Phenoxy resin, composition, cured product, and method for producing phenoxy resin

Abstract

To provide a phenoxy resin capable of giving a cured product having a high biomass component ratio and high pencil hardness.SOLUTION: The phenoxy resin contains: a structure derived from a phenol substituted with a C10-18 hydrocarbon group at the 3-position, such as cardanol; a structure represented by the following formula (2); and a structure derived from a terpene phenol resin. (In the formula (2), X represents a C1-10 divalent linking group derived from a hydrocarbon; R represents a C10-18 hydrocarbon group; and m represents an integer of 1-10.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a phenoxy resin, a composition, a cured product, and a method for producing the phenoxy resin. [Background technology]

[0002] Phenoxy resins are useful compounds that are widely used as coating materials, adhesives, insulating materials, etc., because of their excellent properties such as flexibility, heat resistance, insulating properties, and adhesion. Therefore, various researches are being conducted with the aim of creating new phenoxy resins having excellent properties.

[0003] For example, Patent Document 1 discloses a phenoxy resin obtained by reacting a specific difunctional epoxy compound with a specific difunctional phenol compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-98836 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, in fields such as paints, materials with a high biomass component ratio have been attracting attention from the perspective of their potential contribution to the creation of a recycling-oriented society.

[0006] Conventional phenoxy resins have not been adequately examined with regard to the biomass component ratio, leaving room for improvement.

[0007] As a result of intensive research, the present inventors have found that the biomass component ratio can be increased by introducing a structure derived from a plant resource (for example, a structure derived from cardanol) into a phenoxy resin.

[0008] However, the phenoxy resins incorporating the above-mentioned plant-resource-derived structures have a problem in that, although they have flexibility, they have low hardness (pencil hardness).

[0009] Therefore, an object of the present invention is to provide a phenoxy resin which has a high biomass component ratio and can give a cured product with high pencil hardness. [Means for solving the problem]

[0010] That is, the present invention relates to a phenoxy resin including a structure represented by the following formula (1), a structure represented by the following formula (2), and a structure derived from a terpene phenol resin.

[0011] [ka] (In formula (1), R is a hydrocarbon group having 10 to 18 carbon atoms, and l is an integer of 1 to 10.)

[0012] [ka] (In formula (2), X is a divalent linking group derived from a hydrocarbon and having 1 to 10 carbon atoms, R is a hydrocarbon group having 10 to 18 carbon atoms, and m is an integer of 1 to 10.)

[0013] In the phenoxy resin of the present invention, in the above formulas (1) and (2), R is preferably a hydrocarbon group having 12 to 16 carbon atoms. In the phenoxy resin of the present invention, the above formula (1) is preferably derived from cardanol. In the phenoxy resin of the present invention, the structure derived from the terpene phenol resin is preferably derived from a terpene phenol resin having a softening point of 90°C or higher and 150°C or lower. The compositions of the present invention include the phenoxy resins of the present invention. The composition of the present invention preferably further comprises a curing agent. The composition of the present invention preferably further comprises a curing catalyst. The cured product of the present invention is obtained by curing the above-mentioned phenoxy resin and / or the above-mentioned composition. The method for producing a phenoxy resin of the present invention includes a step of reacting a compound represented by the following formula (3), a compound represented by the following formula (4), and a terpene phenol resin.

[0014] [ka] (In formula (3), R is a hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 2 to 20.)

[0015] [ka] (In formula (4), X is a divalent linking group having 1 to 10 carbon atoms derived from a hydrocarbon.) Effect of the Invention

[0016] The present invention can provide a phenoxy resin which has a high biomass component ratio and can give a cured product with high pencil hardness. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] (Phenoxy resin) The phenoxy resin of the present invention contains a structure represented by the following formula (1), a structure represented by the following formula (2), and a structure derived from a terpene phenol resin.

[0018] [ka] (In formula (1), R is a hydrocarbon group having 10 to 18 carbon atoms, and l is an integer of 1 to 10.)

[0019] [ka] (In formula (2), X is a divalent linking group derived from a hydrocarbon and having 1 to 10 carbon atoms, R is a hydrocarbon group having 10 to 18 carbon atoms, and m is an integer of 1 to 10.)

[0020] In the above formula (1), R is a hydrocarbon group having 10 to 18 carbon atoms. The hydrocarbon group having 10 to 18 carbon atoms may be linear or branched. The hydrocarbon group having 10 to 18 carbon atoms may be saturated or unsaturated. Among them, the hydrocarbon group having 11 to 17 carbon atoms is preferred, and from the viewpoint of the balance between the biomass component ratio and the pencil hardness of the cured product of the present invention, the hydrocarbon group having 12 to 16 carbon atoms is more preferred.

[0021] The above formula (1) is preferably derived from cardanol from the viewpoint of easy availability of raw materials. The structure derived from cardanol includes, for example, a cardanol structure in which R is a hydrocarbon group having 15 carbon atoms and 25 to 31 hydrogen atoms.

[0022] In the above formula (1), l means the number of constitutional units represented in parentheses in the above formula (1) in the phenoxy resin. In the above formula (1), l is an integer of 1 to 10. The constitutional units represented in parentheses in the above formula (1) may be present consecutively (as a block) or randomly in the phenoxy resin.

[0023] In the above formula (2), R is a hydrocarbon group having 10 to 18 carbon atoms. The hydrocarbon group having 10 to 18 carbon atoms may be linear or branched. The hydrocarbon group having 10 to 18 carbon atoms may be saturated or unsaturated. Of these, the hydrocarbon group having 11 to 17 carbon atoms is preferred, and from the viewpoint of the balance between the biomass component ratio and the pencil hardness of the cured product of the present invention, the hydrocarbon group having 12 to 16 carbon atoms is more preferred.

[0024] In the above formula (2), from the viewpoint of easy availability of raw materials, R may have a cardanol structure, which is a hydrocarbon group having 15 carbon atoms and 25 to 31 hydrogen atoms.

[0025] In the above formula (2), X is a divalent linking group having 1 to 10 carbon atoms derived from a hydrocarbon. The divalent linking group having 1 to 10 carbon atoms may be linear or branched, or may have a cyclic structure. Specific examples thereof include an alkylene group, an alkenylene group, an alkynylene group, and a cycloalkylidene group. Among these, from the viewpoint of availability, an alkylene group having 3 to 7 carbon atoms is preferred. The divalent linking group having 1 to 10 carbon atoms may contain a molecule other than carbon, such as an oxygen atom or a nitrogen atom, in the linking group. The divalent linking group having 1 to 10 carbon atoms may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, an alkoxy-substituted alkyl group, and a carboxyl group.

[0026] In the above formula (2), O 1 may be in the ortho, meta or para position relative to X, O 2 may be in the ortho, meta or para position relative to X, but from the viewpoint of availability, is preferably in the para position relative to X.

[0027] In the above formula (2), m means the number of constitutional units represented in parentheses in the above formula (2) in the phenoxy resin. In the above formula (2), m is an integer of 1 to 10. The constitutional units represented in parentheses in the above formula (2) may be present consecutively (as a block) or randomly in the phenoxy resin.

[0028] The structure derived from the terpene phenol resin has a terpene structure and a phenol structure. By having such a structure, it is possible to improve the biomass component ratio and pencil hardness.

[0029] The terpene structure is a structure derived from a terpene monomer. The terpene monomers are classified into, for example, hemiterpenes, monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, sesquaterpenes, and tetraterpenes depending on the number of isoprene units. Among these, a structure derived from a monoterpene is preferable.

[0030] Examples of the monoterpenes include pinene (α-pinene, β-pinene), terpineol (α-terpineol, β-terpineol, γ-terpineol), myrcene, camphene, limonene (d-limonene, l-limonene, dipentene), ocimene (α-ocimene, β-ocimene), alloocimene, phellandrene (α-phellandrene, β-phellandrene), terpinene (α-terpinene, γ-terpinene), terpinolene (α-terpinolene, β-terpinolene, γ-terpinolene, δ-terpinolene), 1,8-cineole, 1,4-cineole, sabinene, paramentadiene, and carene (δ-3-carene).

[0031] The structure derived from the terpene phenol resin is preferably derived from a terpene phenol resin having a softening point of 90°C or higher and 150°C or lower. The structure derived from the terpene phenol resin has a softening point of 90° C. or higher and 150° C. or lower, so that the biomass component ratio and pencil hardness can be sufficiently improved. The structure derived from the terpene phenol resin is more preferably derived from a terpene phenol resin having a softening point of 100°C or higher and 145°C or lower. The softening point is a temperature determined by the method specified in JIS K 6910:2007.

[0032] Examples of the structure derived from the terpene phenol resin include the structures shown below.

[0033] [ka] (In formula (5), x is an integer from 1 to 10, and y is an integer from 1 to 10.)

[0034] The phenoxy resin of the present invention has a weight average molecular weight (Mw) of preferably 1,000-10,000, and more preferably 1,500-5,000. The weight average molecular weight is measured, for example, as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0035] The phenoxy resin of the present invention has a high biomass component ratio. The biomass component ratio here refers to the ratio of biomass-derived components contained in the phenoxy resin component, and is expressed by the following formula. Biomass component ratio (%) = (mass of biomass-derived components / mass of phenoxy resin components) x 100 If the biomass component ratio is 25% or more, the biomass component ratio can be evaluated as being sufficiently high.

[0036] (Method of producing phenoxy resin) The method for producing a phenoxy resin of the present invention includes a step of reacting a compound represented by the following formula (3), a compound represented by the following formula (4), and a terpene phenol resin. Specifically, it is preferable to heat a compound represented by the following formula (3) and the above-mentioned terpene phenol resin in the presence of a catalyst, and then react the compound represented by the following formula (4) therewith.

[0037] First, the step of heating the compound represented by the following formula (3) and the above-mentioned terpene phenol resin in the presence of a catalyst (hereinafter also referred to as the heating step) will be described.

[0038] [ka] (In formula (3), R is a hydrocarbon group having 10 to 18 carbon atoms, and n is an integer of 2 to 20.)

[0039] [ka] (In formula (4), X is a divalent linking group having 1 to 10 carbon atoms derived from a hydrocarbon.)

[0040] In the method for producing a phenoxy resin of the present invention, a compound represented by the above formula (3) is prepared. The compound represented by the above formula (3) may be commercially available or may be synthesized by the following method.

[0041] An example of a method for synthesizing the compound represented by the above formula (3) is a method in which a compound represented by the following formula (6) is reacted in the presence of an acid catalyst.

[0042] [ka] (In formula (6), R 1 is a hydrocarbon group having 10 to 18 carbon atoms.

[0043] In the above formula (6), R 1 is a hydrocarbon group having 10 to 18 carbon atoms. The hydrocarbon group having 10 to 18 carbon atoms may be linear or branched. The hydrocarbon group having 10 to 18 carbon atoms may be saturated or unsaturated. Among them, the hydrocarbon group having 11 to 17 carbon atoms is preferable, and from the viewpoint of improving the biomass component ratio of the phenoxy resin and the cured product of the present invention and suppressing a decrease in the pencil hardness of the cured product, the hydrocarbon group having 12 to 16 carbon atoms is more preferable.

[0044] In the above formula (6), R 1 In terms of availability of raw materials, 1 Examples of such aryl groups include those having a cardanol structure, which is a hydrocarbon group having 15 carbon atoms and 25 to 31 hydrogen atoms.

[0045] As the acid catalyst, known acids can be used, for example, inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid, citric acid, propionic acid, oxalic acid, and p-toluenesulfonic acid. Among these, it is preferable to use p-toluenesulfonic acid from the viewpoints of catalytic activity and solubility in a solution. The content of the acid catalyst is about 0.1 to 4.0 parts by mass relative to 100 parts by mass of the compound represented by the formula (6).

[0046] The reaction temperature when the compound represented by the above formula (6) is reacted in the presence of an acid catalyst is, for example, about 120 to 180° C. The reaction time is, for example, about 1 to 10 hours. The fact that the target compound represented by the above formula (3) has been obtained can be confirmed, for example, by using gel permeation chromatography (GPC) to confirm a decrease in the peak derived from the above formula (6) and the distillation of a new component.

[0047] The apparatus used in the above reaction (eg, stirring apparatus, reflux apparatus) may be appropriately selected from known apparatuses. After the reaction, the product may be purified by a known method or may not be purified. It is more preferable to purify the product by a known method.

[0048] The terpene phenol resin can be obtained by copolymerizing the terpene monomer with phenol.

[0049] The softening point of the terpene phenol resin is preferably 90°C or higher and 150°C or lower, and more preferably 100°C or higher and 145°C or lower. The softening point can be measured by the method described above.

[0050] The terpene phenol resin preferably has the structure of the above formula (5). Commercially available products of such terpene phenol resins include, for example, YS Polystar T100, YS Polystar T115, YS Polystar U115, YS Polystar K125, and YS Polystar S145 (all manufactured by Yasuhara Chemical Co., Ltd.).

[0051] The method for producing a phenoxy resin of the present invention preferably includes the heating step.

[0052] In the heating step, the mass ratio of the compound represented by formula (6) to the terpene phenol resin (compound represented by formula (6) : terpene phenol resin) is preferably 1:0.2 to 1.0 from the viewpoint of the physical properties of the coating film when cured.

[0053] The heating step is carried out in the presence of a catalyst, preferably an acid catalyst. As the acid catalyst, known acids can be used, for example, inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as acetic acid, citric acid, propionic acid, oxalic acid, and p-toluenesulfonic acid. Among these, it is preferable to use p-toluenesulfonic acid from the viewpoints of catalytic activity and solubility in a solution.

[0054] The amount of the acid catalyst used varies depending on the type of acid catalyst, but is, for example, about 0.1 to 5.0 parts by mass per 100 parts by mass of the compound represented by the formula (6) above.

[0055] In the heating step, a solvent may be used. The solvent is not particularly limited, but preferred examples thereof include water, alcohols such as methanol, ethanol, and 2-propanol, aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, methyl ethyl ketone, methyl isobutyl ketone, methylene chloride, and dimethylformamide, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, chloroform, and carbon tetrachloride, but are not limited to these. The above solvents may be used alone or in combination of two or more kinds.

[0056] The amount of the solvent used is, for example, about 30 parts by mass or less per 100 parts by mass of the compound represented by the formula (6) above.

[0057] The reaction temperature in the heating step is, for example, about 60 to 150° C. The reaction time is, for example, about 0.25 to 10 hours.

[0058] The equipment used in the heating step (eg, stirring equipment, reflux equipment) may be appropriately selected from known equipment.

[0059] It is preferable to have a step of reacting the compound represented by the above formula (4) after the above heating step. In the step of reacting the compound represented by the above formula (4), it is preferable to react the compound represented by the above formula (4) under basic conditions. This gives the phenoxy resin of the present invention.

[0060] In the step of reacting the compound represented by formula (4) above, the epoxy group of the compound represented by formula (4) above reacts with the hydroxyl group having a structure derived from the compound represented by formula (6) above or the hydroxyl group having a structure derived from the terpene phenol resin. The sites at which the epoxy groups of the compound represented by the above formula (4) react may be continuous (blocked) or random.

[0061] In the compound represented by the above formula (4), X is a divalent linking group having 1 to 10 carbon atoms derived from a hydrocarbon. The divalent linking group having 1 to 10 carbon atoms may be linear or branched, or may have a cyclic structure. Specific examples thereof include an alkylene group, an alkenylene group, an alkynylene group, and a cycloalkylidene group. Among these, from the viewpoint of availability, an alkylene group having 3 to 7 carbon atoms is preferred. The divalent linking group having 1 to 10 carbon atoms may contain a molecule other than carbon, such as an oxygen atom or a nitrogen atom, in the linking group. The divalent linking group having 1 to 10 carbon atoms may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, an alkoxy-substituted alkyl group, and a carboxyl group.

[0062] In the above formula (4), O 1 may be in the ortho, meta or para position relative to X, O 2 may be in any of the ortho, meta, and para positions relative to X. From the viewpoint of availability, O 1 and O 2 is preferably in the para position relative to X.

[0063] In the step of reacting the compound represented by the above formula (4), the amount of the compound represented by the above formula (4) used in the heating step is preferably such that the mass ratio of the compound represented by the above formula (6) used in the heating step to the compound represented by the above formula (4) (the compound represented by the above formula (6) : the compound represented by the above formula (4)) is 1:0.7 to 5.0 from the viewpoint of the coating film properties upon curing.

[0064] In the step of reacting the compound represented by formula (4) above, a base may be added to the reaction solution in the heating step.

[0065] The base is not particularly limited, but examples thereof include alkali metal hydrides, alkaline earth metal hydrides, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogencarbonates, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal fluorides, amines, and organic phosphorus compounds. The amount of the base used varies depending on the type of base, but is, for example, about 0.1 to 2.0 parts by mass per 100 parts by mass of the compound represented by formula (4) above.

[0066] In the step of reacting the compound represented by the above formula (4), a solvent may be used. The solvent is not particularly limited, but for example, the same solvent as that used in the heating step can be used. The above solvents may be used alone or in combination of two or more kinds. The amount of the solvent used is, for example, about 30 parts by mass or less per 100 parts by mass of the compound represented by the formula (6) above.

[0067] The reaction temperature in the step of reacting the compound represented by the above formula (4) is, for example, about 60 to 120° C. The reaction time is, for example, about 30 minutes to 10 hours. The desired phenoxy resin can be confirmed by, for example, using gel permeation chromatography (GPC), confirming a decrease in the peak derived from the raw material (for example, the compound represented by the above formula (4)) and the distillation of new components.

[0068] The apparatus used in the above reaction (eg, stirring apparatus, reflux apparatus) may be appropriately selected from known apparatuses. After the reaction, the product may be purified by a known method or may not be purified. It is more preferable to purify the product by a known method.

[0069] (composition) The compositions of the present invention include the phenoxy resins of the present invention. Since the composition of the present invention contains the above-mentioned phenoxy resin, it is possible to obtain a cured product having a high biomass component ratio and excellent pencil hardness.

[0070] The composition of the present invention preferably further comprises a curing agent.

[0071] Examples of the curing agent include amine curing agents, phenolic curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. The curing agents may be used alone or in combination of two or more.

[0072] The content of the curing agent is preferably 20 to 90 parts by mass relative to 100 parts by mass of the phenoxy resin.

[0073] From the viewpoint of shortening the curing time, it is preferable that the composition of the present invention further contains a curing catalyst.

[0074] Examples of the curing catalyst include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol; and imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole. The above curing catalysts may be used alone or in combination of two or more.

[0075] The content of the curing catalyst is preferably 0.1 to 2.0 parts by mass relative to 100 parts by mass of the phenoxy resin.

[0076] The composition of the present invention may further comprise a solvent.

[0077] Preferred examples of the solvent include water, alcohols such as methanol, ethanol, and isopropyl alcohol, aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, methyl ethyl ketone, methyl isobutyl ketone, methylene chloride, and dimethylformamide, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, chloroform, and carbon tetrachloride, but are not limited to these. The above solvents may be used alone or in combination of two or more kinds.

[0078] The composition of the present invention may further comprise additives.

[0079] The additives include a photopolymerization initiator, a phosphorus-containing compound, a binder resin, an inorganic filler, and the like. These may be appropriately selected from known ones.

[0080] (cured product) The cured product of the present invention is obtained by curing the phenoxy resin of the present invention and / or the composition of the present invention. Since the cured product of the present invention contains the phenoxy resin of the present invention, it is possible to obtain a cured product having a high biomass component ratio and excellent pencil hardness.

[0081] The cured product of the present invention can be obtained by curing the phenoxy resin of the present invention and / or the composition of the present invention using a conventionally known method. For example, the phenoxy resin of the present invention, the curing agent, and the curing catalyst are thoroughly mixed until homogeneous using an extruder, kneader, roll, or the like as necessary to prepare a composition, which is then applied to a substrate by a known method, and then allowed to stand at 20 to 40° C. for 12 to 48 hours, to obtain the cured product of the present invention. The temperature and time during standing are not limited to the above ranges, and may be appropriately selected depending on the type of curing agent, etc. If necessary, the composition may contain additives.

[0082] The cured product of the present invention has high pencil hardness. The pencil hardness can be evaluated, for example, by preparing a cured product (100 mm long x 100 mm wide, 200 μm thick) on a glass plate (100 mm long x 100 mm wide) and measuring according to JIS K 5600-5-4:1999. If the pencil hardness is F or more, it can be evaluated as having sufficient pencil hardness. The pencil hardness is more preferably H or more.

[0083] The cured product used for pencil hardness is prepared, for example, by the following method. The amounts of the curing agent and catalyst used are adjusted according to the phenoxy resin, etc. 100 parts by mass of phenoxy resin is taken, 51 parts by mass of a curing agent (ST11, manufactured by Mitsubishi Chemical Corporation) and 1 part by mass of 2,4,6-trisdimethylaminomethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) are added and mixed to obtain a composition. The above composition is applied onto a glass plate (100 mm long x 100 mm wide) and allowed to stand at room temperature for 3 days to prepare a test cured product (100 mm long x 100 mm wide, 200 μm thick).

[0084] The cured product of the present invention has a high biomass component ratio. The biomass component ratio of the cured product refers to the ratio of biomass-derived components contained in the cured product, and is expressed by the following formula. Biomass component ratio (%) = [mass of biomass-derived components / (total mass of phenoxy resin components + hardener + hardening catalyst + solvent + additives)] x 100 A biomass component ratio of 15% or more can be evaluated as being sufficiently high.

[0085] The present specification discloses the following:

[0086] The present disclosure (1) is a phenoxy resin containing a structure represented by the above formula (1), a structure represented by the above formula (2), and a structure derived from a terpene phenol resin. The present disclosure (2) is the phenoxy resin according to the present disclosure (1), in which in the above formulas (1) and (2), R is a hydrocarbon group having 12 to 16 carbon atoms. The present disclosure (3) is the phenoxy resin according to the present disclosure (1) or (2), in which the above formula (1) is derived from cardanol. The present disclosure (4) is the phenoxy resin according to any one of the present disclosures (1) to (3), in which the structure derived from the terpene phenol resin is derived from a terpene phenol resin having a softening point of 90° C. or higher and 150° C. or lower. The present disclosure (5) is a composition containing the phenoxy resin according to any one of the present disclosures (1) to (4). The present disclosure (6) is the composition according to the present disclosure (5), further comprising a curing agent. The present disclosure (7) is the composition according to the present disclosure (5) or (6), further comprising a curing catalyst. The present disclosure (8) is a cured product obtained by curing the phenoxy resin according to any one of the present disclosures (1) to (4) and / or the composition according to any one of the present disclosures (5) to (7). The present disclosure (9) is a method for producing the phenoxy resin according to any one of the present disclosures (1) to (4), the method including a step of reacting a compound represented by the above formula (3), a compound represented by the above formula (4), and a terpene phenol resin. EXAMPLES

[0087] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass".

[0088] Example 1 In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 100 parts by mass of purified cardanol was weighed out while purging with nitrogen, and 40 parts by mass of YS Polystar T100 (manufactured by Yasuhara Chemical Co., Ltd., softening point 100°C) and 3.1 parts by mass of p-toluenesulfonic acid monohydrate were added to prepare a reaction solution. The reaction solution was then heated to 100°C and stirred for 4 hours. To the reaction solution, 19 parts by mass of an aqueous sodium hydroxide solution (1.2 parts by mass of sodium hydroxide dissolved in 17.8 parts by mass of ion-exchanged water) was added, and the mixture was stirred for 30 minutes while being cooled to 75°C. Next, 260 parts by mass of bisphenol A type epoxy resin jER-828 (manufactured by Mitsubishi Chemical Corporation) was added, and the mixture was stirred at 75° C. for 1 hour. The reaction temperature was returned to room temperature, and the aqueous layer was extracted three times with ethyl acetate, and then the organic layer was dehydrated over sodium sulfate. Thereafter, the sodium sulfate was removed by filtration, and the solvent was removed by an evaporator to obtain a phenoxy resin containing the structure represented by the above formula (1), the structure represented by the above formula (2), and a structure derived from a terpene phenol resin. Gel permeation chromatography (GPC) confirmed the decrease in the peak derived from bisphenol A type epoxy resin and the distillation of new high molecular weight components, confirming that the desired phenoxy resin had been obtained. The biomass content of this phenoxy resin was 30.5%. The biomass component ratio was calculated using the method described in this specification.

[0089] Example 2 A phenoxy resin was synthesized in the same manner as in Example 1, except that YS Polystar T100 was changed to YS Polystar T115 (manufactured by Yasuhara Chemical Co., Ltd., softening point 115°C) and that the mixture was temporarily heated to 130°C immediately after addition and stirred for 30 minutes in order to dissolve the YS Polystar T115. The biomass content of this phenoxy resin was 31.0%.

[0090] Example 3 A phenoxy resin was synthesized in the same manner as in Example 1, except that YS Polystar T100 was changed to YS Polystar U115 (manufactured by Yasuhara Chemical Co., Ltd., softening point 115°C) and that the mixture was temporarily heated to 130°C immediately after addition and stirred for 30 minutes in order to dissolve the YS Polystar U115. The biomass content of this phenoxy resin was 32.0%.

[0091] Example 4 A phenoxy resin was synthesized in the same manner as in Example 1, except that YS Polystar T100 was changed to YS Polystar K125 (manufactured by Yasuhara Chemical Co., Ltd., softening point 125°C) and that the mixture was temporarily heated to 130°C immediately after addition and stirred for 30 minutes in order to dissolve the YS Polystar K125. The biomass content of this phenoxy resin was 29.5%.

[0092] Example 5 A phenoxy resin was synthesized in the same manner as in Example 1, except that YS Polystar T100 was changed to YS Polystar S145 (manufactured by Yasuhara Chemical Co., Ltd., softening point 145°C) and that the mixture was temporarily heated to 150°C immediately after addition and stirred for 30 minutes in order to dissolve the YS Polystar S145. The biomass content of this phenoxy resin was 31.5%.

[0093] Comparative Example 1 Bisphenol A type epoxy resin jER-828 (manufactured by Mitsubishi Chemical Corporation) was prepared. The biomass content of this epoxy resin was 0.0%.

[0094] Comparative Example 2 [Synthesis of the compound represented by the above formula (3)] In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 100 parts by mass of purified cardanol was weighed out while purging with nitrogen, and 0.8 parts by mass of p-toluenesulfonic acid monohydrate was added to prepare a reaction solution. The reaction solution was then heated to 150° C. and stirred for 3 hours. The reaction temperature was returned to room temperature, and the mixture was neutralized with an aqueous sodium hydroxide solution. The aqueous layer was extracted three times with ethyl acetate, and the organic layer was then dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the solvent was then removed by distillation using an evaporator. The obtained crude product was heated to 300°C and stirred under reduced pressure for 3 hours to remove the distillate components, thereby obtaining a compound represented by the above formula (3) (in formula (3), R is a hydrocarbon group having 15 carbon atoms). Gel permeation chromatography (GPC) confirmed the decrease in the peak derived from cardanol and the distillation of new high molecular weight components, confirming that the compound represented by formula (3) above was obtained.

[0095] [Synthesis of compound represented by formula (7)] In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 100 parts by mass of the compound represented by the above formula (3) was weighed out while purging with nitrogen, and 9 parts by mass of methanol, 2.5 parts by mass of water, 134 parts by mass of epichlorohydrin, and 29 parts by mass of sodium hydroxide were added, followed by stirring at 75°C for 3 hours. The reaction temperature was returned to room temperature, the solid components were removed by filtration, and the solvent and epichlorohydrin were then distilled off using an evaporator. The resulting reaction solution was extracted three times with ethyl acetate, and the organic layer was then dehydrated over sodium sulfate. Thereafter, the sodium sulfate was removed by filtration, and the solvent was removed by an evaporator to synthesize an epoxy resin represented by the following formula (7). The infrared absorption spectrum of the obtained epoxy resin was measured, and -1 The appearance of a peak derived from an epoxy group in the vicinity of 3100–3600 cm -1 The disappearance of the peaks derived from the hydroxyl groups was confirmed, and it was confirmed that an epoxy resin represented by the following formula (7) was obtained. The biomass content of this epoxy resin was 76.6%.

[0096] [ka] (In formula (7), R is a hydrocarbon group having 15 carbon atoms, and z is an integer of 2 to 20.)

[0097] Comparative Example 3 In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 100 parts by mass of the compound represented by the above formula (3) was weighed out while purging with nitrogen, and 100 parts by mass of bisphenol A type epoxy resin jER-828 (manufactured by Mitsubishi Chemical Corporation), 1.3 parts by mass of sodium hydroxide, 18 parts by mass of methanol, and 5 parts by mass of water were added to prepare a reaction solution. The reaction solution was then heated to 75°C and stirred under reflux for 3 hours. The reaction temperature was returned to room temperature, and the aqueous layer was extracted three times with toluene, and then the organic layer was dehydrated with sodium sulfate. Thereafter, the sodium sulfate was removed by filtration, and the solvent was removed by distillation using an evaporator to obtain a phenoxy resin containing a structure represented by the above formula (1) (in formula (1), R is a hydrocarbon group having 15 carbon atoms) and a structure represented by the above formula (2) (in formula (2), X is a linking group having 3 carbon atoms, and R is a hydrocarbon group having 15 carbon atoms). Gel permeation chromatography (GPC) confirmed the decrease in the peak derived from bisphenol A epoxy resin and the distillation of new high molecular weight components, confirming that the desired phenoxy resin had been obtained. The biomass content of this phenoxy resin was 50.0%.

[0098] Comparative Example 4 A phenoxy resin was synthesized in the same manner as in Comparative Example 3, except that the amount of the compound represented by the above formula (3) was changed to 60 parts by mass and the amount of the bisphenol A type epoxy resin jER-828 was changed to 140 parts by mass. The biomass content of this phenoxy resin was 30.0%.

[0099] Comparative Example 5 A phenoxy resin was synthesized in the same manner as in Comparative Example 3, except that the amount of the compound represented by the above formula (3) was changed to 20 parts by mass and the amount of the bisphenol A type epoxy resin jER-828 was changed to 180 parts by mass. The biomass content of this phenoxy resin was 10.0%.

[0100] [Preparation of test cured material] 100 parts by mass of the phenoxy resin synthesized in Example 1 was taken, and 51 parts by mass of a curing agent (ST11, manufactured by Mitsubishi Chemical Corporation) and 1 part by mass of 2,4,6-trisdimethylaminomethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and mixed to obtain a composition. The above composition was applied onto a glass plate (100 mm long x 100 mm wide) and allowed to stand at room temperature for 3 days to prepare a test cured product (100 mm long x 100 mm wide, 200 μm thick). The biomass component ratio of this hardened test material was 20.1%. The biomass component ratio of the cured product was calculated by the method described in this specification.

[0101] As in Example 1, the resins obtained in Examples 2 to 5 and Comparative Examples 1 to 5 were mixed in the parts by mass shown in Table 1 to obtain compositions. From these compositions, test cured materials were prepared in the same manner as in Example 1. The biomass component ratios of these test cured materials are also shown in Table 1. In Comparative Example 2, the resin and the curing agent were not compatible with each other, and a composition could not be obtained.

[0102] <Compatibility with hardener> The resin, curing agent, and catalyst were mixed in the amounts shown in Table 1, and the mixture was allowed to stand for 5 minutes before being inspected for appearance and evaluated according to the following criteria. The results are shown in Table 1. Good: Resin and hardener are mixed evenly. Poor: The resin and hardener do not mix uniformly and separate.

[0103] <Pencil hardness> The pencil hardness of the obtained test cured products was measured in accordance with JIS K 5600-5-4:1999. The results are shown in Table 1.

[0104] [Table 1]

[0105] It has been confirmed that the phenoxy resin having a structure derived from the terpene phenol resin of the present invention has a biomass component ratio of 25% or more, a high biomass component ratio of 15% or more, and can give a cured product having an excellent hardness of pencil hardness of F or more. [Industrial Applicability]

[0106] The present invention can provide a phenoxy resin which has a high biomass component ratio and can give a cured product with high pencil hardness.

Claims

1. A phenoxy resin comprising a structure represented by the following formula (1), a structure represented by the following formula (2), and a structure derived from a terpene phenol resin. 【Chemistry 1】 (In formula (1), R is a hydrocarbon group having 10 to 18 carbon atoms, and l is an integer from 1 to 10.) 【Chemistry 2】 (In formula (2), X is a divalent linking group having 1 to 10 carbon atoms derived from a hydrocarbon, R is a hydrocarbon group having 10 to 18 carbon atoms, and m is an integer of 1 to 10.)

2. 2. The phenoxy resin according to claim 1, wherein in the formulas (1) and (2), R is a hydrocarbon group having 12 to 16 carbon atoms.

3. The phenoxy resin according to claim 1 or 2, wherein the formula (1) is derived from cardanol.

4. The phenoxy resin according to claim 1 or 2, wherein the structure derived from the terpene phenol resin is derived from a terpene phenol resin having a softening point of 90° C. or higher and 150° C. or lower.

5. A composition comprising the phenoxy resin of claim 1.

6. The composition of claim 5 further comprising a curing agent.

7. The composition of claim 5 further comprising a curing catalyst.

8. A cured product obtained by curing the phenoxy resin according to claim 1 and / or the composition according to claim 5.

9. A method for producing the phenoxy resin according to claim 1 or 2, A method for producing a phenoxy resin, comprising the step of reacting a compound represented by the following formula (3), a compound represented by the following formula (4), and a terpene phenol resin: 【Chemistry 3】 (In formula (3), R is a hydrocarbon group having 10 to 18 carbon atoms, and n is an integer from 2 to 20.) 【Chemistry 4】 (In formula (4), X is a divalent linking group having 1 to 10 carbon atoms derived from a hydrocarbon.)

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