subject, the phenol resin which is one form of this invention uses the compound containing the structure represented by following General formula (1) as a raw material.

(Wherein R ¹ represents a (n + l) valent polyhydric alcohol derivative, R ² represents a substituted or unsubstituted aromatic ring, and R ³ represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ represents any of a substituted or unsubstituted aromatic ring, m and n are integers of 1 or more, and l represents 0 or an integer of 1 or more)

The phenol resin which uses the compound of such a structure as a raw material can suppress environmental load, and can obtain favorable characteristic.

Moreover, the phenol resin of one form of this invention is characterized by including the structure represented by following General formula (2).

(Wherein R ⁴ represents a (l + n + p) valent polyhydric alcohol derivative, R ⁵ and R ⁷ each independently represent a substituted or unsubstituted aromatic ring, and R ⁶ and R ⁸ each independently represent CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ aromatic ring, q represents an integer of 1 to 5, R ⁹ represents H or OH (at least one OH), m, p, o are integers of 1 or more, and l and n represent 0 or an integer of 1 or more)

By the phenol resin of such a structure, environmental load can be suppressed and a favorable characteristic can be acquired.

Moreover, the phenol resin of one form of this invention is obtained by making monocarboxylic acid which has a phenol group react with the depolymer which depolymerized polyester to the polyol which has two or more hydroxyl groups in 1 molecule.

By the phenol resin of such a structure, environmental load can be suppressed and a favorable characteristic can be acquired.

In such a phenol resin, it is preferable that recycled polyethylene terephthalate is used as polyester. In this way, it is possible to suppress environmental load by using regenerated polyethylene terephthalate.

Moreover, in such a phenol resin, it is preferable that a polyol contains trimethylol propane. By using trimethylolpropane, it becomes possible to depolymerize with higher stability.

Moreover, a thermosetting resin composition can be obtained by mixing the phenol resin with the thermosetting component which has at least any one of a some cyclic ether group and a cyclic thioether group in a molecule | numerator. By such a thermosetting composition, the cured film which has favorable characteristics excellent in heat resistance, chemical-resistance, flexibility, etc. can be formed.

Moreover, the manufacturing method of the phenol resin of one form of this invention is obtained by making monocarboxylic acid which has a phenol group react with the depolymer which depolymerized polyester to the polyol which has two or more hydroxyl groups in 1 molecule.

Such a structure makes it possible to suppress environmental load and to produce a phenol resin having good characteristics.

Moreover, in the manufacturing method of the phenol resin of one form of this invention, it is preferable to use recycled polyethylene terephthalate as polyester. In this way, it is possible to suppress environmental load by using regenerated polyethylene terephthalate.

Moreover, the epoxy resin of one form of this invention is obtained by making epichlorohydrin react with the raw material compound containing the structure represented by following General formula (1), or the compound obtained from the said raw material compound.

(Wherein R ¹ represents a (n + l) valent polyhydric alcohol derivative, R ² represents a substituted or unsubstituted aromatic ring, and R ³ represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ represents any of a substituted or unsubstituted aromatic ring, m and n are integers of 1 or more, and l represents 0 or an integer of 1 or more)

The epoxy resin which uses the compound of such a structure as a raw material can suppress environmental load, and can obtain favorable characteristic.

In addition, the epoxy resin of one embodiment of the present invention reacts at least one of a polybasic acid, a polybasic anhydride and a monocarboxylic acid having a phenol group with a depolymerized polymer obtained by depolymerizing a polyester into a polyol having two or more hydroxyl groups in one molecule. It is obtained by making epichlorohydrin react with the obtained compound. It is characterized by the above-mentioned.

Such a structure makes it possible not only to suppress environmental loads and to obtain favorable characteristics, but also to obtain an epoxy resin with high reactivity.

In such an epoxy resin, it is preferable that recycled polyethylene terephthalate is used as polyester. In this way, it is possible to suppress environmental load by using regenerated polyethylene terephthalate.

Moreover, in such an epoxy resin, it is preferable that a polyol contains trimethylol propane or neopentyl glycol. By using these polyols, it becomes possible to depolymerize with higher stability.

It is preferable that the resin composition containing such an epoxy resin is used for any one of an adhesive agent, a coating material, an ink, and a coating material. When used in these, favorable coating film characteristics and hardened | cured material characteristics can be expressed.

At least one of a polybasic acid, a polybasic anhydride and a monocarboxylic acid having a phenol group is reacted with a depolymerized polyester obtained by depolymerization of a polyester into a polyol having two or more hydroxyl groups in one molecule, and epichlorohydrin is further reacted. It is done.

By the production method of such an epoxy resin, not only an environmental load can be suppressed and an epoxy resin having good characteristics can be produced, but also an epoxy resin can be produced with high reactivity.

Moreover, in the manufacturing method of the epoxy resin of one form of this invention, it is preferable to carry out depolymerization after heat-dissolving polyester. By depolymerizing in this way, depolymerization can be carried out without using a solvent, and it becomes possible to suppress environmental load.

Moreover, in the manufacturing method of the epoxy resin of one form of this invention, it is preferable to use recycled polyethylene terephthalate as polyester. In this way, it is possible to suppress environmental load by using regenerated polyethylene terephthalate.

According to the phenol resin, the epoxy resin, and the manufacturing method of one embodiment of the present invention, it becomes possible to suppress the environmental load and to provide a phenol resin and an epoxy resin having good characteristics.

1 is an infrared absorption spectrum of an epoxy resin obtained in Synthesis Example 1 of an epoxy resin.
2 is an infrared absorption spectrum of an epoxy resin obtained in Epoxy Resin Synthesis Example 2. FIG.
3 is an infrared absorption spectrum of an epoxy resin obtained in Synthesis Example 3 of the epoxy resin.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

The phenol resin and epoxy resin of this embodiment are produced | generated from the process of depolymerizing polyester, and the process of reacting this depolymer.

First, polyester is depolymerized. At this time, depolymerization is carried out with a polyol having two or more hydroxyl groups in one molecule. It is preferable to add a liquid polyol to depolymerization by heat-dissolving polyester without using a solvent here. By depolymerization without using a solvent, environmental load such as reduction of CO ₂ can be reduced. When a polyol is solid, it can heat-dissolve and add it as a liquid phase. It is also preferable to carry out the reaction at about 200 to 300 캜 in the presence of the depolymerization catalyst.

The polyester used for the production of the phenol resin of the present embodiment is not particularly limited, and known polyesters can be used. Specifically, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN) can be used suitably.

In particular, recycled PET and recycled PET recovered from waste such as plastic bottle waste are suitably used. Recycled PET can be obtained by crushing and washing the recovered PET, and recycled PET can be washed and pelletized from the market. Moreover, as mentioned later, it is not necessary to remove water at the time of regeneration, and it can use it at high concentration.

In such polyester, although the shape is not specifically limited, It is preferable that it is a pellet form and / or a flake form. Moreover, although it does not need to grind finely in powder form, it may be crushed.

The polyol used for production of the phenol resin of the present embodiment has two or more hydroxyl groups in one molecule. Specific examples of the bifunctional polyol include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3 Butanediol, neopentylglycol (NPG), spiroglycol, dioxane glycol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,1,4- Cyclohexanedimethanol, 2-methylpropanediol1,3, 3-methylpentanediol1,5, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, Ethylene oxide modified compound of bifunctional phenol, such as bisphenol A, Propylene oxide modified compound of bifunctional phenol, such as bisphenol A, Ethylene oxide of bisphenol A, propylene oxide copolymer modified compound, Copolymer type polyether polyol of ethylene oxide and propylene oxide , Polycarbonatediol, adamantanediol, polyetherdi Allols, polyesterdiols, polycaprolactonediols, hydroxyl group-terminated polyalkanedienediols (e.g., 1,4-polyisoprenediol 1,4- and 1,2-polybutadienediol and hydrogenated products thereof) Elastomer).

As these commercial items, for example, as polycaprolactone diol, Flaccel (registered trademark) 205, Flaccel L205AL, Flaccel 205U, Flaccel 208, Flaccell L208AL, Flaccel 210, Flaccel 210N, Flaccel 212, PLACEL L212AL, PLACEL 220, PLACEL 220N, PLACEL 220NP1, PLACEL L220AL, PLACEL 230, PLACEL 240, PLACEL 220EB, PLACEL 220EC (all of which are manufactured by Daicel Chemical Industries, Ltd.), Hyde Examples of the carboxyl-terminated polyalkanedienediol include Epol (registered trademark) (hydrogenated polyisoprendiol, molecular weight 1,860, average degree of polymerization 26, Idemitsu Seki Chemical Co., Ltd.), PIP (polyisoprendiol, molecular weight 2,200, average degree of polymerization 34, Idemitsu Sekiyu Kagaku Co., Ltd., polytail (registered trademark) H (hydrogenated polybutadiene diol, molecular weight 2,200, average degree of polymerization 39, Mitsubishi Chemical Corporation), R-45HT (polybutanediol, molecular weight 2,270, average degree of polymerization 42 , Idemitsu Sekiyu Kagaku Co., Ltd.) Can.

Moreover, as a trifunctional or more than trifunctional polyol, specifically, glycerin, trimethylol ethane, trimethylol propane (TMP), sorbitol, pentaerythritol, ditrimethylol propane, dipentaerythritol, tripentaerythritol, and adamantane tree Examples of the polyol having an all-polycaprolactone triol and an aromatic ring include isocyanuric acid triethanol and the like as ethylene oxide, a propylene oxide modified product of a trifunctional or higher functional phenol compound, and a polyol having a heterocycle.

As these commercial items, for example, as a polycaprolactone triol, Plaxel 303, Plaxel 305, Plaxel 308, Plaxel 312, Plaxel L312AL, Plaxel 320ML, and Plaxel L320AL (all of which are Daicel Chemical Industries, Ltd.) Seiko (manufactured by Shikoku Kasei Co., Ltd.), etc. are mentioned as isocia tri acid ethanol).

Among these polyols, it is particularly preferable to include trimethylolpropane (TMP) or neopentylglycol (NPG).

As the polyol, an alcohol component derived from a plant may be used, and specific examples thereof include glycerin, diglycerin, triglycerine, ethylene glycol, 1,3-propanediol, 1,4-butanediol and castor oil alcohol components. Can be.

As a commercial item of the castor oil alcohol component, URIC H-30, URIC H-31, URIC H-52, URIC H-56, URIC H-57, URIC H-62, URIC H-73X, URIC H- 92, URIC H-420, URIC H-854, URIC Y-202, URIC Y-403, URIC Y-406, URIC Y-563, URIC AC-005, URIC AC-006, URIC PH-5001, URIC PH- 5002, URIC PH-6000, URIC F-15, URIC F-25, URIC F-29, URIC F-40, URIC SE-2010, URIC SE-3510, URIC SE-2606, URIC SE-3506, URIC SE- 2003, POLYCASTOR # 10, POLYCASTOR # 30 (all are the Itosei company make), etc. are mentioned.

These polyols can be used individually or in combination of 2 or more types.

At this time, a depolymerization catalyst can be used to promote depolymerization. As the depolymerization catalyst, for example, monobutyltin hydroxide, dibutyltin oxide, monobutyltin-2-ethylhexanoate, dibutyltin dilaurate, stannous oxide, tin acetate, zinc acetate, manganese acetate And cobalt acetate, calcium acetate, lead acetate, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate and the like.

It is suitable that the usage-amount of these depolymerization catalysts is 0.005-5 weight part normally with respect to 100 weight part of total amounts of polyester and a polyol. More preferably, it is 0.05-3 weight part.

Moreover, although it is not a depolymerization catalyst, water can also be used as an additive which accelerates depolymerization. Since water is present as an impurity in recycled PET and causes a decrease in molecular weight when recycling PET, it is usually removed by a drying process that consumes a lot of energy. However, in the present embodiment, the depolymerization does not need to be removed because it promotes depolymerization, and water may be further added. For example, by using recycled PET pellets once melt kneaded with a pellet maker such as an extrusion machine by adding water, the recycled PET can be depolymerized for a short reaction time because of its low molecular weight. Moreover, since the viscosity at the time of melting is low, high concentration reaction is attained.

Generally, although the IV value (intrinsic viscosity) of the polyester pellets marketed is about 1.0-1.2, the IV value of recycled PET or recycled PET is low as 0.6-0.7. For this reason, the time required for depolymerization in recycled PET or recycled PET can be shortened. In addition, although the IV value of what was repelted by the extrusion molding machine is 0.1 at a low thing without removing water at the time of regeneration of PET, it can be used as a polyester in this embodiment as it is.

Thus, by depolymerizing polyester to a polyol, the compound (raw material compound) containing the structure represented by following General formula (1), for example is produced | generated.

(Wherein R ¹ represents a (n + l) valent polyhydric alcohol derivative, R ² represents a substituted or unsubstituted aromatic ring, and R ³ represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ represents any of a substituted or unsubstituted aromatic ring, m and n are integers of 1 or more, and l represents 0 or an integer of 1 or more)

Subsequently, a phenol resin and an epoxy resin are produced by reacting the polyester obtained in this way using a depolymerized by depolymerization with a polyol as follows.

(Production of phenol resin)

The depolymer obtained by depolymerizing the polyester obtained as described above with a polyol and a monocarboxylic acid having a phenol group are reacted. At this time, it is preferable to add the monocarboxylic acid which has a phenol group to the depolymerized polyester which depolymerized, and to react at about 150 degreeC-250 degreeC in presence of a catalyst.

As monocarboxylic acid which has a phenol group used at this time, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-amino-3-hydroxyphenyl propionic acid, 3,4-, for example Dihydroxyphenylalanine, 3,4,5-trihydroxybenzoic acid, and the like. Among these, it is especially preferable to contain hydroxybenzoic acid.

In this way, the phenol resin which has a structure represented by following General formula (2), for example is produced | generated.

(Wherein R ⁴ represents a (l + n + p) valent polyhydric alcohol derivative, R ⁵ and R ⁷ each independently represent a substituted or unsubstituted aromatic ring, and R ⁶ and R ⁸ each independently represent CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ aromatic ring, q represents an integer of 1 to 5, R ⁹ represents H or OH (at least one OH), m, p, o are integers of 1 or more, and l and n represent 0 or an integer of 1 or more)

The obtained phenol resin is an amorphous solid, semisolid, or fluid liquid with a solid content of 100%, and is preferably solvent soluble. Such a phenol resin can be used as a raw material of coatings, inks, coating agents, adhesives, and epoxy resins for paper, wood, metal, plastic, glass, and ceramics, for example.

When a phenol resin is semi-solid at 100% of solid content, it can use suitably as an adhesive agent or sealing agent. Moreover, it can use suitably as various coating agents and coating materials by adding an organic solvent and a reactive diluent and adjusting a viscosity.

(Generation of thermosetting composition using phenol resin)

Thus, the thermosetting composition is mix | blended with the phenol resin obtained by combining with the thermosetting component which has several cyclic ether group and / or cyclic thioether group (hereinafter abbreviated as cyclic (thio) ether group) in a molecule | numerator. Can be generated.

The thermosetting component which has a some cyclic (thio) ether group in such a molecule | numerator is a compound which has two or more groups of 3, 4 or 5 membered cyclic ether group, or cyclic thioether group, or 2 types of groups in a molecule | numerator, for example A compound having a plurality of epoxy groups in a molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, namely episulfide resin, and the like. Can be mentioned.

As the polyfunctional epoxy compound, epoxidized vegetable oil, bisphenol A type epoxy resin, brominated epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydanto Doll epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, Heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylenoylethane resin, naphthalene group containing epoxy resin, epoxy resin with dicyclopentadiene frame | skeleton, glycidyl methacrylate copolymer type epoxy resin, cyclohexyl Copolymerization epoxy resin of maleimide and glycidyl methacrylate, polybuta of epoxy modified Yen may be mentioned derivatives of rubber, CTBN modified epoxy resins or the like. Among these, it is especially preferable to contain a bisphenol-A epoxy resin.

As a commercial item, for example, epoxidized plant oil is Adeka sizer (trademark) O-130P, Adeka sizer O-180A, Adeka sizer D-32, Adeka sizer D-55 (all the above) Adeka Co., Ltd.); As bisphenol A type epoxy resin jER (registered trademark) 828, jER834, jER1001, jER1004 (all are manufactured by Mitsubishi Chemical Corporation), EHPE (registered trademark) 3150 (made by Daicel Chemical Industries, Ltd.), epiclone (registered trademark) ) 840, epiclon 850, epiclon 1050, epiclon 2055 (all manufactured by DIC Corporation), Efototo (registered trademark) YD-011, YD-013, YD-127, YD-128 (all above) Manufactured by Kakusa, DER (registered trademark) 317, DER331, DER661, DER664 (all manufactured by Dow Chemical Co., Ltd.), Araldite (registered trademark) 6071, Araldite 6084, Araldite GY250, Araldite GY260 (all are manufactured by BASF (BASF) Japan company), Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128 (all are manufactured by Sumitomo Chemical Co., Ltd.), AER (registered trademark) 330, AER 331, AER661, AER664 (all are manufactured by Asahi Kasei Kogyo Co., Ltd.); As the brominated epoxy resin, jERYL903 (manufactured by Mitsubishi Chemical Corporation, Epiclone 152, Epiclone 165 (all manufactured by DIC Corporation), Efototo YDB-400, Efototo YDB-500 (all of which are manufactured by Shinnitetsu Chemical Co., Ltd.) ), DER542 (manufactured by Dow Chemical Co., Ltd.), Araldite 8011 (manufactured by BASF Japan), Sumiepoxy ESB (registered trademark) -400, ESB-700 (all manufactured by Sumitomo Chemical Co., Ltd.), AER711, AER 714 (all of which are manufactured by Asahi Kasei Kogyo Co., Ltd.); As a novolak-type epoxy resin, jER152, jER154 (all of which are manufactured by Mitsubishi Chemical Corporation), DEN (registered trademark) 431, DEN438 (all by Dow Chemical Co., Ltd.), Epi Clone N-730, Epiclone N-770, Epiclone N-865 (all made by DIC Corporation), Efototo YDCN-701, YDCN-704 (all made by Shinnitetsu Chemical Co., Ltd.), Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 (all made by BASF Japan), EPPN (registration) Table) -201, EOCN (registered trademark) -1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 (all Nippon Kayaku Co., Ltd.), Sumiepoxy ESCN (registered trademark)-195X, Sumiepoxy ESCN -220 (all of which are produced by Sumitomo Chemical Industries, Ltd.), AERECN-235, ECN-299 (all of which are manufactured by Asahi Kasei Kogyo Co., Ltd.); Epiclone 830 (manufactured by DIC Corporation), jER807 (Mitsubishi as bisphenol F type epoxy resin) Manufactured by Kagaku Co., Ltd., Efototo YDF-170, YDF-175, YDF-2004 (all of which are manufactured by Shinnitetsu Chemical Co., Ltd.), Araldite XPY306 (manufactured by BASF Japan Co., Ltd.); with hydrogenated bisphenol A type epoxy resin EPOTO ST-2004, ST-2007, ST-3000 (all of which are manufactured by Shin-Nitetsu Chemical Co., Ltd.); jER604 (manufactured by Mitsubishi Chemical Corporation) and Efototo YH-434 as glycidylamine type epoxy resins. (Manufactured by Shin-Nitetsu Chemical Co., Ltd.), Araldite MY720 (manufactured by BASF Japan Co., Ltd.), Sumiepoxy ELM (registered trademark) -120 (manufactured by Sumitomo Chemical Industries, Ltd.); Hydantoin type epoxy resins include Araldite CY-350 (manufactured by BASF Japan); As an alicyclic epoxy resin, Celoxide (trademark) 2021 (made by Daicel Chemical Industries, Ltd.), Araldite CY175, CY179 (all are the BASF Japan company make); Examples of the trihydroxyphenylmethane type epoxy resin include YL-933 (manufactured by Mitsubishi Chemical Corporation), T.E.N., EPPN-501, and EPPN-502 (all manufactured by Dow Chemical Company); Bixylenol type or biphenol type epoxy resins or mixtures thereof include YL-6056, YX-4000, and YL-6121 (all of which are manufactured by Mitsubishi Chemical Corporation); As a bisphenol S-type epoxy resin, EBPS-200 (made by Nippon Kayaku Co., Ltd.), EPX-30 (made by Adeka Co., Ltd.), EXA-1514 (made by DIC Corporation); As bisphenol A novolak-type epoxy resin, jER157S (made by Mitsubishi Chemical Corporation); As tetraphenylol ethane type epoxy resin, jERYL-931 (made by Mitsubishi Chemical Corporation), Araldite 163 (made by BASF Japan); As a heterocyclic epoxy resin, Araldite PT810 (made by BASF Japan), TEPIC (registered trademark) (made by Nissan Chemical Industries, Ltd.); As diglycidyl phthalate resin, Bremermer (registered trademark) DGT (made by Nichiyu Corporation); As tetraglycidyl xylenoyl ethane resin, ZX-1063 (all are the Shin-Nitetsu Chemical Co., Ltd. make); Examples of the naphthalene group-containing epoxy resin include ESN-190 and ESN-360 (all manufactured by Shinnitetsu Chemical Co., Ltd.), HP-4032, EXA-4750, and EXA-4700 (all manufactured by DIC Corporation); As an epoxy resin which has a dicyclopentadiene frame | skeleton, HP-7200 and HP-7200H (all are the said DIC Corporation make); As glycidyl methacrylate copolymer type epoxy resin, CP-50S and CP-50M (all are the Nichiyu Corporation make); Examples of the epoxy-modified polybutadiene rubber derivative include PB-3600 (manufactured by Daicel Chemical Industries, Ltd.) and CTBN-modified epoxy resins, including YR-102 and YR-450 (all manufactured by Shinnitetsu Chemical Co., Ltd.). It is not limited to these.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [( 3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methylacrylic Latex, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or these In addition to polyfunctional oxetanes such as oligomers or copolymers, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), cardo-type bisphenols, calix arenes, calyx resorcinrenes, or seals Ether ether with resin which has hydroxyl groups, such as a sesquioxane, etc. are mentioned. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As episulfide resin, bisphenol A episulfide resin is mentioned, for example. As a commercial item, YL7000 (made by Shin-Nitetsu Chemical Co., Ltd.) etc. is mentioned. An episulfide resin in which the oxygen atom of the epoxy group of the novolac epoxy resin is substituted with a sulfur atom can also be used by using the same synthetic method.

These thermosetting components can be used individually or in combination of 2 or more types, and the compounding ratio is suitable for the range of 20-300 mass parts with respect to 100 mass parts of phenol resins.

By heat-hardening the thermosetting composition obtained in this way, the cured film which is excellent in heat resistance and chemical-resistance and has flexibility and favorable hardness can be formed. Such a thermosetting resin can be used suitably as an adhesive agent of film bonding, such as an IC card, a touch panel, an organic electroluminescent display, a sealing agent, a printed wiring board, a coating material, and various coating agents, for example.

(Production of Epoxy Resin and Thermosetting Composition Using the Same)

The polyester obtained as mentioned above is epoxidized by making the depolymerized by depolymerization with a polyol, and epichlorohydrin, and an epoxy resin is produced | generated.

The obtained epoxy resin is an amorphous solid, semisolid, or fluid liquid with a solid content of 100%, and is preferably solvent soluble. Such epoxy resins can be used, for example, as adhesives, coatings, inks, coatings for paper, wood, metals, plastics, glass, ceramics, etc., from their favorable coating film properties and cured product properties.

When an epoxy resin is semisolid with 100% of solid content, it can use suitably as an adhesive agent or a sealing agent. Moreover, it can use as various coating agents and coating materials by adding an organic solvent and a reactive diluent and adjusting a viscosity.

It can be used as a thermosetting composition by adding thermosetting components, such as an epoxy resin hardening | curing agent and a thermosetting catalyst, to the epoxy resin of this embodiment. And by thermosetting such a thermosetting composition, the cured film which is excellent in heat resistance and chemical-resistance, and has flexibility and favorable hardness can be formed. Such a thermosetting resin can be used suitably as an adhesive agent of film bonding, such as an IC card, a touch panel, an organic electroluminescent display, a sealing agent, a printed wiring board, a coating material, and various coating agents, for example.

In the phenol resin, epoxy resin, and thermosetting composition thus obtained, colorants such as pigments and dyes, antioxidants, stabilizers, ultraviolet absorbers, flame retardants, and inorganic fillers for enhancing mechanical strength can be added as necessary. . Moreover, adhesive imparting agents, such as a silane coupling agent, an antifoamer, a leveling agent, and another additive can be used. Moreover, it can also be used as a conductive composition by adding metals, such as silver and copper, and conductive materials, such as carbon.

[Example]

Hereinafter, although an Example and a comparative example are given and this embodiment is demonstrated concretely, this invention is not limited to these Examples. In addition, below "part" and "%" are a mass reference | standard unless there is particular notice.

(Synthesis of PET Depolymer)

First, PET depolymer was synthesized as follows.

PET Depolymer Synthesis Example 1

Into a 500 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, 192 parts of recycled PET flakes having an IV value of 0.6 to 0.7 were added, and the flask was heated to 300 ° C after the nitrogen atmosphere. Soak in a salt bath. As soon as the PET was dissolved, stirring was started and 0.65 parts of dibutyltin oxide was added.

Subsequently, 134 parts of trimethylolpropane (TMP) previously heated and dissolved at 130 ° C. were added in small portions, taking care not to solidify the PET. In the meantime, the stirring speed was raised to 150 rpm in the stage where the viscosity fell. Furthermore, it exchanged with the oil bath previously heated up to 240 degreeC from the salt bath, and maintained inside the flask at 220 degreeC (+/- 10 degreeC), reacted for 5 hours, and cooled to room temperature.

The obtained depolymer is called depolymer A.

PET Depolymer Synthesis Example 2

Into a 500 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, 192 parts of recycled PET flakes having an IV value of 0.6 to 0.7 were added, and the flask was heated to 300 ° C after the nitrogen atmosphere. Soak in a salt bath. As soon as the PET was dissolved, stirring was started and 0.65 parts of dibutyltin oxide was added.

Subsequently, 45 parts of trimethylolpropane (TMP) previously heated and dissolved at 130 ° C. were added in small portions, taking care not to solidify the PET. In the meantime, the stirring speed was raised to 150 rpm in the stage where the viscosity fell. Furthermore, it exchanged with the oil bath previously heated up to 240 degreeC from the salt bath, and maintained inside the flask at 220 degreeC (+/- 10 degreeC), reacted for 5 hours, and cooled to room temperature.

The obtained depolymer is called depolymer B.

Thus obtained PET depolymer was reacted with the monocarboxylic acid having a phenol group as follows.

[Phenol Resin Synthesis Example 1]

Into a 500 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, 200 parts of depolymerized A, 250 parts of 3-hydroxybenzoic acid and 0.5 parts of dibutyltin oxide were added, and the flask was placed in a nitrogen atmosphere. It was set as. The condensed water was removed over about 4 to 6 hours while gradually heating the hot water bath to 200 ° C, the oil content was lowered when the acid value had sufficiently decreased, and the flask contents were taken out to obtain a phenol resin having a PET content of 26%. This is called phenol resin A.

Furthermore, the obtained phenol resin was diluted with carbitol acetate and the varnish of 80% of solid content was obtained. The obtained varnish is called varnish A.

[Phenol Resin Synthesis Example 2]

Into a 500 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, 200 parts of depolymerized A, 250 parts of parahydroxybenzoic acid, and 0.5 part of dibutyltin oxide were put into a nitrogen atmosphere. It was. The condensed water was removed over about 4 to 6 hours while gradually heating the hot water bath to 200 ° C, the oil content was lowered when the acid value was sufficiently lowered, and the flask contents were taken out to obtain a phenol resin having a PET content of 26%. This is called phenol resin B.

Furthermore, the obtained phenol resin was diluted with carbitol acetate and the varnish of 80% of solid content was obtained. The obtained varnish is called varnish B.

[Phenol Resin Synthesis Example 3]

Into a 1000 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, 433 parts of depolymerizer B, 250 parts of 3-hydroxybenzoic acid and 0.5 parts of dibutyltin oxide were added, and the flask was placed in a nitrogen atmosphere. It was set as. The condensed water was removed over about 4 to 6 hours while the hot water bath was gradually heated to 200 ° C, the oil content was lowered when the acid value was sufficiently lowered, and the flask contents were taken out to obtain a phenol resin having a PET content of 51%. This is called phenol resin C.

 Furthermore, the obtained phenol resin was diluted with carbitol acetate and the varnish of 80% of solid content was obtained. The obtained varnish is called varnish C.

[Phenol Resin Synthesis Example 4]

Into a 1000 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, 433 parts of depolymerizer B, 250 parts of parahydroxybenzoic acid and 0.5 part of dibutyltin oxide were added, and the flask was placed in a nitrogen atmosphere. It was. The condensed water was removed over about 4 to 6 hours while the hot water bath was gradually heated to 200 ° C, the oil content was lowered when the acid value was sufficiently lowered, and the flask contents were taken out to obtain a phenol resin having a PET content of 51%. This is called phenol resin D.

Furthermore, the obtained phenol resin was diluted with carbitol acetate and the varnish of 80% of solid content was obtained. The obtained varnish is called varnish D.

[Carboxylic acid synthesis example]

Into a 500 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, 100 parts of depolymerizer A was placed in a nitrogen atmosphere, and the flask was heated to 145 ° C ± 5 ° C. It was immersed. About 30 minutes after starting stirring, 42.8 parts of tetrahydro phthalic anhydride was added, and stirring was continued. Thus, the carboxylic acid resin of acid value 98 mgKOH / g was obtained. This is called carboxylic acid resin A.

The PET depolymer, phenol resin, and carboxylic acid resin thus obtained were epoxidized as follows to synthesize an epoxy resin.

Epoxy Resin Synthesis Example 1

130 parts of depolymerizer A was poured into a 500 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, and the inside of the flask was placed in a nitrogen atmosphere, and then immersed in an oil bath heated to 60 ° C. . 1.2 parts of boron trifluoride ether solutions were added in 3 times, and 74 parts of epichlorohydrin was dripped over 2 hours. The content temperature at this time was adjusted by the water bath so that it might become 60-70 degreeC.

After the exotherm was stabilized, 10.8 parts of 16% by weight aqueous potassium hydroxide solution was added and stirred to neutralize the catalyst. After the whole amount of epichlorohydrin was dripped, 35.2 parts of sodium hydroxide were divided into 4 times, and stirring was continued. At this time, it adjusted in the water bath so that the temperature of content might be 70-90 degreeC.

After the heat was stabilized, it was transferred to a 500 ml eggplant flask, and water and excess epichlorohydrin were removed using an evaporator. The obtained white mucus and chloroform were mixed and transferred to the separating lot. The mixture was washed with water, and the aqueous phase was discarded to remove the salt. After the same washing with water twice, the solvent was removed by gradually heating to 90 ° C. with an evaporator to obtain a high viscosity epoxy resin. This is called epoxy resin A.

Infrared absorption spectrum of epoxy resin A is shown in FIG.

Epoxy Resin Synthesis Example 2

Into a 1000 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, 128 parts of phenol resin A was placed, and the flask was placed in a nitrogen atmosphere. Then, 578 parts of epichlorohydrin and triethylbenzyl were added. 0.6 parts of ammonium chloride was added and dissolved. Then, it was immersed in 110 degreeC oil bath and made to react for 2 hours.

Next, internal temperature was cooled to 60 degreeC, and 52.5 parts of 45 weight% sodium hydroxide aqueous solution were dripped over 2 hours. At this time, in order to prevent the hydrolysis of the ester bond, the content temperature was adjusted to be 60 to 70 ° C. After the exotherm was stabilized, the mixture was diluted with methyl isobutyl ketone, transferred to a separating lot, washed with water to remove salt. Transfer to a 1000 ml eggplant flask, and slowly heated from 50 ℃ to 120 ℃ using an evaporator to remove excess epichlorohydrin and solvent to obtain an epoxidized resin. This is called epoxy resin B.

The infrared absorption spectrum of epoxy resin A is shown in FIG.

Epoxy Resin Synthesis Example 3

87 parts of phenol resin B was put into a 1000 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, and the flask was placed in a nitrogen atmosphere. Then, 352 parts of epichlorohydrin and triethylbenzyl were added. 0.45 part of ammonium chloride was added and dissolved. Then, it was immersed in 110 degreeC oil bath and made to react for 2 hours.

Subsequently, internal temperature was cooled to 60 degreeC, and 35.5 parts of 45 weight% sodium hydroxide aqueous solution were dripped over 2 hours. At this time, in order to prevent the hydrolysis of the ester bond, the content temperature was adjusted to be 60 to 70 ° C. After the exotherm was stabilized, the mixture was diluted with methyl isobutyl ketone, transferred to a separating lot, washed with water to remove salt. Transfer to a 1000 ml eggplant flask, and slowly heated from 50 ° C to 120 ° C using an evaporator to remove excess epichlorohydrin and solvent to obtain an epoxidized resin. This is called epoxy resin C.

 Fig. 3 shows an infrared absorption spectrum of the epoxy resin A. Fig.

[Epoxy Resin Synthesis Example 4]

Into a 500 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, 87 parts of phenol resin C was added, and the flask was placed in a nitrogen atmosphere. Then, 117 parts of epichlorohydrin and triethylbenzyl were added. 0.45 part of ammonium chloride was added and dissolved. Then, it was immersed in 110 degreeC oil bath and made to react for 2 hours.

Subsequently, internal temperature was cooled to 60 degreeC, and 35.5 parts of 45 weight% sodium hydroxide aqueous solution were dripped over 2 hours. At this time, in order to prevent the hydrolysis of the ester bond, the content temperature was adjusted to be 60 to 70 ° C. After the exotherm was stabilized, the mixture was diluted with methyl isobutyl ketone, transferred to a separating lot, washed with water to remove salt. Transfer to a 1000 ml eggplant flask, and slowly heated from 50 ° C to 120 ° C using an evaporator to remove excess epichlorohydrin and solvent to obtain an epoxidized resin. This is called epoxy resin D.

Epoxy Resin Synthesis Example 5

87 parts of phenol resin D was put into a 500 ml four-neck round bottom separable flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, and the flask was placed in a nitrogen atmosphere. Then, 117 parts of epichlorohydrin and triethylbenzyl were added. 0.45 part of ammonium chloride was added and dissolved. Then, it was immersed in 110 degreeC oil bath and made to react for 2 hours.

Subsequently, internal temperature was cooled to 60 degreeC, and 35.5 parts of 45 weight% sodium hydroxide aqueous solution were dripped over 2 hours. At this time, in order to prevent the hydrolysis of the ester bond, the content temperature was adjusted to be 60 to 70 ° C. After the exotherm was stabilized, the mixture was diluted with methyl isobutyl ketone, transferred to a separating lot, washed with water to remove salt. Transfer to a 1000 ml eggplant flask, and slowly heated from 50 ° C to 120 ° C using an evaporator to remove excess epichlorohydrin and solvent to obtain an epoxidized resin. This is called epoxy resin E.

[Epoxy Resin Synthesis Example 6]

After adding 70 parts of carboxylic acid resin A to the 500 ml four-neck round bottom separable flask equipped with the stirrer, the nitrogen inlet tube, and the cooling tube, and making the inside of the flask into a nitrogen atmosphere, 90 parts of epichlorohydrin and tree 0.45 parts of ethylbenzyl ammonium chloride was added and dissolved. Then, it was immersed in 110 degreeC oil bath and made to react for 2 hours.

Subsequently, internal temperature was cooled to 60 degreeC, and 35.5 parts of 45 weight% sodium hydroxide aqueous solution were dripped over 2 hours. At this time, in order to prevent the hydrolysis of the ester bond, the content temperature was adjusted to be 60 to 70 ° C. After the exotherm was stabilized, the mixture was diluted with methyl isobutyl ketone, transferred to a separating lot, washed with water to remove salt. Transfer to a 1000 ml eggplant flask, and slowly heated from 50 ° C to 120 ° C using an evaporator to remove excess epichlorohydrin and solvent to obtain an epoxidized resin. This is called epoxy resin F.

The following evaluation was performed about the phenol resins A-D and varnish A-D obtained by the phenol resin synthesis examples 1-4, and the epoxy resins A-F obtained by the epoxy resin synthesis examples 1-6.

[Phenol Resin Composition Evaluation]

<Regenerated polyester content rate>

The content rate of the recycled resin component of the phenol resin obtained by the phenol resin synthesis examples 1-4 was computed.

The results are shown in Table 1 below.

Solvent Solubility Test

The solvent solubility of the phenol resin obtained in the phenol resin synthesis examples 1-4 was confirmed as follows.

For each 50 parts of the phenol resins obtained in Synthesis Examples 1 to 4, 50 parts of various solvents were added and stirred to prepare a 50% by weight solution of the depolymerized product, and the transparency of the solution was evaluated. The evaluation criteria are as follows.

Fully transparent: ○

Slightly cloudy: △

Turbidity: ×

The results are shown in Table 1 together.

Moreover, the obtained phenol resin was mixed with an epoxy resin by the mixing ratio shown in following Table 2, and the performance as a coating agent was evaluated about the composition of the obtained compounding examples 1-4.

* 1 jER828 (manufactured by Mitsubishi Chemical Corporation)

* 2 Cure sol 2E4MZ (manufactured by Shikoku Kasei Co., Ltd.)

<Gelling test>

In order to confirm the hardenability of the composition of the compounding examples 1-4, the gelation test was done as follows.

As a gelation tester, the time until gelation was measured at 170 degreeC using the gelation tester 1563 (made by Emoto Seisakusho Co., Ltd.).

The measurement results are shown in Table 3 below.

[Hardware Evaluation]

The composition of the compounding examples 1-4 were apply | coated to the glass plate with the film thickness of 30 micrometers with an applicator. This was dried in a hot air circulation drying furnace at 70 ° C. for 20 minutes and then cured at 120 ° C. for 30 minutes. The following tests were done about the obtained hardened | cured material.

<Rubbing test>

A rubbing test was performed as follows to evaluate the curability of the cured product.

The obtained hardened | cured material was rubbed 50 times with the waste cloth containing acetone, and the surface state was visually observed. The evaluation criteria are as follows.

No surface melting (sufficient curing): ○

Some dissolution visible on the surface (insufficient hardening): ×

The evaluation results are shown in Table 3 together.

&Lt; Pencil Hardness Test >

The pencil of B-9H grind | pulverized so that the tip of a pencil core might be flat to the cured coating film was pressed by applying the load of 1 kg with an angle of 45 degreeC with respect to a coating film. The coating film was scratched about 1 cm in the state which applied this load, and the hardness of the pencil which does not peel off the coating film was recorded.

The evaluation results are shown in Table 3 together.

As described above, the phenol resin of the present embodiment can be synthesized without using any solvent. In addition, since the recycled resin can be used with high efficiency, it is possible to reduce the load on the environment.

Moreover, it turns out that the phenol resin of this embodiment has favorable sclerosis | hardenability, and also has favorable chemical-resistance and hardness also in the hardened | cured material.

[Epoxy Resin Composition Evaluation]

<Regenerated polyester content rate>

The content rate of the recycled resin component of obtained epoxy resins A-F was computed.

The results are shown in Table 4 below.

<Epoxy equivalent>

About 0.1 g of each of the epoxy resins measured in a 100 ml Erlenmeyer flask, 10 ml of chloroform, and 20 ml of acetic acid were added and dissolved, and then 10 ml of 0.25 g / ml tetraethylammonium bromide solution was added thereto. In addition, 5 drops of crystal violet indicators were added, and titration was performed with a 0.1 mol / l perchloric acid acetic acid solution. In addition, it was made into the end point when green started to appear.

The results are shown in Table 4 together.

<Molecular Weight>

The molecular weight of epoxy resins A to F was measured by GPC (gel permeation chromatography). For the measurement, Shodex GPC KF-806L × 3 (manufactured by Showa Denko) was used for the column, and the column temperature was 40 ° C. Standard polystyrene was used as reference material and tetrahydrofuran was used as eluent at a flow rate of 1 ml / min.

The results are shown in Table 4 together.

Solvent Solubility Test

The solvent solubility of epoxy resins A-F was confirmed as follows.

In the epoxy resins A to G, 50 parts of various solvents were added to the 50 parts of the depolymer and stirred to prepare a 50% by weight solution of the depolymerized product, and the transparency of the solution was evaluated. The evaluation criteria are as follows.

Fully transparent: ○

Slightly cloudy: △

Turbidity: ×

The results are shown in Table 4 together.

Moreover, the obtained epoxy resin was mixed with a solvent and a hardening | curing agent in the ratio shown in following Table 5, and the performance as a coating agent was evaluated about the obtained composition of Examples 1-6.

* 1 Cure sol 2E4MZ (manufactured by Shikoku Kasei Co., Ltd.)

<Gelling test>

In order to confirm the hardenability of the composition of the compounding examples 1-6, the gelation test was done as follows.

As a gelation tester, the time until gelation was measured at 170 degreeC using the gelation tester 1563 (made by Emoto Seisakusho Co., Ltd.).

The measurement results are shown in Table 6 below.

[Hardware Evaluation]

The composition of the compounding examples 1-6 was apply | coated to the glass plate with the film thickness of 30 micrometers. This was dried in a hot air circulation drying furnace at 70 ° C. for 20 minutes and then cured at 120 ° C. for 30 minutes. The following tests were done about the obtained hardened | cured material.

<Rubbing test>

A rubbing test was performed as follows to evaluate the curability of the cured product.

The obtained cured product was rubbed with a waste cloth containing acetone 50 times, and the surface state was visually observed. The evaluation criteria are as follows.

No surface melting (sufficient curing): ○

Slight dissolution on surface (insufficient hardening): ×

The evaluation results are shown in Table 6 together.

&Lt; Pencil Hardness Test >

The pencil of B-9H grind | pulverized so that the tip of a pencil core might be flat to the cured coating film was pressed by applying the load of 1 kg with an angle of 45 degreeC with respect to a coating film. The coating film was scratched about 1 cm in the state which applied this load, and the hardness of the pencil which does not peel off the coating film was recorded.

The evaluation results are shown in Table 6 together.

As described above, the epoxy resin of the present embodiment can be synthesized without using any solvent. In addition, since the recycled resin can be used with high efficiency, it is possible to reduce the load on the environment.

Moreover, it turns out that the epoxy resin of this embodiment has favorable sclerosis | hardenability, and also has favorable chemical-resistance and hardness also in the hardened | cured material.

Claims (16)

The phenol resin characterized by using as a raw material the compound containing the structure represented by following General formula (1).

(Wherein R ¹ represents a (n + l) valent polyhydric alcohol derivative, R ² represents a substituted or unsubstituted aromatic ring, and R ³ represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ represents any of a substituted or unsubstituted aromatic ring, m and n are integers of 1 or more, and l represents 0 or an integer of 1 or more) The phenol resin characterized by including the structure represented by the following general formula (2).

(Wherein R ⁴ represents a (l + n + p) valent polyhydric alcohol derivative, R ⁵ and R ⁷ each independently represent a substituted or unsubstituted aromatic ring, and R ⁶ and R ⁸ each independently represent CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ aromatic ring, q represents an integer of 1 to 5, R ⁹ represents H or OH (at least one OH), m, p, o are integers of 1 or more, and l and n represent 0 or an integer of 1 or more) A phenol resin obtained by reacting a polycarboxylic acid having a phenol group with a depolymer obtained by depolymerizing polyester with a polyol having two or more hydroxyl groups in one molecule. The phenolic resin according to claim 3, wherein the polyester is regenerated polyethylene terephthalate. The phenolic resin according to claim 3 or 4, wherein the polyol comprises trimethylolpropane. The thermosetting resin composition containing the phenol resin as described in any one of Claims 1-4, and the thermosetting component which has at least any one of a some cyclic ether group and a cyclic thioether group in a molecule | numerator. A monocarboxylic acid having a phenol group is reacted with a depolymer obtained by depolymerization of a polyester with a polyol having two or more hydroxyl groups in one molecule. 8. The method of claim 7, wherein the polyester is recycled polyethylene terephthalate. Epoxy resin obtained by making epichlorohydrin react with the raw material compound containing the structure represented by following General formula (1), or the compound obtained from the said raw material compound.

(Wherein R ¹ represents a (n + l) valent polyhydric alcohol derivative, R ² represents a substituted or unsubstituted aromatic ring, and R ³ represents CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ represents any of a substituted or unsubstituted aromatic ring, m and n are integers of 1 or more, and l represents 0 or an integer of 1 or more) Epichlorohydrin is reacted with a compound obtained by reacting a depolymerized polyester with a polyol having two or more hydroxyl groups in one molecule, at least any one of a polybasic acid, a polybasic anhydride and a monocarboxylic acid having a phenol group. Obtained epoxy resin. The epoxy resin according to claim 10, wherein the polyester is regenerated polyethylene terephthalate. The epoxy resin according to claim 10 or 11, wherein the polyol comprises trimethylolpropane or neopentylglycol. The resin composition containing the epoxy resin in any one of Claims 9-11, and is used for any one of an adhesive agent, a coating material, an ink, and a coating agent. At least one of a polybasic acid, a polybasic anhydride and a monocarboxylic acid having a phenol group is reacted with a depolymerized polyester obtained by depolymerization of a polyester into a polyol having two or more hydroxyl groups in one molecule, and epichlorohydrin is further reacted. The manufacturing method of the epoxy resin made into. The method for producing an epoxy resin according to claim 14, wherein the polyester is heated and dissolved and then depolymerized with the polyol. The method for producing an epoxy resin according to claim 14 or 15, wherein the polyester is recycled polyethylene terephthalate.

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