Phenol-modified, aromatic hydrocarbon / formaldehyde resin composition and method for producing phenol-modified, aromatic hydrocarbon / formaldehyde resin composition

Abstract

A phenol-modified, aromatic hydrocarbon / formaldehyde resin composition comprising a phenol-modified, aromatic hydrocarbon / formaldehyde resin A obtained by reaction between phenol and an aromatic hydrocarbon / formaldehyde resin and a compound (1) represented by general formula (1), wherein the content of the compound (1) in the resin composition is 5-50 mass%.

Description

A phenol-modified aromatic hydrocarbon formaldehyde resin composition, and a method for producing the phenol-modified aromatic hydrocarbon formaldehyde resin composition.

[0001] The present invention relates to a phenol-modified aromatic hydrocarbon formaldehyde resin composition and a method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition.

[0002] Various resins, such as acrylic resins, urethane resins, epoxy resins, and rubber, are used as raw materials for adhesives, sealants, paints, and coatings and encapsulants used in electronic components. Aromatic hydrocarbon formaldehyde resins are known to be useful as additives that improve various physical properties of these resins, such as water resistance, corrosion resistance, impact resistance, curability, and tackiness. For example, Patent Document 1 discloses a method for producing a low-viscosity phenol-modified aromatic hydrocarbon formaldehyde resin (C) by condensing an aromatic hydrocarbon formaldehyde resin (A) and phenols (B) in the presence of an acidic catalyst, with the aim of providing a method for producing a low-viscosity phenol-modified aromatic hydrocarbon formaldehyde resin that has a small amount of unreacted phenols, a small increase in viscosity even after removal of low-boiling components, and maintains its liquid state. The method is characterized by including the steps of adding an inorganic basic compound and / or a tertiary amine compound with a boiling point of 300°C or higher to stop the condensation reaction when the viscosity of the reaction mixture at 25°C is in the range of 200 to 1500 mPa·S, and removing unreacted phenols (B) and low-boiling components by distillation after stopping the condensation reaction.

[0003] Japanese Patent Publication No. 2007-297610

[0004] When epoxy resins are used as raw materials for adhesives and paints, improved impact resistance is required to enhance the durability of the product. Furthermore, improved low-temperature curing properties are also required to improve processability at low temperatures, such as below 10°C in winter. The low-viscosity phenol-modified aromatic hydrocarbon formaldehyde resin obtained in Reference 1 is easy to add to various resins such as epoxy resins and has sufficient processability, but there was room for improvement in terms of low-temperature curing properties and impact resistance of the resulting epoxy resin composition.

[0005] The present invention aims to provide a phenol-modified aromatic hydrocarbon formaldehyde resin composition and the phenol-modified aromatic hydrocarbon formaldehyde resin composition that can improve the low-temperature curability and impact resistance of epoxy resins.

[0006] As a result of diligent research to solve the aforementioned problems, the present inventors have found that a phenol-modified aromatic hydrocarbon formaldehyde resin composition comprising a phenol-modified aromatic hydrocarbon formaldehyde resin A and a compound (1) having a specific structure, wherein the content of compound (1) is 5% by mass or more and 50% by mass or less, can solve the aforementioned problems, and have completed the present invention.

[0007] In other words, the present invention is as follows: [1] A resin composition comprising a phenol-modified aromatic hydrocarbon formaldehyde resin A obtained by the reaction of phenol with an aromatic hydrocarbon formaldehyde resin, and a compound (1) represented by the following general formula (1), wherein the content of the compound (1) in the resin composition is 5% by mass or more and 50% by mass or less. [2] The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to [1], wherein the viscosity of the phenol-modified aromatic hydrocarbon formaldehyde resin A at 25°C is 500 mPa·s or more and 6,000 mPa·s or less. [3] The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to [1] or [2], wherein the content of compound (1) in the phenol-modified aromatic hydrocarbon formaldehyde resin A is less than 5% by mass. [4] The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of [1] to [3], wherein the hydroxyl value of the phenol-modified aromatic hydrocarbon formaldehyde resin A is 20 mg KOH / g or more and 200 mg KOH / g or less. [5] The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of [1] to [4], wherein the weight-average molecular weight of the phenol-modified aromatic hydrocarbon formaldehyde resin A is 200 or more and 2,000 or less. [6] The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of [1] to [5], wherein the reaction mass ratio (phenol / aromatic hydrocarbon formaldehyde resin) of phenol to the aromatic hydrocarbon formaldehyde resin A is 0.1 or more and 1.5 or less. [7] The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of [1] to [6], wherein the compound (1) is included as a resin mixture B containing the compound (1). [8] The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to [7], wherein the content of the compound (1) in the resin mixture B is more than 50% by mass. [9] The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of [1] to [8], wherein the viscosity at 25°C is 500 mPa·s or more and 10,000 mPa·s or less.

[10] A phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of [1] to [9], wherein the hydroxyl value is 40 mg KOH / g or more and 300 mg KOH / g or less.

[11] A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition comprising the following steps 1 to 3, wherein the content of compound (1) represented by the following general formula (1) in the phenol-modified aromatic hydrocarbon formaldehyde resin composition is 5% by mass or more and 50% by mass or less. Step 1: A step of reacting phenol with an aromatic hydrocarbon formaldehyde resin to obtain a phenol-modified aromatic hydrocarbon formaldehyde resin A. Step 2: A step of reacting phenol with compound (a) represented by the following general formula (a) to obtain a resin mixture B containing compound (1) represented by the following general formula (1). Step 3: A step of mixing the phenol-modified aromatic hydrocarbon formaldehyde resin A and the resin mixture B. (However, R represents one of the following: a hydrogen atom, a methyl group, or a methoxymethyl group.)

[12] A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to

[11] , wherein in step 1, the reaction mass ratio of phenol to the aromatic hydrocarbon formaldehyde resin (phenol / aromatic hydrocarbon formaldehyde resin) is 0.1 or more and 1.5 or less.

[13] A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to

[11] or

[12] , wherein in step 2, the reaction mass ratio of phenol to compound (a) (phenol / compound (a)) is 0.3 or more and 2.0 or less.

[14] A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of

[11] to

[13] , wherein the viscosity of the resin mixture B at 25°C is 500 mPa·s or more and 20,000 mPa·s or less.

[15] A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of

[11] to

[14] , wherein the content of compound (1) in the resin mixture B is more than 50% by mass.

[16] A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of

[11] to

[15] , wherein the hydroxyl value of the resin mixture B is 100 mg KOH / g or more and 350 mg KOH / g or less.

[17] A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of

[11] to

[16] , wherein the weight-average molecular weight of the resin mixture B is 200 or more and 1,500 or less.

[18] A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of

[11] to

[17] , wherein in step 3, the mixed mass ratio of the phenol-modified aromatic hydrocarbon formaldehyde resin A and the resin mixture B is 0.1 or more and 30.0 or less.

[0008] According to the present invention, a phenol-modified aromatic hydrocarbon formaldehyde resin composition and the phenol-modified aromatic hydrocarbon formaldehyde resin composition can be provided, which can improve the low-temperature curability and impact resistance of epoxy resins and the like.

[0009] [Phenol-Modified Aromatic Hydrocarbon Formaldehyde Resin Composition] The phenol-modified aromatic hydrocarbon formaldehyde resin composition of this embodiment (hereinafter also simply referred to as "resin composition") is a resin composition comprising a phenol-modified aromatic hydrocarbon formaldehyde resin A obtained by the reaction of phenol with an aromatic hydrocarbon formaldehyde resin, and a compound (1) represented by the following general formula (1), wherein the content of the compound (1) in the resin composition is 5% by mass or more and 50% by mass or less.

[0010]

[0011] The resin composition of this embodiment contains the phenol-modified aromatic hydrocarbon formaldehyde resin A, and when used in epoxy resins, it can improve the low-temperature curability and impact resistance of the resin. Furthermore, the resin composition of this embodiment can further improve the low-temperature curability of epoxy resins by having a compound (1) content of 5% by mass or more, and can suppress the decrease in impact resistance of epoxy resins by having a compound (1) content of 50% by mass or less. Therefore, from the above viewpoint, the resin composition of this embodiment can improve the low-temperature curability and impact resistance of epoxy resins.

[0012] The resin composition of this embodiment contains the phenol-modified aromatic hydrocarbon formaldehyde resin A and compound (1), and therefore offers superior handling. In this invention, "handling" refers particularly to the ease of handling when manipulating the resin composition, and "superior handling" indicates that the resin composition is easy to handle.

[0013] In the resin composition of this embodiment, the content of compound (1) in the resin composition is preferably 6% by mass or more and 45% by mass or less, more preferably 6% by mass or more and 30% by mass or less, even more preferably 6.5% by mass or more and 20% by mass or less, even more preferably 7% by mass or more and 15% by mass or less, and even more preferably 7.5% by mass or more and 12% by mass or less, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. The content of compound (1) in the resin composition can be measured by the method described in the examples. If compound (1) is contained in a small amount in the phenol-modified aromatic hydrocarbon formaldehyde resin A, the content of compound (1) in the resin composition will also include the compound (1) contained in the phenol-modified aromatic hydrocarbon formaldehyde resin A.

[0014] In the resin composition of this embodiment, the viscosity at 25°C is preferably 500 mPa·s to 10,000 mPa·s from the viewpoint of improving handling properties and improving the low-temperature curability and impact resistance of the epoxy resin. Furthermore, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin, it is more preferably 2,500 mPa·s to 10,000 mPa·s, even more preferably 3,000 mPa·s to 8,000 mPa·s, even more preferably 3,500 mPa·s to 7,000 mPa·s, and even more preferably 4,000 mPa·s to 5,000 mPa·s. In addition, because the resin composition of this embodiment has a viscosity of less than 2,500 mPa·s, it can be efficiently mixed with epoxy resins when used with epoxy resins, etc. Furthermore, the viscosity of the resin composition of this embodiment is less than 2,500 mPa·s, which makes it easier to handle from the storage container and reduces loss due to adhesion to the walls of the storage container. In other words, the resin composition of the present invention has excellent handling properties because its viscosity is less than 2,500 mPa·s. Therefore, from the viewpoint of improving handling properties, as well as improving the low-temperature curability and impact resistance of the epoxy resin, it is more preferably 500 mPa·s or more and less than 2,500 mPa·s, even more preferably 600 mPa·s or more and 2,000 mPa·s or less, even more preferably 650 mPa·s or more and 1,800 mPa·s or less, and even more preferably 700 mPa·s or more and 1,500 mPa·s or less. The viscosity of the resin composition at 25°C can be measured using an E-type viscometer, and specifically can be measured by the method of the example.

[0015] In the resin composition of this embodiment, the hydroxyl value is preferably 40 mg KOH / g or more and 300 mg KOH / g or less, more preferably 45 mg KOH / g or more and 200 mg KOH / g or less, even more preferably 50 mg KOH / g or more and 150 mg KOH / g or less, and even more preferably 55 mg KOH / g or more and 120 mg KOH / g or less. When the hydroxyl value of the resin composition is 50 mg KOH / g or more, the low-temperature curability of the epoxy resin can be further improved. Also, when the hydroxyl value of the resin composition is 300 mg KOH / g or less, the impact resistance of the epoxy resin can be further improved. The hydroxyl value of the resin composition can be measured by the method described in the examples.

[0016] In the resin composition of this embodiment, the number average molecular weight is preferably 200 to 2,000, more preferably 210 to 1,500, even more preferably 230 to 1,000, even more preferably 250 to 400, and even more preferably 250 to 300, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. Furthermore, in the resin composition of this embodiment, the weight average molecular weight is preferably 200 to 2,000, more preferably 250 to 1,500, even more preferably 280 to 1,000, even more preferably 300 to 500, and even more preferably 320 to 400, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. The number average molecular weight and weight average molecular weight of the resin composition can be measured by gel permeation chromatography (GPC), specifically by the method described in the examples.

[0017] <Phenol-Modified Aromatic Hydrocarbon Formaldehyde Resin A> In this embodiment, phenol-modified aromatic hydrocarbon formaldehyde resin A is obtained by the reaction of phenol with an aromatic hydrocarbon formaldehyde resin. In this embodiment, phenol-modified aromatic hydrocarbon formaldehyde resin A can be obtained, for example, by reacting phenol with an aromatic hydrocarbon formaldehyde resin in the presence of an acidic catalyst.

[0018] (Aromatic hydrocarbon formaldehyde resin) Aromatic hydrocarbon formaldehyde resin is a resin obtained by reacting aromatic hydrocarbons with formaldehyde. In this specification, aromatic hydrocarbon formaldehyde resin means an unmodified aromatic hydrocarbon formaldehyde resin that has not been modified with other functional groups, etc.

[0019] Examples of aromatic hydrocarbons include at least one selected from the group consisting of benzene, toluene, xylene, mesitylene, pseudocumene, ethylbenzene, propylbenzene, decylbenzene, cyclohexylbenzene, biphenyl, methylbiphenyl, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, anthracene, methylanthracene, dimethylanthracene, ethylanthracene, and binaphthyl. Among these, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin, the aromatic hydrocarbon preferably includes at least one selected from the group consisting of toluene, xylene, mesitylene, and pseudocumene, and more preferably includes xylene.

[0020] As formaldehyde, industrially readily available formalin and paraformaldehyde, as well as formaldehyde-generating compounds such as trioxane, can be used.

[0021] The aromatic hydrocarbon formaldehyde resin preferably comprises at least one selected from tolueneformaldehyde resin obtained by reacting toluene with formaldehyde, xyleneformaldehyde resin obtained by reacting xylene with formaldehyde, mesityleneformaldehyde resin obtained by reacting mesitylene with formaldehyde, and pseudocumeneformaldehyde resin obtained by reacting pseudocumene with formaldehyde, and more preferably comprises xyleneformaldehyde resin.

[0022] The viscosity of aromatic hydrocarbon formaldehyde resin at 25°C is preferably 30 mPa·s to 1000 mPa·s, more preferably 35 mPa·s to 500 mPa·s, even more preferably 40 mPa·s to 300 mPa·s, and even more preferably 45 mPa·s to 150 mPa·s, from the viewpoint of improving handling properties and the low-temperature curability and impact resistance of epoxy resins. The viscosity of aromatic hydrocarbon formaldehyde resin at 25°C can be measured using an E-type viscometer.

[0023] The hydroxyl value of aromatic hydrocarbon formaldehyde resin is preferably 10 mg KOH / g or more and 45 mg KOH / g or less, more preferably 12 mg KOH / g or more and 40 mg KOH / g or less, even more preferably 15 mg KOH / g or more and 35 mg KOH / g or less, and even more preferably 20 mg KOH / g or more and 30 mg KOH / g or less, from the viewpoint of improving the low-temperature curability and impact resistance of epoxy resin. The hydroxyl value of aromatic hydrocarbon formaldehyde resin can be measured according to the anhydride acetate-pyridine method (JIS K 1557-1:2007).

[0024] The number-average molecular weight of aromatic hydrocarbon formaldehyde resin is preferably 200 to 2,000, more preferably 205 to 1,000, even more preferably 210 to 500, and even more preferably 220 to 300, in terms of standard polystyrene, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. Furthermore, the weight-average molecular weight of aromatic hydrocarbon formaldehyde resin is preferably 200 to 2,000, more preferably 230 to 1,000, even more preferably 250 to 500, and even more preferably 280 to 350, in terms of standard polystyrene, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. The number-average molecular weight and weight-average molecular weight of aromatic hydrocarbon formaldehyde resin can be measured by gel permeation chromatography (GPC).

[0025] Aromatic hydrocarbon formaldehyde resins may be commercially available or manufactured by known methods. Examples of methods for producing aromatic hydrocarbon formaldehyde resins include the method described in Japanese Patent Publication No. 37-5747, which involves a condensation reaction of aromatic hydrocarbons and formaldehyde in the presence of a catalyst. Examples of commercially available aromatic hydrocarbon formaldehyde resins include "Nikanol Y-50," "Nikanol Y-100," and "Nikanol Y-300," which are xylene formaldehyde resins manufactured by Fudo Co., Ltd.

[0026] In this embodiment, the viscosity of the phenol-modified aromatic hydrocarbon formaldehyde resin A at 25°C is preferably 500 mPa·s or more and 6,000 mPa·s or less, from the viewpoint of improving handling properties and improving the low-temperature curability and impact resistance of the epoxy resin. Furthermore, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin, it is more preferably 2,000 mPa·s or more and 6,000 mPa·s or less, even more preferably 2,500 mPa·s or more and 5,000 mPa·s or less, even more preferably 2,800 mPa·s or more and 4,000 mPa·s or less, and even more preferably 3,000 mPa·s or more and 3,500 mPa·s or less. Furthermore, from the viewpoint of improving handling ease, as well as improving the low-temperature curability and impact resistance of the epoxy resin, it is more preferably 500 mPa·s or more and less than 2,000 mPa·s, even more preferably 500 mPa·s or more and 1,800 mPa·s or less, even more preferably 550 mPa·s or more and 1,500 mPa·s or less, and even more preferably 600 mPa·s or more and 1,000 mPa·s or less. The viscosity of phenol-modified aromatic hydrocarbon formaldehyde resin A at 25°C can be measured using an E-type viscometer, and specifically can be measured by the method described in the examples.

[0027] In this embodiment, the phenol-modified aromatic hydrocarbon formaldehyde resin A may contain a small amount of compound (1). In this embodiment, the content of compound (1) in the phenol-modified aromatic hydrocarbon formaldehyde resin A is preferably less than 5% by mass, more preferably 4.5% by mass or less, and even more preferably 4.0% by mass or less, from the viewpoint of setting the content of compound (1) in the resin composition to a desired range and improving the low-temperature curability and impact resistance of the epoxy resin. The content of compound (1) in the phenol-modified aromatic hydrocarbon formaldehyde resin A can be measured by the method described in the examples.

[0028] In this embodiment, the hydroxyl value of the phenol-modified aromatic hydrocarbon formaldehyde resin A is preferably 20 mg KOH / g or more and 200 mg KOH / g or less, more preferably 30 mg KOH / g or more and 180 mg KOH / g or less, even more preferably 40 mg KOH / g or more and 150 mg KOH / g or less, even more preferably 45 mg KOH / g or more and 120 mg KOH / g or less, and even more preferably 45 mg KOH / g or more and 80 mg KOH / g or less, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. The hydroxyl value of the phenol-modified aromatic hydrocarbon formaldehyde resin A can be measured by the method described in the examples.

[0029] In this embodiment, the number-average molecular weight of the phenol-modified aromatic hydrocarbon formaldehyde resin A is preferably 200 to 2,000, more preferably 210 to 1,500, even more preferably 230 to 1,000, even more preferably 250 to 400, and even more preferably 250 to 300, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. Also in this embodiment, the weight-average molecular weight of the phenol-modified aromatic hydrocarbon formaldehyde resin A is preferably 200 to 2,000, more preferably 250 to 1,500, even more preferably 300 to 1,000, even more preferably 320 to 600, and even more preferably 340 to 450, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. The number-average molecular weight and weight-average molecular weight of the phenol-modified aromatic hydrocarbon formaldehyde resin A can be measured by gel permeation chromatography (GPC), specifically by the method described in the examples.

[0030] In this embodiment, the reaction mass ratio (phenol / aromatic hydrocarbon formaldehyde resin) between phenol and the aromatic hydrocarbon formaldehyde resin in the phenol-modified aromatic hydrocarbon formaldehyde resin A is preferably 0.1 to 1.5, more preferably 0.2 to 1.3, even more preferably 0.3 to 1.0, and even more preferably 0.4 to 0.6, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin.

[0031] Furthermore, in this embodiment, the phenol-modified aromatic hydrocarbon formaldehyde resin A can be a commercially available product. Examples of commercially available products include "Nikanol YP," a phenol-modified xylene formaldehyde resin manufactured by Fudo Co., Ltd.

[0032] In this embodiment, since the phenol-modified aromatic hydrocarbon formaldehyde resin A is obtained from an aromatic hydrocarbon formaldehyde resin having a structure that is difficult to identify by analysis, it is also difficult to identify the structure of the phenol-modified aromatic hydrocarbon formaldehyde resin A by analysis.

[0033] <Compound (1)> In this embodiment, compound (1) is obtained, for example, by the reaction of phenol with a compound (a) represented by the following general formula (a). More specifically, compound (1) can be obtained by reacting phenol with a compound (a) represented by the following general formula (a) in the presence of an acidic catalyst.

[0034] (However, R represents any one of a hydrogen atom, a methyl group, and a methoxymethyl group.)

[0035] In this embodiment, compound (1) may be included as a resin mixture B containing compound (1). The resin mixture B can be obtained, for example, by reacting phenol with compound (a) or a mixture containing compound (a). More specifically, the resin mixture B can be obtained by reacting phenol with compound (a) or a mixture containing compound (a) in the presence of an acidic catalyst. Also, the resin mixture B can be obtained by step 2 in the method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin described below.

[0036] In this embodiment, when compound (1) is included as a resin mixture B containing compound (1), the content of compound (1) in the resin mixture B is set to a desired range for the content of compound (1) in the resin composition. From the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin, it is preferably more than 50% by mass, more preferably more than 50% by mass and 100% by mass or less, still more preferably 55% by mass or more and 100% by mass or less, even more preferably 58% by mass or more and 90% by mass or less, and even more preferably 60% by mass or more and 80% by mass or less. The content of compound (1) in the resin mixture B can be measured by the method described in the examples.

[0037] In this embodiment, when compound (1) is included as resin mixture B containing compound (1), resin mixture B may also contain other components besides compound (1). Examples of other components besides compound (1) include unreacted phenol, unreacted compound (a), the above-mentioned aromatic hydrocarbon formaldehyde resin, and phenol-modified aromatic hydrocarbon formaldehyde resin. The phenol-modified aromatic hydrocarbon formaldehyde resin contained in resin mixture B may be the same as or different from the above-mentioned phenol-modified aromatic hydrocarbon formaldehyde resin A. Since these other components besides compound (1) include aromatic hydrocarbon formaldehyde resins and phenol-modified aromatic hydrocarbon formaldehyde resins that have structures that are difficult to identify by analysis, it is difficult to analyze and identify the structures of the other components besides compound (1) in the mixture containing compound (1).

[0038] In this embodiment, the content of phenol-modified aromatic hydrocarbon formaldehyde resin A in the resin composition is preferably 10% by mass or more and 98% by mass or less, more preferably 55% by mass or more and 96% by mass or less, even more preferably 70% by mass or more and 95% by mass or less, even more preferably 80% by mass or more and 94% by mass or less, and even more preferably 85% by mass or more and 93% by mass or less, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin.

[0039] Furthermore, in the resin composition of this embodiment, if compound (1) is included as resin mixture B containing compound (1), the resin composition may also contain other components. These other components are the same as the other components other than compound (1) in the resin mixture B described above.

[0040] <Applications> Because the resin composition of this embodiment has the above-described characteristics, when used as an additive to epoxy resin, it can improve the low-temperature curability and impact resistance of the resulting epoxy resin composition. Therefore, the resin composition of the present invention can be suitably used as an additive to epoxy resin. Furthermore, because epoxy resin compositions containing the resin composition of this embodiment have excellent low-temperature curability and impact resistance, they can be suitably used as raw materials for adhesives, sealants, paints, coatings and encapsulants used in electronic components, etc.

[0041] (Epoxy Resin) The epoxy resin is preferably a polyfunctional epoxy resin having two or more epoxy groups in its molecule. The epoxy resin may be a saturated or unsaturated linear aliphatic epoxy resin, or an epoxy resin having a cyclic structure such as an aromatic ring, alicyclic structure, or heterocyclic structure.

[0042] Specific examples of epoxy resins include epoxy resins having glycidylamino groups derived from metaxylylenediamine, epoxy resins having glycidylamino groups derived from paraxylylenediamine, epoxy resins having glycidylamino groups derived from 1,3-bis(aminomethyl)cyclohexane, epoxy resins having glycidylamino groups derived from 1,4-bis(aminomethyl)cyclohexane, epoxy resins having glycidylamino groups derived from diaminodiphenylmethane, and epoxy resins having glycidylamino groups and / or glycidyloxy groups derived from para-aminophenol. Examples include at least one resin selected from epoxy resins having a glycidyloxy group derived from bisphenol A, epoxy resins having a glycidyloxy group derived from bisphenol F, epoxy resins having a glycidyloxy group derived from phenol novolac, epoxy resins having a glycidyloxy group derived from hydrogenated bisphenol A, epoxy resins having a glycidyloxy group derived from hydrogenated bisphenol F, epoxy resins having a glycidyloxy group derived from hydrogenated phenol novolac, and epoxy resins having a glycidyloxy group derived from resorcinol. One or more of the above epoxy resins can be used. Furthermore, there are no particular limitations on the curing agent for the epoxy resin, but for example, amine compounds, polyfunctional phenols, acid anhydride compounds, amide compounds, etc., can be used.

[0043] [Method for Producing a Phenol-Modified Aromatic Hydrocarbon Formaldehyde Resin Composition] The method for producing the phenol-modified aromatic hydrocarbon formaldehyde resin composition of this embodiment (hereinafter also simply referred to as the "production method") comprises the following steps 1 to 3, wherein the content of compound (1) represented by the following general formula (1) in the phenol-modified aromatic hydrocarbon formaldehyde resin composition is 5% by mass or more and 50% by mass or less. Step 1: A step of reacting phenol with an aromatic hydrocarbon formaldehyde resin to obtain a phenol-modified aromatic hydrocarbon formaldehyde resin A. Step 2: A step of reacting phenol with compound (a) represented by the following general formula (a) to obtain a resin mixture B containing compound (1) represented by the following general formula (1). Step 3: A step of mixing the phenol-modified aromatic hydrocarbon formaldehyde resin A and the resin mixture B.

[0044] (However, R represents one of the following: a hydrogen atom, a methyl group, or a methoxymethyl group.)

[0045]

[0046] <Step 1> Step 1 is a step of reacting phenol with an aromatic hydrocarbon formaldehyde resin to obtain phenol-modified aromatic hydrocarbon formaldehyde resin A. In Step 1, the reaction between phenol and aromatic hydrocarbon formaldehyde resin is preferably carried out in the presence of an acidic catalyst. That is, Step 1 is preferably a step of reacting phenol with an aromatic hydrocarbon formaldehyde resin in the presence of an acidic catalyst to obtain phenol-modified aromatic hydrocarbon formaldehyde resin A.

[0047] When an acid catalyst is used in step 1, the acid catalyst is not particularly limited, but p-toluenesulfonic acid, metaxylenesulfonic acid, or p-toluenesulfonic acid chloride can be used. In step 1, the reaction temperature of the reaction between phenol and aromatic hydrocarbon formaldehyde resin is preferably 70°C to 130°C, more preferably 80°C to 110°C. The reaction time is not particularly limited, but is preferably 0.5 hours to 5 hours, more preferably 1 hour to 3 hours. In step 1, the reaction between phenol and aromatic hydrocarbon formaldehyde resin may be carried out in an atmospheric environment or in an inert gas atmosphere such as a nitrogen atmosphere.

[0048] Step 1 is preferably a further purification after the reaction of phenol with aromatic hydrocarbon formaldehyde resin, from the viewpoint of removing unreacted phenol, unreacted aromatic hydrocarbon formaldehyde resin, and by-products. As a purification method, distillation purification is preferred from the viewpoint of efficiently removing unreacted phenol, unreacted aromatic hydrocarbon formaldehyde resin, and by-products. When distillation purification is performed in Step 1, the temperature during distillation purification is preferably 140°C to 200°C, more preferably 160°C to 180°C. Furthermore, the pressure during distillation purification is preferably under reduced pressure, specifically, an absolute pressure of preferably 5 kPa or less, more preferably 3 kPa or less.

[0049] In step 1, when distillation purification is performed, the distillate obtained from the distillation purification mainly contains unreacted phenol, as well as a large amount of compound (a). Therefore, this distillate can be recycled and reused as a raw material for the resin composition of the present invention.

[0050] In step 1, the reaction mass ratio of phenol to the aromatic hydrocarbon formaldehyde resin (phenol / aromatic hydrocarbon formaldehyde resin) is preferably 0.1 to 1.5, more preferably 0.2 to 1.3, even more preferably 0.3 to 1.0, and even more preferably 0.4 to 0.6, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin.

[0051] <Step 2> Step 2 is a step of reacting phenol with compound (a) to obtain resin mixture B containing compound (1). In Step 2, the reaction between phenol and compound (a) is preferably carried out in the presence of an acidic catalyst. That is, Step 2 is preferably a step of reacting phenol and compound (a) in the presence of an acidic catalyst to obtain resin mixture B.

[0052] In compound (a), R in the above general formula (a) is preferably one or more selected from a hydrogen atom, a methyl group, and a methoxymethyl group, from the viewpoint of adjusting the content of (1) in the resin composition and making it easier to set the content of (1) in the resin composition to a desired range. Furthermore, compound (a) may be just one type or a mixture of two or more types. Here, compound (a) is present in large quantities in the distillate when distillation purification is performed when producing unmodified aromatic hydrocarbon formaldehyde resin, which is a raw material for phenol-modified aromatic hydrocarbon formaldehyde resin. That is, compound (a) can be mainly obtained as the main component of the distillate when distillation purification is performed when an aromatic hydrocarbon and formaldehyde are reacted to obtain an aromatic hydrocarbon formaldehyde resin.

[0053] Step 2 may be a step of reacting phenol with a mixture containing compound (a) to obtain resin mixture B. As the mixture containing compound (a), for example, the distillate from distillation purification when reacting the aromatic hydrocarbon with formaldehyde to obtain aromatic hydrocarbon formaldehyde resin may be used. When compound (a) is used in Step 2, the mixture containing compound (a) may also contain other components other than compound (a). Other components other than compound (a) include unreacted phenol, the above-mentioned aromatic hydrocarbon formaldehyde resin, etc. Since these other components other than compound (a) include aromatic hydrocarbon formaldehyde resin which has a structure that is difficult to identify by analysis, it is difficult to analyze and identify the structure of the other components in the mixture containing compound (a). When a mixture containing compound (a) is used in Step 2, the content of compound (a) in the mixture containing compound (a) is preferably 80% by mass or more, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin, while keeping the content of compound (1) in the resin composition within a desired range. Furthermore, the content of other components in the mixture containing compound (a) is preferably 20% by mass or less, from the viewpoint of setting the content of compound (1) in the resin composition to a desired range.

[0054] When an acid catalyst is used in step 2, the acid catalyst is not particularly limited, but p-toluenesulfonic acid, metaxylenesulfonic acid, or p-toluenesulfonic acid chloride can be used. In step 2, the reaction temperature for the reaction with compound (a) is preferably 110°C to 160°C, more preferably 120°C to 150°C. The reaction time is not particularly limited, but is preferably 0.5 hours to 5 hours, more preferably 1 hour to 3 hours. In step 2, the reaction between phenol and compound (a) may be carried out in an atmospheric environment or in an inert gas atmosphere such as a nitrogen atmosphere.

[0055] Step 2 is preferably a further purification after the reaction between phenol and compound (a), from the viewpoint of removing unreacted phenol, unreacted compound (a), and by-products. As a purification method, distillation purification is preferred from the viewpoint of efficiently removing unreacted phenol, unreacted compound (a), and by-products. When distillation purification is performed in Step 2, the temperature during distillation purification is preferably 140°C to 200°C, more preferably 160°C to 180°C. Furthermore, the pressure during distillation purification is preferably reduced pressure, specifically, an absolute pressure of preferably 5 kPa or less, more preferably 3 kPa or less.

[0056] Furthermore, in step 2, it is preferable to react phenol with compound (a) to obtain resin mixture B, and then isolate and purify compound (1) from the obtained resin mixture B. In step 3, it is preferable to use the isolated and purified compound (1) instead of resin mixture B, as this makes it easier to adjust the content of compound (1) in the resin composition to a desired range and to further reduce impurities in the resin composition. As a method of isolation and purification, one method is to distill and purify the resin mixture B obtained in step 2, and then further fractionate it. As a method of fractionate fractionate compound (1), for example, after distilling and purifying the resin mixture B obtained in step 2, compound (1) can be recovered with a high purity of 98% or more by further recovering a fraction with an absolute pressure of 0.6 kPa or more and 0.7 kPa or less, and a vapor temperature of 188°C or more and 200°C or less.

[0057] In step 2, when distillation purification is performed, the distillate obtained from the distillation purification mainly contains unreacted phenol, as well as a large amount of compound (a). Therefore, this distillate can be recycled and reused as a raw material for the resin composition of the present invention.

[0058] In step 2, the reaction mass ratio of phenol to compound (a) (phenol / compound (a)) is preferably 0.3 to 2.0, more preferably 0.5 to 1.8, even more preferably 0.6 to 1.5, and even more preferably 0.8 to 1.2, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin.

[0059] (Physical properties of resin mixture B) The viscosity of resin mixture B at 25°C is preferably 500 mPa·s to 20,000 mPa·s, more preferably 2,000 mPa·s to 12,000 mPa·s, even more preferably 3,000 mPa·s to 8,000 mPa·s, even more preferably 2,500 mPa·s to 6,000 mPa·s, and even more preferably 3,000 mPa·s to 5,000 mPa·s, from the viewpoint of improving handling properties and improving the low-temperature curability and impact resistance of the epoxy resin. The viscosity of resin mixture B at 25°C can be measured using an E-type viscometer, and specifically can be measured by the method of the example.

[0060] The content of compound (1) in resin mixture B is preferably more than 50% by mass, more preferably 55% by mass or more, even more preferably 56% by mass or more, even more preferably 58% by mass or more, and even more preferably 60% by mass or more, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin, while keeping the content of compound (1) in the resin composition within a desired range. Furthermore, the upper limit of the content of compound (1) in resin mixture B is preferably 100% by mass or less, and even more preferably 99% by mass or less from the viewpoint of productivity. The content of compound (1) in resin mixture B can be measured by the method described in the examples.

[0061] The hydroxyl value of resin mixture B is preferably 100 mg KOH / g or more and 350 mg KOH / g or less, more preferably 150 mg KOH / g or more and 300 mg KOH / g or less, even more preferably 180 mg KOH / g or more and 280 mg KOH / g or less, and even more preferably 200 mg KOH / g or more and 250 mg KOH / g or less, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. The hydroxyl value of resin mixture B can be measured by the method described in the examples.

[0062] The number-average molecular weight of resin mixture B is preferably 200 to 1,500, more preferably 210 to 1,000, even more preferably 230 to 500, and even more preferably 250 to 330, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. Furthermore, the weight-average molecular weight of resin mixture B is preferably 200 to 1,500, more preferably 210 to 1,000, even more preferably 230 to 500, and even more preferably 250 to 330, from the viewpoint of improving the low-temperature curability and impact resistance of the epoxy resin. The number-average molecular weight and weight-average molecular weight of resin mixture B can be measured by gel permeation chromatography (GPC), specifically by the method described in the examples.

[0063] <Step 3> Step 3 is a step of mixing the phenol-modified aromatic hydrocarbon formaldehyde resin A obtained in Step 1 with the resin mixture B obtained in Step 2. Furthermore, if compound (1) is isolated and purified in Step 2, it is preferable that Step 3 is a step of mixing the phenol-modified aromatic hydrocarbon formaldehyde resin A obtained in Step 1 with compound (1) obtained in Step 2. As for the mixing method in Step 3, it can be done by known methods such as stirring or shaking. The temperature during mixing in Step 3 is preferably 60°C to 100°C, more preferably 70°C to 90°C, from the viewpoint of keeping the viscosity of the resin composition at 25°C within the above range.

[0064] In step 3, the mixed mass ratio of phenol-modified aromatic hydrocarbon formaldehyde resin A and resin mixture B (phenol-modified aromatic hydrocarbon formaldehyde resin A / resin mixture B) is preferably 0.1 to 30.0, more preferably 1.0 to 20.0, even more preferably 5.0 to 15.0, and even more preferably 8.0 to 12.0, from the viewpoint of setting the content of compound (1) in the resin composition to a desired range and improving the low-temperature curability and impact resistance of the epoxy resin.

[0065] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0066] [Measurement] <Identification of compound (1) and compound (a)> １ H-NMR was performed to identify the cells under the following measurement conditions. (Measurement conditions) Instrument name: AVANCE NEO 400 (manufactured by Bruker Corporation) Measurement frequency: 400 MHz Solvent: Deuterated chloroform (CDCl ３ ) Sample concentration: 0.8–1.0 wt% Chemical shift correction: Solvent peak (Proton of chloroform in deuterated chloroform) １ Peak of H: δ ｐｐｍ (7.26) was used as the baseline.

[0067] <Content of Compound (1)> The content of Compound (1) was measured using a gas chromatograph (model: GC-2010, manufactured by Shimadzu Corporation) with a nonpolar column (DB-1, manufactured by Agilent) under the following measurement conditions. (Measurement conditions) Carrier gas: Nitrogen gas Total gas flow rate: 58.1 mL / min Vaporization chamber temperature: 250°C Column temperature: 100-280°C Column heating rate: 5°C / min Detector temperature: 280°C

[0068] <Content of Compound (a)> The content of compound (a) in the raw materials of resin mixture B was measured using a gas chromatograph (model: GC-2010, manufactured by Shimadzu Corporation) with a nonpolar column (DB-1, manufactured by Agilent) under the following measurement conditions. (Measurement conditions) Carrier gas: Nitrogen gas Total gas flow rate: 58.1 mL / min Vaporization chamber temperature: 250°C Column temperature: 100-280°C Column heating rate: 5°C / min Detector temperature: 280°C

[0069] <Viscosity at 25°C> Viscosity was measured using an E-type viscometer (rotor No. 1, manufactured by Tokyo Keiki Co., Ltd.) under the conditions of a sample temperature of 25°C and a rotation speed of 3 rpm.

[0070] <Hydroxyl Value> Measured according to the acetic anhydride-pyridine method (JIS K 1557-1:2007).

[0071] <Number-average molecular weight (Mn), weight-average molecular weight (Mw)> The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured using polystyrene as a standard substance by gel permeation chromatography (GPC) under the following conditions. (Measurement conditions) Apparatus: Shodex GPC-101 (manufactured by Resonaq Corporation) Column: Shodex LF-804 x 3 (manufactured by Resonaq Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Column temperature: 40°C Detector: RI (Differential Refraction Detector)

[0072] [Production of Resin Composition] <Example 1> (Step 1: Production of phenol-modified aromatic hydrocarbon formaldehyde resin A1) 550 g of Nikanol Y-100 (manufactured by Fudo Co., Ltd.), 303 g of phenol, and 0.064 g of p-toluenesulfonic acid monohydrate were charged into a 1000 mL separable flask equipped with a thermometer and a stirrer, and heated to 88°C while stirring. After reacting at the above temperature for 1.5 hours, 0.038 g of potassium hydroxide was added to stop the reaction. Then, unreacted phenol was removed under conditions of 175°C and a pressure of 1.5 kPa (absolute pressure) to obtain phenol-modified aromatic hydrocarbon formaldehyde resin A1. The obtained phenol-modified aromatic hydrocarbon formaldehyde resin A1 is shown in Table 1.

[0073] Table 1 shows the following details regarding Nikanol Y-100, which was used as the aromatic hydrocarbon formaldehyde resin in Step 1: Nikanol Y-100: Manufactured by Fudo Co., Ltd., xylene formaldehyde resin, viscosity (25°C): 100 mPa·s, hydroxyl value: 25 mgKOH / g, number average molecular weight (Mn): 238, weight average molecular weight (Mw): 335

[0074]

[0075] (Step 2: Production of Resin Mixture B) 475 g of a mixture containing compound (a) described in Table 2 (content of compound (a): 87.8% by mass), 380 g of phenol, and 0.064 g of p-toluenesulfonic acid monohydrate were charged into a 1000 mL separable flask equipped with a thermometer and a stirrer, and heated to 135°C while stirring. After reacting at the said temperature for 1.5 hours, 0.038 g of potassium hydroxide was added to stop the reaction. Next, unreacted phenol was removed under the conditions of a temperature of 175°C and a pressure of 1.5 kPa (absolute pressure) to obtain resin mixture B. The obtained resin mixture B is shown in Table 3.

[0076]

[0077]

[0078] (Step 3: Mixing of Phenol-Modified Aromatic Hydrocarbon Formaldehyde Resin A1 and Resin Mixture B) The phenol-modified aromatic hydrocarbon formaldehyde resin A1 obtained in Step 1 and the resin mixture B obtained in Step 2 were each heated in a hot water bath at 80°C for 10 minutes. Next, the heated phenol-modified aromatic hydrocarbon formaldehyde resin A1 and resin mixture B were filled into a container in the blending amounts described in Table 4, and the container was shaken by hand to mix them, obtaining a resin composition. The obtained resin composition is shown in Table 4.

[0079] 1H-NMR data of compound (1) are shown below.・Compound (1): １ 1H-NMR (400 MHz, CDCl １ , δ ３ ): 2.26 (s, 3H), 2.31 (s, 3H), 3.93 (s, 2H), 4.70 (s, 1H), 6.79 - 7.15 (m, 7H) ｐｐｍ

[0080] 1H-NMR data of compound (a) are shown below.・Compound (a) (in the above general formula (a), R is a hydrogen atom): １ 1H-NMR (400 MHz, CDCl １ , δ ３ ｐｐｍ): 1.51 (t, J=11.5 Hz, 1H), 2.32 (s, 3H), 2.34 (s, 3H), 4.66 (d, J=5.6 Hz, 2H), 7.01-7.02 (m, 2H), 7.21-7.23 (m, 1H) • Compound (a) (In the above general formula (a), R is a methyl group): １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 2.31 (s, 6H), 3.38 (s, 3H), 4.42 (s, 2H), 6.98-7.00 (m, 2H), 7.18-7.19 (m, 1H) • Compound (a) (In the above general formula (a), R is a methoxymethyl group): １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 2.31 (s, 3H), 2.33 (s, 3H), 3.42 (s, 3H), 4.57 (s, 2H), 4.70 (s, 2H), 6.99-7.01 (m, 2H), 7.21-7.23 (m, 1H)

[0081] <Examples 2-7, Comparative Examples 1-2> Resin compositions were obtained in the same manner as in Example 1, except that the amounts of phenol-modified aromatic hydrocarbon A1 and resin mixture B in step 3 were changed to the amounts shown in Table 4.

[0082] [Evaluation] The resin compositions obtained in the examples and comparative examples were evaluated by the following method. The evaluation results are shown in Table 4.

[0083] <Preparation of Evaluation Samples> (Preparation of Epoxy Resin Composition for Evaluation) A liquid epoxy resin having a glycidyloxy group derived from bisphenol A (Mitsubishi Chemical Corporation, "jER828", epoxy equivalent: 186 g / equivalent) was used as the epoxy resin, and an alicyclic polyamine adduct (Evonik, "ANCAMINE1618", amine equivalent: 105 g / equivalent) was used as the epoxy resin curing agent. Under conditions of 5°C and 80% R.H., 33.6 parts by mass of epoxy resin and 16.4 parts by mass of epoxy resin curing agent were weighed into a 100 mL disposable cup and thoroughly stirred with a wooden spatula for 2 minutes. Then, a blank epoxy resin composition was obtained by degassing using an orbital mixer at 1200 rpm for 5 minutes. Similarly, 30.5 parts by mass of epoxy resin, 14.9 parts by mass of epoxy resin curing agent, and 4.6 parts by mass of the resin composition obtained in the examples and comparative examples were mixed to obtain an epoxy resin composition for evaluation. In Table 4, "blank" refers to the evaluation results when no resin composition was mixed as the epoxy resin sample for evaluation. The "blank" data is shown in Table 4 as data when the resin composition of this embodiment was not used.

[0084] <Low-Temperature Curability> The epoxy resin compositions used for evaluation in each example and comparative example were applied to a substrate (glass plate, size: 2 × 25 × 350 mm) using an applicator under conditions of 5°C and 80% R.H. (film thickness immediately after application: 0.076 μm), and the half-dry time was measured using an RCII type paint drying time measuring instrument (manufactured by TP Giken Co., Ltd.). The half-dry time was evaluated according to ASTM-D5895, at the point when the scratch marks became thinner. A shorter half-dry time under these 5°C and 80% R.H. conditions indicates superior low-temperature curability. The evaluation results are shown in Table 4.

[0085] <Impact Resistance> The epoxy resin compositions of each example and comparative example were applied to a substrate (zinc phosphate treated SPCC steel plate, "SPCC-SD PB-N144" manufactured by Paltec Co., Ltd., size: 0.8 x 70 x 150 mm) using an applicator under conditions of 5°C and 80% R.H. (coating thickness immediately after application: 200 μm), and then left to stand for one week under conditions of 5°C and 80% R.H. to obtain a cured coating film for impact resistance evaluation. The above cured coating film for impact resistance evaluation was subjected to a DuPont impact test using a DuPont impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) under conditions of 23°C and 50% R.H. The evaluation was conducted in accordance with JIS K5600, using a drop weight of 500 ± 1 g, a striking mold with a radius of 6.35 ± 0.03 mm, and a support stand with a radius of 6.35 ± 0.03 mm. The maximum drop distance at which the coating film did not crack or peel was evaluated. The DuPont impact test was performed on both the coated surface and the back surface (substrate side) of the cured coating film used for impact resistance evaluation. A larger maximum drop distance indicates superior impact resistance. The evaluation results are shown in Table 4.

[0086]

[0087] <Example 8> (Production of Resin Composition) (Step 1: Production of Phenol-Modified Aromatic Hydrocarbon Formaldehyde Resin A2) 570 g of Nikanol Y-100 (manufactured by Fudo Co., Ltd.), 285 g of phenol, and 0.064 g of p-toluenesulfonic acid monohydrate were charged into a 1000 mL separable flask equipped with a thermometer and a stirrer, and heated to 88°C while stirring. After reacting at the above temperature for 1.5 hours, 0.038 g of potassium hydroxide was added to stop the reaction. Then, unreacted phenol was removed under conditions of 175°C and a pressure of 1.5 kPa (absolute pressure) to obtain phenol-modified aromatic hydrocarbon formaldehyde resin A2. The obtained phenol-modified aromatic hydrocarbon formaldehyde resin A2 is shown in Table 5.

[0088]

[0089] (Step 2: Production of resin mixture B) Resin composition B was obtained in the same manner as in Step 2 of Example 1.

[0090] (Step 3: Mixing of phenol-modified aromatic hydrocarbon formaldehyde resin A2 and resin mixture B) The phenol-modified aromatic hydrocarbon formaldehyde resin A2 obtained in Step 1 and the resin mixture B obtained in Step 2 were each heated in a water bath at 80°C for 10 minutes. Then, the heated phenol-modified aromatic hydrocarbon formaldehyde resin A2 and resin mixture B were filled into a container in the proportions shown in Table 6, and the container was shaken by hand to mix and obtain a resin composition. The obtained resin composition is shown in Table 6.

[0091] (Evaluation of Example 8) The resin composition obtained in Example 8 was evaluated for low-temperature curability and impact resistance in the same manner as in Examples 1 to 7. The evaluation results are shown in Table 6. Also, as in Table 4, "blank" data is shown in Table 6 as data for when the resin composition of this embodiment was not used.

[0092]

[0093] <Example 9> (Production of Resin Composition) (Step 1: Production of Phenol-Modified Aromatic Hydrocarbon Formaldehyde Resin A3) 590 g of Nikanol Y-100 (manufactured by Fudo Co., Ltd.), 265.5 g of phenol, and 0.026 g of p-toluenesulfonic acid monohydrate were charged into a 1000 mL separable flask equipped with a thermometer and a stirrer, and heated to 90°C while stirring. After reacting at the above temperature for 80 minutes, 0.015 g of potassium hydroxide was added to stop the reaction. Then, unreacted phenol was removed under conditions of 175°C and a pressure of 1.5 kPa (absolute pressure) to obtain phenol-modified aromatic hydrocarbon formaldehyde resin A3. The obtained phenol-modified aromatic hydrocarbon formaldehyde resin A3 is shown in Table 7.

[0094]

[0095] (Step 2: Production of resin mixture B) Resin composition B was obtained in the same manner as in Step 2 of Example 1.

[0096] (Step 3: Mixing of phenol-modified aromatic hydrocarbon formaldehyde resin A3 and resin mixture B) The phenol-modified aromatic hydrocarbon formaldehyde resin A3 obtained in Step 1 and the resin mixture B obtained in Step 2 were each heated in a water bath at 80°C for 10 minutes. Then, the heated phenol-modified aromatic hydrocarbon formaldehyde resin A3 and resin mixture B were filled into a container in the proportions shown in Table 9, and the container was shaken by hand to mix and obtain a resin composition. The obtained resin composition is shown in Table 8.

[0097] (Evaluation of Example 9) The resin composition obtained in Example 9 was evaluated for low-temperature curability and impact resistance in the same manner as in Examples 1 to 7. The evaluation results are shown in Table 8. Also, as in Table 4, "blank" data is shown in Table 8 as data obtained when the resin composition of this embodiment was not used.

[0098]

[0099] Tables 4, 6, and 8 show that the epoxy resin compositions containing the resin compositions of Examples 1 to 9, which are the resin compositions of this embodiment, exhibit significantly improved low-temperature curability and impact resistance compared to the blank data. Furthermore, it is confirmed that the epoxy resin compositions containing the resin compositions of Examples 1 to 9 exhibit a well-balanced improvement in low-temperature curability and impact resistance compared to the epoxy resin compositions containing the resin compositions of Comparative Examples 1 to 2.

[0100] According to the present invention, the low-temperature curing properties and impact resistance of epoxy resins and the like can be improved.

Claims

1. A resin composition comprising a phenol-modified aromatic hydrocarbon formaldehyde resin A obtained by the reaction of phenol with an aromatic hydrocarbon formaldehyde resin, and a compound (1) represented by the following general formula (1), wherein the content of compound (1) in the resin composition is 5% by mass or more and 50% by mass or less.

2. The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to claim 1, wherein the viscosity of the phenol-modified aromatic hydrocarbon formaldehyde resin A at 25°C is 500 mPa·s or more and 6,000 mPa·s or less.

3. The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to claim 1 or 2, wherein the content of compound (1) in the phenol-modified aromatic hydrocarbon formaldehyde resin A is less than 5% by mass.

4. The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 1 to 3, wherein the hydroxyl value of the phenol-modified aromatic hydrocarbon formaldehyde resin A is 20 mg KOH / g or more and 200 mg KOH / g or less.

5. The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 1 to 4, wherein the weight-average molecular weight of the phenol-modified aromatic hydrocarbon formaldehyde resin A is 200 or more and 2,000 or less.

6. The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 1 to 5, wherein the reaction mass ratio (phenol / aromatic hydrocarbon formaldehyde resin) of phenol to the aromatic hydrocarbon formaldehyde resin A is 0.1 or more and 1.5 or less.

7. The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 1 to 6, wherein the compound (1) is included as a resin mixture B containing the compound (1).

8. The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to claim 7, wherein the content of compound (1) in the resin mixture B is more than 50% by mass.

9. The phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 1 to 8, wherein the viscosity at 25°C is 500 mPa·s or more and 10,000 mPa·s or less.

10. A phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 1 to 9, wherein the hydroxyl value is 40 mg KOH / g or more and 300 mg KOH / g or less.

11. A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition comprising the following steps 1 to 3, wherein the content of compound (1) represented by the following general formula (1) in the phenol-modified aromatic hydrocarbon formaldehyde resin composition is 5% by mass or more and 50% by mass or less. Step 1: A step of reacting phenol with an aromatic hydrocarbon formaldehyde resin to obtain a phenol-modified aromatic hydrocarbon formaldehyde resin A. Step 2: A step of reacting phenol with compound (a) represented by the following general formula (a) to obtain a resin mixture B containing compound (1) represented by the following general formula (1). Step 3: A step of mixing the phenol-modified aromatic hydrocarbon formaldehyde resin A and the resin mixture B. (However, R represents one of the following: a hydrogen atom, a methyl group, or a methoxymethyl group.) 12. A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to claim 11, wherein in step 1, the reaction mass ratio (phenol / aromatic hydrocarbon formaldehyde resin) between phenol and the aromatic hydrocarbon formaldehyde resin is 0.1 or more and 1.5 or less.

13. A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to claim 11 or 12, wherein in step 2, the reaction mass ratio (phenol / compound (a)) of phenol to compound (a) is 0.3 or more and 2.0 or less.

14. A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 11 to 13, wherein the viscosity of the resin mixture B at 25°C is 500 mPa·s or more and 20,000 mPa·s or less.

15. A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 11 to 14, wherein the content of compound (1) in the resin mixture B is more than 50% by mass.

16. A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 11 to 15, wherein the hydroxyl value of the resin mixture B is 100 mg KOH / g or more and 350 mg KOH / g or less.

17. A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 11 to 16, wherein the weight-average molecular weight of the resin mixture B is 200 or more and 1,500 or less.

18. A method for producing a phenol-modified aromatic hydrocarbon formaldehyde resin composition according to any one of claims 11 to 17, wherein in step 3, the mixed mass ratio of the phenol-modified aromatic hydrocarbon formaldehyde resin A and the resin mixture B is 0.1 or more and 30.0 or less.

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